Water or Stop Bath

Discussion in 'Black and White' started by rowland_mowrey, Sep 22, 2004.

  1. Moderator's notes - This thread has, regrettably, been locked from further participation for the following reasons:

    1. Numerous references to color processes which are irrelevant to this forum and this thread in particular. Many of us have never and will never do any color processing. So any such references only serve to muddy the waters and tax our patience. If you ever find it impossible to avoid a reference to a color process or material in the b&w forums be prepared to defend - briefly - why it is necessary to include such a reference here. Otherwise I'm likely to delete it immediately. If I'm in a good mood I'll send to you an e-mail explaining why I deleted your comment, altho' I'm not obligated to do so - the guidelines for topics appropriate to these forums is clearly explained before you ever write a comment.

    Otherwise I'm likely to begin deleting entire paragraphs which may, unfortunately, include information that is related to b&w photography in the interest of keeping the discussion on track.

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    And if there's a moral to the demise of this thread it's that a manifesto can undermine the best of intentions.

    Lex Jenkins
    Moderator, photo.net b&w photography forums


    The following begins the originating post for this thread, from Rowland Mowrey:

    Throughout this forum I have seen several posts stating that stop
    baths after development are not desirable. I see that Anchell and
    Troop are also against it.

    I would like to address their comments on p103 of "The Film
    Developing Cookbook"

    1. the pH change from developer to stop can generate molecular heat
    and cause grains in the film to clump.

    I have never heard of this at all under any circumstances after 32
    years at EK. I would like to have a reference cited for this
    statement as they seem to have statements for many of their other
    assertions.

    2. Acid stop baths cause pinholes and reticulation with developers
    containing carbonate.

    In the time I spent doing process research, I heard exactly one
    comment on this. With color paper using a carbonate P122 developer,
    or some B&W and color films in DEEP TANK PROCESSES ONLY (note that),
    the hydrostatic pressure caused bubbles to form in the emulsion as it
    emerged from the deep tank which resulted in pinholes. This problem
    ceased after about 1970 since most all manufacturers changed film and
    paper hardeners so that they can survive higher temperature
    processes. At no time did I ever hear of reticulation caused by stop
    baths.

    3. Acid stop baths cause excessive swelling which leads to a loss in
    image integrity.

    Never heard of this one either.

    In any case, if this happened, do you think that acid stop baths
    would continue to be manufactured? I don't think so! If stop baths
    did cause swelling and reticulation, it would be a snap to design a
    hardening stop. In fact, the C-22 and P122 processes had them.

    Stop baths promote uniformity by stopping development rapidly and
    uniformly. Water stop baths can cause different results based on
    water supply (hardness, softness, pH and etc. I know, I've run quite
    a few experiments on washes following development).

    If you are worried about swell, look more to your water supply for
    the source of the problem, not the stop bath. OTOH, you can make up
    a hardening stop. Oh, BTW, distilled water can promote swell due to
    the absence of salts. As a rule of thumb, salts reduce swell.

    As for hardeners, they should not be needed if you use modern films
    or papers from EK, Ilford, Fuji, Konica, and Agfa. In any event,
    alum hardeners should not be used without a stop, as the alum can
    cause scum to form. They are ok fresh, but exhaust rapidly without a
    stop and then begin to verge on precipitation of the alum due to an
    increase in alkalinity of the fix.

    On page 121 of their book, A&T recommend glutaraldehyde and
    succinaldehyde hardeners due to the problems with formaldehyde. The
    only problem is that these compounds can also cause fogging of films
    or papers unless neutralized before development (remember the E4
    neutralizer?). They are aldehydes just like formaldehyde. They do
    harden, but they allow much more swell of the hardened gelatin due to
    the longer carbon chain length. This has been studied by EK years
    ago during the E4 process years. The gelatin is certainly hard, but
    swollen more than with formaldehyde, as the carbon chains linking the
    gelatin are 5 and 6 atoms longer respectively with these two
    aldehydes.

    So, after reading all of those posts, and getting to what appears to
    be the source of some of the comments I have read here on the forum,
    I thought it might be of interest to post my actual observations from
    my years of research in this field.

    I hope that my observations and experience help those of you that
    have posted these questions time and again. I'm sorry if these
    observations differ from those of A&T, but as I said, I have run the
    experiments myself more than once.

    With apologies to A&T.

    Ron Mowrey
     
  2. 1)Well - I hadn't heard of this either but it stands to reason. Many acid-base reactions are exothermic and produce heat. If the chemical kinetics of grain clumping are a function of temperature (and probably other things) then an increase in grain clumping seems to follow. It may be (probably is) an imperfect analogy but sudden application of extreme thermal gradients causes grains to coalesce in many alloy systems.
    2) I've heard numerous references to the reaction to carbonate alkali and acid stop baths inducing pin holes. In fact, I can say that this is the *only* one of the three concerns I had heard of before buying the Film Developing Cookbook. The colloquial term "pin hole" seems a poor (pore?) description, so perhaps this prompts the confusion.
    3) Well, I'm not sure how the gelatin swelling impairs image quality per se, but as per #1 I would expect an exothermic acid-base reaction to cause the gelatin to swell simply from thermal expansion.
     
  3. Perhaps the image quality concern in #3 applies to reticulation...
     
  4. Al;

    Actually, development itself generates heat in the emulsions of film and paper both, and the pH drops considerably during the development process. In some developers, the pH in high silver areas is quite low, in fact, acidic in some cases.

    I have heard of development taking place at temperatures up to over 120 deg C without severe reticulation or clumping in a dry process, and up to 120 deg F in wet processes without clumping. I've done it in fact.

    Pinholes from stop baths were never a problem except in the rare cases that I cited above. B&W papers never suffered from the problem even in the severest cases. Pinholes were either as cited above in very rare cases, or due to airbells (bubbles) during development itself.

    Ron Mowrey
     
  5. Rowland:

    You put it better than I can, but your observations mirror mine. I am only a hobbyist in this craft, but I have never had a problem using an acid stop bath. The only time I don't use it is if there is a specific recommendation not to, I use Diafine, since the manufacturer recommends against it. I ran a few trials for a while without stop bath and found that my fixer did not last nearly as long but encountered no other significant problems. The way I figure, stop bath is cheap and pays for itself in increased fixer life. I see no reason not to use it unless there is a specific recommendation not to.
     
  6. I've never used a stop bath for film. My reasons were totally unscientific as it was just something else to buy and deal with.

    Since my negs are fine, I'm staying in the "If it ain't broke, don't fix it" school of thought. Of course, the same logic applies if you are using a stop bath.

    Question: if you currently have good negs, is there any reason to use a stop bath, other than increased fixer life?
     
  7. Dear Rowland,

    Thank you for your post. I like controlling when the development is complete. To date, I have never had any problems due to stop bath (or fixer for that matter), always due to human error.

    Neal Wydra
     
  8. Your observations are excellent Rowland, and it's refreshing to see someone disspelling the myths most of us grow to believe and keep teaching the next generations.

    I have for years used only 3 or 4 changes of water as stop bath, with no ill results in image or fixer life. I have, however, used acid stop ocasionally for film and almosy always for paper.

    I guess the only reason I'd advise acid stop is if you are using alkaline fixer.
     
  9. Bob;

    OTOMY, the only reasons to use a stop bath are:

    1. Uniformity due to the variations in water quality around the world, agitation, and the variations in development rate with different developers.

    2. Preservation of fix whatever the type.

    3. Prevention of scum if you use an acid hardening fix.

    I may think of more. I'll let you know if I think of them.

    Ron Mowrey
     
  10. Reasons not to use a stop with film:

    more chemical to buy, store, mix, dispose of

    no observable difference in film processed without it

    water smells better than stop bath
     
  11. Ron:

    You mentioned in passing that distilled water can cause swell due to the absence of salts.

    After my own seven-year absence from the darkroom, I'm planning to resume developing film this week and had planned to use distilled water. Way back when, I used to use tap water. My negs were okay but, I suppose, not perfect; however, I never determined whether my water supply was the culprit.

    Now, I'm willing to use whatever is really best -- tap, distilled, even so-called Smart Water (distilled water with some salts added back in).

    Any words of guidance?

    Jonathan
     
  12. When employees here dont use acid stop bath; they get fired. The graphics art developer we still use is very alkaline; the acid stop makes the rapid fixer last way longer. When the acid stop is replaced with water; the fixer poops out early; and we get staining; customer returns. Having to redo customers work is bad. Having cocky employees who skip steps; and then dont check the fixer; and turn out crap work is bad too. One should understand when one can get away with just water as a stop; and know when ones fixer is till good. Blindly replacing a step can be dangerous. <BR><BR>In pictoral and smaller negatives; we sometimes use a weaker stop; top reduce pinholing.
     
  13. I have done some strange things, as everyone here knows. One would almost believe I deliberately tried to get pinholes and reticulation. I have had reticulation, but it was a long time ago, and I attributed it to drying film too slowly. When you use moderate heat in drying, the film does not heat until the water is gone due to the cooling effect of evaporation. I think a longer wet time is worse than a little moving, warm, air.

    I use an alkaline fixer without either acid stop or plain water. It stops development right away, at least as quickly as a water bath. The developer carried over seems not to have any appreciable effect on life of an alkaline fixer such as TF4. Often, I pour fixer concentrate into the developer at the end of development in the amount of 1/16 to 1/8 of the developer, pouring out a little developer if there is not room in the tank. I have had no problems with uneven development, pinholes or reticulation with modern films. It is possible that the transition directly from alkaline developer to alkaline fixer is a lesser strain on the emulsion, but I have not seen any effects of such strains in acid fixers either, nor have I seen increased grain in one case or the other.

    I am not recommending this process for precision work such as lithography, or that any long standing and effective process be changed. I am simply pointing out that, as Ron has said, many theories about what happens to film are based on ancient history, or superstition.

    Surely I am sloppy sometimes, but often it is a matter of finding out for myself if a certain theory is fact. I was born in West Virginia, where montani semper liberi, and raised in Missouri, where one is supposed to say "Show me."
     
  14. Ron, glad you raised this issue, it's caused me a few sleepless nights. I have always used an acid stop bath (Kodak Indicating) and have never had a problem with pinholing even with developers using carbonate as the alkali. Having said that when using Jacobson Pyrocatechin I did use a water stop bath as advised. The argument re: the generation of heat, while theoretically correct, I doubt that the heat generated by such small amounts at such high diltuions could generate sufficient heat to cause the effects claimed. As for the effects of pH, gelatin contracts to a minimum volume at pHs in the range 4.5-5.0. Acid stop bath may, when fresh, have a lower pH than this and thus cause swelling, but that can be remedied by buffering with sodium acetate. On the alkaline side gelatin swells moderately at pHs between 5.0-8.0 then more markedly at higher pHs. Thus I would expect highly alkaline developers to pose more problems with swelling that acid stop.

    All that said I use Rodinal which contains the highly alkaline potassium hydroxide and yet use an acid stop but have never experienced reticulation.
     
  15. As a P.S. perhaps I could direct readers to 'www.screensound.gov.au', and the section headed 'Gelatin'. It makes interesting reading.
     
  16. Ron-great post. I was always a little skeptical about the A&T comments on acid stop baths but, afterall, they are the experts. From now on, to me, you are to be known as Rowland "R. Henry" Mowrey, and that is a huge compliment as far as I'm concerned. Would you expand a little on your subsequent comment "actually, development itself generates heat in the emulsions of film and paper both --". For quite some time I have played a little game trying to get the film developer temperature to start and end the same. No matter what I do it's always higher at the end of development. Even with a carefully controlled water bath, a temperature stabilizing presoak and very little direct hand contact with my 32oz stainless tank the temperature will rise .2 to .5 degrees. I could never figure out why this was happening. Could the heat generation you referred to be enough to account for the temperature shifts I'm seeing or is something else causing this? Incidently, I realize controlling developer temp within 1 degree is probably all the control anyone needs but, as I said, it has just been a game I play.
     
  17. Very interesting. I have not read the book in question myself, but I haven't had problems with using an acid stop (I've had prints from 35 mm mistaken to be from medium format by other photographers, so I guess image quality has not been compromised...)
     
  18. Wallace Hanson wrote ("The Great Stopbath Squabble";Pop Photo;1975)an article in which he detailed experiments, by himself, trying to explore/create these very touted effects. He was unable to produce any of the defects often cited by the anti-acid proponets.
    I've cited this article over the years, but the stopbath myths, like the energizer bunny,just keep on going.
    As to extra cost, smell. and time- can't argue against that.
     
  19. In order to avoid any temperature rise during development, it seems to me that one would have to avoid agitation. The mechanial energy of agitation is converted into heat. That would be a minimum requirement, and it does not take into account heat due to chemical reactions.

    If a rise in temperature is a consequence of successful development, why worry about it? If you are going to worry about it anyway, then reduce the temperature of the water bath to take away the heat of mechanical motion and chemical reaction, but IMHO it will be a waste of resources. Sometimes it's better not to know too much.

    Ascorbate developers reduce the pH locally by generation of acidic bromide and dehydroascorbic acid. That is the source of the edge sharpness and of part of the difference between ascorbic acid and hydroquinone. I have seen no sign of increase in grain or reticulation or any other cause for worry when using ascorbic or erythorbic acid developers.
     
  20. Hi Rowland, Fascinating, thankyou for taking the time out to dispell some of the myths with hard evidence. However, with fear of opening up this thread to a different (but closely related topic)I thought we were all over acid rapid fixers now that we have such good alkaline fixers like TF-4? I believe alkaline fixers wash out of the emulsion more easily and, therefore, improve archival permanence of our negatives? The price of alkaline fixers is pretty much the same as acid ones and surely their improved washing characteristics mean they are to be promoted? We do not use acid stop baths with alkaline fixers (which can be used with any developer - not just staining/tanning soups).Water stops film developing at no cost and no effect on the final product (as long as you are consistent and have factored it into your developing time - the change is miniscule) and alkaline fix is the way forward I would have thought?

    Your comments on these beliefs/opinions would be welcome sir.
     
  21. Patrick, have you tried skipping the stop bath when printing as well? Wouldn't mind getting rid of one of the trays....
     
  22. Partick wrote, "Ascorbate developers reduce the pH locally by generation of acidic bromide and dehydroascorbic acid."

    Patrick - perhaps you made a typo in that sentence, but I think you'll find that bromide itself is not acidic. It is in fact a weak base, which when combined with a hydrogen ion which is considered a strong acid, makes a compound, HBr, which is a very strong acid. But bromide ions themselves are not acidic in aqueous solutions.

    Measure the pH of a sodium bromide solution (weak acid combined with weak base = neutral aqueous solution) to demonstrate this.

    Perhaps you meant that the release of bromide by the action of the ascorbic acid on silver bromide causes an acidic condition?
     
  23. Chris - excellent link - Thanks!
     
  24. Ron, expanding on John's comments, A&T also claim that non-sodium thiosulfate fixers must be used to correctly fix modern films. Though I now use TF-4 for film, I've never had a bit of trouble using plain 'ol Kodak powdered fixer, and I still use that for RC prints, in spite of the lack of recommendations for it. I claim that there is absolutely no problem using standard acid hardening fixer (fresh, 2-bath preferred for fiber papers) if correct wash procedures are followed. I've never had any problem with selenium toning after washing either- I'd never go directly from the fixer to the toner, as it exhausts the toner faster. Comments?
     
  25. I agree with Mr. Mowrey. Water is not a STOP BATH! The purpose of stop bath is to change the pH which halts development in the emulsion; also when using HYPO or an alkaline fixer, the stop helps to buffer them against alkaline "build-up". Acid fixers don't need a stop because they are "stop-fixes" by definition. Many people prefer to use them anyway.
     
  26. Ron - Thanks again for posting some of your excellent and practical knowledge.

    I too have issues with several things in A&T' Film Cookbook book, but I'll stay on topic!

    I found Point 1 to be pretty hypothetical on A&T's part. Exactly, where is their proof? It's not like we are adding concentrated acetic acid to dry sodium carbonate or some other base. These are actually pretty dilute solutions we are working with.

    I do know that stirring water baths will most certainly raise the temperature of the bath - just try some bomb calorimetry to measure the heat of combustion of something and you will see that the water bath used increases in temperature. But it is on the order of less than a few tenths of a degree Celsius over ten or 15 minutes. And it certainly must be accounted for in this test where temperatures are measured to 0.001C. But for film processing, I'm sure it's a non-issue. How precisely do people control the temps of their chemicals - certainly not to a level where this kind of affect can be seen.

    Point 2 - if I was processing in a dip and dunk several feet deep I might be more concerned about this, but with a hand tank or Jobo, I've never seen this. I've seen airbells when I started in photography, but never pin holes. And as you point out, I've found modern films to be pretty resistant to reticulation. I've yet to see it on my films.

    If you keep your stop bath above pH 4.5 or so, you will not get much gaseous CO2 forming in carbonate solutions anyway. And for developers that use non-carbonate compounds to raise pH, it is a non-issue there.

    Point #3, as Chris' link above showed, the volume of the gelatin actually reaches a minimum at pH 4.8. So it's not so much that the gelatin "swells" as a result of the acid stop, but it shrinks. Follwing the acid stop with a standard Rapid Fix, which has a pH of around 5.5, will cause a very small amount of swelling to occur.

    If we use A&T's recommendation, a running water rinse and then alkaline fix, we would be causing the film to shrink less than a pH 4-5 stop but it will shrink some as the water bath should take the pH of the film to around 7, but then causing it to swell back up more by using the alkaine fix which probably has a pH of around 8 or 9. At this pH level, then film has probably swelled back up to near it's original volume when the film was placed in the developer.

    So what's best - 1) shrinking the film with a properly made stop and then using a weakly acidic rapid fix which will not change the volume of the film much, or 2) use a water rinse, which again causes the film to shrink, but not as much as the stop, and then swell the film back up with an alkaline fix?

    And if we consider the change in volume from dry, unprocessed film, to wet during processing, and back down to dry again after processing, how much does this pH induced swelling/shrinking matter. I suspect not much. Ron, do you have any comments on this?

    Perhaps A&T, of which Mr. T is the inventor of the most popular alkaline fix on the market, are making an issue out of nothing because they have something to sell? I don't know. I would certainly like to see thier proof in this issue, which is something their book woefully sidesteps.
     
  27. advise about stopbaths,developers, and processing procedures are a lot like Texas weather- if you don't like it, wait a while and it will change.
     
  28. I very much agree... water is not a stop bath and a stop bath is very useful if we use 'short'
    developing times; because we need to stop development accurately. But with development
    times in access of 10 minutes and, to take it to the extreme perhaps, sometimes having
    development times running into hours, do we really need to stop the film so abruptly when
    a couple of rinses will wash out the developer and stop the film, for all intense and
    purposes, developing? Is using a stop bath, for reasonable development times of 10 plus
    minutes something we do 'because we can'? When I process a film I'm washing out the
    developer so it does not contaminate my fixer, not because I have to stop the film on the
    button. I just factor in the very slight deveopment that continues, as I rinse the film, and
    get perfect results every time. How do I factor it in? By doing it the same every time.
     
  29. So, Ron, for a simple stop bath made from 28% acetic acid and water, what ratio would you recommend?

    Also, is it worth using distilled water, or is tap water OK. I have good water, but no filter. I suppose distilled water at least removes a source of dust.
     
  30. Lowell, as others have noted, the difference in using an acid stop bath and a water bath are very small in most cases, and important in only the most precise work. In the interest of precision, you wrote "The purpose of stop bath is to change the pH which halts development in the emulsion". Change the Ph of what? The developer saturated in the film? Are you suggesting that the developer solution saturated in the film is the same Ph as plain water, or that replacing the developer with plain water doesn't affect the Ph of the developer saturated in the film? Or does a plain water bath also change the Ph, and thereby stop the progress of development? If so, doesn't that make it a stop bath? A bath that stops development? The relative merits of an acid stop bath or a plain water rinse are very small, mostly insignificant, and do not warrant the use of absolute statements like yours. If you hope to encourage others to work with precision, you should write with precision as well.
     
  31. I'll try to answer all of you in one post, but if I miss anything, let me know.

    1. I was unclear about distilled water. I am not against distilled water. I just meant that distilled water alone vs tap water alone will show a difference in swell of gelatin. The distilled water causes more swell, as the salts in tap water tend to repress swell. This varies with water hardness and the type of salts in your tap water. If you use distilled water to mix your chemistry, the added salts cause this difference to vanish. Moral: Don't use distilled water to rinse or wash your film or paper though! You could cause excessive swell.

    2. I don't have any preference regarding fix, whether alkaline or acidic. I use what I have at hand. Color products require neutral fix and not alkaline or acid. B&W products can use either. As noted above, an acid pH tends to reduce swell somewhat. I have no evidence as to whether either pH is good or bad for B&W, but do have some for color products. Ammonium based fixes, regardless of pH fix about 2X faster than Sodium based fixes.

    Finally; how did I come by this experience. Some want to have evidence. Ok, here is as much as I can describe for you. I used a device called a swellometer that measures the swell of a photographic material in microns vs time. The gelatin thickness is measured at the start and then each solution to test is placed on the material(s) and swell vs time is measured.

    For hardness, an abrasive device is used to scrape the gelatin surface when dry and wet with each solution to measure the g/cm sq that causes abrasion by a graded sandpaper like device.

    For pH, a surface electrode is used to measure the internal pH of the emulsion during this treatment.

    Duplicate experiments are run for each test to get an averaged result and find out your 'precision' and 'accuracy'.

    As for the heat during reaction, development is a redox reaction that generates acid. The reactions involved generate a miniscule amount of heat. The stop bath is an acid base neutralization that also generates a miniscule amount of heat. I'm trying to point out that heat is generated during development, stopping, and even fixing. Almost all chemical reactions generate heat. One exception is the dissolution of hypo in water. This absorbs heat.

    AFAIK, there is absolutely no evidence that shows that heat generated by any reactions during photographic processing causes image degradation.

    The chemicals involved in development are much larger in size than the hydrogen ion which is the active part of a stop bath. Therefore, since the neutralization of development by the stop bath involves the movement (diffusion) of these molecules a stop bath is faster by several orders of magnitude than the neutralization of development by water immersion. In one case, hydrogen ions diffuse inward rapidly, but in the other, huge organic molecules must diffuse outward through gelatin. Hydroxide, sulfite, and carbonate or borate must also move out of the film. Therefore, a stop is several orders of magnitude faster than a rinse in water for shutting off development. It is also more uniform due to the small size of the hydrogen ion.

    My preferred stop bath is 20 ml/l of glacial acetic acid (~2%) or 10 ml/l of glacial acetic acid (~1%). This is only approximate due to the density of the acid not being 1.00000. I mix it in 5 liter batches of 100 ml of acid in 5 liters. Then if I want 1%, I dilute 1:1 with water. I buy glacial acetic acid in a gallon jug from EK for about $23. It lasts me several years. (In fact, that price is probably low as my current bottle is so old, and it is still half full).

    I may comment further on some things in A&T if there is any interest. (seems that there is!)

    Ron Mowrey
     
  32. Water is not a stop bath, but is likely to be inadequate if:

    1. It is too brief, and

    2. The developer is strong, for example the graphic arts process described above, or if the dev time is quite short (Neopan in Microphen)

    I think that sometimes we are just lucky that what we do works as a result of factors that we have not considered, such as water supply, or choice of certain materials.

    I don't use acid stop, but why it works I don't fully understand. Most of my developers are either very dilute, or in the case of fast acting Microphen, it's not very alkaline.

    If water stop is making your fixer deteriorate faster, then it is inadequate.
     
  33. More comments about gelatin.

    For those of you interested, there are three types used in photographic products. There is bone gelatin discussed here: 'www.screensound.gov.au' as referenced above. This has its minimum swell at its isoelectric point of 4.8. Then there is pig gelatin which has an isoelectric point of around 9. The final type is either bone or pig gel modified by reaction with organic materials to modify the structure of the gelatin for better photographic properties. I cannot discuss this latter type of gelatin for obvious reasons.

    There are also polymers that are added to gelatin to change their properties. I cannot discuss those either.

    All of these ingredients determine the final physical properties of the photographic products you use. I can say that most major companies seem to use bone gel and therefore, the data presented at the reference above appears to be representative of what you will find with your materials from EK, Fuji, Agfa, Konica and Ilford.

    Use of pig gel, for example, will result in a product that differs substantially from the norm that you usually see, and will resemble a film from the 40s or so (hint, hint). It will swell differently, and will harden differently.

    But, it should be remembered that a stop bath will not adversely affect any of these products either. A stop bath is a non-problem.

    Oh, if the odor bothers you, use citric acid stop then. If the cost bothers you, you probably can't afford to be in conventional photography in the first place. Stop baths represent such a miniscule part of the cost, I really can't believe that anyone would remark on this.

    In testing photographic products in R&D or for quality control during manufacturing, a stop bath is a must in all B&W processes for accurate process control! I can state categorically that without a stop bath, the results would not be consistant enough for the demanding needs of quality control. I hasten to add that an acid stop-fix is suitable, but will exhaust rapidly unless replenished. In color processes, the situation is slightly different, but a stop bath is essential in the RA process at least, to prevent streaking of prints. Also, in color, silver development can be allowed to continue, as long as dye formation is stopped. (consider that for a bit if you will, and the implications inherent in it)

    Regards.

    Ron Mowrey
     
  34. >>Actually, development itself generates heat in the emulsions of film and paper both, and the pH drops considerably during the development process. In some developers, the pH in high silver areas is quite low, in fact, acidic in some cases.

    I have heard of development taking place at temperatures up to over 120 deg C without severe reticulation or clumping in a dry process, and up to 120 deg F in wet processes without clumping. I've done it in fact.

    I'm sure that these assertions are both true but if the grain clumping mechanism is sensitive to thermal gradients rather than absolute temperature than it's still possible that rapid changes in PH induce sever thermal gradients during the stop that would cause grain clumping while the (I would expect) less abrupt changes in PH during normal development are safe. And still allows for high temperature free of reticulation.

    The above, admittedly, is a rationalization of the A&T stance and I don't have any empirical data to prove it.

    The problem with A&T's Film Developing Cookbook is that many of these observations are owed to researchers (Zawadski, Crawley, Haist) whose work (if not the conclusions in the work) are still the intellectual property of various entities. So while the results of their research may be freely shared with A&T, details of the research may not.
     
  35. >>Acid fixers don't need a stop because they are "stop-fixes" by definition. Many people prefer to use them anyway.

    Lowell...I think you'd be hard-pressed to find anyone who prefers an acid fix these days. REAL hard-pressed as a matter of fact given:

    1) Alkaline fixer is a lot easier to wash out of negs or paper...
    2) It's possible to overfix using an acid fixer

    And for those of us using staining developers acid fixers are simply out of the question altogether since they reduce image stain.
     
  36. Al;

    Sorry, but the only comment you made that I can agree with is the one about staining developers! Even there, the evidence against acid fixes and stops is weak, but I would tend to believe it until proved otherwise.

    The heats of reaction for development and for acid-base neutralization are not sufficient for the effect you and A&T postulate. If it did exist, it would be front page news in the photographic journals.

    Since it would be possible to formulate around this supposed problem, it would probably be a patentable item, or at the least a major publication in the SPSE Journal or someplace similar. I have never heard of either.

    Grant never mentioned anything like that to me, nor in any of his publications either AFAIK. I have never heard of it internally at EK either.

    The bottom line is this. Development continues in post development water rinses. Whether it is a problem to you or others is debatable, but a difference can be proven to exist. I have done it. More than once. In fact, patents and publications exist to show that rinses after development can be used for further milder development with advantages to image structure. Konica used post development wash for their color negative film to improve image structure and dye hue. Edge effects were enhanced by this process, not worsened.

    I could go on and on, but I have enough evidence to prove it satisfactorily to myself, and have proven it and seen it proven during the course of development and testing of photographic products.

    Ron Mowrey
     
  37. Al;

    One last fact that I forgot to address. Alkaline fixes may indeed wash out faster from film and paper, but it is probably due to the fact that the gelatin is more swollen (as per the URL above) when the pH is high.

    The result may be more rapid washing at the expense of tender swollen gelatin in your film and paper. IDK for sure, but without evidence either way, I would be cautious.

    And, if you remember, EK made an alkaline hardener fix years ago. It wasn't very fast IIRC. So hardening in an alkaline fix is not necessarily the solution. In addition, ammonium based alkaline fixes have a very strong odor, which is far worse than the vinegar odor of stop baths, and the sulfite odor of fixes. Sodium based alkaline fixes are not very fast.

    In addition, you must be careful about the formation of Silver Hydroxide in your coating if the pH goes too high. If that happens, you may have a real problem.

    I hope that this has given you some things to think about.

    Ron Mowrey
     
  38. Kirk,

    Hydrogen bromide is an acidic bromide. Dehydroascorbic acid is more acidic than ascorbic acid. The alkali metal salts of dehydroascorbic acid are more acidic than the corresponding salt of ascorbic acid. Whichever way you want to say it is OK by me.

    When bromine ions are set free as part of the reduction of silver bromide, two of them combine with one molecule of an ascorbate salt to form 2 HBr molucules and one molecule of the dehydroascorbic salt. Does this sound better? The net result is lower pH in the areas of higher activity which of course results in some self limiting. I think this means the the edge effects of ascorbate developers will be on one side of the edge while those of hydroquinone will be on the other.

    I forgot why I got off on this tangent.
     
  39. "When bromine ions are set free as part of the reduction of silver bromide, two of them combine with one molecule of an ascorbate salt to form 2 HBr molucules and one molecule of the dehydroascorbic salt. Does this sound better?"

    Patrick, yes, that sounds better - although components in ionic solutions can't really be said to have combined. But yes, thanks for the clarification.
     
  40. Al wrote, "And for those of us using staining developers acid fixers are simply out of the question altogether since they reduce image stain."

    Al, can you point me to some tests where this has been demonstrated? I have compared stain levels in PMK processed film processed as best to identical as I can using a water bath and a stop bath and I have found the water bath gave slightly higher density than the stop bath - for both stain and silver density. It was such a small difference that I attribute the results to the stop having halted development much faster than the water rinses, as it should have.

    My stop was much more acidic than any rapid fix so I'm at a loss as to where an alkaline fix would preserve more stain than a rapid fix.

    Have you done any tests in this regard?
     
  41. I'm with Kirk. Has anybody acually done side-by-side comparison tests
    with any staining developer as to;
    acid/water stopbath effects on the stained images or
    acid/alkaline fixer effects on stained image?
     
  42. Ron said:
    "In addition,
    ammonium based alkaline fixes have a very strong odor, which is far worse than the
    vinegar odor of stop baths, and the sulfite odor of fixes. "

    I have had open 16 X 20 trays of TF4 diluted 1+3 in my very small darkroom without that strong odor. OTH, it is also not true that alkaline fixers do not bleach. They will, given enough overtime.
     
  43. >OTH, it is also not true that alkaline fixers do not bleach. They >will, given enough overtime.

    Given enough time and weak dilution, Acetic Acid will bleach. Use to
    use 28% (straight form the cubetainer) to "clean" silver from old developer trays- outdoors of course.
     
  44. Patrick;

    If you have an alkaline ammonium thiosulfate fix, then you cannot avoid having an ammonia odor. The vapor pressure of ammonia over the tray would be quite considerable. Probably the concentration of ammonia over the tray would be higher than sulfite over a tray of acid fix just due to concentration alone. (~10 g/l of sulfite salts vs ~100 g/l thiosulfate salts)

    So, either the pH is more like 6.5 or so (ie, not alkaline), or the fix is not ammonium based which slows it down considerably. Even at pH 6 - 7 there is some ammonia odor in an ammonia based fix. This is especially true if no stop is used.

    I have never expressed an opinion on bleaching of silver images by hypo, but have stated my opinion above about washing rate when using one of the alkaline fixes.

    Art, others;

    As far as heat generated by stop baths, I have given more thought to it, and I guess Kirk would probably have more concrete information, but here is my opinion. Due to the energy of the development reaction, more heat would be liberated during development than during stopping. In any case, this heat is very tiny, but measurable by a calorimeter.

    Therefore if (I emphasize IF) any effects on image structure are caused by heat, it is more likely to take place in the developer when there is more heat generated, and the gelatin is more swollen, and there are more solvents present to influence any clumping. If anything, the stop bath would probably tend to quench clumping if any were to be taking place. That is my opinion.

    I think Kirk's observation above about higher D-min (fog) when using a wash instead of a stop bath is important to note here. This is not uncommon and supports all of my experiments.

    I would like to add that clumping would tend to lower micro contrast. This is contrary to other posts and some printed statements that I have seen.

    It does that by smearing out the image of the finer lines such as 1 and 10 micron, thereby lowering the density of such lines (yes, the density is lower, as the majority of the 'clump' will come, in part, from the center or peak of the line). It would therefore decrease sharpness of these fine lines. My reference is Mees "The Theory of the Photographic Process".

    Ron Mowrey
     
  45. Ron - it's not in the Dmin of the film that I saw a difference between stop bathed and water bathed film - it was in the higher densities. Which is where I would expect to see a difference. And the difference was small - around 0.03-0.04 OD if I remember correctly. Not a big difference.

    So again I ask, has any one else actually done a test to compare water bath vs. stop bath, or even acid fix vs. alkaline fix?
     
  46. Sorry Kirk, I guess I misunderstood your answer. When you said stain was higher, I took that as D-min.

    Ron Mowrey
     
  47. Ron,

    Thanks for the response to my last post. I admit, my postulation was a stretch. Odd that this should be found in that book without apparent justification.

    For what it's worth A&T do not summarily dismiss Acid Stop Baths in the Darkroom Cookbook - they simply say to avoid those that produce CO2 gas during upon contact with Carbonates. They cite Kodak SB-1 as an acid stop bath that should not cause pinholes.

    But I have to hold my ground on Acid Stop Baths and pinholes because I've heard too many second-hand storie from folks.
     
  48. Al;

    I can agree with your comment. I too have heard lots of 'second hand' stories, but when checked out, none have any foundation other than possible air bells in the developer or anecdotal evidence.

    I have articles going back to 1941 which support the use of stop baths even with the softer films of that era, and refuting the issues against stop baths brought up here.

    As others here point out, no one has been able to generate pinholes or has ever seen or gotten them 'first hand'. That is the problem Al. You see, with myth busting you have to see it first hand. I have been using stop baths and doing research on stops, fixes, bleaches, blixes, developers, films and etc for about 50 years and 32 of them at EK, and have only heard that one reference. I have never seen it or heard of the problem otherwise.

    You see the problem. I have tried to make it happen. It can happen actually, but under conditions that are preposterous for a commercially viable photographic system. I made it happen under these conditions:

    1. Unhardened photographic material.

    2. Unsubbed material (no adhesive layer/material) to make gelatin stick to support.

    With that case and 50 g/l of carbonate and 2% acetic acid at temperatures above 75 degrees (this was run using C-22 and P-122 type chemistry with temperature variations), I was able to generate pinholes and actually blow the gelatin off the support. Now, you have to admit that that is kind of extreme! No such material would ever be sold. That is how hard I had to try, to generate pin holes with a stop bath, so I have first hand experience with those conditions necessary to create the problems cited by A&T, and find that they are impossible to create outside of a lab, and only with non-viable photographic materials.

    The problem is, that even my experiment is weak, as my supervisor at the time pointed out, the temperature where the pinholes and 'blowoff' took place was nearing the melting point of gelatin and therefore the experiment only showed that gelatin could be forced to leave the support by CO2 if near its melting point, and not just by the force of the CO2 gas bubbles. So, I only proved that this could take place near the melting point of unhardened gelatin on a non-adhesive support, otherwise I could not make it take place. Therefore, the conclusion was that it could not happen in the 'real world'.

    I have run dozens of experiments to try to prove/disprove this. It will not happen. I rest my case.

    Ron Mowrey
     
  49. Ron, you said:
    "So, either the pH is more like 6.5 or so (ie, not alkaline), or the fix is not ammonium
    based which slows it down considerably. Even at pH 6 - 7 there is some ammonia odor
    in an ammonia based fix. This is especially true if no stop is used. "

    TF4 is definitely ammoniacal. I didn't say there was absolutely no odor, but that it is not a strong odor. TF4 concentrate is actually what you might call a slurry. At 1+3 dilution, it is still very strong, clearing film in about 30 seconds when freshly mixed. I have not measured pH, but am taking the word of Photographer's Formulary that it is alkaline. It certainly causes no effervescence when mixed with carbonate developers.

    It appears that you are not reporting observed behavior of TF4, but are stating theories. Isn't that what you advised someone else against?
     
  50. Yes, Mr. Mowerey, I wish you would actually
    try my product before spouting off about it
    all over the Internet. At last I know how
    Mssrs Bush and Kerry must feel, first hand,
    thanks to you!

    The information and technology I have published
    with regard to alkaline fixers comes straight
    from Grant Haist (still alive) and H.D. Russell,
    whom Grant considered Kodak's greatest practical
    engineer. That goes for the glutaraldehyde/succinaldehyde
    stuff as well, all of which Russell used in the X-o-mat
    process, but I guess you don't know anything about that.

    Please, if anybody ever did his homework, I did. That
    should be obvious. And it should also be obvious that
    I gave as much detail and sourcing as I could without
    compromising my informants.

    Why don't you at least try to check your facts
    before you criticize me? Or have the courtesy
    to bring these issues to my attention? I would
    never have heard of this except by the sheerest
    accident of someone telling me about this thread.

    What I find particularly galling is that you
    are posing as an expert from Kodak. Maybe
    you are. But you're not an expert in what
    you're talking about here, and you don't
    have the experience of having discussed these
    particular issues over a 25-year period with scientists
    of the stature of Haist, Russell, James, and Henn,
    or for that matter, Zawadzki and Dickerson

    You know, in all the years that I have had my
    relationships with the top people at Kodak,
    nobody ever told me, 'oh, go to Mowerey - he
    really knows something special about this.'
    Are you really in that class? If so, I'd like
    to get to know better!

    I talked to the people who _did_ know something
    special about this. I spent 20 years doing that
    before I published my book. I think I have the
    right to resent someone coming in and saying,
    oh, no, that's all crap. And this, without even
    the courtesy of letting me know that
    he's doing it.

    There isn't a syllable in FDC I am ashamed of
    or would change now. I worked very hard, for
    many years to get the best information I could,
    out to the photographic community. I am damned
    proud of that work. Now you accuse me of making
    it up. But that book was read, over and over again,
    by Haist, by James, by Dickerson and Zawadzki,
    by Crawley. I don't see how I could have done
    a better job. - Bill Troop
     
  51. Yes Patrick, I did. I assure you, I take my own advice, and try not to comment on things I have not experienced first hand.

    I have used TF4 with a water rinse, and observed an objectionable ammonia odor to it both before use as the concentrate and as the working solution during use with no stop. I have used it for film in tanks, and for paper in large trays.

    I don't notice an ammonia odor with RA Bleach Fix even when used directly after the RA developer. The bleach fix is at about 6.5, and I use a stop almost all the time. I did observe an odor with the TF4, indicating that it is higher in pH than the bleach fix. I didn't have a pH meter then, but I do now. When next I buy some TF4, I will measure it. I have to add though that I usually mix my own fix from scratch. I use several 'super fix' formulas that I've worked up. They are not alkaline, but are ammonia based, and have little or no odor.

    You said "no strong odor", and I merely disagreed with the extent of the odor which is a subjective measure anyhow. I have worked with it, and find it objectionable in a closed dark room even when well ventilated and large. Besides, ammonia is a fogging agent for film, and I like to keep the level down in my darkroom.

    If you enjoy the smell of ammonia, then go ahead and use it any way you want.

    My comments still stand, including direct experimental evidence of the items brought up in this thread. I do notice that you addressed my qualitative comment in this matter, but have not commented on the quantitative evidence I have reported from experimental data. Do you have any comments on that?

    Ron Mowrey
     
  52. Bill; Please cite your references then regarding my original post. I know Grant, Dick Henn, Bill Lee, and Howard James personally, along with Dick Dickerson and Sylvia Zawadski. Grant is a personal friend who lives about 5 miles from my home and he and Bill Lee are the only two I worked with to any extent. Grant, Jim King and I share a few patents together, and I edited the color portion of Grants 2 volume work. You may see my name in the credits at the front of the book. Unfortunately, Grant has been in poor health recently and has suffered a severe stroke. Since your work was in B&W and mine was primarily color and emulsion work, I would hardly think that our paths would cross. I can assure you though, over the years Grant and I have had a long series of conversations about B&W and color processing. I learned a lot from him about photography as well. My data goes back through years of work by other experts at EK that totally agree with my comments in my original post. For example, if heat caused clumping, then higher process temperatures should also cause clumping, but none has ever been observed from 68 to 100 deg F or 20 - 38 deg C. I have my formal education in Chemistry and have spent about 50 years making a living in photography and chemistry applied to photography, 32 years of it at EK. I am discussing your work on a public forum and have adhered to the facts and not attacked anyone in person. Here is a picture for you. Ron Mowrey
    009bgE-19798784.jpg
     
  53. Mr. Troop,

    Thank you for making an appearance here. However, it seems that you have taken this discussion personally and I'm sure that's not Ron's (or my) intent in our observations on your and Mr. Anchell's book. And certainly no one here is accusing you of making anything up, we are just looking for the justifications behind some of the statements in your book.

    As far as using your product before commenting on it, I will say that I have never used any of your alkaline fixers. I have read your book, "The Film Developing Cookbook", and I found that your arguements about the benefits of alkaline fixers, especially when applied to stained films, to be a bit unsustantiated. Perhaps this was a space issue in publishing the book. But you really did not give much data to support many of the recommendations that you give in the book.

    Are you telling us that the information you have on alkaline fixers is second-hand knowledge as supplied to you from a few of Kodak's engineers? You say you did your homework - did you merely copy into the book what was given to you or did you actually do some testing to find if the claims you have made/repeated are true? Perhaps you would be willing to share some of your first-hand results of testing in regards to this issue?

    I fail to buy your arguement that one has to try (or buy in the case of TF-4) one of your products before spouting off all over the internet about it. Some ideas can be argued merely on the merits of the idea based on scientific principles without actually trying them. However, if you would like to send me a few liters of your TF-4 fixer, I would be happy to try some and report my findings back to the forum.

    Perhaps you could support some of your claims that you have made in your book here - and without making allusions about the credentials of people that are merely desiring to learn more about photographic chemistry...

    After all, that's why we bought your book.
     
  54. Steve and I will be responding, but it might
    take us a day or two to work it out, so please
    have patience, anyone who is actually interested
    in this. - Bill
     
  55. Bill and Patrick;

    You may wish to consider the following additional information.

    1. Swell is not equal to hardness. They are different phenomena entirely and one is often not a measure of the other. Glutaraldehyde, Succinaldehyde, and Formaldehyde all harden well, but allow different degrees of swell at roughly equivalent hardness. Depending on process conditions, they should be followed by a neutralizer bath.

    2. EK made alkaline fixes, but they were hardening type based on sodium hypo to avoid the odor of ammonia, and also to prevent excess swell and lower hardness caused by the alkaline pH.

    3. Swell (and sometimes hardness) is best (lower swell and greater hardness) at the isoelectric point of the gelatin used (pH ~4.5 for bone gel used in most products today and pH ~9 for pig gelatin considered obsolete by most major manufacturers). It is for this reason, among others, that the ammonium based fixers used in color today are at a slightly acidic pH or about 6.5. (see the URL referenced above)

    4. I gave the formula for a super fix to Bud Wilson at the formulary expecting nothing in return. It is ammonium based and near neutral in pH. I include it here for reference. It is not free to use for profit by anyone but Bud if he desires. I wish to get nothing for this formula. I disclaim any liability that might arise from its use.

    Ammonium Hypo solution 150 - 200 ml/l

    Ammonium Sulfite 10 g/l

    Ammonium Thiocyanate 10 - 100 g/l

    pH 6.5 - 6.7 at 20 deg C with 28% acetic acid.

    If you wish extra power add:

    Thiourea 10 - 100 g/l

    KI 1 g/l

    In any event, do not use KI with papers, as it slows fixing rate, but accelerates fixing rate of films. Use with caution with color films, as it can cause or accentuate any cyan leuco dye problems. Don't go overboard and use the max of all of those ingredients. That is a possible range for any one of them at a time. If you max out all of them, you can actually slow down fixing rather than increase it. I used to test variations with strips of film snipped off a roll for this purpose.

    It is a very rapid fix for films and papers (minus the KI for papers of course) and can be made even faster by the group of proprietary materials patented by EK which I will not get into here of course. These are of particular use in color fixes.

    Make sure you wash film/paper, equipment and hands well, and take precautions for toxic materials used. This fix like most all fixes is a powerful fogging agent for film if small amounts get into a developer. Thiourea and all thiocyanates increase the hazard of photographic solutions.

    This formula is loosely based on USP 3,706,561 granted to Rowland Mowrey, Keith Stephen, and Eugene Wolfarth.

    5. Of interest to me are these important facts. At EK several things were true:

    a) If we had discussions with outside individuals, we reported the entire conversation in writing to the legal department. We were cautioned that disclosure of confidential material would lead to disciplinary measures or dismissal. No individual that I know of working at EK could be entirely candid in such a discussion at their certain peril. Therefore, no one outside EK knew what really went on within the halls of KRL or elsewhere with any degree of accuracy.

    b) There are experts at EK on FIXERS and experts on FIXING. One is the practical application of the technology learned from the other. When people who worked on FIXERS had questions, their resources were the experts on FIXING. This same held true for DEVELOPERS and DEVELOPMENT. When I had a question on developers, I went to an expert on development, usually a physical chemist. Nowhere do I see references in any article or book to the many internal experts that Grant and I along with many others in process development went to for assistance with the sticky problems in design of fixers or developers. Well, I have to take that back, T. H. James was one such internal resource.

    c) Required reading by new engineers at EK is not Anchell and Troop nor any other book of similar ilk. We read Mees or Mees and James, Eaton, Evans Hanson and Brewer, Zwick and Thirtle, Rodgers and Kapecki and etc. (some internal monographs should be included among this list) We are required to take an internal course that includes (depending on division) the precipitation of an emulsion, coating a B&W and color material and exposing and processing them, and evaluating them. During this, we are thrown curves in the 'test' to pose problems for solution like a 'battle simulator' or 'flight simulator'. I took that course in my first year at EK, which we affectionately called "Ding Dong School".

    With regards to everyone out there reading this.

    Ron Mowrey
     
  56. Yes, please do. And I am especially interested what you may have to say in regards to the issue of molecular heating caused by the pH gradient/neutralization and swelling having an affect of image integrity - are these effects actually noticable at a scale that could affect photographic quality?
     
  57. I am still on the road but have had a moment to look at Rowland's latest post addressed to me and Patrick, and I am concerned enough to make an immediate answer to some points he raises.

    >You may wish to consider the following additional information.

    Glutaraldehyde, Succinaldehyde, and Formaldehyde ...

    Rowland, have you compared the toxicity data for these chemicals? Once you have done so, you may want to rethink your priorities.

    >2. EK made alkaline fixes

    Are you specifically aware of HD Russell's alkaline fixers? Are you aware of the fact that it was known at Kodak from the early 1950s that thiosulfate removal was increased by a factor of at least ten by the simple device of using alkaline fixers? You'll find that in Haist. Not easily, but it's there.

    >4. I gave the formula for a super fix to Bud Wilson at the formulary expecting nothing in return.

    Rowland, I am profoundly disturbed that you are advocating the use of ammonium thiocyanate in the home darkroom and, for that matter am distressed that you advocate the use of glacial acetic acid in the home darkroom. These are both extremely dangerous chemicals. Tell me Rowland, what is likely to happen, the next time I accidentally spill my containers of ammonium thiocyanate and glacial acetic acid on the floor of my darkroom and they mix together? Pretty certain death? or just a moderate mess on the floor? Now what if I happen to be still standing and decide to clean up the mess with my handy bottle of Clorox? Rowland, these chemicals do not belong in the home darkroom. Surely we can agree on that? We are talking about l-i-v-e-s, here.

    And you propose that Bud Wilson sell this stuff?

    >I disclaim any liability that might arise from its use.

    Right. You sure do. You know, Rowland, we thought we'd ended the numerous 19th century tragedies that resulted from accidents in home darkrooms with thiocyanates. Yet you're advocating a return to that sad era of hazard. You disclaim liability. But what are you going to feel if some fool photographer says, "well, that's just legal talk - I'm going to use this great fixer - hey, it's from a U.S. patent and this guy is from KODAK. - - - what can go wrong?"

    Well, an accident with heat or an acid is what can go wrong. The evolution of cyanide gas is what can go wrong.

    Not a pretty death. Not a necessary death.

    >It is ammonium based and near neutral in pH. I include it here for reference. It is not free to use for profit by anyone but Bud if he desires.

    Then you go on to say that it is derived from your Blix patent. But Rowland, you are not at liberty either to give or withhold the information that describes the embodiment of a patent. That patent is in the public domain from the day it is published. While the term of the patent exists, no commercial use can be made of any embodiment. But private use can be made of it ad librum. All the patent does is protect you against commercial exploitation during its term. The term of this patent has expired. You can't make a gift of it because it belongs to us all anyway. So what's the point? In any case, _you_ aren't the owner of the patent and never had any say in what anybody could do with it. EK is - or rather, was, the owner.

    >I wish to get nothing for this formula.

    You are suggesting that you could, if you wished,
    profit from the embodiment of an expired patent
    that you do not now and never did own.

    I don't get that.

    >Use with caution with color films

    To what extent have you tested this formula (if I may
    so describe something so approximate) on contemporary
    black and white materials? Have you conducted aging tests,
    washing tests, image tests?

    >It is a very rapid fix for films and papers

    It fixes rapidly. But how quickly does it wash out?
    That is what we are interested in.

    May I suggest that you ask Grant Haist, who I
    earnestly hope is well now, the following question:
    'what is the difference between the washing time of a
    thiosulfate-containing fixer below pH 7 compared to
    the washing time of a thiosulfate-containing fixer
    above pH 7?'

    Let me suggest something further. Why don't you ask
    Grant the following question: 'Grant, what is the
    most useful, innovative, practical, and beneficial
    fixer formula I could place before the public today?'

    This is what Grant will tell you.

    'Well Rowland, as you know, the problem with thiocyanates
    is that they are too dangerous to use. And the problem with
    thiosulfates is that they are so hard to get out of the
    material. The best thing would be to look at some of the
    mercaptans I worked with. They fix the film or paper
    rapidly, wash out almost instantly. Just have a look at
    my book. It's all there. No need to use thiosulfates or
    thiocyanates at all. That's old technology.'

    I know this is what Grant will say because I've had this
    conversation with him a dozen times over the years.

    >Thiourea and all thiocyanates increase the hazard of
    photographic solutions.

    Don't you think that given the profound, life-threatening
    depth of that hazard, that you should be more explicit about
    this?

    You are not addressing an audience of professional
    chemists.

    You are addressing an audience of _photographers_.

    >a) If we had discussions with outside individuals,
    we reported the entire conversation in writing to the
    legal department.

    We didn't if were retired. Of course you know the
    story about how Henn's Blue Book was sold on the
    open market. Also, we didn't report these conversations
    if we didn't give a damn. And there were some great
    old guys who didn't.

    >Nowhere do I see references in any article or book to
    the many internal experts that Grant and I along with many
    others in process development went to for assistance with the
    sticky problems in design of fixers or developers.

    Of course not. Who would blow the cover of such a source?

    >Well, I have to take that back, T. H. James was one such
    internal resource.

    And remained so, externally, for many of us as late as 1999.
    If, that is, he cared to talk to you.

    >c) Required reading by new engineers at EK is not Anchell and Troop nor any other book of similar ilk.

    Now Rowland, what's the point of that remark, except to make it all personal?

    Lord in Heaven, do you think my audience was EK or RIT? You
    have sadly misconstrued the intent of my book if you think it was
    not intended for ordinary photographers.

    >We read Mees or Mees and James, Eaton, Evans Hanson and Brewer, Zwick and Thirtle, Rodgers and Kapecki and etc. (some internal monographs should be included among this list)

    And not Haist?

    >I took that course in my first year at EK, which we affectionately called "Ding Dong School".

    Thank you for that memorably descriptive nugget.

    >With regards to everyone out there reading this.

    Those of you who are still alive.

    I want to emphasize something yet again, Rowland. We are not talking to chemists here. We are talking to photographers. We have to think of safety first. For a perspective on that, may I suggest you look at FDC, the chapter on darkroom safety? (prepared with Grant's help). I won't recommend the use even of glacial acetic acid and any hydroxide in the home darkroom, much less a chemical that can fairly easily cause the evolution of cyanide gas. I don't think anyone else should be doing so either.

    Safety first.

    Rowland, I hope you will allow me say, without offense, that there is a profound difference between us. I am an author with an audience about whom I care deeply. You are not. I have profound responsibilities to that audience. You don't. Before you become overly intoxicated with your newfound role of internet pundit, you might consider giving some thought to who it is you are speaking to, why it is you are speaking to them, and what might be the consequences of your speech.

    - Bill Troop
     
  58. Bill,

    Thanks for your reply.

    However, I would hope you would get more of your facts straight. As someone that is supposed to be knowledgable on photographic chemistry, I would at least hope that you would be better versed in basic chemsitry as well. Since I am not an expert in photographic chemistry, please allow me to address the basic chemistry part of your reply.

    You are making a big deal about Ron supplying a formula that contains ammonium thiocyanate - perhaps because you are confusing thiocyante (SCN-) compounds with cyanide (CN-) compounds. They are not the same.

    "Thiocyanate are not normally dissociated into cyanide; they have a low acute toxicity." That sentence is quoted from "Dangerous Properties of Industrial Materials" by Sax. It goes on to list the Oral LD(lo)(mouse) at 330 mg/kg. Compare that with glycerine with an Oral LD50 (mouse) at 440 mg/kg or hydroquinone with an Oral LD50 (rat) at 320 mg/kg. So it is no more accutely toxic via oral introduction than glycerine or hydroquinone. Why I don't see you making a claim that we will drop dead from those compounds?

    Certainly, thiocyantes will liberate cyanide when exposed to acid, but only when strong heat is involved. These same conditions are required to liberate cyanide from potassium ferricyanide. I would be surprised if you have the right conditions in your home darkroom to do this. I perform cyanide analysis in an environmental laboratory, and you have to boil these samples at a very low pH for the analysis. Thiocyanates are not simple cyanides.

    Thiocyanates will react with free chorine found in bleach to release cyanogen chloride - which is accutely toxic. Is this what you are hinting at when you mention Clorox? If so, please do not beat around the bush when making safety suggestions and be forthright with your information. Afterall, as you said, the audience here are photographers, not professional chemists that would know this.

    I'm also suprised at you making a fuss about glacial acetic acid. While the fumes can be quite strong, it can be easily handled in the home darkroom with adequate ventilation. You can have contact with glacial acetic acid and you could get burns, but before that happens, I think you will find that you are very strongly compelled to wash it off as the itching/stinging sensation grows before you will get any actual burn from it.

    Bill, it sounds like you have a different definition of "extremely dangerous chemicals" from myself, and perhaps Ron. And I certainly would not recommend to anyone reading this that they handle any of the chemicals without educating themselves on the hazards and risks involved.

    Part of this education must be directed towards learning ways to minimize and hazards that may be encountered in their pursuit of photography. That means learning basic principles in handling chemicals, and also learning about and using personal protective equipment. For these chemicals, a simple lab coat or dedicated chemical handling clothing, safety glasses or goggles, and neoprene gloves are the basic safety equipement that should be used. As I've pointed out above, these chemicals are no more "dangerous" than many of the chemicals we all used in our home darkrooms.

    And I'm glad you do address some of these issues in your book. I can understand your concern about people buying your book and then not following you advice. You are probably right to feel concerned about any possible liability. And we should have the same concern here as well.

    I do see at the end of your post here you say that you will not recommend the use of any hydroxide in the home darkroom. But you include a few developers in the FDC that include have sodium hydroxide in them. Are you recommending that we use these formulas, or are they included to better eduacte your readers?

    Despite what you just said in your post, it does sound like you ARE recommending them to the readers as you give very specific instructions on dissolving the sodium hydroxide for your so-called "traditional rodinal" formula. I would suggest that there are greater risks involved in mixing up a 50% sodium hydroxide solution than using thiocyanate or glacial acetic acid in the home darkroom in the fixer formula Rin gave. It is quite easy to boil that solution over if one rushes the preparation. (I've even been told by an opthalmologist after getting a 10% HCl solution spashed into my eyes (it ran down behind my safety glasses) that bases are much more corrosive to the eye tissue than acids are - the base binds with the tissue and is much harder to remove and it will etch the tissue.) I would like to suggest to you that you include the suggestion to use a running cold water bath to place the mixing container for the NaOH solution to help cool it down when you print the second edition of the FDC.

    I'm looking forward to your and Troop's response to the original questions of this thread before we get off on a big tangent here.

    Kirk
     
  59. >I'm looking forward to your and Troop's response to the original questions of this thread before we get off on a big tangent here.

    >Kirk

    Exactally, can we get back to water vs. acid stopbaths?
     
  60. Kirk writes,

    >However, I would hope you would get more of your facts straight.

    Kirk, the problem here, as so often with Internet threads, is that you are more interested in arguing for the sake of arguing, than you are in getting some useful information out to the community. My job is to get useful information out to the photographic community. I don't have much time to do that, and what little time I do have to do it with is cut into when I have to respond to people who just want to argue for the pleasure of arguing. This is why sensible people like Gordon Hutchings and Grant Haist stay off the Internet. I also want to make clear, since you have made some pretty personal remarks about it, that I don't make any substantial amounts of money out of my involvement with photochemistry. Photographers Formulary pays me a fair royalty for my products. I can remember royalty checks of five or six dollars. I may still have one or two I can send you as a curiosity. I also get a fair royalty from Focal Press which is a very modest amount of money in the low four figures. So please, let's drop this suggestion you have made, that I am in it for the money. Now let's look at what you write today. You want the attention. I'll give it to you, point by point.

    >As someone that is supposed to be knowledgable on photographic chemistry, I would at least hope that you would be better versed in basic chemsitry as well. Since I am not an expert in photographic chemistry, please allow me to address the basic chemistry part of your reply.

    >You are making a big deal about Ron supplying a formula that contains ammonium thiocyanate - perhaps because you are confusing thiocyante (SCN-) compounds with cyanide (CN-) compounds. They are not the same.

    No, Kirk, I am not confused. And I don't think you think I am. Have a look at your Haist. I am on the road and can't give you a page number, but look at the section where he describes the history of fixation. You will find some interesting statistics on the mortality of photographers who worked with thiocyanate fixers.

    >"Thiocyanate are not normally dissociated into cyanide; they have a low acute toxicity." That sentence is quoted from "Dangerous Properties of Industrial Materials" by Sax. It goes on to list the Oral LD(lo)(mouse) at 330 mg/kg. Compare that with glycerine with an Oral LD50 (mouse) at 440 mg/kg or hydroquinone with an Oral LD50 (rat) at 320 mg/kg. So it is no more accutely toxic via oral introduction than glycerine or hydroquinone. Why I don't see you making a claim that we will drop dead from those compounds?

    Because we don't normally drink thiocyanate. The danger of the chemical does not primarily lie in its _oral_ toxicity.

    >Certainly, thiocyantes will liberate cyanide when exposed to acid, but only when strong heat is involved.

    You are confused, and the mistake could be fatal. Thiocyanates will liberate cyanide when EITHER heat OR a strong acid is involved. Please, please, check these salient facts before your write so irresponsibly!

    >I would be surprised if you have the right conditions in your home darkroom to do this.

    Again, Kirk, look at the statistics in Haist. I assume you have the book? If not, you can buy it from Grant for about $200. Now if I recall correctly, you asked me to send you a few litres of TF-4 fixer to test. So you don't seem to be a fellow that likes to spend money. But this is an investment I would advise you to make.

    >Thiocyanates will react with free chorine found in bleach to release cyanogen chloride - which is accutely toxic. Is this what you are hinting at when you mention Clorox? If so, please do not beat around the bush when making safety suggestions and be forthright with your information. Afterall, as you said, the audience here are photographers, not professional chemists that would know this.

    Kirk, I do not view this forum as a place to vent spite. I view it as a place to contribute useful information. I don't think I'm beating around the bush. We would all be better served if you would use your expertise to help us.

    >I'm also suprised at you making a fuss about glacial acetic acid.

    Glacial acetic acid is much cheaper to buy than the 28% solution usually sold to photographers. Why do manfacturers like EK dilute it 1:4 before selling it to photographers? Because glacial acetic acid is too dangerous to use in the home darkroom.
    >While the fumes can be quite strong, it can be easily handled in the home darkroom with adequate ventilation. You can have contact with glacial acetic acid and you could get burns, but before that happens, I think you will find that you are very strongly compelled to wash it off as the itching/stinging sensation grows before you will get any actual burn from it.

    Tell that to my 75-year-old reader whose reactions are no longer very fast. You plainly don't have a background in product safety, or much of a concern for it. But would you let your grandmother or your toddler work with glacial acetic acid or, for that matter, ammonium thiocyanate, in their home darkroom?

    >Bill, it sounds like you have a different definition of "extremely dangerous chemicals" from myself, and perhaps Ron.

    I do!

    >And I certainly would not recommend to anyone reading this that they handle any of the chemicals without educating themselves on the hazards and risks involved.

    And do you personally undertake to conduct that training for everyone who reads either your or Ron's suggestions? And then supervise them every time they use the chemicals? How many photographers have you trained? How much time did it take? How much sunk in?

    >Part of this education must be directed towards learning ways to minimize and hazards that may be encountered in their pursuit of photography. That means learning basic principles in handling chemicals, and also learning about and using personal protective equipment. For these chemicals, a simple lab coat or dedicated chemical handling clothing, safety glasses or goggles, and neoprene gloves are the basic safety equipement that should be used. As I've pointed out above, these chemicals are no more "dangerous" than many of the chemicals we all used in our home darkrooms.

    You say this, yet you know that most photographers don't use any of the basic safety equipment you recommend, even when they are told to a hundred times over. It is for this reason that we try to make the darkroom as safe an environment as possible.

    >And I'm glad you do address some of these issues in your book.

    But you may be one of the very few people who has read that section or paid any heed to it.

    >I can understand your concern about people buying your book and then not following you advice. You are probably right to feel concerned about any possible liability. And we should have the same concern here as well.

    Kirk, I'm not worried about liability. I don't have any insurance, I don't have any property, and I don't have any money, so there is nothing anybody can get out of me. What I have is a conscience. I don't want to do anything that will harm anyone - slightly, or gravely. I don't want to cause harm, and I don't even want to cause the slightest discomfort. One thing, however, I can give you is my time. So far, this morning, you have had half an hour of it.

    >I do see at the end of your post here you say that you will not recommend the use of any hydroxide in the home darkroom. But you include a few developers in the FDC that include have sodium hydroxide in them. Are you recommending that we use these formulas, or are they included to better eduacte your readers?

    Earlier I suggested that you might have read my section on toxicity carefully. Now I find you haven't. I wrote the thing myself, and even I can't remember everything I said, as I don't have the book with me. But one thing I do remember stating in that chapter was that it was easy to avoid the dangers associated with strong acids and alkalis. Simply don't use formulas that contain them. That is my best advice.

    >Despite what you just said in your post, it does sound like you ARE recommending them to the readers as you give very specific instructions on dissolving the sodium hydroxide for your so-called "traditional rodinal" formula.

    Kirk, look at the darkroom hazards section again, if you want to know my opinion. And again, with 'so-called' and fright quotes, could we please keep spite out of this? Do you have a better suggestion as to how I should denominate what I call traditional Rodinal? I spent a lot of time thinking about that.

    >I would suggest that there are greater risks involved in mixing up a 50% sodium hydroxide solution than using thiocyanate or glacial acetic acid in the home darkroom in the fixer formula Rin gave.

    Kirk, I'm not interested in calculating whether one substantial risk is 5 or 10% greater than another substantial risk. If handling the chemical carries substantial risk, then that is enough for me to place it in the category of 'very dangerous, best to avoid completely'.

    >It is quite easy to boil that solution over if one rushes the preparation. (I've even been told by an opthalmologist after getting a 10% HCl solution spashed into my eyes (it ran down behind my safety glasses) that bases are much more corrosive to the eye tissue than acids are - the base binds with the tissue and is much harder to remove and it will etch the tissue.)

    You were lucky if you did not permanently damage your eyes. And your story shows the limited value of safety glasses.

    >I would like to suggest to you that you include the suggestion to use a running cold water bath to place the mixing container for the NaOH solution to help cool it down when you print the second edition of the FDC.

    Thanks for that suggestion. If you had confined yourself to that, we could have saved a lot of time and bandwidth, and might have had a chance that your suggestion would actually get noticed by someone reading this thread. Again, though, you have to consider, that most photographers will either not have a running cold water bath near where they are mixing their chemicals, or will not know how to make one, or will just be tempted to say, 'let me try it without.' Photographers, you know, are a pretty varied and independent lot. You can't control them!

    >I'm looking forward to your and Troop's response to the original questions of this thread before we get off on a big tangent here.

    But Kirk, I _am_ Troop. If we haven't established that, what have we established? Who do you think I am? Yet, I believe you have, here, raised perhaps the one profound point in this thread. I am Troop. I have been responding to you for days. Yet you are so confused, or inattentive, that you don't know I am Troop. Given that, what chance do you think there is that any safety recommendations discussed in this thread will be heeded?

    Ok, Kirk. You have now had an hour of my time this morning. More than that, I can't give you today. With best wishes, your friend, Bill Troop
     
  61. Bill;

    Here are some answers for you again.

    1. Glutaraldehyde, Succinaldehyde, and Formaldehyde.

    You infer that I recommend any of these. I don't. I have a patent on the removal of formaldehyde in stabilizers and EK has completely abandoned glutaraldehyde and succinaldehyde due to toxicity.

    OTOH, your book does recommend glutaraldehyde and succinaldehyde - so be consistant and please point your finger in the right direction. I am against the use of all of these aldehydes for hardening and merely pointed out the differences among the three.

    2. EK made alkaline fixes.

    Yes, Bill, they did, but the fixes caused softening and swell in films and papers. That was not good. But, they did allow for faster wash, which was good. It was due to the higher swell imparted by the alkaline fix (at least in part). I believe that all major EK fixes have a higher pH limit below 7.0 as I previously stated.

    3. I gave a fix formula to Bud Wilson.

    Of course I did. The patent mentioned was related to Blixing or Bleach Fixing. My formula is a privately developed FIX formula loosely based on work done at EK on BLIXING. It is one of my own personal formulas. Any private citizen could have developed it after reading the patent and knowing a bit about chemistry. I am free to use it or give out the formula, and I don't expect a profit from it. In any case, the patent has expired as you point out. It is interesting that you point this out, as you get a profit from sales of your book and probably a cut of the profit from sales of your alkaline fixer. I really don't know or care actually, but it does have some significance here, I think.

    The fix formula will wash out of film and yield suitable stability if the same precautions are followed as used for normal acid or near neutral fixes.

    4. Thiocyanate is toxic.

    How interesting that you bring this up. Please see Kirk Keyes comment above. I think it interesting that your book advocates the use of the following toxic or corrosive chemicals: Sodium Hydroxide, Glacial Acetic Acid, Pyrocatechin, p-phenylenediamine, pyrogallol, glutaraldehyde, and - GASP - sodium thiocyanate! And, Ammonia fumes from leaking refrigerators back in the good old days has killed more people, or blinded more people than most people would imagine.

    This is just a small example to again redirect that finger to point in the correct direction.

    5. Proprietary information.

    Well, you say that if a person is retired, he can say anything he/she wants. I don't beleive that. My ethics prevents me from talking about many things related to my work at EK, things I know that I would never divulge even though retired. OTOH, you have categorically stated that you have gotten this type of information, and you have implied that you did it before the individual had retired.

    As you said "Of course not. Who would blow the cover of such a source?" This, of course, means that you are illegally in the posession of information proprietary to Eastman Kodak. What is more, you have profited by it. You do realize this, don't you? And, you have tacitly admitted that here in this public forum! I would hope that no one from the EK legal staff reads your last post.

    Bill, the points I raised in my first post are correct. You have not been able to refute them and instead have tried to attack me personally. In this post, I have pointed out that rather than me, the finger should be pointed instead back at your work as having referred to these same toxic chemicals and more. In addition, some claims you have made are unsupported, and I believe those claims of yours that I pointed out in my original post are, as I said, incorrect.

    I spent virtually 8 hours / day, 5 days a week for 15 years in a darkroom or lab running experiments with photographic materials and solutions before I went into the emulsion end of things. I doubt if anyone here except the other EK people I see as members here can match that. I am not, nor never have been one of the 'super experts' at EK, just merely one who wishes to share those portions of his experience with other interested parties, and along the way correct or dispel some myths. I owe my knowledge, the portion I can share here publicly and the part that ethically I cannot, to those 'super experts' who do not participate in this forum.

    One last note. Grant Haist is probably not in good health. He was under constant supervision by an attending nurse or companion the last time I saw him and could barely speak. She had to explain the situation to me when I went over to say hello to him, and said that his road to recovery may be long and hard, if possible. He has been spending his summers in Rochester and winters in Florida. I have been reluctant to call his home either here or in Florida due to his condition.

    As a bottom line on stop baths. Acid is ok, it does no harm, but use what works for you, either plain water or acid. Any fix that works for you is ok, it really does not matter what the pH is.

    Ron Mowrey
     
  62. Bill, Kirk;

    A funny thing just happened to me. I was sitting here reading up on thiocyanate reactions (my textbooks say reaction with acid will not cause release of cyanide) when the doorbell rang.

    It was Bill Farley, a chemist who worked for Dick Henn and with Grant Haist, and a friend of mine. He just stopped over for something, and I shared this discussion with him. He has allowed me to quote him and tell you a little story.

    He said that thiocyanate mixed with acid will not release cyanide unless it is pyrolized at high temperature. (to you laypeople, that means heating the bejeebers out of it till it everything begins to turn to a gunky goo and then bubble)

    Now, here is his story from C&E News. (Thats Chemical and Engineering News, the 'newspaper' of the ACS (American Chemical Society) for you laypeople). It seems that during WWII, the synthesis for artificial rubber was held up because laypeople were afraid of the reaction as it used a solvent called methyl cyanide. "They were afraid of the cyanide involved".

    Well, the chemists renamed methyl cyanide to Acetonitrile, and the synthesis went ahead. Today, the name sticks, and no one complains, and there is no cyanide released by acetonitrile which is methyl cyanide under another name.

    Oh, he added that in all of his years working on chemical products with Henn and Haist, he never heard of thiocyanate being a problem as you describe Bill. Kirk is right!

    Oh, Bill, I believe you asked in your previous post if I had even read Haist. I thought I mentioned before that Haist asked me to help him edit his 2 volume work, so I read it in galley proof. I used to bring the proofs home with me a chapter at a time in my briefcase. I mainly edited the color section and was Grant's 'touchstone' for that material. I used several experts myself in doing that for Grant. I am in the 'credits' section at the front of the book IIRC.

    Ron Mowrey
     
  63. Moderator's note to all participants in this discussion: Please discontinue imputations that others involved in this discussion are motivated for pecuniary reasons. At best they are cheap shots that diminish what has otherwise been an informative and vigorous debate involving varied and interesting points of view. I'll delete any futher such comments that I see.
     
  64. Again, apologies for not being at home and not
    really dealing with this properly but I want to
    address some new points briefly in the time I have.

    >EK has completely abandoned glutaraldehyde and succinaldehyde due to toxicity.

    Rowland, have you looked at the present Versamat and X-omat formulas? Seems to me EK is still using glutaraldehyde, as I have recommended, where necessary, in line with EK practice.

    >2. EK made alkaline fixes.

    >Yes, Bill, they did, but the fixes caused softening and swell in films and papers. That was not good. But, they did allow for faster wash, which was good. It was due to the higher swell imparted by the alkaline fix (at least in part).

    I think you know, Row, that that is not an adequate explanation of the mechanism at work.

    >I believe that all major EK fixes have a higher pH limit below 7.0 as I previously stated.

    But are you aware of the magic threshold number which is necessary to get extremely rapid washing out of thiosulfate?

    >The fix formula will wash out of film and yield suitable stability if the same precautions are followed as used for normal acid or near neutral fixes.

    You have tested it? Published results? In what journal?

    >4. Thiocyanate is toxic.

    Yes. In addition to re-consulting Haist's book, you might want to get in touch with the group at Kodak that deals with occupational safety hazards, toxicity, etc. I have a wonderful contact there but I can't give you the name until I get back home. Get in touch with that group, and talk with them, and I think you might begin to see things a little differently when you're addressing a group of photographers.

    >Well, you say that if a person is retired, he can say anything he/she wants. I don't beleive that. My ethics prevents me from talking about many things related to my work at EK, things I know that I would never divulge even though retired. OTOH, you have categorically stated that you have gotten this type of information, and you have implied that you did it before the individual had retired.

    >As you said "Of course not. Who would blow the cover of such a source?" This, of course, means that you are illegally in the posession of information proprietary to Eastman Kodak. What is more, you have profited by it. You do realize this, don't you? And, you have tacitly admitted that here in this public forum! I would hope that no one from the EK legal staff reads your last post.

    Rowland, I wish again, that you would think before you speak. Personally, I love litigation. It's a pastime for me, a hobby. But I would hate to see a lot of your most distinguished colleagues - fellows so very much more distinguished than you - hauled into court, at the edge of the grave, for doing what they the felt they had to do to advance the science and practice of photography. Do you dislike your colleagues so much that you would wish their twilight years to be spent in litigation over what they might have said to me? Is that why you raise this spectre for them? Or is it just that you wish that you actually had done something that was worth divulging, and have discovered - perhaps too late - that you never did? But Rowland, it is never too late. Harold Russell was planning experiments in his 90s, and I don't think you are nearly so old. Why not get back into the lab, and start working on those mercaptan fixers of Grant's?

    >Bill, the points I raised in my first post are correct. You have not been able to refute them

    Just give me another day or two, you tiresome old windbag. I do have a living to make, you know. I only have a few minutes in the day I can devote to being a windbag myself.

    >the finger should be pointed instead back

    such language!

    >I am not, nor never have been one of the 'super experts' at EK

    That I know. So why do you want EK to haul into court those who are?

    Sorry! Gotta run or I'll miss my bus!
     
  65. Hi Bill,

    Sorry about the name mix up - I'm wrong, you're right. I see your name is Troop. I really did mean to put Anchell's name in there. I apologize for that mixup. It was nearly midnight and I'll claim that as my excuse.

    Bill wrote. "Kirk, I do not view this forum as a place to vent spite. I view it as a place to contribute useful information. I don't think I'm beating around the bush. We would all be better served if you would use your expertise to help us."

    I think that if you askeuse my expertise to help people. Just as I did when d around here you would find that I do try to I pointed out your mistake about the ease of the release of cyanide from thiocyanates.

    Anyway, I am still standing by my claim that thiocyanate compounds are not the "extremely dangerous chemicals" that you are making them out to be.

    Let's be more specific in our use of the term heat. I will agree with you that heating thiocyanates to decomposition will release cyanide. That is a known property. But by what mechanism are you going to be heating them to decomposition? I'm hard pressed to find a way in the darkroom other than pouring some on a hot enlarger bulb, and who's going to do that? I don't think hot or boiling water will do it - I have some onfo on that around here and I need to find it so I'll get back to you on that.

    Exposure to strong acid - let's look at that. I am quoting from the 20th Ed. of Standard Methods for the Examination of Water and Wastewater (this book is the nationally recognized set of methods for the analysis of the types of samples mentioned in the title), Method 4500-CN says, "Thiocyante (SCN-) is not very toxic to aquatic life." And "Thiocyanate is biodegradable; ammonium is released in this reaction." And yet more, "Thiocyanate may be analyzed in samples properly preserved for the determination of cyanide (Kirk here - This preservation is achieved by adjusting the pH to above 12 along with storage at 4C); however, thiocyanate also can be preserved in samples by acidification with H2SO4 to a pH less than or equal to 2."

    It really would not make sense to allow a preservation condition for thiocyanate compounds by putting them in a state that will cause the thiocyanate to decompose. That's why they call it "sample preservation".

    This means that adjusting the pH of a solution containing thiocyanate to less than 2 (very acidic) and even using a strong acid (H2SO4) to adjust it will not break thiocyanate into free cyanide. These contitions would certainly release a simple cyanide into the air, but not a thiocyanate.

    Other than Haist, do you have any other sources that would refute this? I see Ron has found several that confirm this.

    You also need to consider that people using these things in the old days could not have been as well educated in the hazards of these things as people today can be. Perhaps that is what has happened with Haist's statistics. I work with a guy that worked in the plating industry in the 70s and it is shocking to hear how cavalier people were back then - both from personal safety and environmental viewpoints. He had several large exposures to percent level cyanide plating baths. And I know there are still people out there that behave in those ways today, but we need to help them better learn about these risks.

    But part of educating them is not to have a knee-jerk response when certain types of compounds are mentioned. That does no one any good.

    Certainly thiocyanates are not without risk - what in life is? I agree they are toxic and they have risks associated with thier use. And accordingly, when using these things, you need to be educated in thier use and in methods to minimize any hazards associated with using them so that you can use them in reasonable safety. However, I think you will find that you are in much greater risk of injury or death from getting in your automobile and going to the corner store than you are from properly using some of these formulations.

    And I'll also say here that each person needs to make a personal assesment as to whether thay wish to assume the risks involved in using any photographic process. Using photographic solutions do have risks - even developers that are normally considered safe by the majority of photographers can cause dematitis or even allergic reactions - which can last a lifetime. Some may want to avoid using these things, and other willing accept the risk with no protection, and others will take measures to reduce their risk my using gloves. But all I ask that that we try to better educate people on these risks, and the methods that can be used to minimize the risk.

    Bill, I don't know about your grandmother, but mine is 92 and going strong. And yes, if she was interested in using some of the formulas, I would not have a problem, as she is the type of person that enjoys learning, and she is also the type of person that would learn the proper methods of using these things. Your 75 year-old reader, with the poor reaction time, may not want to assume the risks. And you have decided that you do not want to assume some of these risks. That's fine! I respect all of those people's rights to make their choice. I just want to see that they have the proper information with which to make that choice.

    Perhaps instead of trying to scare people off from doing certain things, we could all make a better effort to help people learn about the avenues that are available to them in regards to safety and the proper use of personal protective equipement. I have taught a few photographers over the years, and whenever I talk with them about using certain types of chemicals, I do try to let them know what they can do to protect themselves.

    I'm sorry to hear that I may be one of the few people to have read your appendix on safety. Here's another suggestion for your second edition - put that info in the front of the book. Make it a preface, and not an appendix. That way your reader is more likely to find it and read it. Don't put it in the back of the book where they may never get to it.

    By the way, you say you "that most photographers will either not have a running cold water bath near where they are mixing their chemicals, or will not know how to make one, or will just be tempted to say, 'let me try it without." Well, there is not much we can do about the last scenario other than express how easy it is. And I find it interesting that you say that most photographers will not have a source of running water nearby while mixing up a developer. Well, I would be suprised if you were right about the "most" part of that sentence. In fact, I would suggest that most photographers do have a source of running water nearby and if they do not, they still have the ability to make a bath even if the water is not running which will help cool the solution much faster. And if the reaction gets too hot, they can always submerge the container into the bath. This is much, much better than trying to quench a hot, foamy, boiling-over continer of sodium or potassium hydroxide with some ice. And as far as not knowing how, it's really easy - just get a container to hold some water in it that you can swirl the solution container in while you are mixing the solution. Pretty simple. I think you are underestimating the abilities of your readers.

    I really had to laugh when you asked about toddlers using the formulas like Ron's fixer or your's from your book. That just about made me fall out of my chair! ! ! I find it really hard to take you seriously when you use ridiculous hyperboles like that! ! ! I hope you were joking about that!

    And no, I have not looked in Haist. I do not have the books - I would like to get them, but even if one volume were available from him for $200, that is a bit of money. You imply that I am a cheapskate, and while I may let my wife get away with that claim, I do not believe you have the right to. I would ask for an apology, but after seeing the behaviour that you have exhibited in this thread and in the other photo.net thread that you participated extensively in the past, I suspect I would not get one.

    =============================

    Moderator's note: Comments dealing with imputations of pecuniary gain as primary motivatitors in positions taken has been deleted.

    ===================================

    And I'm not arguing for argument sake. I just have a thing about people giving out information that I believe to be incorrect. So it's not anything personal or spiteful towards you.

    Bill said, "My job is to get useful information out to the photographic community."

    I think that is the goal of every person here - to not only share the knowledge that they have aquired, but to learn from others. You do not have the franchise on that. I'm glad that you have taken so much time from your life to come here and discuss these things with us. I'm sorry that you feel that we are cutting into your valuable time.

    Finally, here's another suggestion - instead of "traditinal Rodinal", what about calling it a "Rodinal-like" developer. Just a thought.

    So, are we going to get to hear about your information on the stop bath questions?

    Kirk Keyes
     
  66. In regards to Ron's concern with EK and lawsuits, I suspect that he is really concerned that you have put these people into a difficult position.

    If this information that you have obtained that will advance the science and practice of photography that much, don't you think that EK will have little difficulty determining who these people were that you talked to? Especially since you seem to enjoy dropping the names of many of them?

    It is you that are putting these people at risk.
     
  67. I'm so irritated at constantly hearing the 'but you don't back up your claim' song that though it is 3:15 am on a day I vowed I would never spend more time on this indescribable thread - well, let's get started. What irritates me most is that you guys don't go to the trouble of reading anything, yet feel at perfect liberty to make me do so.

    Let me start by addressing Row's original points 1 and 3 together.

    >1. the pH change from developer to stop can generate molecular heat and cause grains in the film to clump.]

    >3. Acid stop baths cause excessive swelling which leads to a loss in image integrity.

    Have a look at page 543 of Grant?s book:

    'An emulsion layer still containing developing solution may swell to a dangerous extent when immersed in a strong acid bath of low salt content.'

    _Dangerous_ is what he said. And that's not a word that Haist, the consummate scientist, uses lightly.

    Let me ask you, Row, to have a look at the 1200 or so pages of Grant?s work, and ask you how many times such dramatic language is employed?

    Grant was trying to convey something to us there.

    That language interested me greatly, so I asked him about it, and I remember the conversation as if it took place yesterday ? and of course I took notes.

    'Grant, what do you mean by dangerous?'

    'Bill, the forces there are so great that of course there is an effect on the silver image. It may be subtle. It may not be so subtle. But it's there. There may be severe reticulation. There may only be very moderate reticulation, not visible as such, which causes a moderate, not fatal, but visible, and measurable, loss of image quality. Now, you can avoid that completely by avoiding the unnecessary use of acid solutions in black and white processing. So why not do it?'

    Now, Row, and Kirk, as I understand it, what you have trouble accepting is that there can be actual physical movement, molecular movement, due to the commonplace action of placing alkaline film in an acid bath. We have established that Haist considers it not just possible, but dangerous. You will also notice something rather interesting here: this statement isn?t footnoted. That means it is based on unpublished, proprietary research, because Grant never made a statement that was based on published research without footnoting it. So what you?ll be asking, at this point, is ? well, OK. You have one scientist and one company, stating this. So what? What about the rest of the photographic community? What about Agfa?s scientists? What about Ilford?s?

    OK. Let?s turn to Ilford's LFA Mason, 1975, p. 207 discussing what occurs when alkaline film is placed in dilute acid baths: 'in severe cases ? some movement of the image silver may accompany the mechanical relief pattern. The fine particles of image silver tend to migrate to the edges of the relief pattern ... When this happens, graininess is very much worse than would normally be expected.?

    Funny thing. Mason?s statement isn?t footnoted either. These guys aren?t talking about what is published. They?re talking about what they _know_.

    And there you are.

    Now along come Kirk Keyes and Rowland Mowrey, with a different viewpoint. OK.

    You know I?m asking myself why I?m wasting time arguing with you guys? I love the retrograde ? I believe it should be cherished. I would like to shake hands with someone who still thinks the earth is flat. Row, Kirk, where are your publications? Where are your books? Where is your research?

    [2. Acid stop baths cause pinholes and reticulation with developers containing carbonate.

    In the time I spent doing process research, I heard exactly one comment on this.]

    That I can well believe. However, the literature has a different view. Let?s start with LFA Mason (1975), p. 207. '[reticulation] can also be produced by immersion in dilute acid baths.' Also see Haist, pages 543, 544, with illustration. Crabtree, p. 119: 'One of the disadvantages of the carbonated alkalis is their tendency to cause blisters within the gelatin layer as a result of the release of carbon dioxide gas when the alkaline developer is neutralized by the acid fixing bath.' It is because of this practical necessity that Russell invented Kodalk.

    Ron, one of your problems is that your perspective is ? well, I wouldn?t say wrong, but I think I might say, simple-minded. You're only considering gross effects. You note that films and papers are now harder, so that gross, visible, reticulation is less likely. That is so. But the chemical reality of what happens when an alkalized film is stuck into an acid solution, which I think we have established pretty clearly over the course of the 20th century, doesn't change. The image altering affects are still there - all that has changed is the degree. An image isn't as sharp as you are sure it should be. Why? Well, acid processing is one of many possible causes. Even if acid processing caused only 0.1% degradation of image quality, on average, wouldn't it still be worthwhile to address the issue? Especially for the cases that weren't so average?
     
  68. On Rowland's disclosure of a 'formula' for a thiosulfate/ thiocyanate fixers here is Haist, pp. 597-598.

    "Today, the combination of thiocyanate and thiosulfate is often used for the rapid fixaton of photographic materials, particularly for those applications where rapid access to the image is more important than the long-time keeping characteristics of the image."

    Thank you Grant!
     
  69. More on stop baths:

    >As a rule of thumb, salts reduce swell.

    That is true, and a commonplace. I had an extensive, beautifully researched chapter on stop baths, the first I wrote, and the best loved, that I had to throw out - there wasn't room. I advocated buffered stop baths with additional sulfate to tame swelling. If you look at your Haist carefully, you will see the research which indicates that any ordinarily constituted stop bath does not, in fact, stop development rapidly. Only a buffered stop bath will stop development rapidly.

    Rowland, the simple fact is that the kind of stop bath you are advocating is not only potentially damaging to the image, but it doesn't do what you say it does -- stop development rapidly. Yet you don't seem to be aware of this research. Yet, it's all in Haist. See in particular the chapter on stop baths. Can you explain the paradox that you seem to be completely unaware of anything Haist wrote on black and white? Well, you have partly done so. You have put forth that you assisted him in color, your area of expertise.

    But even if your expertise is only in color, I am disturbed by the fact that you seem never to asked yourself such fundamental questions as these: how long does it take for a stop bath to stop development? how long does it take for the stop bath I am using to actually stop development? what kind of stop bath might be better? what can I do to disseminate better information and better formulae for stop baths?

    And so on. And then you might start thinking a little more deeply about what a stop bath does and why we use it and why we might want not to use it.

    Row, why don't you do us all a favor and read deeply what Haist wrote about black and white? I have read Haist vol. 1 cover to cover at least a hundred times, and I am constantly learning new things. I believe there are very few people capable of reading this book deeply, and then helping others with practical dissemination of some very dense information. I believe that you are a person who could do this. So, considering that you're actually a contributor to the book, why don't you give it a try?

    Now, let's get back to stop baths. We have established that the ordinary dilute acetic acid bath (a) causes unnecessary swelling and (b) does not stop development rapidly. The mechanisms for dealing with this are clearly described in Haist, and partly by me. The relevant pages in Haist are 539 to 557. However, the foundational paper is Henn & Crabtree, PSA J., 17B:14 (1951), which must be read in its entirety to gain a complete understanding of the mechanism of the stop bath.

    Let me quickly summarize Henn and Crabtree's findings. At pH 4.8, a 1.3% solution of acetic acid takes nearly 30 seconds to neutralize the developer. But by increasing the total acidity to 10%, with an acetic acid/sodium acetate buffer, the time to stop development can be reduced to 2 or 3 seconds.

    But who is going to go to the trouble to making a buffered stop bath? I regretfully decided to leave all that stuff out. Most people who use stop baths will use ordinary acetic acid. This isn't a good idea for so many reasons. Rather than explain why it isn't, and explain exactly what you have to do to make a proper acid stop bath, I decided to do the sensible thing: advocate alkaline processing for black and white materials. In this I had the support of my two favorite scientists at Kodak, Haist and Harold Russell. Nevertheless, on page 104 of my book, you will see three paragraphs headed 'Composition of acid stop baths' which compresses the 25 pages of information I would have liked to include. You will please notice that I give here the correct technique for both using an acid stop bath that actually stops development _and_ avoiding reticulation. Apparently, you didn't notice this section. I think if you are going to recommend an acid stop bath, you should at least try to discover what might be less than ideal about what you are recommending, and try to find out what might be the _best_ possible acid stop bath to recommend. Best, Best, Best. That is what FDC is about.

    Let me state explicitly what I think most people already understand. FDC isn't about ordinary processing. It is about optimal processing, it is about luxury processing. Nobody working in black and white today is doing it to save time and money. What we are interested in is not the adequate, but the best. That is a an important aspect in which my book diverges from many others.

    >On page 121 of their book, A&T recommend glutaraldehyde and succinaldehyde hardeners due to the problems with formaldehyde. The only problem is that these compounds can also cause fogging of films or papers unless neutralized before development (remember the E4 neutralizer?). They are aldehydes just like formaldehyde. They do harden, but they allow much more swell of the hardened gelatin due to the longer carbon chain length. This has been studied by EK years ago during the E4 process years. The gelatin is certainly hard, but swollen more than with formaldehyde, as the carbon chains linking the gelatin are 5 and 6 atoms longer respectively with these two aldehydes. ]

    This seems unusually careless for you, Row -- are you sure you wouldn't like a chance to reconsider it? You're saying, as I understand it, that the problem with my recommending glut/succ is that they will cause fogging/hardening of film. You are implying that formaldehyde, by contrast, doesn't do this. That formaldehyde doesn't fog. That formaldehyde is just a non-photo-active chemical that just hardens. Well, let's start with Mason, 1975. He considers formaldehyde a weak developing agent, citing Ehrenfried, PSA Journal, 18B, 2, (1952). James (TPP III) also considers formaldehyde to be a developing agent. Now look at Haist's chapter on lith development which gives some hints on the complex role of formaldehyde in development. Now, let's go back to what I wrote on hardeners, on page 121. That is all straight from H.D. Russell, and it is based on his extensive experience with the x-omat/versamat machines. Every piece of useful information that I have there is from Russell, including the suggestion that the pH must be 10 and that the solution should not be kept over one week. That may not be published material. That may be technically a trade secret that Russell divulged. But hey, the book's full of those. Now who was Russell? Well, he started at Kodak in the 1920s. He was the man who discovered that borates must be added to acid fixers if they are to have any useful life. He formulated all the modern Kodak fixers. He invented Kodalk. He published extensively, patented extensively. In the 40s and 50s, he was the engineer Kodak chose to lead their huge investment in automated technology that produced the x-omat and versamat machines. And in spite of all the foundational work he did to make acid fixing work, he didn't like acid processing. And he didn't use it in his machines. And he didn't use it at home. His processing chemistry was all-alkaline. Russell was probably the man with the most practical experience with alkaline processing, and I had the benefit of many conversations with him about it. Even at late as what - the late 1980s? could it have been as late as the early 90s? - he was planning an experiment we were to work on together. He hadn't had adequate funding from Kodak in the early 30s when he was working on chrome alum fixers -- and he was still mad about it. He suspected there was no reason why borates wouldn't work as beneficially for chrome alum as he had demonstrated they would work for potassium alum. He wanted to resolve it once and for all. It would have made a very elegant study, and I wish someone would do it. But we never did. (Haist's opinion was that Russell was probably right, but that of course you'd have to test it.) That's who Harold Russell was. Now tell me, Row, who are you?

    Haist and Russell were absolutely adamant that formaldehyde should not be allowed near any B/W silver photographic material, because it could cause a range of image-destructive effects. As a practical matter, both recommended glutaraldehyde or, where cost permits, succinaldehyde. Russell used glutaraldehyde in the all-alkaline x-omat and versamat film processing solutions he developed. If you have a look at current Kodak literature, you'll find those chemicals are still being used. Russell would have preferred succinaldehyde, which is less pH dependent for optimum hardening than glutaraldehyde, but it was, and remains, too expensive for common use.

    >So, after reading all of those posts, and getting to what appears to be the source of some of the comments I have read here on the forum, I thought it might be of interest to post my actual observations from my years of research in this field.

    Which is in color, not black and white.

    Now let me deal briefly with Kirk Keyes's post.

    >I found that your arguements about the benefits of alkaline fixers, especially when applied to stained films, to be a bit unsubstantiated.]

    Can't help saying this Kirk: if you took a bit more trouble with your spelling, you might also find yourself taking more trouble with your thinking.

    OK. Alkaline fixers and tanning. Start with Crabtree, p. 244. It has always been known that the performance of staining developers is impeded by acid solutions. This is extensively and meticulously described by Gordon Hutchings in the Book of Pyro, which I extensively quote and cite. Have you read it? Have you worked with these chemicals? Have you talked with Gordon Hutchings about it?

    >Perhaps you would be willing to share some of your first-hand results of testing in regards to this issue?

    If you want a specific answer, you'll have to ask a specific question, and you haven't done that. You are speaking so generally that I can't figure out what you mean.

    >However, if you would like to send me a few liters of your TF-4 fixer, I would be happy to try some and report my findings back to the forum.

    You seriously want a freebie? But why?

    Have you looked up David Vestal's article about TF-4?

    >Perhaps A&T, of which Mr. T is the inventor of the most popular alkaline fix on the market, are making an issue out of nothing because they have something to sell? I don't know. I would certainly like to see thier proof in this issue, which is something their book woefully sidesteps.

    And you don't expect me to take this personally? But you go on and on and on, without ever saying specifically _what_ your problem with TF 4 is. Could you please try to be specific? And by the way, do you not think it would be a little boastful if I mentioned in my own book that there were several articles, for instance by David Vestal, singing the praises of my fixer? I'm sorry, but that would strike me as being in very bad taste. It is no business of mine to do that. It is the business of other, respected commentators. And that is just what they have done. But what could be more repugnant than for me to boast of that?

    Finally,

    >The problem with A&T's Film Developing Cookbook is that many of these observations are owed to researchers (Zawadski, Crawley, Haist) whose work (if not the conclusions in the work) are still the intellectual property of various entities. So while the results of their research may be freely shared with A&T, details of the research may not.

    Thank you, Al, for realizing this. That says it all.
     
  70. Just two more things:

    Kirk writes:

    >And no, I have not looked in Haist. I do not have the books - I would like to get them, but even if one volume were available from him for $200, that is a bit of money.

    One word: Library.

    Three more words: Inter - Library Loan.

    >You imply that I am a cheapskate, and while I may let my wife get away with that claim, I do not believe you have the right to. I would ask for an apology, but after seeing the behaviour that you have exhibited in this thread and in the other photo.net thread that you participated extensively in the past, I suspect I would not get one.

    You want me to apologize because I find it annoying that you ask me for free chemicals _after_ accusing me of being an unethical profiteer?

    >And if you think I was unfair in pointing out above in this thread that you have a vested interest in the sales of TF-4 and your book - well, you certainly do. You claim that your interest is not financial, then appears to be one of personal pride. And that is understandable, as I understand that you have put a lot of work into the collection of the information that went into the book. That's great that you did that! But I think you need to not attack people personally when discussing them, especially on forums like this where someone in the future will be able to see how you like to discuss things. Remember that what you type here reflects on you personally, for a long time.

    You know, I'll just have a to live with that fear.

    And now, after all of that, Kirk is still at it:

    >I'll tell you what - instead of the couple bottles of TF-4, you can send me a copy of Haist, and let's make it both volumes. Then we can be on an equal footing.

    Do you often ask men that you don't know for presents?
     
  71. Bill,
    Your long explanation on the dangers of acetic acid stop baths is enlightening.. thanks for
    taking such time to present it to us.
    By the way.. your book is fantastic... Thanks for that too.
     
  72. Well this debate has been both informative and interesting- though
    a little slow/careful reading at times.
    Let's bring it back to the central/original question- acid stopbaths.

    does time in solution-pH level-heat exchange-composition of stopbaths cause clumping=>increased grain?

    do stopbaths cause "pinholes"?

    do films have to be "processed ASAP" thereby justifing the dropping the stopbath step and(tang.) the use of alkaline fixers?

    unless your using a "staining developer" do acid stopbaths concern you?

    and Bill, what page did you say that stopbath formula was on in FDC?
     
  73. Bill,

    Sorry I don't have as much time today to devote to you, but here's a few comments for now.

    I regards to your one word answer on finding a copy of Haist, aka "Library", I'm sure that this is the kind of book that borrowing from a library with just not do justice. I have looked into this, and the nearest ones are out of state about 250 miles away. But thanks for the kind suggestion.

    "You want me to apologize because I find it annoying that you ask me for free chemicals _after_ accusing me of being an unethical profiteer?"

    No, I was suggesting an apology as you were making comments about me being a cheapskate. I did not call you an unethical profiteer - and after all, you certainly to gain financially from the formulas and the book and therefore it is in your best interest for them to do well. That's all I'm pointing out.

    And you close with, "Do you often ask men that you don't know for presents?"

    Bill, that made me laugh as well - not as much as the toddler thing above, but close. After reading your posts in this thread and in http://www.photo.net/bboard/q-and-a-fetch-msg?msg_id=006fc5 I feel I know you quite well! Thanks again for pointing out a typographic error in my post - that really does advance the dicussiion here. So what about it - you going to send me a copy of Haist?

    So - back to the real subject at hand.

    I have not looked at Vestal's comments on your fixer. Even though Vestal is no Grant Haist, I would be interested in reading what he has to say. Would you care to cite the references you mention?

    My perspective is that saying alkaline fixer is better than acid fixers and saying that Haist says so really does not quantify it very well for the average reader. You mention image degredation from using stop baths - so just how much degradation is there - how about some charts or values showing the loss in sharpness, acutance, or resolution? Just how significant is it?

    And you only give a few scant paragraphs in FDC to ammonium-based rapid fixers, which are getting pretty close to neutral in pH. How significantly different is using a rapid fixer from an alkaine fixer? Again, in terms that can actually be quantified, and not merely because Haist says so.

    And to get it out of the way - I would like to appolloggizze now for any speliing errors I may have made in this post.

    I will be away for a few days, so I'm sorry I will not be able to contribute here for a bit.

    Kirk
     
  74. Bill;

    In your book you say "Acid stop baths CAN cause pinholes..." but in the conversation with Haist that you say you remember just like yesterday you say "may cause...". Which is it? Is it 'may' or 'can'? There is a difference here you know.

    Grant did discuss fixing at length with me. We worked on mercaptan fixing agents together, and we discussed stop baths. While my memory is not as perfect as yours, here is what I can say regarding your points.

    1. There is NO publication at EK relating to image distortion caused by stop baths, nor is there any report about heat generated during stopping causes problems in coatings. It was discussed with you as a theoretical possiblility, I'm sure, but not as FACT.

    2. It is well known that relief images generated by the tanning effect of many developers causes image sharpness increases. This is reported by Mees, and also by Ctein in his book "Post Exposure". This relief image is generated by the tanning effect of the developer in B&W materials or by the formation of the color image in color products as well as tanning. It can also be generated by some hardeners.

    3. In no way do I recommend any aldehyede for hardening. Read my post. EK is doing away with them as fast as possible. In some cases, that has not been possible, but work is going ahead to remove it (them). Read my post please. I had one of the first patents at EK on eliminating formaldehyde as a color film stabilizer and using a less harmless chemical. Please get off this track and don't misquote me or put words in my mouth.

    4. Regarding bubbles caused by acid fixes, I ran specific photographic tests making coatings and solutions to test the use of carbonate followed by an acid stop, and was unable to generate the pinhole effect in any way except using unsubbed material with no hardener and processing near the melting point of the gelatin! (this was considered to be an expected result and a non-commercially encounterable condition but was used as the reference or check)

    The reason for this was that EK considered the possiblility of a problem arising from carbonate developers and acid stop baths, but postulated that it was a myth as there was no verified experimental data. The reason that they wanted experimental verification was the fact that many developers used borates and the EPA had warned EK that borates were toxic to citrus crops in Fla and Cal, and we had a deadline to remove it in certain products, so I was one of several people asked to verify the truth or falsity of this 'urban legend'. NO ONE was able to verify any bad effect caused by a stop bath, and therefore, stop baths were given the ok along with carbonate developers to replace borates. In color products, this took place in 1970 with the introduction of the EP3 process which replaced the P122 process as my part of the project.

    Stop baths at up to 100 deg F remain common in C41 and RA processes with mulitlayer color products with no hardness, swell, or image problems. B&W films are processed in rapid access conditions in the tropics with no problems.

    5. Fixers using thiosulfate and thiocyanate mixtures were well known at EK and were often used for stabilization processes however mercaptans or thoureas were also used. Read more in Haist and you will find that those fixers could be used either for normal or rapid access processes (these latter processes used reduced washes and were espeically used by the newspaper industry and military photographers). In fact, I'm sure that the complete sentence or paragraph (whatever full context applies to your excerpt) states that he is referring to a stabilization (reduced wash process as noted above - or other expectedly less permanent process) when he qualifies the image permanence. The thiocyanate and thioura salts wash out of film just as well as the thiosulfate or mercaptan salts. I have had silver analyses run by X-ray fluorescence to show that the silver - silver complex is completely washed out.

    6. Yes, I have read Haist's work, no, I don't have a copy. Yes, I can get to a copy in the EK KRL Library in B83 at Kodak Park, 5 miles from here.

    7. I have mentioned several points in your joint work that seem to run counter to everything I learned at EK, heard at EK, or have experienced personally through experimental evidence at EK. I started out by limiting my comments to evidence or making a request for evidence and this has rapidly become personal. I did not intend that at all, but it seems that you don't like having anyone make comments that don't agree with or praise your work.

    8. In spite of the evidence from my text resources here, and two other chemists, you have ignored the question about thiocyanate decomposition into cyanide. You instead keep saying that it does decompose into cyanide, is very toxic when acidified, and accuse me of being insensitive to the health and safety of individuals who read these posts. Nothing could be further from the truth than that last statement Bill. Please refrain from any further comments in that vein.

    ----

    Let me just say this then. Your work is merely a restatement of the work of Haist and the formulas in the Photo Lab Index. It includes a lot of unsupported additional information which we are expected to take on faith. I cannot do that when it is counter intuitive, or goes against what I know from experience or from conventional wisdom at EK. When you requote yourself, you chage verbs from 'can' to 'may', or you just ignore the issue when we give you concrete information on specific chemistry.

    My comment on using proprietary information was not directed at my fellow EK researchers. If you read that carefully, I was pointing at you, not them! Again, please don't put words in my mouth, or misquote me. You seem to be misreading my posts or something.

    ----

    I recommend that you try to get a copy of "Journey: 75 Years of Kodak Research". In it you will find the names some of the most famous EK people, and some of the ones you should have talked to are listed there. Indeed they have their own chapters. You will find, for example that the most senior and respected researcher was not T. H. James as you seem to infer, but rather was Dr. George Lucky. George was a "Research Fellow". Dr James was a very respected and important researcher, but by no means the most senior, nor the only one at EK. As I remember, neither Grant nor I are even mentioned in the book, even though we both became Research Associates. You had to be quite a bit above that level to merit mention in this book.

    Bill, you have dropped a lot of names. I know virtually all of those people on a first name basis, met with many of them daily, went to lunch with them, visited their homes or they visited mine, etc, all as part of the friendship and business relations we all had during my work at EK. And, I did research with them, presented data to them and had them present data to me! This is something entirely apart from any relationship you ever had with them. We all shared this 'detail' of our work that cannot be discussed with you adequately, as you are not privy to the kind of work we did at any possible level.

    You are a hobbyist who has done a remarkable service, with a few tiny unsupported potentially erronious statements that I'm trying to clear up. They are not serious, but I wanted clarification and to present the alternative in a better light than you portrayed it and based on personal experimental data. In response, you have attacked me personally and in general taken the criticism poorly.

    If you show me to be wrong, I will say "I'm sorry, but I'm wrong" and that will be the good grace I would hope from you in the case that you are proven wrong.

    With best wishes to all.

    Ron Mowrey
     
  75. Well, I re-read some parts of the KRL history and did indeed find the team of Haist, King, and Pupo mentioned with regards to dry processing on page 101. Sorry, I had forgotten that and missed it in rechecking earlier.

    Ron Mowrey
     
  76. First, apologies to all who raised interesting points that I couldn't get to. It was difficult enough to focus on a few points. Now Garry brings us back to the main points:

    >does time in solution-pH level-heat exchange-composition of stopbaths cause clumping=>increased grain [or other undesirable image irregularities]? [BT comment in brackets]

    Some influential leading scientists at the end of the 20th century strongly held this conviction. Haist, Mason, Russell are three. There is some inferential basis in the literature to support this, but there is no explicit, decisive proof. I chose to go out on a limb and advocate what these scientists believed. So far the heat exchange has been visibly demonstrated, but not in film, rather, in the decomposition of my ego. It is undeniable that I took a controversial position. My question to readers is, would you rather I did that, or would you rather I played it safe with conventional wisdom? Believe me, I had my doubts! Up until the moment of publication, I pestered Grant Haist about this. (I couldn't pester Russell; I could no longer find him, and I fear he is no longer with us.) My doubts were removed by Haist. Of all the things he said to me on this topic, the one I remember best is, 'Bill, they can't prove you wrong.'

    Let me give another perspective, drawn from medical research. These scientists had a clincal view, not an epidemiological view. Their opinion was based on decades of highly qualified observation. But they did not quantify their observations statistically. The reason is simple. Even in the heyday of lavish photographic research, they could not get it funded.

    >do stopbaths cause "pinholes"? [or reticulation or other gross image irregularities?]

    They can, but only when the stop bath is fresh and the pH approaches 3. This can be avoided, and the power of the stop bath to stop development can be increased by a factor 10 (measured in time) by using a buffered stop bath as suggested in FDC, p. 104. The formula, which is not obvious because it is contained in the text, is

    120 ml 28% acetic acid
    80 grams sodium acetate
    to a litre of water

    [or an equivalent amount of sodium di-acetate]

    That is an expensive stop bath. But it's the best that science offers us. I strongly recommend reading the Crabtree and Henn article on which it is based, which I cited earlier. It is one of the great, finite, experiments in photographic science.

    Just as important to ask, though, is whether acid processing can cause fine, subtle, image irregularities? That is harder to answer.

    >do films have to be "processed ASAP" thereby justifing the dropping the stopbath step and(tang.) the use of alkaline fixers?

    I don't understand this. Is the question, "is there a need to use stop baths to stop development completely and instantly?"

    If so, the answer is yes, under some conditions. In practical photography, those conditions are, whenever the developing time is short and and difficult to control. But there is more to it than just the chemistry to consider. There is the draining time. Unless you have a way to move the film instantly from the developer to the stop bath, you will have a hard time getting any precision. Thus, short development times dictate open tanks. You will also have to decide on a draining time. The shorter your draining time, the faster you will get your material into the stop bath and actually stop development; but the shorter the draining time, the more you will decrease the life of the stop bath by bringing in more alkaline solution.

    Because my only consideration is fine photography, I don't have to consider rapid access issues, and I didn't. But this was an important consideration in the past. Now, it seems that digital has taken over a lot of rapid access requirements, such as much press photography.

    I have just had a look at the fixer chapter I handed to Steve Anchell. Steve Anchell is the most long suffering and loyal co-author anybody ever had. It has a lot of information, and a lot of it is geared to improving acid fixation. But it seems to me so quaint and out of date that I can't imagine what use it would be to anyone today. As I look at that, and I look at what Steve and I finally came up with, it is hard for me to understand the relationship between what I started with and what I ended with. I would have to say that both Steve and Grant encouraged me to look towards the future, not the past.

    Someone had to do it. I don't want to give the impression that all of my collaborators and advisors are in agreement with my position. Some points were surprising to Crawley. It was clear to me that that Dickerson and Zawadzki had reservations, but they did not care to state them explicitly and I could not press them any more than I did. If I had to guess what they were thinking, it would be this: 'this is interesting, it is not what I would have written.' Howard James passed it without comment.

    >unless your using a "staining developer" do acid stopbaths concern you?

    Is the question, 'if you are not using a staining developer, should you worry about avoiding acid stopbaths?'

    First, there may be some films where the staining action is so deterred that it does not make any difference. I doubt it, but Gordon Hutchings would be the person to discuss that.

    Second, I would say that my position is that stop baths may cause harm and can under most circumstances that exist for ordinary photographers, beneficially be avoided. But, equally strongly, I hold that if you are going to use a stop bath, today, it should be an intelligent (albeit expensive) stop bath formulated along the lines suggested by Henn and Crabtree. Otherwise there's little point in using it. Let me also suggest that alkaline stop baths can be used and should be further researched. The best information I could get and give is contained on p. 120 of FDC.

    Finally, I would like to say, that what I really would like to see is more research on alternate fixation processes.

    There are two problems expressed in the literature by Mason (p. 198) and I think Haist (and certainly by Haist in conversation), with mercaptans. They are, as known in the 1980s, either too smelly, or too toxic, and some are both. Perhaps something has changed since then?

    However, there is a further objection that can be made. Both of these authors wrote before the time of W.E. Lee's shattering but still preliminary experiments in the mid-1980s, which suggested that image stability is increased by the retention of an extremely small amount of thiosulfate in the silver image.

    We need more research along these lines.

    Where does that leave alkaline processing as advocated by me? I think in an OK place. Alkaline processing does not eliminate every trace of thiosulfate. It merely removes thiosulfate much, much faster than acid processing. (It is very important to realize that these results cannot be approached by alkalizing the material after it has been processed in an acid or neutral fixer.) Therefore, alkaline processing leaves just as much residual thiosulfate as careful acid processing does - it just does so more elegantly, in much shorter time, and with much less use of water and without the requirement of post-fixation washing aids. Obviously, it is far more generally useful for papers than for films, but FDC is primarily about films.

    There is one other point I wanted to raise that I think is interesting, but for the life of me I can't remember it anymore. It may come back to me later.
     
  77. > ...W.E. Lee's shattering but still preliminary experiments in the mid-1980s, which suggested that image stability is increased by the retention of an extremely small amount of thiosulfate in the silver image. <

    Has anyone done any new research into this work? I remember that this study was about High contrast documentary films and never addressed any work-a-day films(e.g.Tri-X). It has been the justification for the whole "to much washing is bad" movement for paper.Do we know that 'a little contamination' is better than
    'total chemical elimination' for films and/or paper.

    Do silver grains clump?
    does solution time-temperature-composition have any clumping affects?
    Does a 'ASAP' processed film have less grain/clumping than a equal
    film that has had 'hours' of careful processing?
     
  78. Bill writes, "My question to readers is, would you rather I did that, or would you rather I played it safe with conventional wisdom?"

    I have time for this one - I would rather you state speculation as speculation, even if it comes from a leading authority. Simply saying "While there is no proof at this point, there is the theory that (fill in the blank)" would do it.

    As it is - you flat out state speculation as truth! In the FDC, you state:

    1. pH variations occur when a film is moved from an alkaline developer into an acid stop bath. This can generate enough molecular heat to cause the grains of the film to clump together.

    OK - so that first sentence is certainly true. The second sentence is pure speculation. And despite Haist et. al. believing in the possiblity of it, that does not make it a true statement.

    Thank you for finally addressing this issue. That is what we have been wondering about here, and after having to undure your personal attacks on both Ron and myself for days, you have finally addressed it. Thank you.

    This also implies that if the statement is pure speculation (even if based on good supporting facts), perhaps the effect so small that it really is inconsequential.

    You state Haist as saying, "My doubts were removed by Haist. Of all the things he said to me on this topic, the one I remember best is, 'Bill, they can't prove you wrong.'"

    Conversely, you can't prove you are right. Thanks for getting around to clarifing that statement.

    Well, that's really all I have time for, for now.
     
  79. OK - I found a little more time.

    So Point 1 in regards to stop baths at the top of page 103 of FDC has been shown to be speculation. Point 2 is an unlikely event. Point 3 - excessive swlling causes a loss of image integrity. Just how much and in what way? Many people actually try to accentiate edge differences - does the clumping you talk about cause and increase in edge differences or is it an overall effect? Do your sources give actual values, or is it a hunch and awaiting further undone research?

    And would you address the use of rapid fixers? Many people now adays do not use "acid" fixers - they use more neutral, slightly acidic rapid fixers. You say that alkaline fixers are only better thiosulfate level wise than acid fixers in an elegant way, as they both can leave similar levels of thiosulates in the film. Is the alkaline fixer that much faster at washing than a rapid fixer?

    Which brings back one of my original points - I have not been convinced that there is a real significant difference to an all alkaline process as you propose vs. a stop bath/rapid fix method that many others use. If the significant difference is only elegance, than perhaps cost and availability of materials will be my deciding factor in choosing which of them to use.
     
  80. In response to the latest:

    >Grant did discuss fixing at length with me. We worked on mercaptan fixing agents together, and we discussed stop baths. While my memory is not as perfect as yours, here is what I can say regarding your points.

    If that is true then you must know a great deal more than you are letting on to here.

    > There is NO publication at EK relating to image distortion caused by stop baths, nor is there any report about heat generated during stopping causes problems in coatings. It was discussed with you as a theoretical possiblility, I'm sure, but not as FACT.

    There is a lot of space, Row, between 'theoretical possibility' and 'fact'. I described the convictions of some very distinguished, very experienced scientists, far more senior to you. Do you consider their convictions to be valueless?

    >2. It is well known that relief images generated by the tanning effect of many developers causes image sharpness increases.

    But what has this got to do with anything we are discussing here?

    >3. In no way do I recommend any aldehyede for hardening. Read my post. EK is doing away with them as fast as possible. In some cases, that has not been possible, but work is going ahead to remove it (them). Read my post please.

    Your post carelessly indicated that they had been eliminated. Now you are backtracking.

    >Please get off this track and don't misquote me or put words in my mouth.

    And you find you don't like to backtrack. Welcome to the club!

    >Regarding bubbles caused by acid fixes, I ran specific photographic tests making coatings and solutions to test the use of carbonate followed by an acid stop, and was unable to generate the pinhole effect in any way except using unsubbed material with no hardener and processing near the melting point of the gelatin! (this was considered to be an expected result and a non-commercially encounterable condition but was used as the reference or check)

    If you want us to take this work seriously, publish it. If you want us to be interested in it, describe it in detail. Describe the films, the formulas of the developers you tested with, the formulas of the stop baths you tested. The pH of the solutions is crucial, as you know. In any case, as you know, we are not just talking about pinholes. We are talking about reticulation, a problem that still exists very much today, and we are talking about much more subtle effects. Please don't focus exclusively on gross effects. That would be to miss the point.

    >The reason for this was that EK considered the possiblility of a problem arising from carbonate developers and acid stop baths, but postulated that it was a myth as there was no verified experimental data. The reason that they wanted experimental verification was the fact that many developers used borates and the EPA had warned EK that borates were toxic to citrus crops in Fla and Cal, and we had a deadline to remove it in certain products, so I was one of several people asked to verify the truth or falsity of this 'urban legend'. NO ONE was able to verify any bad effect caused by a stop bath, and therefore, stop baths were given the ok along with carbonate developers to replace borates. In color products, this took place in 1970 with the introduction of the EP3 process which replaced the P122 process as my part of the project.

    I am aware of that valuable research.

    >The thiocyanate and thioura salts wash out of film just as well as the thiosulfate or mercaptan salts. I have had silver analyses run by X-ray fluorescence to show that the silver - silver complex is completely washed out.

    Again, you will have to publish to refute the literature which is heavily weighted against you. I did not add Mason's devastating comments on thiocyanate fixation; I thought Haist's were enough for one day.

    >Yes, I have read Haist's work, no, I don't have a copy. Yes, I can get to a copy in the EK KRL Library in B83 at Kodak Park, 5 miles from here.

    You could do a much better job of disseminating this wisdom than me - if you wanted to. I can't believe you don't own a copy of the book. I own two, the second set of which Grant gave me when he republished it three or four years ago. My first set contains most of my notes on the errors I found in the book. I don't think Grant ever spent a more depressed hour than when he heard me recite them, and I never alluded to them again. None of us finds evisceration pleasant. He did not incorporate them into the second printing of his book. Yet that does not detract from its value. An interesting paradox.

    >I have mentioned several points in your joint work that seem to run counter to everything I learned at EK, heard at EK, or have experienced personally through experimental evidence at EK.

    You're not the only person to have that response. As Howard James wrote about photography in 1966, "the time is past when one research worker could attain mastery in all fields."

    >I started out by limiting my comments to evidence or making a request for evidence and this has rapidly become personal.

    What you did, Rowland, was to start a blog on me behind my back. That showed from the start a profound contempt for me and my work. Had you considered me a person worth having a discussion with, you would have contacted me first. And there isn't anyone easier to contact than me. I am accessible. Try me. You might like me.

    >I did not intend that at all, but it seems that you don't like having anyone make comments that don't agree with or praise your work.

    Rowland, you know perfectly well one thing: none of the very great men at Kodak I knew would have given a lightweight like me one second of their time had it not been obvious that I had a profound desire to learn and some ability to grasp what they had to say.

    >I recommend that you try to get a copy of "Journey: 75 Years of Kodak Research".

    My copy is inscribed to me from Grant. Did you know that he was not just a contributor, but the principal editor?

    >In it you will find the names some of the most famous EK people, and some of the ones you should have talked to are listed there. Indeed they have their own chapters. You will find, for example that the most senior and respected researcher was not T. H. James as you seem to infer, but rather was Dr. George Lucky. George was a "Research Fellow". Dr James was a very respected and important researcher, but by no means the most senior, nor the only one at EK. As I remember, neither Grant nor I are even mentioned in the book, even though we both became Research Associates. You had to be quite a bit above that level to merit mention in this book.

    And now you're denigrating Howard James? That I don't like. He can't defend himself. At least I can.

    >Bill, you have dropped a lot of names. I know virtually all of those people on a first name basis, met with many of them daily,

    Believe me when I say this Row, they were all a lot nicer than you.

    >You are a hobbyist who has done a remarkable service, with a few tiny unsupported potentially erronious statements that I'm trying to clear up. They are not serious, but I wanted clarification and to present the alternative in a better light than you portrayed it and based on personal experimental data.

    Then you should have contacted me.

    >In response, you have attacked me personally and in general taken the criticism poorly.

    I was not predisposed to courtesy, given the sneakiness of your proceedings.

    >If you show me to be wrong, I will say "I'm sorry, but I'm wrong" and that will be the good grace I would hope from you in the case that you are proven wrong.

    I think we both know that there is no right or wrong here. The truth lies in a continuum around the middle, as it must, in this particular branch of science. Simple conceptions of Right or Wrong belong to blogs, not to photographic science.

    >Well, I re-read some parts of the KRL history and did indeed find the team of Haist, King, and Pupo mentioned with regards to dry processing on page 101. Sorry, I had forgotten that and missed it in rechecking earlier.

    Now you know what I go through all the time.

    So let's have some new fixers! In the 25 years since Grant wrote, there must be some better chemicals. Let's find them, and try them out! One laughable possible paradox would be that you would fix in a mercaptan, and then give a controlled afterbath in thiosulfate, to stablilize the image. There must be a better way.
     
  81. In one of his posts, Bill Troop has asked me 'where are your publications, your books, your research' (paraphrased here for brevity). I think I should clarify this for Bill.

    Here goes. I have 15 patents on process research, over 40 proprietary internal 'inventions', an acceptance letter for a 6 article series in Darkroom Techniques on color system engineering from David Jay, the editor (part of which is in 4 threads here in very condensed form) and which was never published for several reasons. The reasons were that David Jay left DT, then DT ceased publication, and finally I had little time while still working to do the articles justice.

    In addition, I gave one talk to The International Congress of Photography. And, I helped Grant Haist edit the very book that A&T constantly refer to in their book.

    If Bill doubts any of this, I will be glad to offer proof in terms of acceptance letters, patent cover pages, and etc.

    Now, he has shown us that my point #1 was pure speculation on his part. I have shown by extensive laboratory experiment that my point #2 does not happen. The reference here: 'www.screensound.gov.au' supports my point #3. Therefore, there is no question that these statements are unsound on the part of A&T.

    The bottom line is that acid stop baths and fixers are safe to use. They will yield better consistancy and uniformity from process to process, having proven that in the lab as well by experimentation.

    I do suggest that one use a non hardening fix bath and that for color, one must use a bleach, blix or fix with a pH of about 6.5.

    I do not recommend the use of any aldehyde hardener, contrary to what is suggested in A&T and implied by Bill Troop above. I have supplied a formaldehyde hardener formula previously upon request, and I will do so in the future with the understanding that it is not a preferred way to go about hardening film or paper.

    My super fixer is posted above for those that wish to see what a power fixer can do. It is safe to use, but is a powerful fogging agent, and has a higher toxicity level than most other fixers. I have mentioned this before, but Bill Troops claims of 'death' are apparently vastly overstated based on chemical evidence. After all, we did test these solutions in the lab before getting the patent. No one died while adjusting the pH of our Blixes. Silver was removed from the coating to satisfactory levels, as determined by quantitative analysis. The reference to the contrary by Bill Troop was regarding stabilization processes with no wash or reduced wash and was apparently taken out of context from Haist.

    Certain thio ethers and thiol compounds can be added to any fix for greater activity, and are used with no harm or odor in EK color processes contrary to Bill Troops assertions otherwise. I cannot discuss these proprietary ingredients for obvious reasons, but if you want evidence read the labels on the bottles of E6 chemistry.

    I suggest that we now close these arguments. The issues deserve a rest as do we. I thank Bill for his post indicating that he appears to have used hypothetical statements as real observations with no supporting evidence.

    With best wishes to all.

    Ron Mowrey
     
  82. Bill;

    It seems you were busy writing as well as me. And in your usual fashion.

    Your response to the following quote of me from your post is not correct in any way.

    I believe Howard James to be a respected and honored member of the Research labs, and will remain so in my memory of him. It is again you who put words into my mouth. I merely stated that George Lucky was the highest ranking research scientist as stated in the book I referenced. I never denigrated him in any way whatsoever! I merely pointed out that he was not the most senior research scientist. Your copy of the book should show that clearly with the picture of George Lucky and the description of his special position at KRL.

    "George was a "Research Fellow". Dr James was a very respected and important researcher, but by no means the most senior, nor the only one at EK. As I remember, neither Grant nor I are even mentioned in the book, even though we both became Research Associates. You had to be quite a bit above that level to merit mention in this book.

    And now you're denigrating Howard James? That I don't like. He can't defend himself. At least I can"

    You seem able to read dishonorable intent into everything I say, including the original post.

    It was not sneaky or anything else, it was just another post here.

    I suggest that you gain a modicum of tact yourself.

    Ron Mowrey
     
  83. Bill;

    In one of your posts you asked for proof of my statements.

    Well, I could never offer you proprietary data, but in any case the data has probably been destroyed in routine records management, but here is the proof that I can offer.

    1. Kodak, Agfa, Fuji and Ilford to name a few still recommend the use of a stop bath in many processes. In addition, Jobo recommends the use of a stop bath with their drum processors. So, every time you see the words 'stop bath' in a process recommendation from EK at least, it is indirect evidence of the work of my coworkers and myself having proven the lack of merit in the hypotheses that stop baths cause problems.

    2. Such a monumental series of 'discoveries' as you state in your book would be big news in all areas of photographic science and technology, but instead it remains a series of hypotheses that have pretty much been debunked by researchers. I do admit that they are valid as hypotheses to question with regards to processing, but when examined carefully, no proof has been forthcoming to establish them as fact.

    3. Millions of photographers over the span of nearly 100 years have used stop baths and acid fixes and have reported no serious problems. Yes, people have said one thing or another about stop baths, acid fixers, and etc., but proof, hard proof never follows. Many researchers have tried and failed.

    Thats about it.

    Ron Mowrey
     
  84. >In one of his posts, Bill Troop has asked me 'where are your publications, your books, your research' (paraphrased here for brevity).

    No, rather, paraphrased to get away from the point. I know you have some deuxieme echelon publications and patents that are not of the slightest interest either to me or anyone else in black and white photography. I asked you where your publications were that would back up the claims you have made.

    To this you have no made no response.

    Row, where are those publications?

    Failing that test, I have asked you to comment in more detail about your supposed experiments.

    You have offered nothing. Could this be because you already know that there was a fault in your experiments? (Like testing at the wrong pH? Nothing to be ashamed of there. Photochem history is littered with such stories. It's the mistakes that make the most interesting stories.)

    >If Bill doubts any of this, I will be glad to offer proof

    I don't doubt any of it, and I never said I did. What I doubt is that you can offer the slightest proof of any of the assertions you have made here regarding fixers and stop baths. Reciting your background - none of which is in black and white photochemistry - does not constitute an adequate standard of scientific proof, as I am sure you must be the first to admit.

    >Now, he has shown us that my point #1 was pure speculation on his part.

    No, Row, not his part. I have sourced it out to Mason and Haist. If you have a problem with that, take it up with them. I have also included citations to books you - a self-described expert - don't even own. You have provided no citations.

    >I have shown by extensive laboratory experiment that my point #2 does not happen.

    But you have offered no publication or any other documentation that would support these alleged experiments. We need more than fulminations and choleric posturing before we can accept your unsupported conclusions as scientific truth.

    >The reference here: 'www.screensound.gov.au' supports my point #3.
    Therefore, there is no question that these statements are unsound on the part of A&T.

    Really, Row? I invite everyone to have a look at the link Row points us to. It is the homepage of the National Screen and Sound Archive of Australia. OK. So what? There's nothing on that page that touches upon either Row or any issue we have been discussing here. And that, Row, is the great 'therefore' which lets you say 'there is no question that these statements are unsound on the part of A&T'? That's pretty strong language for a pretty feeble webpage.

    >The bottom line is that acid stop baths and fixers are safe to use. They will yield better consistancy and uniformity from process to process, having proven that in the lab as well by experimentation.

    But you have not offered one shred of published documentation for any of the assertions you have made. Maybe that's because the literature does not in fact support you? Row, the literature is against you. How do you suppose I got to the point I did? By _reading_ what people like Haist and Mason were saying, and then by following up with them personally. It's no use for you to tell us that you contributed to Grant's book. What did you do? Proofread a few footnotes? The fact is, you don't have the book, and you don't know what's in it.

    >I do suggest that one use a non hardening fix bath and that for color, one must use a bleach, blix or fix with a pH of about 6.5.

    But we are not talking about color. This is a B&W forum.

    >I do not recommend the use of any aldehyde hardener, contrary to what is suggested in A&T and implied by Bill Troop above. I have supplied a formaldehyde hardener formula previously upon request, and I will do so in the future with the understanding that it is not a preferred way to go about hardening film or paper.

    I cannot believe that you would still formulate a hardener with formaldehyde, when everyone else is completely opposed to it.

    >My super fixer is posted above for those that wish to see what a power fixer can do. It is safe to use, but is a powerful fogging agent, and has a higher toxicity level than most other fixers.

    I'm glad you now admit that. But where is the proof of stability you claim? The established literature suggests otherwise. Your claims are unique and you have offered no support for them. And what other previously undisclosed problems will you next own up to?

    >After all, we did test these solutions in the lab before getting the patent.

    But did you? I have read the patent and I do not find a formula corresponding to what you put forth here.

    >but if you want evidence read the labels on the bottles of E6 chemistry.

    Known everywhere for its great _stability_, eh?

    >I suggest that we now close these arguments.

    Because you're beginning to feel the heat?

    >The issues deserve a rest as do we.

    At just the point where you are asked to prove a single one of your assertions, you say the issues deserve a rest. Don't run just now, Row - show us your proof first.

    >I thank Bill for his post indicating that he appears to have used hypothetical statements as real observations with no supporting evidence.

    Obviously I do not accept that I said anything of the kind.

    >I believe Howard James to be a respected and honored member of the Research labs, and will remain so in my memory of him.

    Then don't denigrate him, merely because you are annoyed that he liked me and supported me. He even gave me a cover blurb, but it appeared too late in the production process to use.

    >You seem able to read dishonorable intent into everything I say, including the original post.

    You seem to put it there.

    >It was not sneaky or anything else, it was just another post here.

    It was sneaky, and dishonorable, because you never made any effort to contact me, and you never had the courtesy to inform me that you were posting or what you were posting. It was low, Row, very low. It's not as if I'm hard to find. My email address is all over the Internet. There are many, many people in Rochester who have my phone number, and funnily enough, you claim to know them all. Equally funny, never once, in 20 years, has a single one of our mutual friends suggested that I contact you for information of value.

    >I suggest that you gain a modicum of tact yourself.

    You gain some honor, and I'll try out the tact.

    >In one of your posts you asked for proof of my statements.

    >Well, I could never offer you proprietary data, but in any case the data has probably been destroyed in routine records management,

    The dog ate my homework? No, that won't fly. Scientists who perform valuable scientific work take steps to preserve it - as you would know had you ever perofrmed any.

    >but here is the proof that I can offer.

    And there follows . . . not a single piece of data, not a single measurement, not a single chart, not a single description of methodology, not a single reference to a colleague or senior, not a single reference to a single publication. Nothing approaching or even hinting at a scientific standard of proof. Row, you know what scientific proof is. Now provide it.

    >but proof, hard proof never follows.

    We're waiting for yours, Row.

    Finally, a word about borates. Row, you noted that EK wanted to eliminate borates. It may have thought about it. But have you looked at the formulas for Kodak Fixer, D-76, and XTOL, lately? Borates cannot be replaced by carbonates. Borates can't be replaced by carbonate/bicarbonate buffers of similar pH. Has it ever occurred to you that one of the reasons why borates are still obligatory in so many developers, in spite of the environmental downside, is that when carbonates are substituted, a deleterious effect on the image is observed? Again, have you spent any time evaluating the image quality of borate buffer systems against carbonate buffer systems of equivalent pH? And if so, please don't tell us again that the dog ate your homework!
     
  85. FINALLY - - ILLUMINATION

    Row wrote:

    >Unfortunately, Grant has been in poor health recently and has suffered a severe stroke.

    >One last note. Grant Haist is probably not in good health. He was under constant supervision by an attending nurse or companion the last time I saw him and could barely speak. She had to explain the situation to me when I went over to say hello to him, and said that his road to recovery may be long and hard, if possible. He has been spending his summers in Rochester and winters in Florida. I have been reluctant to call his home either here or in Florida due to his condition.

    OK, Rowland. I called Grant Haist's daughter today and left her a message asking after her father. Just now, 8:45, I got a phone call from Grant Haist.

    'Reports of my illness have been exaggerated. I am now well and always have been. I have never been under a nurse's care. I have been spending the summer in Michigan as I always do. I am working on a new book. Please don't put that on a blog. It isn't about what you think it is. I can't think where Rowland Mowrey got the idea I was ill. I'll have to have a word with him, the next time I'm in Rochester.'

    Folks - there's something the matter with this picture. And it isn't Grant Haist's health. I cannot even guess why Rowland Mowrey is spreading rumours of Grant Haist's grave illness. Whatever his motive is, the fact is that Grant is perfectly well. 'I don't know for how long, but I'm fine now and I always have been.' Long may this blessed man, who has given us all so much, live.
     
  86. Bill;

    Here is your exact quote:

    "You know I?m asking myself why I?m wasting time arguing with you guys? I love the retrograde ? I believe it should be cherished. I would like to shake hands with someone who still thinks the earth is flat. Row, Kirk, where are your publications? Where are your books? Where is your research?"

    I took this to mean personal credentials, not the actual experiments themselves. There is no indication to me that you meant experimental results as I had given the experimental details in outline form above. The comment quoted here is so vague and confusing it was easily misinterpreted.

    You are quite quick in your vehement and sarcastic criticisms of people. You would be a good candidate for being on the show with Donald Trump. I'll try to answer anyhow from memory.

    This experiment was carried out by a number of people in KRL between 1965 and 1970. My part was done under the direction of Charles Edens (see the 75th anniversary issue of the book I referenced above for Charlie et al). I had just joined the company. The coating type involved was one described in a patent granted to Edens and VanCampen, and so was the process for the most part. (USP 3,582,332) You should be able to find it with your excellent resources. The fixer was a stop fix as described on page 13, the stop was 1 or 2% acetic acid (I cannot remember), and the fix was the same fix as on page 13.

    The series was a hardening series of color paper on subbed and non subbed support with varying levels of hardener and adhesion. This would typically involve about 10 coatings, 5 subbed and 5 unsubbed. The process was P122 with borate and the same developer at the same pH with carbonate substituted for borate.

    The paper samples were exposed and processed in a blix process with develop, blix, wash or develop, stop, fix wash bleach, wash, fix, wash, or develop, stop-fix, wash bleach, wash, fix or develop stop, blix, wash.

    I have described the other details above. The coatings were processed at 68, 75, and 85 deg F and tracked for sensitometry, swell (using a swellometer) and abrasion (using an abrasion meter). Surface pH was tracked using a surface electrode.

    At the end of the process final wash, all samples were treated with P122 stabilizer which is basically a citrate buffer at an acid pH.

    All of the coatings without subbing left the support. The unhardened coatings left as free melted gelatin in the developer, but the hardened coatings floated off intact into the developer solution. Coatings with varying levels of hardness and subbed reacted with swell and hardness varying as per the hardner level but they stayed on the support.

    The coatings without hardener stayed on until the stop fix was entered at which time they blew off the support (we called that blow off), but the hardened coatings survived the entire process depending on temperature.

    All coatings with hardener survived 68 degrees, some 75, and the 'correct' hardner level survived the 85 degree processes. By survival, I mean that the stop fix was not the culprit. In fact, the lowest hardener level coatings decomposed in the developer. In no case was blow off observed in any process that survived the entire process sequence, but in all cases where there was degradation, it began in the developer due to the alkali and temperature. In no case was 'blowoff' observed to be a problem in carbonate vs kodalk comparisons. The problems were more alkali related, hardner related, or temperature related.

    Plots were made of swell (y axis) vs process step / total time in process, and secondary notations were made on these plots tracking the surface pH.

    If you look closely at that URL I gave, you will find the reference to swell.

    http://www.screensound.gov.au/ScreenSound/Screenso.nsf/Web+Pages/75A9F762AFE49430CA256C4D00110973?OpenDocument

    This graph looks pretty much like my swellometer measurements. You would have seen this if you had bothered to read some of the posts in this thread.

    You must also have missed Gary Lewis' post about this: "Wallace Hanson wrote ("The Great Stopbath Squabble";Pop Photo;1975)" in which Hanson could not duplicate any of your claimed problems and his results apparently correlated well with mine.

    In any event, I ran the color paper experiments, others ran B&W film and paper or color film. The answer was that carbonate has no interaction with stop baths. As a result, from 1970 to present, EK recommends the use of a 1% - 2% stop bath for color paper. Jobo has added that a similar stop should be used for C41 films. Stops are not really needed for reversal films or papers due to their nature but have been used for uniformity in some cases. Ilfochrome uses a pH 1.0 bleach bath immediately following the MQ or first developer with absolutely no harm, but IDK if it is a carbonate developer.

    Bottom line, Wallace Hanson outside of EK has apparently pretty much validated the multiple lines of inquiry into the effects or interaction between carbonate developers and acidic stop baths that show no effect whatsoever if the coating is hard enough to survive the developer at the temperature chosen. And, I might add that this is the case for all photographic materials from the 60s to the present day. I'm sorry, but I have not been able to read that reference myself.

    So, that is the best I can reconstruct this from memory. I cannot give exact pH values, or swell values. I'm just not that good at remembering. I cannot draw abrasion tests etc. This is one of the closest looks into internal EK research that I have ever given.

    I understand that the films were tested for image structure as well as the parameters that I tested for paper. The processes were appropriate for the films being tested.

    As a result of these tests, all appropriate developers were changed from Borate to Carbonate. To the present day, I still use 1% or 2% stop after the color developer when processing my color and B&W prints, as well as all of my B&W film. (no pinholes or 'blowoff'). The EK RA stop contains sodium sulfite and sodium acetate IIRC. I quit using it as it wasn't necessary to pay that price. I just use acetic acid.

    The reasoning we came up with to explain the lack of bubbles is this. In the coating, the bubbles, if formed, are micro bubbles capable of diffusing out of the coating. They probably form slowly due to diffusion, as stopping takes up to 30 seconds at 68 deg. OTOH, they may never form, because CO2 is water soluable to a great degree even in acid solutions. The heat generated is miniscule and is apparently not significant. It is similar to the heats of reaction taking place during development, and in any case is moderated by the huge specific heat of water which acts as a cooling agent.

    Before I ran this experiment, indeed before I joined EK, there was apparently one observation of pinholes in films and papers that went through deep tank machines. In a roller transport, it is my understanding that the bubbles formed as the film or paper rose out of the depths of the tank, or formed at the bottom of the rolls in a dip and dunk processor. The problem was solved long before I got involved, by adjusting the hardener level in the emulsions concerned. It was believed to be due to the hydrostatic pressure at the bottom of the tank trapping the CO2 in the emulsion and then releasing it as the photographic material rose and the pressure decreased. Charlie Edens told me this story and related it to me as the one example of this effect ever observed. He added that this effect had never been observed in tray processes, or in basket or hanger processes in hard rubbber or stainless steel 3 1/2 gallon tanks.

    The process temperature was of great concern when C41 and E6 went to 100 deg F, and so therefore image structure was thoroughly studied. There was found to be no correlation between image structure and temperature. In fact, image structure was better at higher temperatures than lower temperatures in some cases. I believe that todays finer grained color films owe their sharpness and grain to the higher temperature process, but that is only my opinion based on some offhand remarks and some conversations with co-workers.

    So, as you all can see, the researchers at EK did a lot of thought experiments and actual experiments to verify the safety of using a stop bath after a carbonate developer. This is mainly an issue in some B&W developers, RA developer, and C41 developer.

    It is true that not all developers have eliminated borates. Some even contain phosphates. Fixes use borates as well for reasons pointed out in this thread. However, at the ratio of Color to B&W products on the market, the biggest concern for pollution and the highest priority for EK was in the targeted color processes, not the B&W processes.

    It has also been pointed out that Dick Henn took another approach to formulating developers with HC110. This is an excellent developer with an entirely new approach to storage stability and alkali as is well known on this forum. Gainers formulas take a similar approach. All are valid, so long as they work to your satisfaction.

    So, there you have my experimental answer to my comments in the original post, and I stand by the results and the supportive material regarding swell substantiate my observations, as far as my memory can serve.

    Sarcasm aside Bill, that was a cheap shot. I did that work nearly 40 years ago. The dog did not eat my homework. It was legally disposed of on a rigid schedule adhered to for years by EK and other major companies. Perhaps you have never worked for a large company and faced the problems of data accumulation.

    The work by all of us on that part of the project was adopted by and is still used by and recommended by EK. You cannot ignore that. And you cannot ignore the billions of dollars of product that used those processes over the years and the millions of satisfied customers.

    Hope this makes you happy.

    Ron Mowrey
     
  87. >This experiment was carried out by a number of people in KRL between 1965 and 1970. My part was done under the direction of Charles Edens (see the 75th anniversary issue of the book I referenced above for Charlie et al). I had just joined the company.

    You took part in an experiment, you had a small part in it. You had just joined the company.

    At least 10 years later, in 1979, Haist wrote, 'The use of carbonates in developers may produce blisters in the emulsion layer of the photographic material when this matieral is transferred from the alkaline developer to any [!] acid afterbath, such as an acid stop bath or acid fixing bath. This tendency is increased during processing at other than normal room temperatures, especially under high-temperature processing conditions. The carbonate still retained in the emulsion layer after development reacts with the acid of the afterbaths to produce carbon dioxide gas bubbles, which may then rupture the gelatin of the emulsion layer.'

    [Haist, I, pp. 243-244.]

    No footnotes. Haist himself had not heard of any persuasive evidence to the contrary, and was writing with unusual vigour and at unusual length.

    If you were working on his book, and disagreed with what he said, why did you not let him know?

    >The coating type involved was one described in a patent granted to Edens and VanCampen, and so was the process for the most part. (USP 3,582,332) You should be able to find it with your excellent resources.

    I have done so. It is by Bertelson and Glanz, and is assigned to the National Cash Register Company.

    I can't comment on anything else you have written, because the patent number you have cited is incorrect. I would add that out of the many thousands of footnotes in Grant Haist's book that I have followed up, I have never come across a single incorrect reference. That is a very great testament to Grant's scholarship.

    >Sarcasm aside Bill, that was a cheap shot. I did that work nearly 40 years ago. The dog did not eat my homework. It was legally disposed of on a rigid schedule adhered to for years by EK and other major companies. Perhaps you have never worked for a large company and faced the problems of data accumulation.

    What I know is this: had your work been important, you could, and would, have retained the relevant data.

    >The work by all of us on that part of the project was adopted by and is still used by and recommended by EK. You cannot ignore that.

    And Haist, knowing this, yet wrote, in a book to which you contributed 'something' - directly the contrary on pp. 243 and 244. He went further: he alludes to the matter again on p. 543 and then gives an entire page to a photo on p. 544, which bears this caption: 'Retciulation is the result of excessive irreversible swelling of the gelatin of the emulsion layer. The fine ruptures can occur during the water rinse or in the stop bath of low salt content following development in an alkaline developer. (Photograph by Grant Haist)'

    Row, you never heard of problems with stop baths. But Grant not only knew all about them, he was experiencing them in his own work. Please note. Photo by Grant Haist. Of that same daughter I left a message with this afternoon.

    Who has the larger credibility here?

    >Hope this makes you happy.

    >Ron Mowrey

    No, I am very sad. I want to know why you spread false rumours of Grant's illness. Did you think that would prevent me from speaking to him?
     
  88. Bill;

    The patent # is correctly 3,582,322. Sorry for the typo, but since this merely describes the generic coating and developer, it has no significant bearing on the experiment itself.

    Yes, I was new to the company, so therefore the work was closely supervised and approved by senior members of research, and in addition, work by other more senior members of the staff verified these experiments with other products and processes as well. Two of those individuals who vetted my work are featured in the KRL history book.

    I was not free to keep proprietary information unless EK granted that permission in writing and the documents were itemized. In no case was I allowed to keep documents beyond the expiration date mandated by record retention regulations. You should know this if you had ever worked for a major industrial organization. That material was not mine to keep.

    As far as Grant is concerned, the last I saw him he was in the care of a nurse or companion after a severe stroke. We spoke at a camera store where I saw him and the nurse/companion at Longridge mall about 5 miles from our home. I have been reluctant to call him, as the individual with him explained that the stroke was severe, that he was undergoing therapy and the recovery might be a long road. I am spreading no rumors.

    I'm glad to hear he has apparently recovered, so I will give him a call myself. Thanks for the information.

    The bottom line is that you denigrate everything I have said, even though I have given experimental details of experiments that I ran in person. You have never run those experiments, but have relied on Grant telling you information which, as you said above,

    "Some influential leading scientists at the end of the 20th century strongly held this conviction. Haist, Mason, Russell are three. There is some inferential basis in the literature to support this, butthere is no explicit, decisive proof. I chose to go out on a limb and advocate what these scientists believed. So far the heat exchange has been visibly demonstrated, but not in film, rather, in the decomposition of my ego. It is undeniable that I took a controversial position. My question to readers is, would you rather I did that, or would you rather I played it safe with conventional wisdom? Believe me, I had my doubts! Up until the moment of publication, I pestered Grant Haist about this. (I couldn't pester Russell; I could no longer find him, and I fear he is no longer with us.) My doubts were removed by Haist. Of all the things he said to me on this topic, the one I remember best is, 'Bill, they can't prove you wrong.' "

    The key words are "THERE IS NO EXPLICIT, DECISIVE PROOF" in your quote above. This was exactly our position at EK in the 60s, and we set out to prove/disprove the hypothesis set out above. We could not prove it. We were able to disprove it.

    Here is proof:

    http://www.kodak.com/global/en/professional/support/techPubs/o3/O3wp4.jhtml

    or here:

    http://www.kodak.com/global/en/professional/support/techPubs/o3/O3wp4.jhtml

    or here (which gives the option of stop or water)

    http://www.kodak.com/global/en/professional/support/techPubs/aj3/aj3.jhtml?id=0.1.14.34.9.16.38&lc=en

    Since there were over 400 hits on the EK site, I went here where there are only about 100:

    http://ilford.com/html/us_english/search/index.asp?target=stop+bath

    I like this one:

    http://www.agfa.com/photo/pdf/products/C-SW16-E16.pdf

    It is one of over 100 again and gives a nice list of advantages of using a stop bath.

    Of course, not all of the developers contain carbonate, but these references put up no caution about carbonate being a problem. I doubt if I will find one either.

    The problem here is your having presented as fact, something for which there is no "explicit, decicive proof" (your words). That was the reason for my initial post, as I had explicit, decisive proof from my own experiments! Please, differentiate between facts and supposition and between what you know, and were told, but have not verified. This is the fundamental basis of scientific research.

    Also, please stop your villifying me and trying to discredit me. Your comments about the use of formaldehyde in the post above is an example. You recommend the use of aldehydes, and give an aldehyde based hardener in your book. You use glacial acetic acid, thiocyanate, and other toxic chemicals in your formulas. So, in truth we both have mentioned the use of what some consider to be toxic chemistry which is the very nature of conventional photography. Don't point at me as the sole culprit when we both have made similar recommendations. If you feel it is wrong for me to recommend the use of X, then it is equally wrong for you to recommend the use of X. A statement saying "Ron and I have both given formulas for aldehyde based hardeners. While these are toxic and I believe that neither of us would recommend them, we recognize that there are those of you who may at some time need this type of formula for special purposes. Please take all precautionary measures to protect yourselves against any potential hazard". Now, there is a diplomatic courteous method of stating what we have both said.

    If we have more discussions like that, you and I would not be at such odds with each other. I mean no ill will. I stated that in my original post "with apologies to A&T" and I meant it sincerely.

    Ron Mowrey
     
  89. Bill;

    I saw Grant at Ritz photo in the summer of last year. He was with a woman. I went over to him and began speaking, but he was hesitant and slow to respond. The woman pulled me aside and told me that story about his illness while he finished a transation at the counter.

    He had been spending time here in Rochester in the summer, and in Naples Fla. in the winter, so he must now be spending time with his daughter in Michigan. I have been loathe to call him since I ran into him, but I have called both phone #s, and have not gotten him or anyone at either number.

    His number in Rochester is working, but in Naples is not, indicating to me that he is 'in residence' in Rochester at this time.

    My previous call to him was in the spring of the year before, one year earlier, when we were to go out photographing spring flowers in the park. When I called, he said he didn't feel up to it and would call back. He did not, and I was unable to contact him until I ran into him at the mall. He asked us to visit him in Fla, several years ago, but on our last visit there it was in the summer and we were unable to go and take him up on his offer to 'take some beautiful sunset pictures from the dock here'.

    By no means would Grant refer to me as Rowland. I never, ever used that at EK. Grant always called me Ron.

    That is the story as far as I know it. Please have him call me in Rochester from his daughters or wherever he is staying then. Have him call collect. I am quite curious as to what is going on as well and I'm totally mystified.

    Ron Mowrey
     
  90. >The patent # is correctly 3,582,322. Sorry for the typo, but since this merely describes the generic coating and developer, it has no significant bearing on the experiment itself.

    First you cite the wrong patent. Then, when that is pointed out, you cite what may be the correct one - who knows, I'm not any longer interested in checking. Because you now say it has no significant bearing anyway. So why did you cite it in the first place?

    >Yes, I was new to the company, so therefore the work was closely supervised and approved by senior members of research, and in addition, work by other more senior members of the staff verified these experiments with other products and processes as well.

    I don't think you understood what you were doing. You were obviously a very small cog in a very big machine. If any of the work you were engaged upon in the 1960s and early 1970s had had the slightest validity, it would not have been directly contradicted by Mason in 1975 and Haist, in four pages, in 1979, and again, in 2000. Moreover, your involvement in photoscience is so slight that you don't even own these foundational books.

    >Two of those individuals who vetted my work are featured in the KRL history book.

    I no longer believe your work was vetted by anyone. You are not now in a position where anything you say has the slightest credibility. I will require original documents to check any claim you may make in the future.

    >As far as Grant is concerned, the last I saw him he was in the care of a nurse or companion after a severe stroke. We spoke at a camera store where I saw him and the nurse/companion at Longridge mall about 5 miles from our home. I have been reluctant to call him, as the individual with him explained that the stroke was severe, that he was undergoing therapy and the recovery might be a long road. I am spreading no rumors.

    Grant tells me he has never had a nurse and has never been ill. You made up this disgusting story about one of my closest friends and upset me and several others to a very great degree. Grant Haist is alive and well. He is 82. He is not now sick and never has been sick.

    >I'm glad to hear he has apparently recovered, so I will give him a call myself. Thanks for the information.

    He has not recovered. He was never ill.

    >The bottom line is that you denigrate everything I have said,

    Because none of it is true. None of what you have said technically is true, none of what you have said personally is true.

    >even though I have given experimental details of experiments that I ran in person. You have never run those experiments,

    You can no longer ask anyone to believe that you have run anything.

    >This was exactly our position at EK in the 60s, and we set out to prove/disprove the hypothesis set out above. We could not prove it. We were able to disprove it.

    You did some work in the 1960s that was not recognized in any scientific publication. It was not reported in Grant Haist's book written in 1979. Grant Haist's book states the opposite. Those are the facts, that is the history of photographic science. That is the truth, as near as we can get to it. This nonsense that you are subjecting us to, from an unknown, third level lab operator, is not credible.

    >Here is proof:

    And you cite some web references. How about a serious publication? How about an author, with proper citations? How about someone recognized in the scientific literature? How about some actual data? A published paper? But no. Nothing. What we have is that the 1979 and 2000 editions of Haist's 'Modern Photographic Processing' directly contradict everything you say.

    >The problem here is your having presented as fact, something for which there is no "explicit, decicive proof" (your words).

    Rowland, you have had to do a lot of backtracking here.

    Now I'm going to do some of my own. I'm going to take back anything I said that moderated my position. I deeply regret having said anything which compromised with it. And I deeply regret ever having taken you seriously. I was so taken aback by your attack, and so impressed with your purported credentials and persuasive manner, and, was frankly, so very far away from the subject, that I unwisely gave ground before I had thought the issue through. I know reclaim that ground. But I don't expect anyone to expect me to discuss it with an established fantasist.

    >That was the reason for my initial post, as I had explicit, decisive proof from my own experiments!

    You have not provided proof of anything. You don't even know the single, overriding fact which helps explain your total confusion on this issue: that colour films are hardened in a manner completely different from black and white films.

    The proof is Grant Haist's photo on page 544. You do not even approach that level of proof.

    >Also, please stop your villifying me and trying to discredit me.

    You are the one who is villfying and discrediting people. You tried to villify and discredit me behind my back. Then you tried it out on Howard James and Grant Haist. You concocted a story that Grant Haist had had a stroke and was unable to talk to anybody, hoping that I would not call him and ask, 'who in the world is Rowland Mowrey? What basis does he have to disagree with you?'

    >Your comments about the use of formaldehyde in the post above is an example. You recommend the use of aldehydes, and give an aldehyde based hardener in your book. You use glacial acetic acid, thiocyanate, and other toxic chemicals in your formulas. So, in truth we both have mentioned the use of what some consider to be toxic chemistry which is the very nature of conventional photography. Don't point at me as the sole culprit when we both have made similar recommendations. If you feel it is wrong for me to recommend the use of X, then it is equally wrong for you to recommend the use of X. A statement saying "Ron and I have both given formulas for aldehyde based hardeners. While these are toxic and I believe that neither of us would recommend them, we recognize that there are those of you who may at some time need this type of formula for special purposes. Please take all precautionary measures to protect yourselves against any potential hazard". Now, there is a diplomatic courteous method of stating what we have both said.

    Except for one thing. It is incorrect to recommend formaldehyde as you have done. It is correct to recommend glutaraldehyde or succinaldehyde as I have done. I am so used to thinking of myself as a supplicant at the feet of genius, that for a moment I considered you an authority. I find now that, little as I understand about photochemistry, I know a great deal more as to the larger picture, and much detail, than you do.

    >I stated that in my original post "with apologies to A&T" and I meant it sincerely.

    I do not believe that you understand the word apology. If you did you would realize that you owe a very great apology to me, and a very, very greater one to Grant Haist, about whom you have said unforgiveable things.

    >I saw Grant at Ritz photo in the summer of last year. He was with a woman. I went over to him and began speaking, but he was hesitant and slow to respond. The woman pulled me aside and told me that story about his illness while he finished a transation at the counter.

    You can't now ask anyone to believe that. It simply isn't true.

    >He had been spending time here in Rochester in the summer,

    Grant spends the summers in Michigan, and has done so for at least a decade. He then makes a brief appearance in Rochester, but only in the late autumn.

    >so he must now be spending time with his daughter in Michigan.

    No. His daughter does not live in Michigan and is not now with him.

    >His number in Rochester is working, but in Naples is not, indicating to me that he is 'in residence' in Rochester at this time.

    Yet one more illustration of your carelessness in evaluating indicia. The number in Rochester is always on, year after year. Grant Haist is not in Rochester.

    >When I called, he said he didn't feel up to it and would call back.

    Maybe he just didn't want to see you. After everything that has transpired on this thread, I could well believe it. But why should I now fall into the trap of assuming that anything you say is true?

    >By no means would Grant refer to me as Rowland. I never, ever used that at EK. Grant always called me Ron.

    Correct. I have examined my transcription. 'I know Ron.' 'I'll have to call him up the next time I go to Rochester.' As far as I can tell, that is the single truthful statement you have made on this thread.

    >That is the story as far as I know it.

    You mean, as far as you have fabricated it.

    >Please have him call me in Rochester from his daughters or wherever he is staying then. Have him call collect. I am quite curious as to what is going on as well and I'm totally mystified.

    Ron, I'm not going to have Grant or anyone else call you. You'll hear from him when, or if, he chooses to make contact. And when he does, he won't need to make it a collect call. Don't you see what you're doing? You're still at it - planting the assumption that Grant Haist is so destitute that he can't afford to call you.

    But I am going to pay the price of getting an even worse reputation for indiscretion than I already have, because it's the only way I can settle this matter once for all, by publishing my transcription of part of the conversation I had with Grant Haist last night.

    GH: Where did he ever get the idea that I was ill? I don't know.

    BT: I - maybe he's - losing his mind.

    GH. Hmm. I don't think you can say that. Can you, on a blog? Can you say that on a blog of some sort?

    BT: Ye-e-e-s.

    GH. Well, I don't know. He's misled. That's the word these days, from the presidential debates. ... I'm OK. I'm fine, I don't know how long I'll be that way, but I'm fine and have been fine. And that's the word.

    I have one final (I hope) comment. In the few lines transcribed above, you will notice that Grant uses the phrase 'I don't know' three times. That, indeed, is his favourite phrase, and one he uses constantly. And so it is with all the great geniuses in every field that I have ever interrogated: 'I don't know'.

    It is only the low level, insecure people, whose primary goal is to establish their authority, who are afraid of those three words, which are the common denominator of all wise people in science or art or philosophy or any other field.
     
  91. Bill;

    I know that Grant has a home in Rochester and one in Naples Fla. I have the phone # and addresses to both. Up to about two years ago, I knew that he was spending his winters in Fla, and summers in Rochester. I have seen him here and talked to him on several occasions. We have met or called each other on an irregular basis since Grant retired in the 80s.

    His number in Fla is disconnected now, but still listed. Probably due to his travels, as I believe that he told me he had it disconnected from April to October. At one time, he supplied me with his schedule of trips back and forth so that we could keep in touch.

    You are right. I do owe him an apology if your story is true. I saw him and the 'nurse/companion or whatever' and that is the story she gave me. I did talk to him at Ritz photo and we parted. I have been unable to contact him since to check up on his health.

    I do not know his daughter. I have seen pictures of her that Grant has taken and that is about it.

    You can consider my role at EK in any way you wish. The fact remains that I have those patents, publications, and presentations that I mentioned above. Go ahead and run my reputation down if you need to build yours up. It will not take away from mine. I think this thread will give a good laugh to us all at the KRL retirees lunch at the end of October, if anyone there even knows who you are.

    I have no proof that you talked to Grant either. So what, no big deal. I really would like to talk to him. Collect if he wishes. That does not imply impoverishment, it is merely a courtesy. Something that you do not seem to understand. I think it interesting that you would not pass along to him my request for a call.

    I didn't have those books you love so much for several reasons. First, I knew almost all of the authors personally and could ask them questions directly. Second, when I couldn't talk to them, I had the library at KRL. Third, there were other, primary resources that I went to for information on development, fixing, bleaching, and etc. These were the people at the forefront of the ever moving field of R&D.

    Finally, you completely bypassed the experiment that we conducted at EK, and waved it away as inconsequential and you retracted your own words in your last post. Well, go ahead. That does not change the facts presented in the web references that I gave, and that others gave which also seem to refute you. You can try to cover it up but you cannot whether I'm involved or not. Someday, someone will come up with additional proof, and this will come back to haunt you. Mark my words.

    I'm looking forward to talking to Grant and getting this matter straightened out. And, if I am proven wrong, I will step forward and admit it with apologies to Grant. After all, I respect and like Grant and treasure the memories I have of our times spent together.

    Ron Mowrey
     
  92. This determined fantasist just won't give up.

    >I know that Grant has a home in Rochester and one in Naples Fla. I have the phone # and addresses to both.

    So much anyone can get off the Internet. What you won't be able to find is his Michigan number.

    >Up to about two years ago, I knew that he was spending his winters in Fla, and summers in Rochester.

    Grant hasn't spent his summers in Rochester for a very long time. Ten, fifteen years.

    >I have seen him here and talked to him on several occasions. We have met or called each other on an irregular basis since Grant retired in the 80s.

    In a parallel universe?

    >You are right. I do owe him an apology if your story is true. I saw him and the 'nurse/companion or whatever' and that is the story she gave me. I did talk to him at Ritz photo and we parted. I have been unable to contact him since to check up on his health.

    If my story is true. You have some nerve, as they say around here. Now let's look at the nurse. First she was a nurse. Then she was a nurse/companion. Now she is a 'nurse/companion or whatever'.

    Ron, Grant is married. He has a wife. Her name is - well, I don't think I'll give out any information that you can use to make your fantastic deceits more plausible. I only risk providing this new information to make clear to the public that that you don't know that Grant remarried quite some years ago. It is clear that you have never been introduced to Mrs. Haist. It is clear that you have never spoken to Mrs. Haist. Mrs. Haist never told you that Grant was ill, you never saw Grant ill, and frankly, because you insist this happened in the summer, I don't think you ever encountered these people at all in recent years, for the simple reason that they are never in Rochester in the summer.

    >I think this thread will give a good laugh to us all at the KRL retirees lunch at the end of October, if anyone there even knows who you are.

    I think, by now, they know who you are. And I don't think they're any too comfortable with that.

    >I have no proof that you talked to Grant either.

    If it is even conceivable that anyone here, besides Ron, doubts what I said, please email me. I have the proof. I knew I'd need it. I recorded the conversation.

    >I didn't have those books you love so much for several reasons. First, I knew almost all of the authors personally and could ask them questions directly. Second, when I couldn't talk to them, I had the library at KRL. Third, there were other, primary resources that I went to for information on development, fixing, bleaching, and etc. These were the people at the forefront of the ever moving field of R&D.

    Such pompousness. Ron, you don't have the books because you aren't much of a scientist and because you're nothing of a scholar.

    >Finally, you completely bypassed the experiment that we conducted at EK, and waved it away as inconsequential and you retracted your own words in your last post. Well, go ahead.

    I bypassed your 'experiment', which you have utterly failed to document, because (1) nothing that you said about it convinced me that it had actually taken place and (2) because the men who really did count for something at Kodak, such as Haist and James, took no account of 'it' and disputed what you claim are its 'conclusions'.

    >You can try to cover it up but you cannot whether I'm involved or not. Someday, someone will come up with additional proof, and this will come back to haunt you. Mark my words.

    Yeah. Right. And Elvis is living in Rochester with a nurse/companion, but is too ill to talk to anyone except Ron Mowrey.

    >I'm looking forward to talking to Grant and getting this matter straightened out. And, if I am proven wrong, I will step forward and admit it with apologies to Grant. After all, I respect and like Grant and treasure the memories I have of our times spent together.

    Gotta admit you have a gift for gab, Ron. I can understand why you would treasure your memories. After all, they're hand-made.

    I am reminded of the famous motto attributed to Sam Goldwyn: 'Sincerity is the most important thing. Once you can fake that, you've got it made.'
     

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