Negatives coming out wrong

1kgcoffee · Dec 25, 2020

Racking my brain trying to figure out what the problem is here.

Originally, I purchased some raw chemicals and mixed up a batch of c41 developer. I used some kodak bleach that I got on sale from a canadian vendor and some ammonium thiosulfate fixer diluted to the correct concentration. 3min15 sec for dev, wash, 6.5 min for bleach, wash, 6.5 min fix. all at 100*F.

First film came out wonky. Negatives too dense, colours off, I couldn't scan or wet print them properly.

Thinking the problem was my developer, I then purchased some official kodak LORR developer. Similar problem with the next roll of film in new developer.

I'm wondering, could it be the fixer or the bleach now? And are the negatives savlageable if I reprocess them? The bleach is kodak bleach replenisher, this stuff:
https://www.bhphotovideo.com/c/product/27627-REG/Kodak_8255549_Flexicolor_RA_C_41RA_Bleach.html

Intended to be used in minilabs with higher agitation and washeless. I figured I could use in a dev tank with high agitation. And washed anyways prior to bleaching as I didn't want the bleach to eat the dev. It says something on the label about a bleach starter, but I can't find that anywhere? The fixer is photographers formulary stuff. Perhaps it went bad.

What do you folks think? I was expecting better results from a non-blix process. I'd prefer not to mix up several more chemicals and waste more film.

cmacd123 · Dec 25, 2020

Look for the threads on C41 fixer. while you can use C-41 fixer for B&W, it has the wrong Ph for colour. Since I cant see your shots I don't know what else to say. The starter is used to adjust the difference between the replenish-er and the actual developer. often it contains some Potassium Bromide which is the restrainer as that is supplied by the film being developed on an ongoing basis and is therefore not in the replenish.

Sirius Glass · Dec 25, 2020

Post the negatives, please.

koraks · Dec 26, 2020

cmacd123 said:
while you can use C-41 fixer for B&W, it has the wrong Ph for colour.

Yes, that's true, but it doesn't explain the problem of too dense negatives. If fixer pH were the issue, the problem would manifest itself in color balance problems and particularly a lack of red (due to cyan dye remaining in its leuco state). Excessive density is certainly not to be expected.

cmacd123 said:
The starter is used to adjust the difference between the replenish-er and the actual developer. often it contains some Potassium Bromide which is the restrainer as that is supplied by the film being developed on an ongoing basis and is therefore not in the replenish.

I think he's talking about bleach starter, while you're talking about developer starter. The bleach starter is much less critical than the developer starter; most likely, a bleach used without starter will yield perfectly fine results (at least that's what I get with Fuji chemistry and *no* bleach starter). However, omitting developer starter can very well explain the problems as briefly described above - i.e. excessive density & color balance issues.
@1kgcoffee can you confirm you're using the LORR developer properly mixed with starter and the right dilution when starter is used?

Sirius Glass said:
Post the negatives, please.

This is going to be an important step in trying to pin down the problem.

1kgcoffee · Dec 26, 2020

Thanks for the responses. Here is the negative, scanned straight into a JPG.

postive_001 by Aaron, on Flickr

Koraks - Yes I used a developer starter with LORR. Fresh chemicals. The bleach however is just straight bleach replenisher, not diluted into a working solution as I couldn't find the data, and no starter as PE mentioned in a previous thread it was unnecessary. I'm beginning to wonder if the pH of is the bleach is problem? In another thread a different brand of bleach is diluted by 1/3. Then comes the question, are the negatives salveable if not properly bleached before being exposed to light?

As you folks can see below there is crossover in the blue/green channel:

crossover by Aaron, on Flickr

As a positive:

positive by Aaron, on Flickr

cmacd123 - Could be the fixer, but I'm using ammonium thiosulfate which is pretty much the same stuff used commercially. I do have some kodak concentrate but rather go through the formulary stuff first. All fresh BTW.

MattKing · Dec 26, 2020

1kgcoffee said:
The bleach however is just straight bleach replenisher, not diluted into a working solution

Could this be the problem?

1kgcoffee · Dec 26, 2020

It's a possibility, but I always thought bleach was to completion and it is not possibly to remove undeveloped dyes? Lower pH should just be faster

koraks · Dec 26, 2020

Does the camera expose correctly? Looking at the top and bottom edges of the frame, I see a suspicious amount of halation.

1kgcoffee · Dec 26, 2020

As much as can be expected from a kiev 6c (I have multiple bodies). There is a bit of a light leak which can be seen on long exposures. The negatives look normal, maybe a bit dense but I tend to overexpose c41 and never had these sorts of issues before.

koraks · Dec 26, 2020

I'd expect cleaner edges on the negatives unless something is massively wrong, such as an aperture that fails to stop down to the taking aperture or a very sticky shutter. However, it's hard to say much about the overall density since we're dealing with scans. Usually a photograph (not a scan) of the negatives gives a little more insight.

If the problem is related to the bleach step (don't think it is, but you can always try/hope), simply bleach them again and the also repeat fixing. Try not to use an acidic fixer as it can prevent the cyan dye from properly turning out. I've never actually seen it happen, but in principle it can be an issue. C41 fixer should be around pH 6.5 as I recall.

Donald Qualls · Dec 27, 2020

Flexicolor bleach works fine without starter. Or at least it has for me, both times I've run Flexicolor chemistry (most currently, fifteen or so rolls through a liter -- about due to mix fresh). Same for fixer -- and fixer mixed from ammonium thiosulfate should work as well, though I've read that fixer pH is important in C-41. As @koraks noted above, acidic fixer can prevent cyan dye formation, which would give an orange negative like what you see (and, without correction but using a color balance based on the mask in the unexposed rebates, a very blue positive).

grat · Dec 27, 2020

I have no idea if this is useful or not, but using Darktable + negadoctor, and some level adjustment, and some curves, and some... well, let's face it-- I was just seeing how much of the photo could be recovered.

I post it simply because it might be useful in figuring out what went wrong.

MattKing · Dec 27, 2020

Adding bleach starter to new bleach replenisher will give similar results to an in spec replenished C-41 developing line. So if a high throughput commercial lab has to dump and replace their bleach for some reason, they can easily and quickly get back into spec with new chemicals.

MattKing · Dec 27, 2020

Old Gregg said:
What does this mean? What's wrong with "out of spec" bleach? Adding or not adding a starter makes no difference in final results or bleaching time.

It does if you are processing in volume using equipment that is set up to complete the bleach step in a specific length of time.
Think of roller transport machines where the time in each bath is fixed, and throughput needs to be maximized. You can't afford to have the bleach activity vary from day to day.

foc · Dec 28, 2020

Can you post a photo of your neg strip (not a scanned one) something like this?

As koraks has mentioned above, the image area edge of negs should be more defined and not bleed into the edge markings. Such bleeding is normally associated with overexposure and/or poor pressure from film pressure plate (in 120 it could be that the pressure plate was set for 220, if available on the camera).

I don't understand correctly when the OP said "The bleach however is just straight bleach replenisher, not diluted into a working solution as I couldn't find the data"
Was the concentrate mixed with water or use straight from the bottle? ( I understand that no started was used)

MattKing · Dec 28, 2020

Old Gregg said:
Matt, you are not answering the question. You are just repeating what's written on a box. I can read too. The question was "why?"

What specifically will be different if I don't use a bleach starter for a fresh batch for continuous/roller-transport processing? Not trying to give you a hard time. After all, I am basically stuck with small-tank 6:30 routine. I am just curious!

You won't waste time and money.
Bleach is one of the most expensive parts of the process. Staffing expenses are even more expensive. Control strips are fairly expensive too. If you use starter, you will quickly arrive at the same control strip results using the same or similar replenishment amounts as before.
With bleach, you use control strips to allow you to minimize replenishment amounts. The starter allows you to get there quickly.

Donald Qualls · Dec 28, 2020

Old Gregg said:
I asked how does a bleach starter work?

Same as developer starter and fixer starter: by artificially introducing exhaustion products to put the solution into a "seasoned" condition almost immediately. With developer starter, this is necessary in order to use the same times as you would with an in-balance replenishment system. With bleach and fixer, the benefits are less clear, since those processes should go to completion -- and in small tanks, we just use a longer bath time for those to be sure they do -- but very likely there are small changes in pH and exhaustion product levels that affect process rate (and in the fixer, can affect final dye formation). Overall, I'd expect the starters to slow down the process as developer starter does, but there may be other balance-related changes.

MattKing · Dec 28, 2020

Old Gregg said:
@MattKing again, you're stating just obvious abstracts regarding a lab operation. I asked how does a bleach starter work?

Actually, you didn't. You asked why you would use it .
Donald's description about what it does and how it works is good.
The "why" remains unchanged - it helps labs be as efficient and economical as possible, because big changes to a processing line cost money.

MattKing · Dec 28, 2020

Apologies for parsing your question(s) - it is a (former) occupational habit, which does not endear me to my wife!
To be clear, I'm not saying you should use the bleach starter. I'm saying the commercial lab down the street that is still processing a lot of film should.

koraks · Dec 29, 2020

Old Gregg said:
if i can try shorten the bleaching time by NOT using a bleach starter.

First of all, obviously: give it a try. You can always repeat the bleach step if it was incomplete.
But the most reliable way to cut your bleach time is to get some rapid access chemistry. That cuts down the minutes like trees in the Amazon...

foc · Dec 29, 2020

koraks said:
First of all, obviously: give it a try. You can always repeat the bleach step if it was incomplete.
But the most reliable way to cut your bleach time is to get some rapid access chemistry. That cuts down the minutes like trees in the Amazon...

+1 for quick bleaching = use RA (rapid access) bleach
For example Fuji Environeg Bleach times are 3 to 6.5 mins
Fuji Environeg RA Bleach times are 45 to 60 seconds, so you can see a big saving in time for a lab.

Donald Qualls · Dec 29, 2020

Old Gregg said:
Maybe I should risk a roll of C41 film to see if i can try shorten the bleaching time by NOT using a bleach starter.

It's tempting to suggest that bleach time without starter may be longer than with, else (since bleaching ought to go to completion) labs wouldn't need starter (unless there's a pH problem with carry-over to the fixer). As noted previously, however, if you find your negatives have high density and poor saturation, you can rebleach and refix without harm.

And if you've already got bleach, there's no sensible reason to switch to RA bleach -- if you're about to buy, or started with a kit and are exploring switching to Flexicolor or Fuji equivalent, then it might. Personally, I've been running bleach (no starter, but now well seasoned after 15+ rolls) and fixer at 4:30, not 6:30, and had no complaints, so it's very likely these steps are complete well before the given process times.

laingsoft · Dec 31, 2020

Isolating problems like this requires that you need to isolate as many variables as possible. The main things that will cause color shifts and crossover in descending order of importance is pH, Temperature, and competing ions.
pH measurements for photography can be made with a pocket pH meter, I've found them to be accurate enough.
Temperature -> Use a cheap sous vide in a water bath to keep all of your chemicals at the correct temperature, and I like to use the water bath to keep the development tank at the correct temperature when not agitating.
Competing Ions -> Use either Kodak Anti-Cal #3 or Distilled/De-Ionized water.

pH being out of the acceptable range will cause the dyes in the emulsion to permanently go clear, so you need to be careful that none of the washes/bleaches/fixes/stabilizers/developers are out of the OK range.

Modern c41 emulsions have 10ish layers that are each tuned to hit the correct point in development after 3min 15s at 100F, any deviation from that is going to cause crossover and weird development. This is where mixing your own C41 dev becomes difficult, because Kodak and Tetenal have the advantage of precision (It's much easier to weigh 10kg of CD4 than it is to weigh 4.8g of CD4) and access to DI water, pure chemistry and preservatives with long names that aren't available to you without a sigma account. That said, you can get close enough to branded chemicals that it's almost irrelevant.

Bleaching and fixing likely won't cause deterioration of the dyes unless you are using a ferricyanide bleach that attacks the dye molecules or the pH is incorrect.

1kgcoffee · Jan 2, 2021

Thanks for the responses.

MattKing said:
Could this be the problem?

I'm beginning to think it might be. I just tested it and my bleach is sitting at 4.1 pH. Fixer is at about 8.5. According to PE, in this thread, ph is supposed to be at 6.5-6.8 for c41. If acidic pH fix can prevent cyan dye formation, then maybe I went too far in the other direction. Bleach ph should be above 5.7, but I don't know if this is as critical? Guess it needs diluting.

koraks said:
I'd expect cleaner edges on the negatives unless something is massively wrong, such as an aperture that fails to stop down to the taking aperture or a very sticky shutter. However, it's hard to say much about the overall density since we're dealing with scans. Usually a photograph (not a scan) of the negatives gives a little more insight.

If the problem is related to the bleach step (don't think it is, but you can always try/hope), simply bleach them again and the also repeat fixing. Try not to use an acidic fixer as it can prevent the cyan dye from properly turning out. I've never actually seen it happen, but in principle it can be an issue. C41 fixer should be around pH 6.5 as I recall.

Having trouble taking a good photo, but I set the range from 0-255 for the scanned strip below. Do you know if very basic fixer ph has the same issue as overly acidic and how this would affect dye formation?

foc said:
Can you post a photo of your neg strip (not a scanned one) something like this?
View attachment 262427

As koraks has mentioned above, the image area edge of negs should be more defined and not bleed into the edge markings. Such bleeding is normally associated with overexposure and/or poor pressure from film pressure plate (in 120 it could be that the pressure plate was set for 220, if available on the camera).

I don't understand correctly when the OP said "The bleach however is just straight bleach replenisher, not diluted into a working solution as I couldn't find the data"
Was the concentrate mixed with water or use straight from the bottle? ( I understand that no started was used)

Forgive the weird scanning artifact.

postive_strip001 by Aaron, on Flickr

Bleach replenish was not mixed with water, just used straight. Perhaps this is part of the problem.
As for the negative strip, it definitely does not expose perfectly but it is fairly close. I sometimes forget to switch the pressure plate back to 120 but I don't believe I made the mistake in this case. Light leaks are fairly normal in this camera.

laingsoft said:
Isolating problems like this requires that you need to isolate as many variables as possible. The main things that will cause color shifts and crossover in descending order of importance is pH, Temperature, and competing ions.
pH measurements for photography can be made with a pocket pH meter, I've found them to be accurate enough.

Using a pocket meter today, I believe this to be the issue. Chems with mixed with pure distilled water and devloped at correct temps.

laingsoft said:
pH being out of the acceptable range will cause the dyes in the emulsion to permanently go clear, so you need to be careful that none of the washes/bleaches/fixes/stabilizers/developers are out of the OK range.

Do you believe that in this case the negatives could not be salvaged if rebleached and fixed at the proper ph?

1kgcoffee · Jan 2, 2021

Planning to shoot and develop a 35mm test roll tomorrow in my trusty Minolta and chemicals at corrected ph. Will report back here with the results.

Anyone good with chemistry know how much water I would have to proportionately dilute by to come up with the correct pH (bleach at 4.1 and fix at 8.5)? Should both be closer to 6.5 if I'm not mistaken.

Negatives coming out wrong

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