Archived posting to the Leica Users Group, 2007/07/25

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Subject: [Leica] Long Xtol rant
From: len-1 at comcast.net (Leonard Taupier)
Date: Wed Jul 25 14:39:30 2007
References: <716410.72587.qm@web56306.mail.re3.yahoo.com>

Peter,

Try this.

http://www.digitaltruth.com/devchart.html

I find the information is this chart is very good. It pretty much  
covers every film with every developer made.

Len





On Jul 25, 2007, at 5:08 PM, pmcc wrote:

> Many thanks Marty.  Your posting was interesting and
> helpful even to a non-chemical DIY'er such as myself.
> You've inspired me to get out the hazmat gear, roll
> down my sleeves and go to work.
>
> Next question:  can you point to or have you derived
> dev'pt times for Xtol at various dilutions -- 1:2 and
> most particularly l:3 -- for various common films?
> Higher dilutions don't appear on the product data
> sheet.  I've seen frequent discussions of the manifold
> benefits of higher dilution, and it would be great to
> have specifics for starting points.
>
> Peter.
> SF, CA
>
> P.S.  Hey, this is a non-digital thread -- feels like
> Y2K.
>
>
>> Since there is a bit of interest in chemical
>> developers after the LuG being almost completely
>> digital, I thought I'd post this.  I wrote it for a
>> newsletter a few of us here in Adelaide write and
>> send around to each other.  A lot of this is based
>> on discussions I've had with LuGer John Black.  The
>> formula for JB9 is entirely his - and it's elegent
>> and effective.  My own experiments in pH were
>> initiated after discussions with him and follow an
>> approach I developed from our discussions.
>>
>> What follows is a long rant about Kodak Xtol.
>>
>> Xtol is probably the best commercially available
>> developer for 35mm film.  Why is it so good?  It is
>> an ascorbate developer.  Ascorbates are effective
>> developers of silver? with about the same
>> efficacy at developing as hydroquinone, but the
>> development by-products of ascorbates are acidic and
>> act as development inhibitors.  These by-products
>> inhibit development proportionally to exposure (i.e.
>> they inhibit more in dense areas of the negative and
>> less in thinner areas).  All ascorbate developers
>> are, therefore, compensating developers with high
>> acutance, dependant to some extent on the other
>> components of the developer.  This is good for
>> tonality.  ?Compensation? is claimed for
>> many developers, but the ascorbate ones are among
>> only a few where it has any real scientific basis or
>> measureable effect.  Kodak?s chemists were
>> clever with Xtol in several ways beyond using an
>> ascorbate as the primary developing agent.  They
>> added enough sulfite that the stock!
>>   solution can be used as a grain-reducing developer
>> and as a replenishment developer where the only
>> replenisher needed is more Xtol. This sulfite
>> concentration, combined with high activity, allows
>> the developer to be used at dilutions of up to 1+1,
>> 1+3 or 1+5 depending on the film being developed.
>> This results in enhanced edge effects; it maximises
>> direct development and minimises solution or
>> physical development (called ?solvent
>> action?), increasing sharpness.  They also
>> used dimezone-S as the superadditive co-developer.
>> Dimezone-S is a potent developer at low
>> concentrations (it is, after all, similar to
>> phenidone) but is easier to dissolve in water than
>> phenidone and is less likely to oxidise once in
>> solution.  Properly mixed Xtol is actually quite
>> stable ? not Rodinal or PMK Pyro stock stable,
>> but very good.
>>
>> So it?s sharp and has great tonality.  Super.
>> Unfortunately, Xtol got a reputation early on for
>> both failing catastrophically and leaving odd
>> artefacts in negatives.  So, what gives?  Is it
>> great or does it suck?
>>
>> As usual, the answer to both is yes. Xtol fails for
>> two reasons.  Ascorbates are strong antioxidants and
>> will scavenge oxygen from solution.  Unfortunately
>> the oxidation products of ascorbates do not develop
>> latent silver images and do not present a colour
>> change in solution.  This explains what we already
>> know ? Xtol can die without warning. The other
>> reason Xtol can fail is that the oxidation of
>> ascorbates is catalysed by metal ions in water
>> ? particularly divalent cations (they are the
>> 2+ ones).  These include calcium and iron, the
>> former common in ?photo grade? chemicals
>> and the latter common in tapwater.  Odd donut-shaped
>> dots on negatives developed in Xtol are seen
>> sometimes even by people who are careful about air
>> and mixing.  I suspect this occurs when impure
>> dilution water is used and a little particle of iron
>> or some other substance ends up onthe film,
>> oxidising the ascorbate (and therefore inhibiting
>> development) forsome distance around.  I!
>>  t?s not likely tobe in the original mix
>> water, since impurities here would probably kill the
>> developer, unless it was mixed and then used almost
>> right away.
>>
>> ?Sudden Xtol death syndrome? can be
>> fixed by keeping bottles completely full and in the
>> dark; ?Xtol spots? can be avoided by
>> always using distilled or deionised and filtered
>> water to mix and dilute Xtol.  Whether you think
>> that is worth the bother is up to you.  I think it
>> is.
>>
>> Can you mix your own Xtol? Sort-of.  Mark Rabiner
>> sent aroundthe basic formula from the patent
>> (that?s not an MSDS ? an MSDS is the
>> ?material safety data sheet? and the one
>> for Xtol can be accessed by going here:
>>
> http://www.kodak.com/eknec/PageQuerier.jhtml?pq- 
> path=2879/4648&CID=go&idhbx=msds&pq-locale=en_US&_requestid=2627
>> and typing Xtol in the product name box) which comes
>> from the patent.  There are, however, indications
>> from the physical behaviour of Xtol that what Kodak
>> sells is somewhat different.  Xtol stock solutions
>> have a pH of 8.2 (what Kodak says); diluted to 1+3
>> the pH rises to 8.3-8.4.  If you make the patent
>> version, the startings olution is 8.35-8.4 and it
>> stays fairly stable with dilution.  Those pH
>> differences might not seem like alot, but
>> they?re important.  The version from the
>> patent is also about 30% less active. What does this
>> tell us?  The?weakly alkaline?
>> (Kodak?s terminology) pH must come from a
>> buffe!
>>  r, rather than just from metaborate and
>> metabisulfite. I suspect a small amount of boric
>> acid (i.e. a metaborate-boric acidbuffer) ? it
>> makes the most sense chemically; I also have some
>> supporting data frommass spectroscopy analysis of
>> commercial Xtol. The EDTA is also probably not
>> enough on its own to sequester the divalent cation
>> concentrations that Xtol can handle ? I did
>> this by adding known concentrations of dilute cation
>> solutions to Xtol and self-made analogues and
>> comparing them.
>>
>> So, what can you really do? Buy Xtol, of course.
>> But if you really want to make a substitute, the
>> following are options:
>>
>> Patrick Gainer?s PC-TEA
>> 9 grams ascorbic acid
>> .25 grams phenidone
>> 100ml triethanolamine (TEA)
>> Heat the TEA in a pyrex container in themicrowave
>> for 30 sec.-1 minute, and add the ascorbic acid.
>> When it isdissolved, add the phenidone.  Be careful,
>> because the TEA will get VERY hot.
>>
>> Dilute the concentrate 1:50 for use.
>>
>> PC-TEA is very good and if you have access to cheap
>> TEA as those in the US do through
>> www.chemistrystore.com it costs hardly anything.
>> It?s grainier than Xtol, however, and
>> doesn?t change its characteristics when
>> diluted more.  It works because it is very alkaline,
>> which I think contributes to the grain
>> characteristics of films developed in it.  Many
>> other ascorbate formulae have these flaws ?
>> the absence of the weakly alkaline pH, low sulfite
>> concentration (but withsome sulfite still present)
>> and the increase in activity with dilution are what
>> make Xtol extraordinary.
>>
>> John Black?s JB9 is functionally the same as
>> Xtol, but you mix it yourself.
>>
>> The developer is made from 3 liquid concentrates
>> that are stable for at least 6 months, perhaps a
>> year (stability testing underway).  Store the
>> solutions in glass bottles, tightly capped. The
>> solution A should be store in the dark (a closed
>> cabinet is fine) or in an amber bottle.
>>
>> Solution A:  (Phenidone, ascorbic acid)
>>
>> Phenidone               1.25 gm
>> Ascorbicacid-           50.00 gm
>> Ethyelene or
>> propylene glycol
>> or dry methanol-        600 ml
>>
>> Warm up solvent to hot tap water temp before
>> dissolvingcomponents. They will dissolve at about
>> 100-125F. Dissolve ascorbic acid first.
>>
>> Solution B:  TBE (Tris-borate-EDTA) Sigma cat# T3913
>> One 1L dry pkg dissolved in 1L DI water
>> Other buffer concentrates may be substituted if made
>> up to about half molar at a pH of about 8.3.  Boric
>> acid-metaborate(BA/Kodalk) would be fine, you may
>> have to fiddle a bit to get the right pH.
>>
>> Solution C:  Saturated Na Sulfite solution
>> Na Sulfite(anhydrous)-           180 gm
>> Distilled water-                 600 ml
>>
>> Stir vigorously for about 30 min.  Temp will rise a
>> bit and it will almost all go into solution.  Let
>> stand overnight to equilibrate (some will
>> crystallize out).  Use after that.
>>
>> JB9 developer:
>> SolA:                     10 ml
>> SolB:                     50 ml
>> Sol C:                    20 ml
>> Distilled H2O             Fill to 250 ml
>>
>> Add sol B and C to water first, mix and then A
>> (protects phenidonefrom oxygen in water).  This is
>> enough todevelop 1 roll of 35mm film.  Scale up as
>> necessary.  Works best as a 1 shot developer at 68F,
>> with moderate agitation.  I use 13 min for Tri-X.
>>
>> I?ve used the tris and metaborate/boric acid
>> versions of JB9 and they are functionally identical
>> to Xtol. You can modify the sulfite concentration as
>> you like.  One of the best things about JB9 from my
>> perspective is that you can mix the developing
>> agents to the same concentration as Xtol stock, but
>> keep the same sulfite as Xtol 1+3 (or any other
>> favoured dilution).  This is great for films like
>> TMX and Acros that run out of developer in Xtol 1+3,
>> or for pushing TMZ.
>>
>> Of course the other option is to mix the patent
>> formula Xtol and addboric acid until the pH of the
>> stock is 8.2, but you may also run into problems
>> with 'photo grade' chemicals.  I really don't think
>> the EDTA alone is enough to chelate ions out of the
>> chemicals or water.
>>
>> Also look at US patents # s 3658527, 5376510,
>> 5503965, 5738979, 6110655, 6489090, 6673528 and
>> 6686135 in addition to the Xtol patent 5756271.
>>
>> I hope this explains a few things and is
>> interesting.
>>
>> Marty
>>
>>
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>
>
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