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  1. #1
    David Lyga's Avatar
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    I offer to show results of my experiments with color developer dilution

    WARNING: This is going to be long and arduous. Either persevere…or stop right here!

    In the past I had written about this, but after carefully honing my procedure, now getting consistent results, and (with this thread) finally being able to SHOW these results to you, I write anew with simple modifications from my previous procedure (but with the prescient understanding that such procedure might be refuted by some). It is amazing how much this quest has meant to me: even to the point of questioning my sanity. While such lack of procedural Kodak orthodoxy veers upon the cusp of both treachery and apostasy, and, with endless curiosity and experimentation surely providing the fodder for such procedural deviation, I am yet not really trying to foment revolution by dethroning either Eastman Kodak or its justifiably obdurate followers; I have too much respect for both. Instead, I merely extend, outwardly, my experiences and experimentation for all to witness. My process here is not inflexible, so make your own decisions and draw your own conclusions. (Or, perhaps more prudently, leave those 'conclusions' inconclusive.) We learn much through brainstorming, even when amongst unrepentant iconoclasts such as David Lyga. A 'photo engineer' I am not. A 'Ron Mowrey' I am not. The respect that I hold for those 'two', the chemist and the person, is necessarily profound. But I cannot always be counted upon to worship a specific truism, ‘proven’ true or not, despite even apparent scientific validation. Instead, I have found my (almost) 63 years to be better spent with uncommitted, neutral observation and I concluded long ago that it is more prudent to deem the very concept of 'loyalty' (to person or theory) to be largely questionable, oftentimes superfluous, and too uncertain in moral scope. It does take 'all kinds' to hold humanity together into a sublimated synergism that benefits all. Now, let us have less subjective digression with my wasteful prolixity. Forthwith, I substitute the relevant, hard facts.

    Lacking a personal computer and scanner, I had to bring the optical prints I made to a copy shop and there had the prints saved to my flash drive as JPEG files. Thus, I hope that there is no reduction in quality with this necessary transition from analog to digital, as I was dependent upon this link.

    Previously, I had fixed first, and then bleached. I have found that this ordering makes NO difference in the final outcome for either RA4 printing or the C41 negative. In fact, here, for ease with C41 processing, I have COMBINED my bleach and fix steps. (Remember that when combining you must almost double the time for that combined step because fix becomes ‘diluted’ by bleach and bleach becomes ‘diluted’ by fix). In fact, if you wish to fix ONLY and NOT bleach, that, also, is OK, as well, for excellent color and permanency, although your negatives and/or prints will be somewhat denser because of the retained metallic silver in addition to the non-silver hues formed by the coupler action.

    KIT SIZE: With color photochemistry, whichever kit size you use, I am assuming (correct me if I am wrong here) that when mixed PER KODAK, there is no difference at all in the final developer mixture, regardless of kit size, as long as the kit is the same item type. I say this because different kit sizes do not necessarily have proportional amounts of concentrate. This was surprising for me to find out through both personal observation and direct contact with Eastman Kodak (Larry Fitzsimmons, Kodak Technical Support: ksstier1support@kodak.com). For example, the 25 gallon size of the RA4 RT dev/repl has a concentrate ratio of A: 10, B: 6, C: 10, whereas the 10 liter size has a concentrate ratio of A: 10, B: 4.6, C: 10. Again, I assume that when mixed per Kodak those final developer mixtures are identical and interchangeable.

    All steps of my C41 procedure are ‘one shot’ (never re-used). Sometimes for RA4 prints I can get away with ‘multiple use’, but be certain to allow AT LEAST 100ml WS per 8 X 10 print. Using somewhat more developer solution is safer.
    NOTE: I draw my concentrates from the large 25 gallon sizes: for negatives: Kodak Flexicolor dev/repl #KF 12-1532753 and for color prints: Kodak RA4 RT (roller transport) dev/repl #KP 36-8477184. I buy everything from PDISUPPLY.COM in Rochester, NY and they ship to me in Philadelphia. I have had no problems with this firm: they are both fast and reasonably priced.

    ABOUT THE PICTURES ENCLOSED: They were taken within the past week in and around Rittenhouse Square (Philadelphia). I used Fuji Super G+ 100 film (expired in 1998 but frozen and perfect condition). Paper was Kodak Supra in cold storage. The indoor picture was taken under tungsten light and was NOT filtered. In it I have included my skin tone for reference, along with common household articles, so that a ready color assessment could easily be made.

    PROCEDURE:
    Although I make my working solution (WS) directly from the concentrates, here I will present an easier way for all to understand my procedure by starting with the actual mixture that Kodak requires. That will allow for neither confusion nor ambiguity.

    First, mix the respective developer, as per Kodak, for either the whole amount or for partial quantities (e.g., to mix only one liter from a 10 liter kit, use 1/10 the amount of concentrates). This is simple enough. Now, to mix what I will refer to as the diluted working solution, do as follows: For negatives, first mix 1 part of the standard Flexicolor developer + 14 parts water. (This becomes a dilution whose volume is 15X what Kodak recommends.) To this 15X dilution add 3 ml per liter of sodium carbonate, monohydrate (washing soda). In other words, take 67ml of the ‘mixed per Kodak’ Flexicolor developer and add 933ml of water plus 3 ml of sodium carbonate, mono to make one liter of the diluted working solution. (Note: I measure the sodium carbonate as a volumetric amount in a calibrated tube just like a liquid is measured, and not as mass that is weighed upon a scale. I have no scale!)

    You develop the C41 film for 12 to 15 minutes (contrast preference) at 90F with either continuous agitation or agitation every 30 seconds. I use a tempered water bath throughout the process (without pre-soak). Then stop bath (weak acetic acid OK: per liter: 18 ml of 28% acetic acid) then bleach-fix for six minutes, also near 90F. The separate blix components are made as follows. BLEACH: 32 grams (or ml) of potassium ferricyanide + 1 ml (1.5g) potassium bromide makes one full liter of bleach. FIXER: you can use standard B&W film strength fixer. For the bleach-fix step: mix one part BLEACH + one part FIXER. (So, for a 300ml tank that would be 150ml of each, but, if you are frugal as I am you can use, for the blix, considerably less than the total 300ml WS and ‘agitate’ the blix by turning the tank on its side and rotating it like a Ferris wheel, but back and forth, not only one way.) This ‘blix’ combination will retain full potency for only about twenty minutes, so combine shortly before use. Then wash and dry the film. 90F is a very easy temperature to maintain at room temperature and your warm hand in the water bath (for continuous or intermittent agitation) keeps that bath very close to the 90F.

    Now, it is ‘known’ that you must not deviate from the 100F C41 process norm. My experiments show that you can and still get virtually the same excellent color results through minor enlarger filtration changes. I have processed C41 film at both 80F and 100F with excellent results, using a Fahrenheit coefficient factor of 1.04, which yields the following development times: for 80F try 18 minutes and for 100F try 8 minutes. With the higher temperature there is a very slight ‘compensating’ effect (ie, the same shadow detail with very slightly attenuated highlights). Perhaps this is what Kodak wants to achieve with the mandatory 100F temperature but I find little difference with the final print. With the 100F temperature I find a necessary printing filtration reduction of about a 20 RED (i.e., 20 less magenta and 20 less yellow).

    For color prints I use trays (as for B&W): Again, first mix RA4 RT dev/repl as per Kodak, then dilute 1 + 4 and add (per liter of diluted working solution) 6 ml of sodium carbonate, mono, to make the diluted developer working solution. This is a 5X dilution from what Kodak mandates and is your color paper developer WS which can be used at ambient temperature. (I usually have a warm environment where I live, with room temp at 80+ F). Develop print for one and one half to two minutes, continuous agitation. Then, use a stop bath, as for film, but either change stop bath frequently or use a stronger one. Then (usually), I use a ‘blix’. I combine the potassium ferricyanide bleach with the fixer, but you will have to refresh frequently because of the short life that the combination has. With the combined step remember to use ‘film-strength’ fix and bleach, as each component ‘dilutes’ the other. And, with combination you will have to change very frequently. I use trays with smooth bottoms and put ONLY ENOUGH to cover the bottom. With emulsion face down you can rock the tray to agitate adequately with this small quantity. OR: Many of you will, instead, continue to use the standard, proprietary C41 or RA4 blixes. This is fine.

    ALTERNATE FIX ONLY, NO BLEACH: After stop bath I sometimes prefer to fix for 60 seconds (paper strength fixer) and then inspect the print in full room light. At this point a good determination can be made as to adequate density and color rendition. Bleaching will impart a very slight degree of warmth (yellow-red) to the color and will also very slightly lighten the print. I might wish to stop here, without bleaching, out of preference for the somewhat muted hues. (I think that Hollywood made a few films this way, with the transfer prints not being bleached, for a subdued, aesthetic effect.) If I DO wish to bleach, I usually wait until the end of the session in order to avoid the extra steps and accumulative fixer carryover problems. (In order to do this effectively you must first acquire a good mental familiarity of the degree of the color/density change resulting from bleaching the print.) For prints, if done separately, the potassium ferricyanide bleach is half film-strength (i.e., only 16ml per liter) for about 30 seconds. Then re-fix for about 10 seconds. Wash and dry. This is a bit cumbersome but if you are set up right it works fairly well.

    A note on developer CAPACITY: My dilutions provide an almost surreal number of films and prints which can be processed. Many who have tried to re-use the standard per Kodak developer mixture for multiple films would readily refute this statement’s accuracy because, in practice, they have found its re-use to be severely limited: They see that, with such re-use, the full-strength developer is quick to ‘run out of steam’. So how can my highly diluted, one shot dilutions really work if even the undiluted developer gets ‘used up’ so fast? Certainly, most of you are certain to posit that merely one tankful (c. 300ml) of regular strength Kodak C41 Flexicolor developer cannot possibly develop 15 (!) ‘36 exposure’ rolls, as my 15X film developer dilution allows through ‘one shot’ use! How so?

    It is my belief that the relatively quick loss of energy from re-use of the standard (per Kodak) color developer mixture is not due to ‘using up’ the color developer itself. Rather, I believe that this slowing down of development is due to the release of bromide (from the film) into the developer with each successive roll developed. We all know that with traditional B&W developers the addition of potassium bromide to suppress fog also slightly slows down the development process. Slower development means (theoretically) lower contrast for the same development time. But, this slight reduction in contrast in the B&W process is countered by a reduction in the B&W film’s (or age-fogged B&W paper’s) base density, so that traditional B&W film materials really do end up being developed with an adequate, final contrast in the standard development time allotted.

    However, with color developers, either CD3 or CD4, addition of (even tiny amounts of) potassium bromide will slow development down FAR MORE than it will with B&W developers. Thus, the re-use of the standard color developer mixture does not ‘deplete’ the color developer CAPACITY (even though that seems apparent) to nearly the same extent as, instead, the increase of bromide greatly, and progressively, RETARDS development. It might seem to us that re-use of the standard developer mixture with additional films being run through ‘uses up’ the color developer capacity but, in reality, that color developer’s energy is being primarily hindered by its ‘shifting into low gear’ because of the increasing bromide presence, and not, instead, from being so ‘exhausted’ with actual developer depletion. There is still plenty of developer capacity present but it cannot be conveniently be utilized because things have become so slow (from bromide) after only a few C41 rolls have been run through the same 300 ml (tankful) of standard-strength developer. Proof? The next time you print, try adding the ‘normal’ amount of 10% potassium bromide solution (maybe the ‘one fluid ounce’ that you would add to one liter of working solution Dektol for B&W prints) to, instead, a liter of color RA4 developer. You will get no density in your ‘color’ print. Summation: Standard color developer formulae have a vast capacity, a ‘hidden’ capacity, which is underscored and confirmed by my one-shot dilutions.

    AGE FOGGED FILM: NOTE: Some might wish to process C41 film that is long past its expiration date. Here is what my experiments have taught me. (NOTE: I will separate the expiration dates (ED) into categories and assume that film storage has been at room temperature.) 1) Up to two years past ED: give one stop more exposure and process normally. 2) Two to five years past ED: give two stops more exposure and develop with a slightly stronger 10X dilution of the C41 developer (i.e., not the 15X dilution of C41 that I use for fresh film). 3) Five to twenty years past ED: this is tricky but ‘worst case’ scenarios (i.e., 10 to 20 years past ED) call for giving up to four stops more exposure and processing in a (much stronger) 5X dilution of C41 developer. (NOTE: This 5X dilution is three times as strong as the 15X dilution used.) Remember to always add the same amount of carbonate per liter of the particular WS dilution of C41 developer that you are using. You will get denser negatives with older, age-fogged film but if you look at the negatives with a magnifying glass, close up, (while illuminating that negative from its rear side with a light bulb) you will see a great image that will make a great print. (In the early 1980s I bought a 100 foot roll of Vericolor 5026 and I can still use it for excellent color printing, even though it has been stored at room temperature and now has a speed of only EI 6.) Also, important: age-fogged film also requires more intense bleaching and fixation: you will probably have to separate the bleach and fix components, using them full strength, so as not to allow the combination to ‘dilute’ one component with the other.

    AGE FOGGED PAPER: here a tiny amount of benzatriozole or potassium bromide (or even sodium bicarbonate, I find) comes in handy. (This is certainly not a ‘cure all’ and, depressingly, in many cases is not a cure at all! But, here I present a feeble attempt towards being able to use age-fogged paper, if only for an excuse not to discard it. You must slow down development so that the nasty yellow base will be lessened: Use only about 1/10th (or less) of the amount of restrainer solution that you would normally use for B&W printing. (Note: you can also try using sodium bicarbonate, or baking soda, to slow things down: try 2g per liter of diluted WS color print developer. Obviously, this slowing down of development just might ‘reward’ you with blue-blacks since the maximum density will not be attained. Modify, plus or minus, as needed.) Experiment with small pieces of color paper and do ‘coin tests’ to determine just how little you can develop the paper (to still get at least somewhat acceptable blacks) while still retaining a ‘mostly’ white base under the ‘coin’ area. (NOTE: However, a coin has raised ‘devices’ which might allow light to creep underneath; either hold down the coin securely or, better, use a dead flat, opaque item to cover the paper.) The restrainer will allow the development TIME to be similar to the normal, two-minute time, even though you are now actually developing LESS because of the need to hold down the fog. Age fogging on color paper begins to manifest deterioration with a slight yellowing of the base. If slight, it will usually not be noticed, but as it gets worse it becomes a problem with the lighter colors because it cannot be filtered out: It’s just there, permanently. You will not be ABLE to achieve pure white. The restrainer does, indeed, help somewhat with holding down this fog, but I do wish there was a ‘reducer’ type of chemical that would ‘remove’ an even layer of the buff-yellow base throughout the print, just like how we can ‘brighten up’ B&W prints so easily in Farmers’ reducer.

    DEVELOPER PRESERVATION:
    Most will say that these developers cannot be successfully stored for long periods. I have stored both of them, in diluted form, for much time (especially the RA4 developer) and there is little, if any, NO reduction in potential. If kept airtight they will last much time. (I am purposely being rather vague with quantification with regard to time here but I have had RA4 developer mixed for a dozen years with no problems. C41 might be a different story, or not, so I do not wish to be absolute here.) How do we do this effectively?

    To preserve the developer CONCENTRATES (once opened) do as follows:
    Flexicolor C41 developer/replenisher: ALL concentrates (A,B,C) can be kept separately in either glass or PET plastic. I believe that the ‘A’ part does not need to be kept airtight, but the ‘B’ and ‘C’ absolutely do need to be kept airtight, without airspace in the bottle.

    RA4 RT developer/replenisher: there is one important exception to the PET plastic here: the ‘C’ part of RA4 RT dev/repl cannot be kept in PET plastic because it is of such intense alkalinity that it will begin to eat through (i.e., greatly weaken) the plastic after a few weeks. Keep this ‘C’ part in either the original container or glass. I do not believe that this ‘C’ part must be kept airtight, as it is the accelerator component, but do be certain to keep the ‘A’ and ‘B’ parts airtight, without air space.

    To store pre-mixed Flexicolor developer or RA4 RT developer: (either mixed per Kodak, or in the dilutions which serve as my ‘diluted working solution’). Feel free to store either mixture in PET plastic or glass, filled to the top rim of the bottle. For tiny quantities I use 50ml plastic liquor bottles with metal caps. Tiny glass marbles, obtainable at arts and craft stores, fit into these ‘narrow neck’ bottles. For the larger PET bottles (ie, Gatorade, sodas, juices) the standard size glass marbles (buy at Walmart) fit easily. Some of the PET plastic long, narrow soda bottles with sheer, unembossed sides (e.g. Pepsi), though still rather brittle, can be squeezed somewhat so as to let out air, relieving the need to add marbles.

    NOTA BENE: PROCESSING C41 FILM IN RA4 RT DEVELOPER: you can do this with minor printing filtration changes. My examples here do not demonstrate this, but I have done this many times. You need to start with my previously stated print developer WS (i.e., 5X dilution of the per Kodak RA4 RT developer) and then further dilute for negative development: (1 part + 1 part water) in order to make the color film dilution (i.e., this total dilution from ‘Kodak strength’ becomes 10X). Use the same 12 minute development at 90F. No additional carbonate need be added beyond that which had ALREADY been added to make the PRINT developer working solution. Naturally, if age fogged, the film needs more exposure and less developer dilution (i.e., stronger developer). Re-read my previous data.

    If you have questions I will try to accommodate your queries: you may contact me either through a PM or call me directly at 215.569.4949. Remember that I do not have a computer where I live, thus patience is needed with the electronic communication. – David Lyga
    Attached Thumbnails Attached Thumbnails Barclay condominium.jpg   indoor tungsten.jpg   jump rope.jpg   flowers and granite.jpg   Santa Claus.jpg  

    Last edited by David Lyga; 12-30-2012 at 01:36 PM. Click to view previous post history.

  2. #2
    David Lyga's Avatar
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    Here is another. - David Lyga
    Attached Thumbnails Attached Thumbnails flowers.jpg  

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    wildbill's Avatar
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    That's it?
    The results look nice.
    www.vinnywalsh.com

    I know what I want but I just don't know how to go about gettin' it.-Hendrix

  4. #4
    ROL
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    Quote Originally Posted by David Lyga View Post
    WARNING: This is going to be long and arduous. Either persevere…or stop right here!
    OK, I did. How about a synopsis for your thesis?

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    ROL: RE: synopsis

    I cannot, without leaving too much out. I duly apologize, but I did forewarn. Please be at least somewhat tolerant for my outpouring. I meant no harm; I offer no purposeful angst. - David Lyga

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    Rudeofus's Avatar
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    That's a very interesting thread and especially the thing with dilute single shot developer sounds very interesting for casual C41 shooters. Makes me curious why nobody sells cheap C41 single shot kits to the Lomo crowd. What makes your results even more impressive is that they went through optical printing process - you can't cover up color crossover, poor contrast or other flaws like you could in a hybrid work flow.

    I would like to note a few things here, though:
    • PE frequently comments that a CD3 based process like RA4 should not be used for processing C41 materials. According to his statements the resulting colors are not long term stable which will obviously only show up in a few years or even later.
    • Your statement about dilute BLIX applies only if you use the proper C41/E6 formulas which mandate Ammonium Ferric EDTA or Ammonium Ferric PDTA bleach, not the Ferricyanide bleach you used. With these EDTA/PDTA based BLIXes you run into solubility limits since high concentrations of both bleaching and fixer components are necessary. If you use Ferricyanide, this is normally sufficiently active as a very dilute bleach and the full amount of Ferricyanide can easily be mixed into full strength fixer. The biggest problem with your Ferricyanide BLIX is, as your post already states, the incredibly short shelf life of this mix.
    • Using such a dilute developer should, if my theory is correct, yield a sharper but also coarser grained image. Since these low res scans won't show this, can you confirm this from looking at your prints?
    Trying to be the best of whatever I am, even if what I am is no good.

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    David Lyga's Avatar
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    Rudeofus: The grain does NOT suffer. Absolute accutance I cannot state, unequivocally, but I make sharp negatives: on the baseboard of the enlarger I max out the head and look with a magnifying glass: and they are SHARP. AS sharp? Don't know if there is a technical trade off. But I have no complaints.

    True, long term stability I cannot ascertain but, so far, no complaints.

    Bleach and fix concentrations: MUCH experimentation here and my dilutions are fine. They 'get' all the silver out. Period. (And, as PE correctly states: that is no small task.)

    Of course, this is full frame 35mm film. - David Lyga
    Last edited by David Lyga; 12-30-2012 at 02:48 PM. Click to view previous post history.

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    Quote Originally Posted by Rudeofus View Post
    That's a very interesting thread and especially the thing with dilute single shot developer sounds very interesting for casual C41 shooters. Makes me curious why nobody sells cheap C41 single shot kits to the Lomo crowd. What makes your results even more impressive is that they went through optical printing process - you can't cover up color crossover, poor contrast or other flaws like you could in a hybrid work flow.

    I would like to note a few things here, though:
    • PE frequently comments that a CD3 based process like RA4 should not be used for processing C41 materials. According to his statements the resulting colors are not long term stable which will obviously only show up in a few years or even later.
    • Your statement about dilute BLIX applies only if you use the proper C41/E6 formulas which mandate Ammonium Ferric EDTA or Ammonium Ferric PDTA bleach, not the Ferricyanide bleach you used. With these EDTA/PDTA based BLIXes you run into solubility limits since high concentrations of both bleaching and fixer components are necessary. If you use Ferricyanide, this is normally sufficiently active as a very dilute bleach and the full amount of Ferricyanide can easily be mixed into full strength fixer. The biggest problem with your Ferricyanide BLIX is, as your post already states, the incredibly short shelf life of this mix.
    • Using such a dilute developer should, if my theory is correct, yield a sharper but also coarser grained image. Since these low res scans won't show this, can you confirm this from looking at your prints?
    I've found grainier but less detailed images in my experience, with worse dMax-dMin. (diluted C-41 developer, not RA-4 on C-41 films).

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    I can second one nugget buried in the long original post. That is the use of benzotriazole to reduce base fog in color papers. I have successfully used 5mg/L BTZ to eliminate slight base fog from some Kodak Edge paper, printing with like new results. I also added 5ml/L h2o2 to the mix bump up the contrast a bit. I also eliminated quite pronounced yellow base fog from some Crystal Archive type C, but experimentation there is ongoing as the resultant print is quite flat.

    We all benefit from unconventional approaches/tests like these.

  10. #10
    RPC
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    You have not shown any sensitometric results. It is difficult to judge where scans and monitors are involved. You need to run control strips through your processes which I believe would show they are out of spec.

    Along similar lines, I have tried Patrick Dignan's divided low temperature C-41 developer and while some prints made from the negatives developed in it would probably look acceptable to some, the sensitometric results clearly showed crossover in the negatives and was visible to me in the prints. In your case you may also have retained silver.

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