Archived posting to the Leica Users Group, 2007/07/26

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Subject: [Leica] Long Xtol rant -- digerati may wish to delete
From: lug at steveunsworth.co.uk (Steve Unsworth)
Date: Thu Jul 26 11:50:14 2007

Yup, I've developed a few hundred rolls of Tri-X in Xtol 1:3. It works very
well.

Other films have a problem at this dilution, Tmax 100 in particular. I found
this out the hard way <grin>

Steve



On 25/7/07 23:00, "pmcc" <pmcc_2000@yahoo.com> wrote:

> Len,
> 
> Thanks!  I've been using the datasheets in the film
> boxes or on the chemistry bags, which tend to be
> limited to plain vanilla combos.  This appropriately
> named little chart seems to be just what I was looking
> for.
> 
> I'd like to know if anyone has had hands-on experience
> with 1:3 Xtol and common films such as Tri-X.
> 
> Now I'm in really deep. ;-)
> 
> Hazmat Pete (cough),
> SF, CA
> 
> --- Leonard Taupier <len-1@comcast.net> wrote:
> 
>> 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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>> for
>>>> more information
>>>> 
>>> 
>>> 
>>> 
>>> 
>>> 
>> 
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Replies: Reply from mark at rabinergroup.com (Mark Rabiner) ([Leica] Long Xtol rant -- digerati may wish to delete)
In reply to: Message from pmcc_2000 at yahoo.com (pmcc) ([Leica] Long Xtol rant -- digerati may wish to delete)