Just how bad is blix vs bleach & fixer?

Discussion in 'Color: Film, Paper, and Chemistry' started by Jacko1729, Oct 1, 2009.

  1. Jacko1729

    Jacko1729 Member

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    I hear and read comments about how icky chemicals are that use the single blix formulation instead of separate bleach and fixer. I understand the arguments, or the logic of using separate chemicals, but is it documented that films are not archival when using a blix formulation?

    One of the things that has spurred my thinking, I've been going through some of my 30yr old films, and some are faded badly and some are pristine, even though they've all been stored identically. I'm assuming maybe the processing is the variable in this.

    I guess what I'm asking is, is there any documentation that shows films as being unstable when processed with blix, or are we just assuming? Or, do you have anecdotal evidence of films being unstable that were processed using blix formulations? Another reason I'm asking, I've been using the so-called '3 step' chemistry kits and am getting very satisfactory results, but am I just wasting film using this 'blix' chemistry?

    Your thoughts are appreciated, thanks.

    Jack O'Brien
     
  2. Photo Engineer

    Photo Engineer Subscriber

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    Jack;

    There is no connection between archival quality and the use of blix or bleach-fix. The argument is removal of silver from color films which affects grain, sharpness and color repronduction. In E6 films, it can also affect whites.

    So, your question misses the true problem.

    A post development treatment of color film (any type) must remove all silver metal and all silver halides. The fix part of a blix or a bleach-fix does remove all silver halides present, but the bleach part may not allow removal of the silver metal completely and that is the problem. It does not affect image stability though.

    PE
     
  3. Jacko1729

    Jacko1729 Member

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    Wow, thanks so much. So, my real concern would have to be image quality, not so much stability. You said "the bleach may not allow removal of the silver metal completely", does that mean that sometimes it *may*?

    Can you guys *see* the difference in films that have been processed in blix vs bleach and fixer chemicals?

    Thanks,

    Jack
     
  4. dwdmguy

    dwdmguy Member

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    I've used both in my Jobo. The Blix solution shows me no difference either way and I'm really quite happy with it. (3 bath)
     
  5. Ian Grant

    Ian Grant Subscriber

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    As Tom says the Blix baths are fine, with one proviso that you stick to the manufacturers staed capacity. I'd also go further and say I only use two reputable manufacturers Photocolor & Tetenal, their Blix's are extremely good but other's not so reliable. (The Photocolor/Paterson line went when Champion moved production from UK to Spain).

    No there's no difference between the good 3 bath kits & the ones using Bleach and Fixer. That's from long experience of using Chrome 6 and the Tetenal kit.

    Ian
     
  6. Athiril

    Athiril Subscriber

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    Ive got on order 5 litres of Agfa bleach, and for fix? Might mix my own up, depending on the price of sodium thiosulphate at the pool supply store, or whether its cheaper to get universal fix, or whether my current fix works on colour films (doesnt state active igredient on bottle).
     
  7. Photo Engineer

    Photo Engineer Subscriber

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    Well, I can see the difference between a bleach - fix and a blix. Sorry, but then whatever makes you happy is ok.

    As for using powdered kits - don't. The films need ammonium thiosulfate to fix out the silver salts properly and in a reasonable time.

    I say the blix "may" work because the reaction goes to completion (sometimes) and a long blix can remove most all silver in some cases. Fast films are harder to blix than slow films for example, or high iodide films are hard to blix. The argument comes from addenda and iodide in films that prevent blixing from going efficiently. In some films, the color droplets surround silver metal and protect them from blix but the bleach can get through more easily.

    PE
     
  8. Ian Grant

    Ian Grant Subscriber

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    Strangely I was mainly processing faster E6 films, initially 400 ISO then when introduced the specialist P800/1600 films from Kodak & Fuji. These were optimised for push processing and I found it better to process my own than send them to a lab in the nearest city.

    I started using the Photocolor Chrome 6 kits very soon after their release and they had been vigorously tested. There were concerns not long after because the Blix's in some competitors kits being imported from the US were found to be inefficient in magazine tests, it didn't need a chemist to spot this either.

    I know that Ilford had tested the Photocolor C41 & E6 products and had found no problems, at the time they were selling re-badged colour films under the Ilford brand name, I still have an unprocessed roll of Ilfochrome (E6). Silver retention is one key issue they'd have tested for.

    While I agree with Ron that a Blix may not be theoretically ideal, some better designed Blix's are quite different and work extremely well. I have seen the difference between poorly blixed film C41 & E6 and a well blixed or/bleached then fixed film and can spot the difference. I've also seen comparative tests done using a Chrome 6 kit & a Commercial (high quality) E6 lab and no-one could spot the differences.

    In answer to Jack's question regarding fading, I've only seen it with slides that have been very extensively projected. I've not noticed any fading in E4 or E6 films both commercially and self processed and many are over 30 years old. I started processing E4 films around 1972 (E3 type kits).

    However without a reference to compare to slight fading might go unnoticed. Harrods store in London had backlit photographs (Duratrans or similar) alongside the lifts on each floor, even after a day if they changed one image in a set they had to change them all as the fading was already just noticeable. Leave a slide in a projector for 6 hours and it will be quite significantly faded.

    Ian
     
  9. Jeff L

    Jeff L Subscriber

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    This is a great thread. I can see that I'll need to be doing my own C41 soon. Thanks guys.
    Jeff
     
  10. Photo Engineer

    Photo Engineer Subscriber

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    I say use what works for you (or what appears to work in this case).

    I ask a question though....

    Don't you think that Fuji, Kodak and Agfa would have come out with a blix for films if it were possible in a reliable fashion? It would be a big selling point, eliminating one step and a few extra bottles. But, they have not. There must be some reason, right? Well, there you are. I know the reasons and I know how to get around them. All I can do is suggest that you see the patent on this subject. I've referred to it and given the # so many times I should remember it, but I do not. That gives as much explanation as is usual in a patent.

    PE
     
  11. Ian Grant

    Ian Grant Subscriber

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    I'd ask a question back, in many previous threads you've indicated that you hadn't come across the Photocolor Chrome 6 kits at Rochester. Kodak's Harrow Research labs would have tested them.

    Yet Pip Pippard the originator was held in very high regard by Ilford & Kodak research chemists because of his innovative colour chemistry because he overcame problems they were struggling with. It wasn't remotely like the Unicolor and other US stuff that was quite poor.

    So please stop running down products you know ZERO about.

    The downside was partially costs as the 3 step process doesn't scale up, it works fine for small scale - re-use each bath 3 times then sling. But the Blix isn't easy to replenish reliably.

    Kodak & Fuji wanted to essentially just repackage their mainstream products with minimal re-formulation.

    There are very few independent companies who made/make B&W or Colour chemistry that I'd recommend Photocolor (previously Johnsons) is one and Tetenal is another. I'm sure there's a few others I've not tried who are equally as good, but then they often have Directors who are ex Major companies (often Kodak). And you know we have mutual contacts at one NY State company :D

    You'll notice that Paterson isn't one of them although they later merged with Photocolor.

    Ian


     
  12. Photo Engineer

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    Ian;

    I am not clueless about R&D into blix processes up to the present date. Kodak had an active blix and bleach-fix project underway the entire time I was at EK and it was nearly 100% in Rochester. Out of this project, they came up with the new persulfate bleach and the quinone bleach which is an updated, safer version of the old quinone bleach. They also came up with Bleach III for C-41 which uses NTA for greater activity and lower pollution and the RA Fix for C-41.

    The point being that throughout this development, not one Blix for film emerged that would pass our tests for quality assurance, scalability and capacity except one! That was the one that we worked on and published in the patent. Kodak declined to introduce it because it was too late for the C41 introduction in 1970 and has been reluctant ever since for reasons that are not clear to any of us.

    In any event, your revered Mr. Pippard says here:

    http://www.photomemorabilia.co.uk/Johnsons_of_Hendon/ARPippard.html

    Quote:

    "In a NEBRO (Neville Brown & Co Ltd) catalogue dated April 1954 there is illustrated a booklet (see left) written by A.R.Pippard B.Sc. entitled "How to Use and Process Ferraniacolor 35mm and Roll Film". It was available free on application. In the same catalogue, 35mm 20exposure Ferraniacolor cassettes cost 15s/3d (76p), 35mm refills cost 11s/10d (59p) and F20 (120) roll films cost 12s/3d (61p). Other roll film sizes were also available.

    Ferraniacolor home processing was based upon the Johnsons Processing Kit, which was divided into 2 parts, Part 1 - contained the first developer and colour developer - cost 5s (25p) and Part 2 - contained the hardener, bleach and fixer - also cost 5s.

    Nebro claimed (at the time) "Ferraniacolor is the only subtractive, integral tripack type of reversal film available with home processsing kits". The speed was officially 25° Scheiner (around 25ASA), though the advise in the bookssslets shown here (left & below, left) was to use 12ASA in all but the brightest of continental sunlight."
    END QUOTE

    Which is incorrect when in fact, E1 Ektachrome was in full use in 1950 here in the USA. When it was available in the UK or Europe, IDK, but the quote shows that he and his company were apparently as clueless as you claim that I am. Or maybe just guilty of a tad of hype?

    Actually, Mr. Pippard went completely under our radar and we never heard of him until you mentioned him some time back. I have no idea what his blixes did, and the reason is that if they worked well, you can be sure that they would have made headline news at the Rochester and Harrow labs. I do know that every C-41 and E6 kit on the market was tested by the EK labs. I personally tested some of them. His did NOT make the cut AFAIK.

    PE
     
  13. RellikJM

    RellikJM Member

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    When you are referring to kits are you referring to small volumes less than say 5 liters or all chemistry produced by other manufacturing firms that EK tested?

    If it is all chemistry how did CPAC/Trebla fair in the EK testing? Am I safe in using Trebla chemicals for C-41, E6 & RA4 or should I use EK until they are no longer viable/unavailable for me to use?

    Trebla seems to copy EK in the number of solutions and mixing instructions and told me to use the EK Z manuals if I had any trouble.
     
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  15. Photo Engineer

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    Trebla is part of CPAC located near Rochester. It is run by ex-Kodak engineers and they produce excellent products.

    PE
     
  16. Ian Grant

    Ian Grant Subscriber

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    That quote comes from the Importers of Frerrania and you've miss read it anyway. It's saying only that it was the only film available of that type with a home processing kit. It's also meaning in the UK market.

    Johnson's was a far older company than Kodak, but it appears the shareholders/owners let it run down, and when Phototechnology emerged as a separate company they went on to uickly win awards for Exports of their colour chemistry.

    They or Pippard most definitely weren't under the radar of Kodak UK, or Ilford, Fuji etc, and they made headline news in all the UK photographic press, amateur, professional & trade, as well as TV and National newspapers when they won awards. It's just you personally didn't come across them.

    We are actually arguing at cross purposes, at some point in the late 60's and very early 70's before Pippard designed the Photocolor Blix Kodak, Ilford and Agfa had all designed Bleach-fixers that overcame the previous drawbacks of Blix with high silver content films. G.I.P. Levenson and A.Green wrote papers in the Journal of Photographic Science and Ilford & Agfa filed Patents.

    Many problems with Blix were caused by a build up of carry over from the Colour Developer. This is a major reason why a blix might work well with films on a small scale such as the Photocolor kits but be far less practical for film processing in a top-up or bleed process

    Ian
     
    Last edited by a moderator: Oct 3, 2009
  17. Photo Engineer

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    Ian;

    Just as you studied Developers, I and a group of associates studied Blixes, Bleaches and Fixes. I have a huge box full of patents from the US, England and Germany covering this subject along with a few English translations of Japanese patents. I even had samples of many of them, and AAMOF, still have a few here in my lab in their original packages.

    Even with a Bleach, Developer carryover can be a problem, and Kodak recommends that if it takes place a 1% - 2% Stop be used in the process. This is no problem. I have never seen patents or articles by Pippard, but have read many by Mason, Levenson and others. In fact, BP 991.412 was a seminal patent that covered a number of approaches to Blxing, but the author missed the main point of why his Blix worked and therefore the claims missed the main point of utility.

    There are acidic Blix/Stop baths that are very very active and can be made to Blix film, but they are essentially one-shot due to the fact that the high oxidation powers and acid environment kills the hypo. There are many possible Blix formulas, but only one or two that really work and work well.

    So yes, we all did discover how to make Blixes, but they will not work well with high silver/high iodide/DIR-DIAR films. Simply read the patent. I was involved in that work and did talk with these guys for nearly 30 years. I've run or been involved in running many Blix and Bleach-Fix processes during that time, testing many films, and I produced what is now the RA-4 Blix and my boss produced the Flexicolor (C-41 Bleach and Fix) Bleach-Fix system. Kodak, Fuji and Agfa all chose this route for a variety of reasons.

    I have a non-scalable version here in my lab running just fine! It will Blix film with any level of the restrainers or silver levels. But that is after an ongoing study of years. And, I have to say that Pippard passed under my radar, yes, but that includes a rather large team of people as well. I was not alone in not having heard of him, but I did know of Mason and Levenson as well as quite a few at Agfa. I knew some of these people personally BTW.

    PE
     
  18. Photo Engineer

    Photo Engineer Subscriber

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    Ian;

    As an afterthought, I think it useful to add here that Pippard probably never heard of me either until the patent issued on film Blixing. IDK. That is irrelevant. What is important is the fact that when another company had something "better" or "more capable" than a Kodak product, everyone knew about it who had something to do with that particular product.

    That is why I, and others tested so many products. We reported on these and they were either "good" or "bad". There was a LOT of hype out there that just was not realized when tested in the lab.

    PE
     
  19. Tim Gray

    Tim Gray Member

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    I just wish I knew where I could buy liquid C41 chemicals with a separate bleach and fix step for a reasonable price.
     
  20. Photo Engineer

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    Tim;

    I have the same wish, but EDTA and NTA complexes with Iron are expensive. And, Ferricyanides are pollutants.

    So, the best I can do is offer that an untried Ferricyanide bleach be used. You see, couplers and dyes are no longer tested for image stability in the presence of Ferricyanide at EK and therfore I cannot say how well the film will hold up to the stronger bleaches the Ferricyanide offers.

    So, we have a choice of an unknown that is fairly inexpensive but a pollutant and an expensive known.

    You do have a very good point though!

    PE
     
  21. brucemuir

    brucemuir Member

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    So is it safe to conclude that the Unicolor C41 powdered 3 bath kits from Freestyle should be avoided?
    http://www.freestylephoto.biz/10123...m-Negative-Processing-Kit-1-Liter?cat_id=1001

    I just started color work here on a low volume and am somewhat dismayed and confused at the choices. I've read quite a bit but mostly from the internet.

    It seems if you try to assemble all the correct chemicals in liquid form, the places that will ship them don't have all the necessary ingredients.

    Is the Tetenal powdered kits better than the Unicolor?
    I'm contemplating trying E6 after I get a handle on the C41 process.
     
  22. Photo Engineer

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    Any powdered kit that uses Sodium Ferric EDTA for bleaching and Sodium Thiosulfate for fixing is too weak for film and marginal for paper. The original kit for the Kodak Blix used Sodium Ferric EDTA and Ammonium Thiosulfate and was marginal for bleaching, which is why the Blix was reworked to use Ammonium Ferric EDTA. This was done with great effort as Ammonium Ferric EDTA was unknown commercially at the time..

    I have to assume, due to the use of Sodium salts in my own Press Kit, that the kit you refer to uses Sodium salts as solid Ammonium salts are very very expensive and in the case of NH4FeEDTA, completely unknown on the market.

    In this case then, that powdered Blix would be too slow to do an adequate job on film, but would work, given enough time, on paper.

    Even with film, it will "appear" to work, but probably will leave some amount of silver behind as a neutral gray image that degrades dye hue and also messes with the sharpness and grain due to the granular nature and positioning of the silver specks.

    I have examined these specks under a microscope and also printed with and without the proper bleaching. It gives somewhat the effect of bleach bypass processing in prints, with a grainier result than normal.

    PE
     
  23. brucemuir

    brucemuir Member

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    Would extending the blix times be a good practice with those kits?

    Could an extended Blix time do any harm?
     
  24. brucemuir

    brucemuir Member

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    These are the ingredients on the Unicolor C41 Powder Kit
    I recently purchased from freestyle and have done 4 roll so far.

    Blix A:
    Ammonium Thiosulfte
    Potssium Carbonate

    Blix B:
    Sodium Iron EDTA
    Sodium Sulfite
    PDTA

    Pleas excuse any inconsistancies but I copied the ingredients straight off the package but it is somewhat jumbled.
     
  25. Photo Engineer

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    Extending the time does no harm and can do some good if Blixing is not sufficient.

    The ingredients posted above are identical to an original version of the Kodak RA-4 Blix. It was marginal for paper and totally unsatisfactory with film.

    Some gain can be gotten by reducing pH. The downside is that it becomes one-shot and the image stability may be questionable as the dyes are not tested with acidic pH values. We did test a pH 4.5 Blix, but it failed primarily due to longevity reasons.

    PE
     
  26. Tim Gray

    Tim Gray Member

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    I should rephrase my wish - by inexpensive I mean in hobby level quantities, not 50 gallons of the stuff.