Wait... so selenium toning does not improve archival properties?

[Bill Burk]

Probably cause the same issue that adding KRST to hypo clear causes... mixing would create a solution that you cannot keep and reuse.

 

[Ian Grant]

Could a little sodium sulphide be added to KRST to achieve the result of it in its previous version? That would streamline my workflow.

If you add Sodium Sulphide to KRST you'll form Flemish toner which gives quite different reddish tones and is much faster acting, so not a good idea for archival use where we don't want big shifts in image colour,

Ian

 

[Bill Burk]

Could it be that the reason following Selenium with Sodium Sulphide shows no color change... is that the Selenium has already acted?

 

[Ian Grant]

Could it be that the reason following Selenium with Sodium Sulphide shows no color change... is that the Selenium has already acted?

Yes the Selenium will already have acted and given a good degree of protection but unless it's been to completion there's still Silver in the image for the Sulphide to react with but it'll probably need a stronger than 0.1% Sodium Sulphide solution to get a colour change with direct toning.

Remember that my test with Polymax prints only showed a slight change in 30 mins with 0.1% Sodium Sulphide, the image (left side) doesn't look toned rather a slight shift towards a warmer toned paper. The 2 minute print in the aulphide solution showed that there was a significant effect in the Sulphide when bleached in Ferricyanide.Bromide 1% soln and yet this was insufficient to cause a colour shift in the other 2 min print.

Ian

 

[Ian Grant]

Bill, some more tests which proved very interesting.

First 3 Polymax prints cut in half, the left hand sides were all toned in KRST 1+9 25ºC for 10 minutes, after washing there was no visible colour or denity shift between left & right halves.

Then one left and corresponding right half were bleached in 1% Ferricyanide.bromide bleach, the left hand side bleached bached back to leave the selenium red/brown base image, the right bleached completely.

The next test was another Selenium toned left side which was then immersed in 0.1% Sodium Sulphide solution 20ºC for 10 minutes, washed and bleached in the saqme 1% Ferricyanide/Bromide solutio. This bleached back giving a similar red/brown base image.

Could it be that the reason following Selenium with Sodium Sulphide shows no color change... is that the Selenium has already acted?

So yes it appears the Selenium has already acted. Another comment is the Selenium toning has protected the highlights and the shadows. While a 0.1% solution of Sulphide isn't srong the previous tests shoed that 2 minutes was sufficient to significantly protect an image, but 10 minutes had no effect on a print already Selenium toned.

In terms of image permanence that 0.1% Sulphide solution is highly significant as it shows how well the Selenium toner has protected the image, and more importantly that the Sulphide step offers no additional protection. So it should be one or the other but not both for archival protection.

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

Of course strong bleahces can still be used where the toning isn't to completion. Bob Carnie is Selenium toning, bleaching the highlights with Ferricyanide/Bromide and then Sepia toning.

It's possible to control the subsequent colour sepia toning by choice of Bleach and subsequent toner, but this varies depending on the paper as well, and Warmtone papers will tend to give far more of a colour shiff.

In general a Ferricyanide/Chloride bleach gives the breatest warmth, Ferricyanide/Bromide is the norm, while Ferricyanide/Iodide is the coldest. Then the proportion of Ferricyanide to Halide has an effect as well, Agfa suggest 4 bleaches and 4 toners, the coldest bleach is 15:1 Ferricyanide to Bromide (by weight) - 600ml 10% Potassium Ferricyanide soln + 40ml 10% Potassium Bromide Solution + 360ml water (to make 1 litre). Ilfords bleach fo IT-1 is 1:1 Ferricyanide/Bromide (by weight).

My choice of Toner is usually the variable tone Thourea type and this gives quite good control of the final warmth.

Ian

 

[Bill Burk]

...
In terms of image permanence that 0.1% Sulphide solution is highly significant as it shows how well the Selenium toner has protected the image, and more importantly that the Sulphide step offers no additional protection. So it should be one or the other but not both for archival protection...

Ah but the question is... does the Sodium Sulphide provide additional protection from some other form of environmental pollutant that the Selenium doesn't protect the print against?

I keep thinking about an inkjet printer I bought before I joined APUG which was advertised to be archival (the ink was lightfast), but prints turned reddish brown in a few weeks because of ozone.

So I'm thinking Selenium-alone could lead to red spots in 30 years, but Selenium followed by 0.1% Sodium Sulphide may give "additional" protection against a different corrosive agent?

Or maybe the result could be redundant but beneficial, like two-bath fixing.

 

[Bob Carnie]

Bill, some more tests which proved very interesting.

First 3 Polymax prints cut in half, the left hand sides were all toned in KRST 1+9 25ºC for 10 minutes, after washing there was no visible colour or denity shift between left & right halves.

Then one left and corresponding right half were bleached in 1% Ferricyanide.bromide bleach, the left hand side bleached bached back to leave the selenium red/brown base image, the right bleached completely.

The next test was another Selenium toned left side which was then immersed in 0.1% Sodium Sulphide solution 20ºC for 10 minutes, washed and bleached in the saqme 1% Ferricyanide/Bromide solutio. This bleached back giving a similar red/brown base image.



So yes it appears the Selenium has already acted. Another comment is the Selenium toning has protected the highlights and the shadows. While a 0.1% solution of Sulphide isn't srong the previous tests shoed that 2 minutes was sufficient to significantly protect an image, but 10 minutes had no effect on a print already Selenium toned.

In terms of image permanence that 0.1% Sulphide solution is highly significant as it shows how well the Selenium toner has protected the image, and more importantly that the Sulphide step offers no additional protection. So it should be one or the other but not both for archival protection.

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

Of course strong bleahces can still be used where the toning isn't to completion. Bob Carnie is Selenium toning, bleaching the highlights with Ferricyanide/Bromide and then Sepia toning.

It's possible to control the subsequent colour sepia toning by choice of Bleach and subsequent toner, but this varies depending on the paper as well, and Warmtone papers will tend to give far more of a colour shiff.

In general a Ferricyanide/Chloride bleach gives the breatest warmth, Ferricyanide/Bromide is the norm, while Ferricyanide/Iodide is the coldest. Then the proportion of Ferricyanide to Halide has an effect as well, Agfa suggest 4 bleaches and 4 toners, the coldest bleach is 15:1 Ferricyanide to Bromide (by weight) - 600ml 10% Potassium Ferricyanide soln + 40ml 10% Potassium Bromide Solution + 360ml water (to make 1 litre). Ilfords bleach fo IT-1 is 1:1 Ferricyanide/Bromide (by weight).

My choice of Toner is usually the variable tone Thourea type and this gives quite good control of the final warmth.

Ian

Hi Ian

I am letting you big brains figure this out before I throw in my layman ideas... but I am bleach sepia first, selenium second... I never work selenium first fyi.

 

[Ian Grant]

Ah but the question is... does the Sodium Sulphide provide additional protection from some other form of environmental pollutant that the Selenium doesn't protect the print against?

I keep thinking about an inkjet printer I bought before I joined APUG which was advertised to be archival (the ink was lightfast), but prints turned reddish brown in a few weeks because of ozone.

So I'm thinking Selenium-alone could lead to red spots in 30 years, but Selenium followed by 0.1% Sodium Sulphide may give "additional" protection against a different corrosive agent?

Or maybe the result could be redundant but beneficial, like two-bath fixing.

In terms of image permanence all the prints I made in the 1960's and through to about 30 years ago show no signs of deterioration, none were treated with Selenium toner, neither did I use a wash aid. So I'd expect prints to last well over 30 years anyway. At least one has been hanging on a wall framed (different locations) for 30 years.

The last 30 years all my exhibition prints etc have been made using 2 bath fixing, wash aid and KRST (or similar), again no problems. The real secret is two bath fixing and good washing, some work prints made 1987 onwards are not Selenium toned and they are fine as well.

Sodium Sulphide is very corrosive so I'd expected it to have acted on the Silver of a Selenium toned image but it didn't over a 10 minute period. So I don't feel a Sulphide bath after Selenium toning has any benefit.

I've never heard of "red spots" with selenium toned prints but then this would indicate we should see something similar in terms of spots of image bleaching with any prints toned or un-toned 0 and we don't. Most issues with prints deteriorating is due to poor fixing and washing or poor storage.

That "Stability of Black-and-White Photographic Images, with Special Reference to Microfilm"report is very woolly and contradicts later Kodak and Ilford recommendations for archival processing and the use of a Selenium toning stage.

So my take is no Selenium toning, no issues in 30-50 years depending on storage, with Selenium you've added a significant extra level of protection.

Instead a 2 minute bath in 0.1% Sodium Sulphide solution should give slightly more protection. However choice is about the image colour you want and for me that means KRST is better.

Ian

 

[Bill Burk]

Thanks Ian,

For me, "depending on storage" is a question to worry about, what if there's ozone or salt and moisture in the air? Some of my prints are stored in the garage and I live near the coast which is a pretty bad place to keep things. Bad but I don't plan to have alkaline batteries leak onto them like I found happened to a toolbox this morning. Yechh

Then again, either kind of toning... takes away the chance that someone might later restore a stained or faded print by bleaching and redeveloping...

You say it's corrosive, but is Sodium Sulphide "less" environmentally hazardous than Selenium? If they both give similar protection, and I don't want any tone change, which would be a better choice?

 

[Ian Grant]

Thanks Ian,

For me, "depending on storage" is a question to worry about, what if there's ozone or salt and moisture in the air? Some of my prints are stored in the garage and I live near the coast which is a pretty bad place to keep things. Bad but I don't plan to have alkaline batteries leak onto them like I found happened to a toolbox this morning. Yechh

Then again, either kind of toning... takes away the chance that someone might later restore a stained or faded print by bleaching and redeveloping...

You say it's corrosive, but is Sodium Sulphide "less" environmentally hazardous than Selenium? If they both give similar protection, and I don't want any tone change, which would be a better choice?

All my prints are stored in the garage in original paper boxes mostly Agfa, you can easily make a safer storage area use bags of Silica gel to cut the moisture, ensure adequate ventilation etc, We have property close to the sea and that isn't an issue.

If you don't want tone change then it depends on the paper, neither cause a change with Bromide papers unless toned excessively, there was noc hange with Seleium in 10 mins or Sulphide in 5 mins in my tests above. Selenium will have caused a reddish shift in half that time with the FB Warmtone papers I use and I expect the same with Sulphide.

Selenium toning is more environmentally friendly as you just replenish it, more Selenium goes into sewers from people taking Selenium supplement tablets than the small amounts used by photographers. For this reason I'd prefer it to Sulphide, also the fume issue.

If prints stain or fade it's rarely possible to recover them, I worked with a museum archive in the 1970's where many prints had suffered when the basement flooded or got very damp. There were techniques to prevent further damage and images were toned to stabilise them.

Ian

 

[Gerald C Koch]

The point from the research done at IPI is that all of the silver grains must be covered with either selenium, sulfur or gold to achieve archival permanence. Any uncovered grains are otherwise a site of attack.

 

[Bill Burk]

Gerald,

Do you think the red spots found in the microfilm research might be due to something other than improperly done archival processing?

I could imagine, for example, that even though it's properly processed, a roll of microfilm, run through a reader a few times, might have abrasion damage that rubs off the "protected" grains on the surface and reveals raw silver beneath.

Then, since we don't abrade our prints (except for shuffling through when showing them to friends)... prints may not be as susceptible to the red spots issue?

 

[Photo Engineer]

If you read the microfilm report, you will find that at the same time, the government had asked that all photographic processes use a reduced wash regime to save money. Then they spent more duplicating the deteriorating records! Some savings.

There was another problem with paper prints that was revealed in a paper from the IPI regarding selenium toning, even if done right. I might be able to dig that one up. It was sent to me years ago by two people.

PE

 

[Gerald C Koch]

Gerald,

Do you think the red spots found in the microfilm research might be due to something other than improperly done archival processing?

I could imagine, for example, that even though it's properly processed, a roll of microfilm, run through a reader a few times, might have abrasion damage that rubs off the "protected" grains on the surface and reveals raw silver beneath.

Then, since we don't abrade our prints (except for shuffling through when showing them to friends)... prints may not be as susceptible to the red spots issue?

It would take a lot of wear and tear to remove the anti-abrasion coating from the film and expose individual silver grains. In addition this would not explain the problem with backup copies which are seldom read.

 

[Ian Grant]

It would take a lot of wear and tear to remove the anti-abrasion coating from the film and expose individual silver grains. In addition this would not explain the problem with backup copies which are seldom read.

With our films and papers yes, microfilm gets abused in comparison,

Ian

 

[Bill Burk]

As we go round and round with this, I realize that we're talking about prints... I've not even considered toning my negatives... which is probably where archival processing would be a better investment in the future... Because I (or someone else) can always make another print if the negative is preserved.

But I'm in too deep now... the order's been placed... and I think I will do Selenium and Sodium Sulfide on my prints... because I think we've concluded that it could offer greater protection than Selenium alone.

I don't know if it's going to make my prints safe from nitrogen dioxide or ozone though.

 

[Vaughn]

I have bleached, fixed and washed...then selenium toned negatives to completion to bump the contrast up some. And have selectively selenium toned negatives for a local contrast boost. Fun stuff!

 

[Bill Burk]

Haa yes, Old Timer often talks about Selenium toning negatives too... in the research papers they talk of toning in terms of creating an "insurance image"... even if the silver bleaches out, you have an image that could be printed.

If you get the chance to stop by Point Arena to visit Jim Alinder's gallery... he's got a scary faded "Moonrise" copy negative on display... (just imagine if that were the original)

 

[Vaughn]

Had a trick played on us -- can't remember by who, but a group of us from a Friends of Photography workshop were up at Ansel's house (after he had died...we got to meet Virginia). We were shown the "Moonrise" negative, supposively...it was almost dropped, to the gasping of the crowd. Who knows...might be the same copy negative.

Just drove by Point Arena two evenings ago. Too late to stop!

 

[warden]

Based on the content of this excellent thread I purchased Photographers' Formulary Sepia Sulfide toner and gave it a try today. I have to say it's much more fun to use than selenium, and a little scary when the print initially disappears in the bleach! But the results are lovely and I'll keep with it. One question though if I may hijack this thread a bit - I can find no mention in the instructions of how many prints can be toned with this kit. The kit I got makes 1l of bleach and 500ml redeveloper. Anyone know? Thanks.

 

[Photo Engineer]

There are some specification sheets on the Formulary web side as pop up pages for some products.

PE

 

[john_s]

If you add Sodium Sulphide to KRST you'll form Flemish toner which gives quite different reddish tones and is much faster acting, so not a good idea for archival use where we don't want big shifts in image colour,

Ian

I was thinking of a trace of sodium sulphide, to try to emulate the "old" KRST, rather than making a brown toner.

 

[Bill Burk]

I was thinking the same john_s,

From what I can tell of this thread, slight toning will put your mind at ease because you "did the right thing" but it will not fully protect your prints from all kinds of pollution. At least with this kind of treatment (or arguably even just good fixing and washing) your prints won't degrade in the first weeks of exposure, or even years. But continued exposure will probably lead to some problems. Even if no fading or red spots occur, you might get bits of dust embedded in the emulsion of the print that you can't get out.

So take care of your negatives (to make replacement prints).

I plan to use two baths, one of KRST 1:20 and one with dilute Sodium Sulphide. I'll keep the KRST in a bottle, but will discard the Sodium Sulphide bath each time.

 

[Ian Grant]

My tests showed That KRST was preventing the Sulphide from acting, Bob Carrie uses the bath first.

Ian

 

[JensH]

Hi,

I'd like to show just three test stripes I kept for 26 years under non archival conditions. In 1991 these tree stripes were made using KRST 1:15 for 0, 3 and 9 minutes at 28°C. I taped them into an Schneider-Kreuznach info folder.

Today, after 26 years they show that even the moderate 3 min toning saved the paper from yellowing.

Details: Fiber based paper Agfa Rekord Rapid RRS1, develped in Dektol, Ilford archival washing method, then toned.

Best
Jens