Help needed with Laut C-41 Developer

OldBikerPete

Member
Joined
Aug 29, 2005
Messages
386
Location
Melbourne, A
Format
4x5 Format
Hi. I've used the Laut Developer with the following formulation.
Sodium Sulphite (Anh.) 4.25g
Potassium Bromide 1.50g
Potassium Iodide 0.002g
Sodium Carbonate 37.50g
Hydroxylamine Sulphate 2.00g
CD-4 4.80g
Distilled water to 1000ml

I have used it without adjusting pH and achieved good results with minor color casts.
I have recently obtained a pH meter and calibration solutions at ph=7.0 and pH=10.0. After calibrating the meter and making up a batch of developer I find that its
pH before adjustment is pH=10.7.

Does that correspond with people's experience?

I adjusted the pH of this developer with acetic acid to pH=10.0 - 10.1 as prescribed - it took 5ml of glacial acetic acid to do so.
Negatives I develop in this adjusted solution are thin and the print colors are muddy with a strong green+cyan cast.

What am I doing wrong?
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
Well, there are better formulas out there. That one has a few things wrong with it such as the carbonate being low (IIRC) and the CD-4 being low. It should be 5.0 or 5.1 g of CD-4.

I suggest you get a better formula.

PE
 

Kevin Caulfield

Subscriber
Joined
Aug 3, 2004
Messages
3,845
Location
Melb, Australia
Format
Multi Format
Wow, I'm a chemist like you, Pete, but I have virtually no knowledge of colour chemistry recipes, but that's a really low concentration of potassium iodide, just 2 thousandths of a gram in a litre. I reckon it would be difficult to weigh that out.
 
OP
OP

OldBikerPete

Member
Joined
Aug 29, 2005
Messages
386
Location
Melbourne, A
Format
4x5 Format
Wow, I'm a chemist like you, Pete, but I have virtually no knowledge of colour chemistry recipes, but that's a really low concentration of potassium iodide, just 2 thousandths of a gram in a litre. I reckon it would be difficult to weigh that out.
Yes, you make up a solution of 0.1g in 100ml of water and use 2ml of that solution. The solution goes off, so it doesn't do to make too much of it.
 

RPC

Member
Joined
Sep 7, 2006
Messages
1,628
Format
Multi Format
I normally use Kodak Flexicolor developer but recently have tried to mix my own in case Flexicolor ever becomes hard to get. I use a formula I found somewhere here on APUG, which is similar to yours:

Distilled water 800ml
Potassium Carbonate 37.5g
Sodium Sulfite 4.3 g
Sodium Bromide 1.3g
Potassium Iodide .002g
Hydroxylamine Sulfate 2g
CD-4 4.8g
Add water to make 1 liter

When mixed the pH is high, around 10.4-10.5 and the printed negatives are contrasty. After adding white vinegar I get the pH down to 10.0-10.1 or so and prints from the negs look good. I have used this formula with Portra 160NC, Portra 160VC, Ultra 100, Fuji Pro 160s and Konica Centuria 100. Using my X-rite 810 densitometer I read and plot densites of the MacBeth color chart gray scale and the curves are nearly as parallel as Flexicolor developer. Can't say whether the negs meet all of Kodak's specs, but I am satisfied with them, so IMHO the formula works.

Just thought I would share my experience. Being fairly new at this game myself I can't say for sure what is causing your problem, except that perhaps the pH is actually lower than you are measuring.
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
The pH for C-41 is 10.4 and the pH of the RA developer is 10.1. The carbonate is 40 g/l. That is all I can remember OTOMH. The HAS seems low and it uses a sequestrant.

PE
 

stefan4u

Member
Joined
Aug 27, 2006
Messages
167
Format
35mm
C-41 Developer

Some time ago I "browsed" for well working C-41 reciepts as well. Aside apug and photo net I looked out for various patents, like "Bromide ion determination" and "ph stabilisation" etc. for getting proper results concerning the Bromide / Iodide and CD4 ratio.

The recommanded DTPA-5Na chelating agent was substituded by more ordinary "Calgon", our tab water is pretty soft and no longer storage of the brewed solution is planned...

Reciept I

Tab water 800 ml
Calgon 2.5g
Potassium carbonate (anhy) 37.5g
Sodium sulfite (anhy) 4.0g
Sodium bromide 1.3 g
Potassium iodide 1.2 mg (!)
Hydroxylaminsulfate 2.0 g
CD-4 4.5 g
Water to make 1.0 Litre
ph should be around 10.04 - 10.07 to be honest I havn't measured it, this reciept works well the way it is, anyhow with "portrait" films, but normal stuff too.
This is IHMO a quite good Developer composition, I used this for Agfa portrait 160, Agfa vista 100, Konica pro 400 and Kodak VR 100. There are NO remarkable color crossovers or color shifts, the used filter pack for enlarging is similar as it is with commercial chemicals (Tetenal).
Please use a stop bath after developing, NO plain water rinse, as "RPC" remarked, this developer can be a bit contrasty, maybe reduce the ammount of CD-4 down to 4.4 till 4.3 g /L.




The similar, slightly buffered reciept II, ist still untested, because I'm very happy with the Results from reciept I

Reciept II

Tab water 800 ml
Calgon 2.5g
Potassium Carbonate (anhy) 34.5g
Potassium bicarbonate (anhy) 2.3g
Sodium sulfite (anhy) 3.75g (+/-0.5g)*
Sodium bromide 1.3 g
Potassium iodide 1.2 mg (!)
Hydroxylaminsulfate 2.0 g (+/- 0.5g)*
CD-4 4.5 g (+/- 0.25g)*


ph should be about 10.04 (+/- 0.05)*
Spec. Gravity 1.036 (+/- 0.004)*

*All these +/- variances are given by Kodak in order not to disclose the reciept complete, but the way Reciept I is working well, the given ammounts semms to be quite close.

Regards from Germany,
Stefan
 

Photo Engineer

Subscriber
Joined
Apr 19, 2005
Messages
29,018
Location
Rochester, NY
Format
Multi Format
Guys;

A correct formula has been posted here and commented on. The level of iodide is either 2 mg/l or close to that value, the carbonate is about 40 g/l etc. etc. I'm sorry but I don't have the thread URL nor do I remember the formula, but the ones are just "close". One Kodak patent claims that the exact formula was printed in the BJP.

I believe that Dan Schwartz has posted it on his web site, and there are several others. The formulas above, I stress, are close but that is all my memory tells me. I handed in my 'black book' quite a few years ago and except for those few I remember for some reason or other, I've forgotten them in detail.

PE
 

stefan4u

Member
Joined
Aug 27, 2006
Messages
167
Format
35mm
Dear PE !!

Sadly Dan's homepage Dead Link Removed
does not contain the desired information, neither for C-41 nor E-6...

But happily compiled process Handbooks can be found there, next to other interesting stuff.

If Dan posted the formulars there, they are perhaps deleted. Maybe just my glasses aren't that good anymore ...

But I've found something other, a kodak patent concerning development time, temperature and film speed. Haven't read that all, but please have a look at page three of the following link , followed the phrase "A type of color negative processing that is widely used is the Kodak Flexicolor color negative process. Since minor adjustments of the C-41 process are undertaken from time to time, the following detailed description is provided"!!

https://publications.european-patent-office.org/PublicationServer/documentpdf.jsp?iDocId=4850661&iebug=.pdf

That is, more or less, equivalent to the Reciept II I've found in a different context (ph stabilisation).

Regards,
Stefan
 
Last edited by a moderator:

stefan4u

Member
Joined
Aug 27, 2006
Messages
167
Format
35mm
C-41 Variarions

...me again...

This is for Pete and RPC (of course not excluvive)

I've went through some more patents from Fuji and kodak. Even if there are minor variations to the merchandised procucts, they have all something in common.

The Hydroxylaminsulfate is higher than in most "homebrew recieps" Hydroxylaminsulfate (HAS) is known as a antioxidant to improve longlivety of the developer. This is just a guess, but it may be a antagonist for the CD-4 as well, at least it have to be in proper relation to CD-4 to get the desired developer activity. A lack of HAS could be the reason for the higer activity of the homebrew's. But more suspect seems to be the ph and the difficulty to measure it. Pete and RPC had both pretty contrasty results, as well I had on consumer film. I'm going down to the cellar and mix another batch with reduced Potassium Carbonate, we'll see...

Here three reciepts, taken from various patents (Keep in mind that these formulations are for research and may deviate from the offical versions)

Fuji
The composition of each processing solution is described below.
<tb><TABLE> Columns=3
<tb>Title: Color Developing Solution
<tb>
<tb>Head Col 1:
<tb>Head Col 2: Tank Solution (g)
<tb>Head Col 3: Replenisher (g)
<tb>Diethylenetriaminepentaacetic Acid<SEP>1.0<SEP>1.3
<tb>Disodium Catechol-3,5-disulfonate<SEP>0.3<SEP>0.4
<tb>Disodium N,N-Bis(2-sulfonatoethyl)hydroxylamine<SEP>2.0<SEP>2.5
<tb>Sodium Sulfite<SEP>4.0<SEP>4.9
<tb>Potassium Carbonate<SEP>30.0<SEP>39.3
<tb>Potassium Bromide<SEP>1.4<SEP>0.25
<tb>Potassium Iodide<SEP>1.5 mg<SEP>-
<tb>Hydroxylamine Sulfate<SEP>2.4<SEP>3.2
<tb>4-[N-Ethyl-N-( beta -hydroxyethyl)-amino]-2-methylaniline Sulfate<SEP>4.5<SEP>6.2
<tb>Water to make<SEP>1.0 l <SEP>1.0 l
<tb>pH (adjusted with potassium hydroxide and sulfuric acid)<SEP>10.05<SEP>10.15
<tb></TABLE

Fuji Variante 2:
Farbentwickler

<tb><TABLE> Columns=2>

<tb><CEL g

<tb><SEP>Natriumsulfit: <SEP>4,0 g
<tb><SEP>Kaliumcarbonat:<SEP>30,0 g
<tb><SEP>Kaliumbromid:<CEL AL=L>1,4 g
<tb><CEL AL=L>Kaliumjodid:<SEP>1,3 mg
<tb><SEP>Hydroxylaminsulfat:<SEP>2,4 g
<tb><CEL AL=L>4-(N-Ethyl-N- beta -hydroxyethylamino)-2-methylanilinsulfat: <SEP>4,5 g
<tb><SEP>Wasser:<SEP>ad 1 l
<tb><CEL AL=L>pH-Wert:<SEP>10,00 (adjusted with potassium hydroxide and sulfuric acid)


Kodak :

Water 800.0 mL
Potassium Carbonate, anhydrous 34.30 g
Potassium bicarbonate 2.32 g
Sodium sulfite, anhydrous 0.38 g
Sodium metabisulfite 2.96 g
Potassium Iodide 1.20 mg
Sodium Bromide 1.31 g
Diethylenetriaminepentaacetic acid pentasodium salt (40% soln) 8.43 g
Hydroxylamine sulfate N-(4-amino-3-methylphenyl)-N-ethyl- 2.41 g
2-aminoethanol 4.52 g
Water to make 1.0 L
pH @ 26.7°C 10.00 +/- 0.05


Well, the interesting part (for me) is that they all use
4.5 g CD-4 (not4.8 or 5g)
2.4 g Hydroxylaminsulfate (more than in common recieps)
1.3 -1.4 g Sodiumbromide
1.2 -1.5 mg Potassium Iodide
and have a
ph 10.00 -10.05


I'm gonna to try this tonight with a slight variation from my former reciept I with three film types I'm familiar with (Agfa portrait, Vista and Konica)

Tab water 800 ml
Calgon 2.5g
Potassium carbonate (anhy) 34 g
Sodium sulfite (anhy) 4.0g
Sodium bromide 1.3 g
Potassium iodide 1.3 mg
Hydroxylaminsulfate 2.4 g
CD-4 4.5 g
Water to make 1.0 Litre,

That ph meter is only a quite cheap one, try to come as close to ph 10.00 -10.05 as possible by adding the necessary amount Potassium carbonate afterwards. Going to post the exact amount later

Hope not boring anybody,
Stefan
 

RPC

Member
Joined
Sep 7, 2006
Messages
1,628
Format
Multi Format
Stefan4u,

Thanks for the all the info. I am tempted to do more experimenting myself. Looking forward to your results.
 

stefan4u

Member
Joined
Aug 27, 2006
Messages
167
Format
35mm
Back on surface again, this was a long run...

I've made three batches of developer

First:
Tab Water 800.0 mL
Calgon 2.5 g
Potassium Carbonate, anhydrous 34 g
Sodium sulfite, anhydrous 4.3 g
Sodium Bromide 1.3 g
Potassium Iodide 1.3 mg
Hydroxylamine sulfate 2.4 g
CD-4 4.5 g
Water to make 1.0 L

That gave a ph of about 10.5 too basic...

Next batch same as above but only 30 g of, in the resulting ph from about 10.3 still too basic

Third batch was made with only 20g of Potassium Carbonate, surprisngly the ph was with 10.2 still off limits.


Two options are possible now, this (or most of the public) reciept does contain substantially to much alkali, or the fact that the ph have to be downgraded to 10.05 is kept secret (more or less). From the public recieps I know only the "Photo Techniques" reciept mention aceteic acid for ph regulation, as well as the "Chapman reciept" mention KOH for the same intention.

But maybe one other couse for the exaggerated ph is my tab water, maybe it's slightly alcalic. Sadly havent measured that...Stupido...

So all these three batches were mixed together and gave me three liters of developer with a ammount of 84g Potassium Carbonate in total, that means 28g / Liter. Next I was for a moment incertain wheather it would be better only downscale the ph with sulfuric acid, or first add a bit more of Potassium Carbonate. Because all reciepts I've seen does contain more alkali and even batch three exeeded the desired ph with only 20 g of Potassium Carbonate, I decided (a bit reluctant) to add more alkali.

I added 15 g more Potassium Carbonateto the whole mix, that gives me 33g / Liter. Next i took sulfuric acid (lead acid battery, 37 %) and diluted it 1:1.
20ml of that solution was added during stirring, slowly and in fractions, et voila the ph came down to desired value.

There is still a overriding problem, my ph meter is far away from beeing a scientific instrument, so beside a calibration I did a crosscheck with Flexicolor Developer.
The flexicolor gave me 10.09, the manipulated homebrew came to 10.10 / 10.11, this is pretty close I think...

So, this is what we get now:

Tab Water 800.0 mL
Calgon 2.5 g
Potassium Carbonate, anhydrous 33 g
Sodium sulfite, anhydrous 4.3 g
Sodium Bromide 1.3 g
Potassium Iodide 1.3 mg
Hydroxylamine sulfate 2.4 g
CD-4 4.5 g
Sulfuric acid 37 % 3.3 ml (1:1 dilution 6.66 ml)
Water to make 1.0 L
ph around 10.1

There are 3 220 Konica400 Film's, two Agfa portrait and 3 Agfa Vista's (125) drying now. They look very well, nothing seems to be uncommon by a first inspection. Printing will follow later (propably monday, but can't promise that), really feel a bit worn out now...

Good night,
Stefan
 

stefan4u

Member
Joined
Aug 27, 2006
Messages
167
Format
35mm
minor update

After spending hours and hours calibrating my cheap ph meter I figured out that the ph from my former developer solution was about 10.16 .

This was close enough to enable developing really nice negatives, the Agfa portrait (a misjudged beauty) and the Konica pro 400 came out very well. The Agfa vista 100 seems to be a bit more contrasty as usual, but we are talking about nuances.

Well, well this encourages me to do an other batch, where I will include a carbonate buffer, similar to a Kodak receipt. Hopefully this is safer as plain sulphuric acid and will end in a more stable ph, not so prone by varying water supply. I used more bicarbonate because not using the acid Sodium metabisulfite and increased the Potassium Carbonate again…

Here comes my “new receipt”

Tab water 800 ml
Calgon 2.5g
Potassium carbonate (anhy) 37 g
Sodium Bisarbonate 7 g
Sodium sulfite (anhy) 4.3g
Sodium bromide 1.3 g
Potassium iodide 1.4 mg
Hydroxylaminsulfate 2.4 g
CD-4 4.5 g

The resulted ph I measured is 10.00 (but we will see…) If anyone is able to calculate the pk's values "on the fly" it would be nice to hear about...
The Chemicals are warming up right now, waiting for another run.

I have to go back to the cellar :rolleyes:




The text below is taken from various patents on patentstorm etc. just to show that we are on the track.


Source: http://www.patentstorm.us/patents/6649331-description.html

This is one of the very rare moments you can read direct the term "C-41" in the receipts, most times only called "as known in the art", "as published in Process C 42 Manual, Januar 1984, Eastman Kodak Company", or the "KODAK C-41 process, as described in the British Journal of Photography Annual of 1988, pp. 196-198" when it comes to numbers which seems to be serious. By the way, if there is anybody out there, who do have access to the C-42 process manual I would be very happy to get a copy of the receipts suggested there…
As far I’m informed Process C-42 is essentially the same as C-41 but the process manual is designed for labs who mix their chemicals from scratch and include receipts…


But back to theme, if you want to follow the original link, scroll down the page, it's all about shortening of the processing time, specifically the color development time.
At the end of the page you find bleach as well fixer receipts.

"The compositions of the developers for the example are shown in Table 2 below. All numbers are concentrations in mol per litre of final solution except for poly(vinylpyrrolidone) which is in grams per litre. The pH of the one litre solution was adjusted to the aim pH with potassium hydroxide or sulfuric acid at 24 C."

Very friendly these mol/L advices, aren’t they ?? The units for bleach and fixer are in gramm again...

TABLE 2
............................C-41 ... Invention...Invention...Invention
Invention
..........................Formula Formula A Formula B Formula C
Formula D
-----------------------------mol/L mol/L mol/L mol/L
mol/L
hydroxylamine sulfate ---0.012 --- 0.018 ---- 0.018 ---- 0.018
0.018
diethylenetriamine ------- 0.005 --- 0.005 ---- 0.005 ----0.005
0.005
pentaacetic acid, sodium
salt
potassium iodide (×10-6) --7.229 ---1.205 ----1.205----------
1.205 1.205
poly (vinylpyrrolidone)-------------3.000 ----3.000 -------3.000
3.000
(g/L)
sodium bromide----------0.013 -----0.0078 ---0.0243 ---- 0.0466
0.0661
potassium carbonate-----0.271------0.289 -----0.289-----0.289
0.289
4-(N-Ethyl-N-2- -------0.015------0.051-------0.051---- 0.051
0.051
hydroxyethyl)-2-
methylphenylenediamine
sulfate
potassium sulfite ----------------- ---0.084------0.084----0.084
0.084
sodium sulfite-----------0.032
adjusted pH-------------10.07--------10.48------10.48-----10.48
10.48


Okay, here are the concentrations converted via molecular weight to Grams /Litre, now this formulation looks quite familiar.


Water 800.0 mL


Diethylenetriaminepentaacetic acid pentasodium salt (DTPA 5-Na, solid) 2.51 g
Potassium Carbonate, anhydrous 37.45g
Sodium sulfite, anhydrous 4.03 g
Sodium Bromide 1.34 g
Potassium Iodide 1.20 mg
Hydroxylamine sulfate 1.97g
CD-4 4.38 g
Water to make 1.0 L
pH @ 24°C 10.07

Very important seems to be the sentence "the pH of the one litre solution was adjusted to the aim pH with potassium hydroxide or sulfuric acid at 24°C".
These receipt are NOT MEANT to reach the ph of aim without exert influence, and probably this is true for other public receipts too! This will be an explanation for the enhanced contrast Pete, RPC and myself noticed. Whatever you do with the various (similar) homebrew's, watch out for the ph, it is supposed to be around 10.05 and has to forced in this direction !!!




Samples of each of these monochrome coatings were imagewise exposed through a graduated density test object and processed at 100° F. according to a modified C-41 process using the following sequence of processing solutions: development, 3 min 15 sec in KODAK FLEXICOLOR Developer (Developer solution D-1); stop bath, 30 sec; bleach, 3 min in KODAK FLEXICOLOR Bleach II; wash, 3 min; fix, 4 min in KODAK FLEXICOLOR Fix; wash, 3 min; and stabilizer, 30 sec in KODAK PHOTOFLO solution. Developer solution D-1 is described below in Table VII
TABLE VII
______________________________________
Anhydrous potassium carbonate 34.30 g
Anhydrous sodium sulfite 0.38 g
Potassium bicarbonate 2.32 g
Potassium iodide 1.20 mg
Sodium metabisulfite 2.78 g
Sodium bromide 1.31 g
Diethylaminetriaminepentaacetic acid 8.43 g
pentasodium salt (40% solution) (KODAK Anti-calcium No. 8)
Hydroxylamine sulfate (HAS) 2.41 g
KODAK Color Developing Agent CD-4 4.52 g
2-((4-amino-3-methylphenyl)ethylamino)- ethanol sulfate (1:1 salt)
Water to make 1 liter, pH 10.0 ± 0.05 80° F.



Here a Fuji Komposition…

The composition of each processing solution was as follows, respectively: (Color-developer) Tank Solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 1.0 1.2
1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2
Sodium sulfite 4.0 4.8
Potassium carbonate 30.0 39.0
Potassium bromide 1.4 0.3
Potassium iodide 1.5 mg -
Hydroxylamine sulfate 2.0 3.0
4-(N-ethyl-N-β-hydroxyethylamino-)-2-methylani line sulfonate 4.5 6.0
Water to make 1,000 ml 1,000 ml
pH 10.05 10.15
 

stefan4u

Member
Joined
Aug 27, 2006
Messages
167
Format
35mm
back on earth... This C-41 developer works !!

Hope you all can forgive me, posting again and again...

Just came back after developing two more Agfa Vista 100 with "the new Formular", and boys, what a lovely grey/colorscale...

The film developes well, slighly softer, looks very balanced but still good saturated. In general the results are similar to the formular Yesterday, just better !

My proposition is this, if you working with normal consumer film and maybe tend to have difficulties with contrast take the reciept below. If you wanna have it a bit more punchy, add one gramm (maybe 2, try it...) less Sodium Bisarbonate to the composition in order to increase the ph a bit.

Tab water 800 ml
Calgon 2.5g
Potassium carbonate (anhy) 37 g
Sodium Bisarbonate 7 g
Sodium sulfite (anhy) 4.3g
Sodium bromide 1.3 g
Potassium iodide 1.4 mg
Hydroxylaminsulfate 2.4 g
CD-4 4.5 g

ph 10.00 (tolerance ?)

Processing at 38 °C Jobo CPP Speed 4 (~50 RPM)

2x warm Prewash for proper tempering (IMO inportant, but opinions vary about this )
3.15 min dev.
1 min stop
1 min rinse
8 min bleach
4 min rinse
4 min Fix1
4 min Fix2
10 min wash, then 1 min stabilizer


Still out of time for printing, spring just began and it's really hard to spend so much time in the "underground", sorry...

Regards from Germany,
Stefan
 
Cookies are required to use this site. You must accept them to continue using the site. Learn more…