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Photo Forum / Film Photography / Darkroom / June 2004

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pure ammonium thiosulfate fixer

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Travis C. Porco - 19 Apr 2004 21:42 GMT
Dear Readers--

I have a question:
is there anything wrong with the use of pure ammonium thiosulfate as a
fixer for pyro-developed film? (I use 35mm Tri-X mostly).  I have some of the
"60% ammonium thiosulfate" made by Formulary.

Is it possible to use borax instead of sodium metaborate in mixing a
fixer?  How much?  Anchell & Troop list a recipe with sodium metaborate,
but not borax.

Thanks kindly.
Jorge Omar - 19 Apr 2004 22:30 GMT
AFAIK you can just replace metaborate with borax (same quantity) in a
fixer.

Jorge

> Dear Readers--
>
[quoted text clipped - 8 lines]
>
> Thanks kindly.
Travis C. Porco - 28 Jun 2004 19:01 GMT
Dear readers--a new question:

I got three rolls of old Panatomic X.  With film so old (~70s) I expect
severe fogging; the film was supposedly stored in a cool closet, but not
refrigerated.  Any suggestions on how to best process it?  The box says
shoot at EI of 32, and use 5 minutes in D-76.  Should I treat it any
differently because it is so old? BTW I'm not shooting anything critical
with it; it's just for the fun of it.

--travis

Also, thanks again everyone for the fixer suggestions:

>AFAIK you can just replace metaborate with borax (same quantity) in a
>fixer.
[quoted text clipped - 13 lines]
>>
>> Thanks kindly.
Ken Nadvornick - 28 Jun 2004 20:11 GMT
> I got three rolls of old Panatomic X.  With film so old (~70s) I expect
> severe fogging; the film was supposedly stored in a cool closet, but not
> refrigerated.  Any suggestions on how to best process it?  The box says
> shoot at EI of 32, and use 5 minutes in D-76.  Should I treat it any
> differently because it is so old? BTW I'm not shooting anything critical
> with it; it's just for the fun of it.

Hi Travis,

Seems that I also have some old Panatomic-X.  It's a nearly complete
100-foot (30.48-meter) bulk roll of 35mm perforated, stamped "Develop
before: Sep 1963."

While I fully intend to bulk load a few frames and test it just for fun, I,
too, will be interested to read any replies to your inquiry.

Good luck with your rolls.

Ken
Gary Beasley - 28 Jun 2004 21:29 GMT
>> I got three rolls of old Panatomic X.  With film so old (~70s) I expect
>> severe fogging; the film was supposedly stored in a cool closet, but not
[quoted text clipped - 13 lines]
>
>Good luck with your rolls.

Slower emulsions are much more durable than the high speed stuff, I'd
try a roll at the recommended times just to see. You may have some
perfectly good film or need just a little benzotriazole to damp the
fogging.
>Ken
Mark A - 28 Jun 2004 21:22 GMT
> Dear readers--a new question:
>
[quoted text clipped - 8 lines]
>
> Also, thanks again everyone for the fixer suggestions:

If you have a new question, start a new post, do not reply to an old one.

I recently developed some Panatomic-X that was exposed 20 years ago, and the
image lost about 2 stops of exposure. Additional development increases the
middle and high values, but does nothing for the shadows. So I would give it
some extra exposure.
Richard Knoppow - 29 Jun 2004 01:04 GMT
> Dear readers--a new question:
>
[quoted text clipped - 6 lines]
>
> --travis

   I would test a clip of the film. The emulsion is
probably pretty stable but heat during storage is the enemy.
One of the main causes of fog in old film is a continuation
of the processes known as ripening. Modern films (I mean
anything made for the last 50 years) have substances added
to the emulsion to eliminate or at least substantially
reduce the amount of after ripening and thus extend the
shelf life of the film. Refrigeration also tends to slow
down or stop this process. The other cause of fogging is the
accumulation of exposure from cosmic rays. This is speed
dependant so does not affect slow films much.
   Make some bracked test exposures and develop _normally_.
Do NOT use an anti-fog agent. If the film is only slightly
fogged the effect will be a loss of speed, the images will
print well. Benzotriazole is the best anti-fog for old film
but the effect is still a loss of speed, the difference is
that the shadows will be clear with the anti-fog and have an
overall fog without it. There is little or no difference in
the resulting printed images providing enough exposure has
been given.

   You may find the film performs normally with no special
treatment.

> Also, thanks again everyone for the fixer suggestions:
>
[quoted text clipped - 15 lines]
> >>
> >> Thanks kindly.

  Neural fixing baths work as well as alkaline baths. A
neutral or slightly alkaline bath results when either Sodium
or Ammonium thiosufate is used with a small amount of sodium
sulfite. The use of sulfite in a fixing bath will insure
against overall stain from developer reaction products from
carried over developer. For either salt about 5 to 10
grams/liter of working solution is enough.

Signature

---
Richard Knoppow
Los Angeles, CA, USA
dickburk@ix.netcom.com

Jorge Omar - 29 Jun 2004 02:33 GMT
I've found that by increasing the sulfite content of an alkali fixer
(could it be neutral?) to 30g/liter, the pinkish base of Kodak films is
completelly gone.
It is carried mostly by first wash (Ilford method).

Jorge

"Richard Knoppow" <dickburk@ix.netcom.com> wrote in news:2kbq0qFirpsU1
@uni-berlin.de:

>    Neural fixing baths work as well as alkaline baths. A
> neutral or slightly alkaline bath results when either Sodium
[quoted text clipped - 3 lines]
> carried over developer. For either salt about 5 to 10
> grams/liter of working solution is enough.
Dan Quinn - 29 Jun 2004 10:08 GMT
RE: Jorge Omar <jorgeomar@ieg.com.br> wrote

>  ...the pinkish base of Kodak films is
>  completelly gone.

 Kodak's films are not the only ones with a pinkish base. On
under fixing Pan F+ I've obtained a pinkish base.
 Do all under-fixed films exhibit the same when under fixed?  Dan
John - 29 Jun 2004 11:58 GMT
>  Kodak's films are not the only ones with a pinkish base. On
>under fixing Pan F+ I've obtained a pinkish base.
>  Do all under-fixed films exhibit the same when under fixed?  Dan

    Nope. Depends on the dyes used in their manufacture. Films
like D3200 use a different sensitizing and AH dyes and usually look
gray (like fog) when underfixed.

Regards,

  John S. Douglas, Photographer -  http://www.darkroompro.com
             Please remove the "_" when replying via email
Richard Knoppow - 30 Jun 2004 00:41 GMT
> >  ...the pinkish base of Kodak films is
> >  completelly gone.
>
>   Kodak's films are not the only ones with a pinkish base. On
> under fixing Pan F+ I've obtained a pinkish base.
>   Do all under-fixed films exhibit the same when under fixed?  Dan

   The pink color in T-Max is from residual sensitizing
dyes which are bound to the gelatin. Kodak says its an
indication of underfixing but, since thiosulfate and fixer
reaction products can also be bound to the gelatin, its
possible the fixing is complete. Sufite wash aid tends to
free bound ions by two means: it adjusts the pH of the
gelatin to above its isoelectric point where the charges in
the gelatin tend to repel the bound ions rather than attract
them; and it acts as an ion exchanger, displacing them from
the gelatin. Since the same forces which bind the
thiosulfate and reaction products also bind the dye the dye
will be removed.
   The isoelectric point of most photographic gelatin is
slightly on the acid side of neutral. Treating the emulsion
in an alkaline or neutral bath will bring the ph to above
(more alkaline) the isoelectric point.
   When an alkaline or neutral fixer is used the emulsion
will leave the bath in this condition (pH above the
isoelectric point) which is one reason it will wash faster
than it will after an acid fixer. However, it is not simply
the acidity of an acid fixer which tends to retard washing.
Most (but not all) acid fixers contain a hardener composed
of Potassium Aluminum Sulfate, AKA white alum or just alum.
The alum, over a range of pH, is an efficient binder of ions
to the emulsion. It is primarily the alum in hardening
fixing baths which retards washing. However, the alum loses
its abiility to bind thiosulfate and silver complexes to the
gelatin when its pH becomes neutral or alkaline. At neutral
pH the hardening action is preserved, at alkaline pH the
hardening is lost. The hardness of the gelatin has no effect
on wash rate.
  Fixing baths made with Potassium chromium sulfate (Chrome
alum) must be much more acid than those using white alum but
the wash rate is no worse than an acid non-hardening bath.
The chrome alum does not act as a binding agent as white
alum does. Unfortunately, chrome alum fixing baths have
short lives and are unsuitable for general use.
  Gelatin is what is called "amphoretic", that is it does
not have a pH of its own, rather it takes on the pH of the
last bath its been in. However, there are some pH specific
properties, the most important one being the isoelectric
point. On the acid side of this point the electrical charges
in the emulsion are one way, on the alkaline side they are
the other way. Also, the swelling of the emulsion is least
when its pH is brouht near its isoelectric point. Low
swelling also increases wash rate because it minimises the
path ions must follow in diffusing out of the emulsion.
   There is some evidence that Ammonium thiosulfate fixer
washes out faster than sodium thiosulfate fixer but this
rate is also dependant on the factors discussed above.
   So, whatever kind of fixer you use a neutral sulfite
bath will increase wash rate and is good practice.
   Ammonium thiosulfate fixers ("rapid fixers") tend to be
less sensitive to accumulated silver and other substances
(bromide or iodide) from the emulsion so have greater
capicity for completing the fixing process. They are
considerably more tollerant of accumulated iodide so they
are very suitble for use with fast films.
   It should be understood that the conversion of the
unused silver halide from a non-soluble form to a soluble
form is not a simple reaction. Rather it takes place in
stages although they are continuous. Since it takes a lot of
thiosulfate to make the conversion there must be a lot of
free thiosufate ions in the fixer. As more silver is
dissolved more of the thiosulfate ions become unavailable.
It is the concentration of dissolved silver which is the
limiting factor in the ability of a fixing bath to fully
convert the unused halide to a form which will wash out.
Partly coverted halide is not fully soluble or it may be
bound to the image silver or the gelatin. Ammonium fixer
will continue complete fixing at silver levels at which
sodium fixers no longer fully fix. The use of two successive
fixing baths helps insure that the fixing conversion process
is completed so that the unused halide is fully washed out.
The use of a buffered sulfite wash aid will help to remove
some incompletely converted silver complexes by unbinding
them from the image silver and gelatin.

Signature

---
Richard Knoppow
Los Angeles, CA, USA
dickburk@ix.netcom.com

Richard Knoppow - 30 Jun 2004 00:17 GMT
> I've found that by increasing the sulfite content of an alkali fixer
> (could it be neutral?) to 30g/liter, the pinkish base of Kodak films is
[quoted text clipped - 13 lines]
> > carried over developer. For either salt about 5 to 10
> > grams/liter of working solution is enough.

   A sulfite after fixing bath will do the same thing. I
think you may be getting something like a combination of a
fixing bath and wash aid with that much sulfite. I use Kodak
Hypo Clearing Agent, the residual dye comes out in the wash
aid which turns a sort of lavender color remeniscent of old
fashioned ladies underwear.

Signature

---
Richard Knoppow
Los Angeles, CA, USA
dickburk@ix.netcom.com

Donald Qualls - 29 Jun 2004 04:39 GMT
> Dear readers--a new question:
>
[quoted text clipped - 4 lines]
> differently because it is so old? BTW I'm not shooting anything critical
> with it; it's just for the fun of it.

Panatomic-X that's only 30-ish years old probably won't have much fog --
the slower the film, the less fog it will pick up over time from either
thermal or cosmic ray sources.  You will, however, most likely find it's
lost about one stop of speed, so you may wish to expose it at EI 16 or
12 rather than 32 (or 25, which was pretty common).

If you develop in HC-110 instead of D-76, you can further reduce the
likelihood of fog problems, with similar grain and sharpness.
Generally, Dilution B times are shorter than D-76 times, but not a bunch
shorter; with this film, you'd probably gain by going to Dilution H
(half strength of Dilution B) or even Dilution G (1:119 from USA syrup
concentrate).  For Dilution H, I'd give 125% of the D-76 time, and for
Dilution G, I'd be tempted to let it stand without agitation (after the
first minute of constant agitation) for forty-five minutes to an hour.

I should mention, however, that I've never actually shot Panatomic-X,
much less developed it -- however, HC-110 is one of my regular
developers and I've used it in the dilutions above for other films,
including microfilms with similar characteristics to Tech Pan.

Signature

I may be a scwewy wabbit, but I'm not going to Alcatwaz!
                                                    -- E. J. Fudd, 1954

Donald Qualls, aka The Silent Observer
Lathe Building Pages  http://silent1.home.netcom.com/HomebuiltLathe.htm
Speedway 7x12 Lathe Pages     http://silent1.home.netcom.com/my7x12.htm

Opinions expressed are my own -- take them for what they're worth
and don't expect them to be perfect.

Lloyd Erlick - 19 Apr 2004 23:43 GMT
>Dear Readers--
>
[quoted text clipped - 8 lines]
>
>Thanks kindly.

apr1904 from Lloyd Erlick,

from:

The Negative by Ansel Adams, page 192, isbn
0-8212-1131-5, (this is the hardcover New York
Graphic Society edition of the early 1980s.)

"I use the Kodak F-6 formula for all fixing baths.
The addition of Kodalk or borax serves to reduce
the acidic odor without affecting the peformance
of the fixer."

Adams is saying that Kodalk and borax are
interchangeable in fixer formulas. They can be
considered equivalent weight-wise. In a fixer,
there really wouldn't be such a thing as 'too much
borax'. There's no point in too much, though, it's
a waste.

regards,
--le
Richard Knoppow - 22 Apr 2004 20:17 GMT
> Dear Readers--
>
[quoted text clipped - 8 lines]
>
> Thanks kindly.

 I am not a believer in alkaline fixers. As far as
effectiveness of fixing the pH does not matter. If you don't
want to use acid fixer neutral fixer works just fine and
will preserve the stain image as well as an alkaline fixer.
Be careful not to confuse the desired stain image with
overall staining, which is not desirable. Pyro negatives
should be pretty much stain free in the clear areas and have
a proportional stain in the image. I think many of those who
complain of lack of stain are really looking at overall
staining.
 Fixer needs to have sodium sulfite in it both to protect
the thiosulfate from oxidation and to prevent staining from
carried over developer which will remain active in neutral
or alkaline fixing baths for long enough to cause problems.
Sulfite is slightly alkaline anyway. You don't need much,
perhaps as little as 5 grams per liter of working solution.
Most acid fixers have about 15 grams per liter but need it
because the sulfite prevents decomposition of the
thiosulfate by the acid. Sodium metaborate is a poor buffer
despite Kodak's claims so Borax is actually a better choice
if you really want to increase the pH. Tri-X is similar to
T-Max in that it needs longer fixing than most other films.
Check the clearing time and fix for three times that time.
Use a two bath system to insure complete fixing, fix in each
bath for half the total time.
 Ammonium thiosufate is not very stable in powder form so
it usually supplied as a 60% liquid concentrat.

Signature

---
Richard Knoppow
Los Angeles, CA, USA
dickburk@ix.netcom.com

Travis C. Porco - 23 Apr 2004 00:33 GMT
Thanks kindly to you and the others who replied; I may try it both without
the sulfite and with it and see what happens.  Is there a "standard" recipe
for ammonium thiosulfate/borax/sodium sulfite?

Also: Anchell & Troop are down on sodium thiosulfate.  If you mix up a
developer with ammonium thiosulfate, sodium metaborate, and sodium sulfite,
it's still got a lot of sodium in it.  Is it just good to have less sodium, or
is it good to have the ammonium present, or does it just plain not matter?

Final question. I've seen some bottles of Formulary TF-4 with a thick layer
of precipitate on the bottom.  Does this indicate that the bottle is absolutely
no good, or could it be redissolved?

Thanks again!

>> Dear Readers--

>> I have a question:
>> is there anything wrong with the use of pure ammonium
>thiosulfate as a
>> fixer for pyro-developed film? (I use 35mm Tri-X mostly).
>I have some of the
>> "60% ammonium thiosulfate" made by Formulary.

>> Is it possible to use borax instead of sodium metaborate
>in mixing a
>> fixer?  How much?  Anchell & Troop list a recipe with
>sodium metaborate,
>> but not borax.

>> Thanks kindly.

>  I am not a believer in alkaline fixers. As far as
>effectiveness of fixing the pH does not matter. If you don't
[quoted text clipped - 23 lines]
>  Ammonium thiosufate is not very stable in powder form so
>it usually supplied as a 60% liquid concentrat.
Patrick Gainer - 23 Apr 2004 01:25 GMT
> Thanks kindly to you and the others who replied; I may try it both without
> the sulfite and with it and see what happens.  Is there a "standard" recipe
[quoted text clipped - 10 lines]
>
> Thanks again!
That's the way it comes. Shake it well if you're only going to mix part
of it. When you dilute it 1+3 or more, it clears up.
John - 23 Apr 2004 06:06 GMT
>Is there a "standard" recipe
>for ammonium thiosulfate/borax/sodium sulfite

    Just mix F24 and leave out the bisulfite.

Regards,

  John S. Douglas, Photographer -  http://www.darkroompro.com
             Please remove the "_" when replying via email
John - 23 Apr 2004 14:34 GMT
>>Is there a "standard" recipe
>>for ammonium thiosulfate/borax/sodium sulfite
>
>    Just mix F24 and leave out the bisulfite.

    Kodak's F-24 Fixer
    Water @ 125F    750ml
    Sod. Thiosulfate    240g
    Sod.Sulfite    10g
    Sod. Bisulfite    25g
    Water to make    1.0L

Regards,

  John S. Douglas, Photographer -  http://www.darkroompro.com
             Please remove the "_" when replying via email
Dan Quinn - 23 Apr 2004 23:11 GMT
> Thanks kindly to you and the others who replied; I may try it both
> without the sulfite and with it and see what happens.  Is there a
> "standard" recipe for ammonium thiosulfate/borax/sodium sulfite?

 The most direct route to what you are after is a one-shot sodium
thiosulfate fix mixed at time of use. I don't work with pyro but from
my reading the S. Thio. fix is much used. The ph of Photo. Formulary
S. Thio has tested 6.8. Try one ounce of the anhydrous in whatever
volume of solution needed.
 The one fluid ounce of A. Thio suggested still stands. The nice
thing about S. Thio. is it's keeping qualities. A bottle with tight
lid should keep for years. To boost it's or A. Thio's ph to about
10 add a 10th part of S. Sulfite.
 I've worked with S. Thio. straight and with S. Sulfite and with
A. Thio. straight. I use fixer, film or prints, one-shot; always
fresh fix. I've determind the amount of S. Thio. needed with Pan F+
to be 15 grams. The one ounce suggested for Tri X should be plenty;
so much silver, so much chemistry.
   

> Also: Anchell & Troop are down on sodium thiosulfate. If you mix up
> a  developer with ammonium thiosulfate, sodium metaborate, and sodium
> sulfite, it's still got a lot of sodium in it. Is it just good to have
> less sodium, or is it good to have the ammonium present, or does it
> just plain not matter?

 Sodium in no way will spoil a fix. It makes for a slower fix. Some
of A&T must be taken guardedly.

> Final question. I've seen some bottles of Formulary TF-4 with a
> thick layer of precipitate on the bottom.  Does this indicate that
> the bottle is absolutely no good, or could it be redissolved?

TF-4 is a B. Troop formulated alkaline RAPID, A. Thio., fix. I'd be
very wary of those bottles. I think that must be sulfer on the bottom.
With the lid off gently warm and see what happens.
                                                                 Dan
Dan Quinn - 24 Apr 2004 22:57 GMT
> > Thanks kindly to you and the others who replied; I may try it both
> > without the sulfite and with it and see what happens.  Is there a
[quoted text clipped - 9 lines]
> lid should keep for years. To boost it's or A. Thio's ph to about
> 10 add a 10th part of S. Sulfite.

 Correction to last sentance: I checked my records and found that a
1% S. sulfite plus 3% S. Thio. Penta solution has a ph of 9.6.   Dan

>   I've worked with S. Thio. straight and with S. Sulfite and with
> A. Thio. straight. I use fixer, film or prints, one-shot; always
[quoted text clipped - 20 lines]
> With the lid off gently warm and see what happens.
>                                                                   Dan
Norman Worth - 23 Apr 2004 07:04 GMT
If you just want to fix a few films or prints, 180ml of 60% ammonium
thiosulfate in water works fine.  But mix it just before use, it
deteriorates quickly.  Sodium sulfite is used as a preservative. I like the
Kodak F-34 formula as a non-hardening fixer.

         Water                                   700 ml
          Ammonium thiosulfate, 58% 185 ml
          Sodium sulfite, anh.                 10 g
          Sodium bisulfite                      8.4 g
          Water to make                          1 l

It was originally intended as the fixer for Eastman 5247 motion picture
film, but it works very well for regular film and prints.  The pH is only
6.5 - near neutral - so washing should not be a problem.  If you must have
an alkline fixer, 200 ml of 60% ammonium thiosulfate plus 20 g of sodium
sulfite per liter will probably do, but I think a fixer should be slightly
acid to make the preservative work properly and to prevent unintended
stains.

> Dear Readers--
>
[quoted text clipped - 8 lines]
>
> Thanks kindly.
 
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