Tuesday, May 24, 2011

TCB - Tylenol, Vitamin C and Borax - mixed and ready to go

I finalized my mix, part A and part B, and are ready to go, I have one film ready to be developed and several in camera, ready to meet their destiny.

I took the opportunity to measure pH as I went along and mixed the ingredients, hopefully this can give Michael and me a better insight and what actions to take, as soon as (if) I meet with failure.
I changed a few bits as I went along, but only practical things that should not matte over all.

here goes:

Part A

Started with 75 ml room temperature water.
Added 2 gram Sodium bicarbonate (Natron)  .......................  pH  8.0
Added 6 gram Ascorbic acid (fizzled, slight green mix) ......  pH 4.4
Added 4 gram Tylenol (paracetamol, Paracet) crushed  .......   no measurement
Added water to 100 ml .........................................................   no measurement
Added  4 gram Lye (Caustic soda, NaOH) ...........................  pH 11.9

Let this stand for 72 hours, there was slurry on the bottom from tylenol-tablet ingredients, this did not dissolve unlike my SALS13 experiment (stronger lye concentration, more fluid....), and the color remained a turbid yellow, unlike my SALS13 experiment where the tylenol mix turned wine-red and even dark brown red. I take this as a sign that the sodium bicarbonate and ascorbic acid worked in unison to protect the tylenol from oxidizing entirely and be spent in soliution before being used at all.

The 100ml tylenol mix was the used to make Part A :

Tylenol mix   100ml ........................................ pH 11.9
Water to 425ml   
Added ascorbic acid   10 gram ....................... pH  8.5
Added Borax  20 gram  .................................. 
Water to 500 ml   ............................................ pH 8.8


part A ios now ready for use with a pH around 8.8


Part B :

Water temepered    600 ml
Added 15 ml KBr 10% mix, for 1,5 gram
Added Borax 30 gram this was har to dissolve, so I heated in a water bath.
Added water to 1000 ml stirred well and heated  ..............pH 9.3

part B is now ready for use after temperature comes down

I have two parts, pH 8.8 and 9.3 respectively. I expect the resulting pH will be around pH 9.1 after mixing.

I will mix up a solution of 1 part A and 2 parts B and store it in a bottle, planning to use that like ordinary, undiluted D76 for at least 6 films

The remainder will first be mixed 1 part a and 2 parts B and used as a single use developer, I will try that first to get a feel for this.

Planning to start with a Kodak Gold 200, exposed 1, -1 and + 1 for 12 images worth on a 36 exp film, and compare this to the similarly exposed Gold 200 that I did last night in Cafenol CM, the 5 film in a brew of 500 ml.

The objective here is both to find out if this developer is suited to repeated use, ore one-shot use, and wether it gives full box speed.  Lots of work ahead.  (need to find time after a local football match to upload pictures from the last 5 films developed in the cafenol-brew, but football gets the priority - a good source for more pictures!)

Monday, May 23, 2011

Cafenol as a staining developer?

A lot has been written about the staining qualities of cafenol. Like much of what has been written some of it is true, some is exaggerated and some is plain BS.

A while back a gentleman asked if Cafenol would stain his developing tanks. This was kind of a surprise, and the answers he got was more of a surprise.  I have watched out for stains from Cafenol since day one, and this is my take on the situation.

- Cafenol contains massive amounts of washing soda. In itself this is a very strong cleaning agent, back in the day this was what my grandmother used to get rid of nasty stuff from cleaning out fish - she came from a fishing village on a small island. Only stronger stuff she ever used was lye - but then only in emergencies!

Since we have concentrated soda in the mix, borth organic and inorganict matter will be dissolved and lifted into solution, given time and repeated exposure.

The relative small amount of coffe, containing caffeine and caffeic acid, among a mix off other stuff is said to have staining abilities.  So will the coffe stain the plastics in developing tanks, or will the soda negate this?

The coffee component will stain photograpic film - to some degree. I have noticed this effect stronger in color films than in B&W films (which is what can be expected), Cafenol will develop most C41 color films jkust like most B&W films.

Recent experiments with Fomapan and Lucky 100 B&W films in Cafenol C-H did not show staining to any degree, straight scans came out nearli pitch dark in the shadows and clear in the hight-lights, the same for TriX, even if my TriX was more than 35 years old and did show considerable chemical fog, it scanned perfectly, however.

And older test with coffe & soda alone, sans vitamine C did show markedly higher stain levels - this probably was connected with the fact that development times had to be increased (doubled) and concentration of the coffe doubled or tripled, because coffe is such a weak developing agent on its own...

Staining in the film works differently from staining of plastics: coffe gets sucked up into the gelatine layer and stains whats inside THERE, personally I think this has to do whith gelatine, more than anything else.

When it comes to developing tanks, few pause and think through what is at hand here.

Developing tanks are made from what is to be stain-free plastics.  However we all know and have seen old spirals blackened from developer....  So what exactly causes that?

There are very few modern-day staining developers, in earlier days, and among a few enthisiasts, amidol-based developers are noted for staining qualities.  Cafenol is nothing like that.

Besides more than 90% of the stains seen on developing tanks stems from quite another mechanism than the developer :

The stains comes from the fixer. To the casual observer the fixer does one thing: dissolves unexposed, undeveloped silver-halides.  Few knows that the exact mechanism that this takes plave varies wildly with both concentration and the dissolved silver in the fixer solution.

Again I have to direct interested partied to my german-language tome :
"Wissenshaftliche und Agewante photographie" von Edwin Mutter, Springer Verlag 1955, page 181.

Fixation takes place in four discrete steps, the first two leaves insolulble silver-sulphur complexes in solution, but as long as the silver concentration is low, and the fresh hypo-concentration is high, the fixing process runs to completion for two more steps and leaves soluble silver salts in solution.  This is what normally takes place as long as the fixer is not exhausted.

If we work with exhasuted fixer, this process doesn not run completely or very slowly, leaving us with fixer stains.

This is what we find in developing tanks, its got nothing to do with the developer.

Alswo sloppy procedures, to little washing and not properly cleaning the tanks will give rise to such stains, with a little bit different mechanism : if we leave fixer on tank parts, they will of course dry out.  As the fix droplets dries, concentration changes in them, if there's enough silver in there, the silver concentration will outrun the hypo concentration, and silver-sulphur complexes will fall out and stain the surface.

This can be seen as brown fingerprints, where spirals, lids etc have been handled with fixer-stained fingers.

IF WE START USING CAFENOL IN STAINED TANKS LIKE THIS, CAFENOL WILL DISSOLVE THE SILVER-SULPHUR HALIDES, SLOWLY WITH TIME AND REMOVE THEM!

THis was brought home to me by 3 Jobo 1000 tanks I got used on €-bight. Theu all came well used, with one or two stained spirals and 3 stained lids. The word JOBO was written in black, from silver fixer stains.

Now after continued use as cafenol-tanks for more than a year, and well used as that might I add, all of the brown-black stains on the lidsa have disappeared, caffenol has cleaned them, I never tried to do anything special, just used them as normal and washed meticously as I always do with films.

The spirals are much cleared too, but difference in the plastic used (more transparent and brittle than the flexible lids) probably makes for this to take a considerable time to clear.

Finishing off : You can safely develop all kind of films in Cafenol, the tanks are designed for it, and high concentration of a strong detergent in the deeveloper, washing soda will clear smudges and stains from previous use.

Good luck.

Tuesday, May 17, 2011

TCB - Tylenol, Vitamin C and Borax revamped.

Michel published a version of this, early on when he joined the team here.

I was most interested, but had no access to borax at the time

(my secret stash of borax, utilized when I took class with one of the country's top blacksmiths, learning how to make knife-blades in the 1000 year old tradition from viking ages simply had vanished. Borax is used in blade-smithing to protect the steel and iron from oxygen and faciliate removal of scales, we vikings make blades in a 3-layer process, fuzing two layers of iron to one layer of hardening steel in the middle, giving rize to a hard, sharp edge, protected by two layers of nonharedned iron, som the blade is flexible and durable). 

I finally got hold of a 1000 gram box, and is ready to give this a spin, while I'm waithing for my box of phenidone to show up.

Looking over Michel's recipe, I still find it too hard to understandt to be popular.  I feel we need to make it simpler, while keeping to good bits.

I ahve a set of objerctives here :

  • I want to get rid of coffe entirely, as its the least understood and controllabel ingredient.
  • I want to use as many easy-to-get ingredients as possible, since everyone can seet that commercial suppliers are fast vinishing.
  • I want to refine MM's recipe, so that anyone can follow this easily.

Discussing the original recipe.

Have a look at MM's instalment back in march, "tylenol and ascorbate - it works!"
There he gives his formula and explanation. My gut-feeling at the time was that this was too imnvolved, too hard to do, and too hard to copy, even for mee, with a chemistry background and many years of labor in a laboratory in my earlier days.

So I set myself the task to refine it, while keeping all the good parts, I still think this has great potential, even if it was placed on the backburner at the time by other and more pressing stuff.

Hopefully Michael will take part in this and offer his advice,  currently I've seen few if any with a deeper understanding of Patric Gainer's writings....

Looing at the original recipe for TCB a few things strikes me :
  • The idea of mixing ascorbic acid with sodium bicarbonate FIRST, then adding tylenol, to protect the tylenol from unwanted oxidation is very good, I thnk that was what sunk my SALS project.
  • The idea of using a little NaOH (0.2M) to convert the Tylenol is splendid.
  • ph is lowered at a later stage by adding massive amounts of Borax, this gives longer, more controllable development times: good idea.

However there are flies in the ointment :

In the description unnecessary uncertainity rises because we talk of several things in a disorderly fashion :
  • we talk about borax saturate solution
  • we talk about tylenol solution
  • we talk about part A, part B
  • what we need is a simple, easy to follow recipe, much like when my grandma baked bread, and passed her secrets on to my mother, my wife and ultimately me....
I will try to correct this and offer a simple, easy to follow recipe, with development times advice and later examples of work done with this.  The rules are simple :

  • the chemicals shall be easy to get, everday chemicals, save for one, borax.
  • the result will be two simple storage bottles, the chemicals used in a mix-before-use and discard fashion.
  • we use realively little of the expensive chemicals, so this will be a cheap developer to use
  • we offer an easy explanation on how to do this, so that anyone can do it

Recipes

We start by mixing part A, then mix part B. Part A needs a little time to finish, in involves a few chemical reactions to take place, this needs time to be controllable and reliable. Therefore we start with part A a few days before we need it. Part B can be mixed the day its needed.

We offer a balanced mix, so that when part A is spent, so is part B, simple and easy to understand.
The objective of part B is mainly to dilute part A, to control fogging and make the developer controllable as far as times goes. A short development time will mean that differences in pour times, might give uneven results from time to time. 15 seconds in and 15 seconds out means more if the time is 5 minutes vs 15 minutes..... if one has a very old develoing tank, like me, I have many and uses many, in-out times easily can reach close to a minute altogether.

Part A is mixed with part B: 1 part A, 2 parts B.

I have lowered the initial concentration for longer development times, from Michels 7 minutes with TriX to about 10 - 11 minutes with TriX, and 14 - 16 minutes with C41 films.

Caution!  These recipes involves working with lye, NaOH at a strong concentration.

Lye is a very dangerous substance, be extremely cautios using this, wear safety glasses, the concentration will initially be 1 molar, which will take out the eyesight in minutes, if one is unlucky.  Also when mixing out lye add just alittle at a time, wix well, and most importantly stand thw mixing bottle in a container of as cold water as possible and have more cooling water AT HAND. If this boils, and fumes are expelled, leave the area immediately, this is very toxic, and make sure the area is ventilated before returning, and discard the boiled stuff after diluting it at least 1:10 with cold water.

Part A

Water     ........................              75 ml
Sodium bicarbonate   .............       2 gram
Ascorbic Acid      ...................       6 gram
Tylenol tablets      tbl @500 mg    4 gram
Water     .....................       fill to  100 ml
NaOH, lye pearls  ................         4 gram

Add the ingredients in the exact order given - there will be two distict chemical reactions, give time for them to take place.

Sodium bicarbonate should dissolve easily, ascrobic acid bubbles and gives microbubbles in solution, let this clear.
Tylenol tablets need to be crushed and dissolved, it reacts with the lye thats added after, and will give a vine-red solution, the idea here is that ascorbic acid protects the tylenol, so its not all oxidised by air (ascorbates will continue to protect the tylenol in solution).

For this reaction to complete, this solution needs to stand in a well closed bottle, as little air in it as possible, preferably in a cool, dark place, for 48 to 72 hours.  After this the part A is finished with further additives given below.

Part A  finished :

Preliminary mix .........................  100 ml
Water ..........................    to         300 ml
Ascorbic acid    ........................    10 gram
Borax      .................................    20 gram
Water ............................   to         500 ml

Part A is now finished and can be used as soon as it is tempered to 20 centigrade.

More ascorbic acid was added to give a 1:4 ratio between ascorbate and tylenol, give time for this to react - both the lye and the borax will convert the ascorbic acid. Borax dissolves slowly and is close to saturation here, if the mix temeperature is too low it might not all dissolve.

This the finished Part A, ready to be diluted for use with Part B.

Part B

Water .....................................   500 ml
Potassium bromide (KBr)    .....    1.5 gram
Borax   ...................................    20 gram
Water    ........................... to     1000 ml

The potassium bromide control chemical fogging, less will give a more active developler and shorter development times, but possibly fog. more works the opposite.
Borax con trol the pH in the mix, countering the lye in part A, keeping fogging at bay, controlling time.

Part B is finished and can be used at 20 centigrade.


  In use.

In use :

Single-shot use. This is what Michael suggested, as I understand him (!) but since concentration is a bit lower, we must adjust the times.

Mix 1 part A  with 2 parts B  use one time, discard the used developer.

This mixture will be enough for 1,5 litre developer, or enough for 5 films at 300 ml per tank, constant development times.  Since we use 16 grams of vitamine C and 4 grams of Tylenol, divide that with 5 and ascertain we are (still) frugal!

Times :  (still experimental, based on Micheals suggestions and plain guesstimates)
 
B/W film 100 - 200 ISO  11 - 13 minutes at 20 centigrade
B/W film  400 ISO and above   15 - 18 minutes at 20 centigrade
C41 colorfilms, developed to B/W   15 - 16 minutes at 20 centigrade

All times will be subject to cange with temperature.
All times based on staandard agitation regime, make sure the film is entirely covered by fluid!
All times based on no form of pre-wetting the film, I do NOT advocate pre-wetting of films!

Agitation regime:
Constant agitation (slow turns or slow rotation) fo theirs 3t 60 seonds.
Thereafter 3 to 4 slow turns once every minute for the duration of time.

I have no advice on stand development.

To be researched :

These solutions should keep well. One of the most interesting bits is to find out wether this developer can be mixed all up and stored like ordinary D76.

If that is possible, it could be used like D76, to develop ca 10 - 12 films from one bottle, its easy to find out, comparing with Cofenol CCM, that we  throw out ca 50% of the ascorbates here.....

If that is possible, if this developer will keep in a closed bottle, semi- or half-used like D76, we simly adjust developing times like this:

1. film 12 minutes
2. film 12 x 1.06 = 12:45 min
3 film  12 x 1.12 = 13:30 min

i.e. keep adding 6% time from start-time per film developed.


To takew this one notch further, compared to D76, 1:1 development.
D76 can be used as a one-shot developer, by diluting 1:1 with water, doubling development times.

If this developer keeps ready-mixed in a bottle, diluted 1:1 with double dev. times as a startpoint should be investigated.

WQhile waiting for my phenidone, this waht I'll be looking into.


Saturday, May 7, 2011

Mintol developer: Introduction

Mintol developer: Introduction: "Introduce a new Pyro-developer, which contains Menthol as Phenol. Pyro-developer has been used in long history as much long as conventiona..."

Sunday, May 1, 2011

PCM + C-41 ... Good Results

As I mentioned in a previous post, I'm trying to standardize on using PCM one-shot developer now.  This developer works very well for stand development due to the buffered alkali and potassium bromide.  My results so far using both standard and stand development have been very good.  What's been bugging me is my stash of Kodak Gold 200 in the freezer.  It's expired and I don't feel like spending on colour development, I have developed it in the past with Rodinal, Caffenol-C, and PCC, but I wanted to see if I could make it work with my "new" standard developer.  Based on my past experience developing C-41 film in B&W chemicals I figured that sticking with stand development was a good bet.  Here is what I got from a test today (it's raining outside so we're back in the messy basement ... sorry):

Kodak Gold 200 @ EI 400, PCM full stand for 1h
As in my previous posts, this image is an un-processed straight scan re-sized and converted to JPEG.  I get a full histogram, good highlights, good contrast, and a +1 push.  There's more grain than proper B&W film but this is my best so far with C-41 processed in B&W chems. It looks like I may finally be able to use my stash with good results.

MM
--