Help Mr. Wizard - my Pt/Pd's aren't clearing.

Dan Dozer · Nov 24, 2007

Just tried a couple of Pt/Pd prints last night and was I ever dissapointed. First one was on Weston paper and since it is somewhat cream in color I didn't notice anything while that print was still wet. Then I tried another on Crane's Platinotype that is very white in color and it the print came out yellow. At that point I went back to the first one on the Westin paper and now i see it is a little yellowish also. Obviously, things aren't clearing properly.

My first thought was the clearing chemical I used (EDTA) but all was freshly mixed. On the second print I even mixed a fourth tray of new solution for a final soaking, and it didn't do any thing more for the print.

This was my first try with Potassium Oxylate as a developer - I used it at about 90 Degrees. Not sure if that had anything to do with it.

I suspect that it might have something to do with the Ferric Oxylate - the No. 2 solution was fairly old and maybe that had something to do with it. I have read that it doesn't keep all that long. I know that some of you will be recommending that I use Sodium Platinum and I do have a bottle on order. However, for now, i was going to keep using the No. 2 solution.

My prints were coated with about 75% palladium and 25% platinum.

Does anyone have any ideas???

Dan

scootermm · Nov 24, 2007

are you doing a water bath between your developer and the first clearing bath?
If yes, try not doing the water bath and leaving the print in the developer for 5mins then putting it straight from the developer into the first clearing bath.
Also, try adding some citric acid to your clearing baths to make sure they are acidic. I use a clearing bath of 8L water, 8tablespoons of EDTA and 8 teaspoons of Citric acid.
Also, check the PH of your developer and make sure it is acidic.

thats my initial brainstorming.

Dan Dozer · Nov 24, 2007

Scottermm - Thanks for the suggestions. I tested the PH of my developer with the strips that I use on the swimming pool. They will only read PH from between about 6.4 and 8.4 but it looks like mine is around 7.6 which according to Dick Arentz's book is slightly alkaline. I have some Citric acid that I'll try adding to the developer as Arentz suggests.

I do use a wash bath between developer and clearing bath and I'll try your suggestions with that and the clearing baths as well.

Thanks loads,

Dan

sdivot · Nov 24, 2007

Scooterman, can you elaborate on your clearing method?
I'm currently using 3 baths of Kodak hypo clear.
Do you just use the one bath of EDTA, citric acid, etc., or is it 3 baths? One tray for clearing would sure save room in my sink.
How long do you clear your prints?
Thanks for the info,
Steve

scootermm · Nov 24, 2007

Dan from my experience the PH of the Clearing baths can have an effect on how well they clear also, so adding citric acid to the clearing bath can assist with this.

Im not sure what effect adding citric acid to the developer will do... when I need to make my potassium Oxalate developer more acid I just add some Oxalic acid to it. Given that the developer is made up of Oxalic acid and potassium Carbonate this just serves to "rebalance" using the same ingredients. Usually doesnt take much.

Steve, for my clearing baths (10mins for each of three baths) I usually either use EDTA and citric acid in all three, or if I happen to be out of EDTA, Ill use a combo of Sodium Sulfite, sodium metabisulfite (this is basically Kodak HCA), and citric acid. I always use the same combo in all three baths so that when one becomes exhausted I can just rotate them, and in the rare case that Im desperate and run out of those clearing chems... Ive even used citric acid/mountain dew or citric acid and CLR (cleaning product you can get pretty much anywhere). Theyve all worked fairly well.
Only downside Ive found is that EDTA can bleach out a print if you happen to forget and leave a print in for too long.

John Kasaian · Nov 24, 2007

Trizzel trazzel trazzel trone.
I dion't know a thing about pt/pd but whenever I see "Help Mr. Wizard" I get Tutor Turtle flashbacks!
Good Luck!

Mark Fisher · Nov 24, 2007

I've been struggling trying to get Pd prints to work properly and I finally decided to modify the instructions I was using a bit. First, I made sure that the developer was acidic using oxalic acid in the same way that scootermm described. I made up my pot oxalate with oxalic acid and pot carbonate anyway so I have plenty of both around. I also bought a cheap pH meter ($20 off ebay) to check pH periodically. It is much easier and more accurate that strips.
I also tried every clearing agent around from EDTA to citric acid to oxalic acid....and then I started using Permawash (like HCA) and it cleared the print in less than a minute...amazing. My water is a little basic (which I did not know before) so I skip the rinse step and go straight to HCA. It is really easy now!

clay · Nov 24, 2007

Tetra-sodium EDTA is a really lousy clearing agent by itself because the pH is basic, which just locks the unused ferric into the paper fibers. Use it in conjunction with HCA, or mix your own with 1 Tbsp EDTA, 1 Tbsp Sodium sulfite, and 1/2 tsp Sodium metabisulfite (to make the solution slightly acidic and act as a buffer) per liter of water. Or just use Permawash or HCA by itself.

Dan Dozer · Nov 24, 2007

I guess I should have been asking these types of questions much earlier rather than try to get all the info out of the books. Now I think I have a better base to work from.

So - It sounds like I need to make sure that my developer and clearing agents are a little acidic.

Scottermm - thanks for all the tips - I know that you are much more experienced in Pt/Pd than I am and I'm going to try out your suggestions.

Mark - The PH meter sounds like a good purchase - I'll start looking. However, now I'll probably be bidding against all the other APUG-ers out there for them. I like your suggestion on permawash. I have plenty of that so it will be easy to use.

Clay - where were you two weeks ago? After just purchasing three bottles of Tetra Sodium EDTA - now I need to acidify it. I'm assuming that I can mix it with Permawash just like you suggest to do with HCA.

Lastly - John - Glad to hear that I'm not the only one to grow up with Tutor Turtle. However, I wasn't expecting to admit it on an open forum like this. Now just think of all those 'younger guys' who don't have a clue what we're talking about.

Thanks again to all,

Dan

boyooso · Nov 24, 2007

clay said:
Tetra-sodium EDTA is a really lousy clearing agent by itself because the pH is basic, which just locks the unused ferric into the paper fibers. Use it in conjunction with HCA, or mix your own with 1 Tbsp EDTA, 1 Tbsp Sodium sulfite, and 1/2 tsp Sodium metabisulfite (to make the solution slightly acidic and act as a buffer) per liter of water. Or just use Permawash or HCA by itself.

Is there a reason for using permawash, rather than Kodak?

(other than mixing from liquid rather than powder?

Thanks!

Corey

Kerik · Nov 25, 2007

I find the HCA and permawash work the same. EDTA (tetra) by itself DOES NOT WORK. And I can't understand why B&S keeps telling people to use it as a clearing bath... Clay's formula work's great, but so do HCA and PW.

Dana Sullivan · Nov 25, 2007

I'd like to lay to rest some mis-conceptions about Tetra-Sodium EDTA as a clearing agent.

All of the Pt/Pd kits at Bostick & Sullivan that come with Tetra-Sodium EDTA also come with Ammonium Citrate as the developer because of a discovery my father made in the early 1980's. He realized that by allowing the prints to sit in the developer for 3-4 minutes, a simple bath of inexpensive Tetra-Sodium EDTA will clear the yellow stain from the paper.

The secret, he figured, was in the Ammonium Citrate Developer: It will combine with the Ferric Oxalate in the coating solution, and convert a good portion of it into Ferric Ammonium Citrate and Ammonium Oxalate. This has its benefits and caveats, though.

Anyone who's ever made their own Cyanotype solutions from scratch knows that Ferric Ammonium Citrate is extremely soluble. In fact, most people can clear the FAC from cyanotypes without any clearing agent at all.

On the other hand, anyone who's done a lot of Platinum/Palladium printing will tell you that Ammonium Citrate developer tends to change the color of your prints from a cool, neutral black when it's fresh, to a warmer tone as it ages. This is due to the ever-increasing Ammonium Oxalate content, which produces a similar warm tone to Potassium Oxalate.

So to sum it up: Tetra-Sodium EDTA works as a clearing agent if you follow the directions as provided by B&S.

If you use Potassium Oxalate or other developers, we recommend a 50/50 mixture of Sodium Sulfite and EDTA. If the stain is extremely stubborn, a 50/50 mix of EDTA and Potassium Metabisulfite will almost certainly work.

Thanks for listening to my rant,

Dana Sullivan

bill schwab · Nov 25, 2007

I haven't seen it mentioned here yet, but adding a little oxalic acid to your ferric oxalate mix can help with this as well. Dick Arentz mentions a formula in his book somewhere that I use when I am having a tough time with clearing.

Bill

Dan Dozer · Nov 25, 2007

Dana - thanks for all the information - it pretty much agrees with some of the things I've found out in using the B&S kits. However, I have a further question related to something you inferred. As I read it, it sounds like you say that if you leave the print in the Ammonium Citrate developer longer (3 - 4 minutes), clearing with Tetra-Sodium EDTA should work fine.

As someone relatively new to Pt/Pd printing, I found the B&S kits very easy to use. Starting out, I followed the directions to the letter. However, one thing that I did experience was a minor problem in the prints clearing completely (Palladium only) when I followed the directions. Note that the B&S directions don't mention anything about leaving the print in the developer longer. In fact, the directions say that the "Development is complete within a few seconds". As a newbie, I figured this meant that I was supposed to remove the print from the developer after several seconds and all would be fine. Does your father's research also mean that leaving the print in the Ammonium Citrate developer longer will also help in clearing problems? The directions for clearing do say if clearing is a problem, to increase the clearing time or increase the concentration of EDTA, but do not mention anything about time left in the developer.

Please don't consider this as a "bashing" of B&S, because it certainly is not. I think B&S is a great company and I will continue to purchase my supplies from B&S in the future. The problems I'm experiencing now are in now way related to B&S at all.

Thanks and keep up the good work,

Dan

Monophoto · Nov 25, 2007

Dana -

Pt/Pd prints are beautiful, but it does take time and practice to learn how to get the results you are looking for. And because there are so few practitioners of this craft, the only way to learn is by word-of-mouth and/or trial-and-error.

While prints do appear almost instantaneously in ammonium citrate developer, I was taught that leaving them in the developer for a few minutes will result in deeper and smoother tonality. And because I an obedient sole who does what he is told, that's the way I've always done it. And I've never had a problem with clearing in EDTA, which I suppose confirms Dana's point.

That said, I was also taught that it it was a good idea to pass the print through a plain water rinse immediately after the developer. That rinse removes most of the developer, and it also starts the clearing process. That's also a practice that I use regularly, and I've noted that much of the yellow ferric oxalate stain washes out in the water bath.

If you have not done so, my experience was that taking a workshop was a great way to be introduced to Pt/Pd printing and to learn some of the tricks that the master's haven't gotten around to writing down.

Dana Sullivan · Nov 25, 2007

Monophoto said:
Dana -

Pt/Pd prints are beautiful, but it does take time and practice to learn how to get the results you are looking for. And because there are so few practitioners of this craft, the only way to learn is by word-of-mouth and/or trial-and-error.

I agree completely. It's statements like the following that really hurt our collective cause, though:

kerik said:
EDTA (tetra) by itself DOES NOT WORK. And I can't understand why B&S keeps telling people to use it as a clearing bath...

We both know that his statement is false. Kerik, though, has a good reputation on APUG and people are going to take his statement as the gospel.

Kerik · Nov 25, 2007

Dana,

OK, let me clarify. EDTA by itself OFTEN DOES NOT WORK WELL to completely clear the print. I've not seen documentation that leaving it longer in citrate developer will make EDTA work better for clearing, but I'll happily take yours and Dick's word for it because I have no reason to doubt it. The problem, especially with beginners, is that they don't even realize the print isn't clearing well and that EDTA (apparently) works under the special condition of ammonium citrate developer and long development time. They read EDTA = clearing agent and run with that assumption. My point is, why not make the standard clearing bath something that works MOST of the time and not only under special conditions. Kodak HCA, Heico Permawash or a mix that Clay suggested will work with most papers and most common developers (Amm. Citrate and the more commonly used Potassium oxalate) MOST OF THE TIME. I'm only ranting a bit here because I can't tell you how many people have brought YELLOW pt/pd prints to workshops and not even realized there was a problem. When I was in Scotland 2 years ago I saw some prints by a friend there who had taken a workshop from another american photographer who used B&S kits and only EDTA to clear and his prints were YELLOW. I pointed him in the direction of HCA as a clearing bath and when I got home I had received an email from him thanking me because that simple change to his workflow made the yellow prints go away.

Look Dana, I'm not bashing B&S here. I've done business happily with you all for almost 20 years now and I've sent LOTS of business your way from the hundreds of workshop students I've taught over the last 10 years. I just think it's a bit of a disservice to continue including EDTA by itself as a standard clearing agent when I see it causing problems time and time again. Why not include some sodium sulfite and sodium metabisulfite along with the EDTA and make some B&S Superclear or whatever you want to call it?

If it's yellow, it ain't mellow!!

Vaughn · Nov 25, 2007

I have been using Weston developed in room temperature Potassium oxalate a lot lately. I use a room temp water rince then into three 5 minute clearing baths of normal working strength Kodak HCA (about 2.5 liters) with a "slug" of EDTA (about 8 oz). I use a water rince between the baths. Since the Weston is a rather thin paper, one can see the yellow from the back side. With the clearing method I use, I can see this yellow disappear by the end of the second bath. On the front side of the print, I can see the yellow flow off the surface of the print. Seems to work fine.

Vaughn

clay · Nov 25, 2007

This is pretty interesting information. Most of the printers I know use potassium oxalate as the developer, and this squares with the experience I have had with EDTA tetrasodium being ineffective. I only rarely use ammonium citrate in those instances where I want a cooler toned print.

Here is an idea: Why not ship it with EDTA di-sodium? This is not quite as soluble as the tetra-sodium variety, but it is acidic in solution and you get the best of both worlds - the chelating effects of the EDTA organic molecule, and the acidic pH of an acid clearing bath? Or just package it with some sodium sulfite and metabisulfite for some homebrew clearing agent. That way, even if a newbie switches from ammonium citrate to potassium oxalate as a developer, they can still use the same clearing regimen, which is not the case with EDTA-tetrasodium used alone.

Dana Sullivan said:
All of the Pt/Pd kits at Bostick & Sullivan that come with Tetra-Sodium EDTA also come with Ammonium Citrate as the developer because of a discovery my father made in the early 1980's. He realized that by allowing the prints to sit in the developer for 3-4 minutes, a simple bath of inexpensive Tetra-Sodium EDTA will clear the yellow stain from the paper.

The secret, he figured, was in the Ammonium Citrate Developer: It will combine with the Ferric Oxalate in the coating solution, and convert a good portion of it into Ferric Ammonium Citrate and Ammonium Oxalate. This has its benefits and caveats, though.

Anyone who's ever made their own Cyanotype solutions from scratch knows that Ferric Ammonium Citrate is extremely soluble. In fact, most people can clear the FAC from cyanotypes without any clearing agent at all.

On the other hand, anyone who's done a lot of Platinum/Palladium printing will tell you that Ammonium Citrate developer tends to change the color of your prints from a cool, neutral black when it's fresh, to a warmer tone as it ages. This is due to the ever-increasing Ammonium Oxalate content, which produces a similar warm tone to Potassium Oxalate.

So to sum it up: Tetra-Sodium EDTA works as a clearing agent if you follow the directions as provided by B&S.

If you use Potassium Oxalate or other developers, we recommend a 50/50 mixture of Sodium Sulfite and EDTA. If the stain is extremely stubborn, a 50/50 mix of EDTA and Potassium Metabisulfite will almost certainly work.

Thanks for listening to my rant,

Dana Sullivan

clay · Nov 25, 2007

This is effective as long as your tap water has a pH lower than 7. Mine is closer to 8, and a straight water rinse right after the developer is a guaranteed way to make the subsequent clearing a real pain in the butt. I just plop it into a tray of citric acid, which is cheap and effective, and makes the next two clearing baths more likely to do their job effectively.

Monophoto said:
That said, I was also taught that it it was a good idea to pass the print through a plain water rinse immediately after the developer. That rinse removes most of the developer, and it also starts the clearing process. That's also a practice that I use regularly, and I've noted that much of the yellow ferric oxalate stain washes out in the water bath.

If

bill schwab · Nov 25, 2007

clay said:
Mine is closer to 8, and a straight water rinse right after the developer is a guaranteed way to make the subsequent clearing a real pain in the butt.

Exactly the problem I have here in the Detroit area. A water bath after development is the kiss of death for any print I make. I've been using Clay's method for a couple years now and haven't looked back. Like Clay, I pretty much use PO exclusively and think that many that take the process further do as well. I've always seen the B&S kits as a rock bottom place to start and they are great for that. There is so much more to the process though and many move away from ammonium citrate as a developer much like they do B&S's FO #2 as a contrasting agent. As Kerik and Clay have both stated, this (in my experience) renders standard EDTA fairly useless as a clearing agent.

I have to wonder if there is some safety or liability concerns that cause B&S to choose the chemical process they do for the starter kits. PO, Na2 and some of the other clearing agents are a little more dangerous than what their basic kit offers and perhaps they are just keeping it simple and safer for those new to the process?

Bill

clay · Nov 26, 2007

No one has mentioned a quick and effective way to test for complete clearing:

Take a sample print through your entire coating, printing and clearing process. Put a drop of 1% potassium ferricyanide on a clear paper area (a masked edge helps here) that has been coated, developed and cleared. If you see any residual color (blue or tan) after you rinse off the potassium ferricyanide, you are not getting complete clearing.

philldresser · Nov 26, 2007

clay said:
No one has mentioned a quick and effective way to test for complete clearing:

Take a sample print through your entire coating, printing and clearing process. Put a drop of 1% potassium ferricyanide on a clear paper area (a masked edge helps here) that has been coated, developed and cleared. If you see any residual color (blue or tan) after you rinse off the potassium ferricyanide, you are not getting complete clearing.

Clay

Thanks for that. I have not heard that one before. This should also work for kallitypes then as well, should it not?

Phill

sanking · Nov 26, 2007

billschwab said:
Exactly the problem I have here in the Detroit area. A water bath after development is the kiss of death for any print I make. I've been using Clay's method for a couple years now and haven't looked back.

Bill

I picked up on the danger of alkaline water rinse years ago and have always taken the print directly from the developer to the first citric acid clearing bath, both in kallitype and in pt./pd. I actually use citric acid at 5% solution for all three clearing baths. Citric acid is less expensive than EDTA and in my experience clears just as well, at least when the developer is ammonium or sodium citrate.

In terms of the quality of tap water, in Greenvile County, SC we have some of the best there is for working with the metal iron processes. The water is very pure and most of the year comes out of the tap slightly acidic, around pH 6.6 - 6.8. Not sure how future water quality may be affected by the severe drought in this area in 2007.

Sandy King

RobertP · Nov 26, 2007

My tap water's ph is 6.0 . I clear in a slightly less than a 1% solution of hydrochloric acid.. buffer in ammonia.. then rinse and wash. Three baths of 5 min. each in the acid. Just make sure if you are using a stainless sink you rinse it well. This allows for single tray processing as each bath is dumped and then refilled. After three baths of acid I buffer with clear ammonia 175ML/3.5L H2O. Rinse then wash. I've never had a problem with prints not clearing well. Plus I don't have to rotate and mix fresh trays of EDTA and Kodak HCA. I have 2 chemical tanks that hold 5 gal each of hydrochloric acid which last through a long printing session. The ammonia is returned to its container after buffering which will do numerous ULF prints. I just allow my nose to determine when its time to mix a new jug of ammonia. This technique is also nice in that you never have to lift the print out of the tray until it is ready for the final wash. This is nice for the more fragile papers.

Help Mr. Wizard - my Pt/Pd's aren't clearing.

Dan Dozer

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