Water or Stop Bath

rowland_mowrey · September 27, 2004

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

rowland_mowrey · September 27, 2004

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<div></div>

kirk_keyes · September 27, 2004

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.

bill_troop1 · September 28, 2004

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

rowland_mowrey · September 28, 2004

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

kirk_keyes · September 28, 2004

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?

bill_troop1 · September 29, 2004

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

kirk_keyes · September 30, 2004

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

garrylewis747 · September 30, 2004

>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?

bill_troop1 · September 30, 2004

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

rowland_mowrey · September 30, 2004

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

rowland_mowrey · September 30, 2004

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

lex_jenkins · September 30, 2004

<i><b>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.</b></i>

bill_troop1 · September 30, 2004

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!

kirk_keyes · October 1, 2004

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

kirk_keyes · October 1, 2004

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.

bill_troop1 · October 1, 2004

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?

bill_troop1 · October 1, 2004

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!

bill_troop1 · October 1, 2004

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.

bill_troop1 · October 1, 2004

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?

john_finch · October 1, 2004

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.

garrylewis747 · October 1, 2004

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?

kirk_keyes · October 1, 2004

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

rowland_mowrey · October 1, 2004

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

rowland_mowrey · October 1, 2004

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

Sign In

Water or Stop Bath

Recommended Posts

Link to comment

Share on other sites

Top Posters In This Topic

Popular Days

Top Posters In This Topic

Popular Days

Posted Images

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Create an account or sign in to comment

Create an account

Sign in