Glycin and Gold Toning FB prints

Discussion in 'Darkroom Developing and Printing' started by Lloyd Erlick, Oct 18, 2006.

  1. Lloyd Erlick

    Lloyd Erlick Guest

    October 17, 2006, from Lloyd Erlick,

    I've just finished 250 grams of Glycin I
    bought in July. That's certainly the shortest
    time I've ever had for actually using up a
    developer!

    I made a bit of a spur of the moment purchase
    when I bought the Glycin. I was running out
    of Metol, and found a reasonable source in
    Canada. They also sold me some Potassium
    Bromide (great, eh?). And some Glycin and
    Potassium Thiocyanate. I already had some
    Gold Chloride.

    When the stuff arrived, I almost reflexively
    started to get ready to mix up some Ansco 130
    developer (Adams version), because that's how
    I've used Glycin in the past. But I began to
    reflect on the developer I've used most,
    Ansco 120. It's a Metol-only developer.
    (Metol is the only developing agent present,
    that is.) It seemed to me if I wanted to get
    familiar with Glycin, I should use it in a
    Glycin-only print developer formula.

    So, based on this rather shallow reasoning, I
    looked for formulas that contained Glycin and
    no other developing agent. I found one
    created by Edmund Lowe, of Edwal fame. I
    believe he created it in the 1930s (don't
    quote me on that). The developer is called,
    variously, Edwal 102, Lowe 102, even ED-102
    (I'd guess that's for Edwal Developer number
    102, hm?).

    I call it 102 Developer, since the number is
    all that's consistent. As a 'full' name I'd
    prefer Lowe 102 developer, if pressed. I have
    several versions of the formula reproduced
    below. The version found online is first, for
    a concentrate that is diluted for use. I
    prefer to mix dry chemicals directly to a
    working solution, so I present the formula
    for one liter of working solution next. But
    also, I like to manipulate the degree of
    warmth of a final print by controlling the
    sodium vs. potassium ions present in the
    developer. More potassium means more warmth,
    which may or may not be desirable depending
    on the paper one uses. I like to use Ilford
    Multigrade Warmtone Fiber Base material
    (MGW), which responds very favorably to
    potassium salts in a developer. (As an aside,
    I have found that Forte Polywarmtone FB
    material responds so strongly to potassium
    salts that even I find it too warm, or at
    least, too 'reddish'.) So my potassium
    instead of sodium salts formula is last.

    *Here are the formulas:


    1)______________________________________________________________________
    Lowe 102 (Glycin-only Print Developer created
    by Edmund Lowe of Edwal.)
    STOCK SOLUTION

    Water (125°F/52°C) 900ml
    Sodium sulfite 80g
    Sodium Phosphate, tri-basic 120g
    Glycin 25g
    Potassium Bromide 3g
    Water to make 1000ml


    Dilute 1+3, 1+4 -- the developer stock
    solution with three parts of water for slower
    papers and four parts of water for faster
    papers.


    2)______________________________________________________________________
    WORKING SOLUTION
    ....for Edwal 102 print developer, a dilution
    of 1+3 implies that one quarter of the
    ingredients are enough for one liter of
    Working Solution.

    Thus:


    Print Developer 102, Working Solution

    Water (125°F/52°C) 900ml
    Sodium sulfite 20g
    Sodium Phosphate, tri-basic 30g
    (Tri Sodium Phosphate, TSP)
    Glycin 6g
    Potassium Bromide 1g (adjust
    to suit, up to 6-8 grams)
    Water to make 1000ml


    This is a slow working formula. The image
    appears slowly. It may be forty to
    seventy-five seconds before any image
    appears. Complete development will take three
    or four minutes.



    3)______________________________________
    102 Print Developer (Potassium Version)
    WORKING SOLUTION


    Print Developer 102 (Potassium), Working
    Solution

    Water (125°F/52°C) 900ml
    Potassium sulfite 25g
    Sodium Phosphate, tri-basic 30g
    (Tri Sodium Phosphate, TSP)
    Glycin 6g
    Potassium Bromide 1g (adjust
    to suit, up to 3-4 or more grams)
    Water to make 1000ml

    This is a slow working formula. The image
    appears slowly. It may be forty to
    seventy-five seconds before any image
    appears. Complete development will take three
    or four minutes.
    _______________________________________________________________




    4)____________________________________________________________________
    {NOTE: experiments with the formula
    containing Tri Potassium Phosphate in place
    of Tri Sodium Phosphate would be very
    interesting. As yet, I have not acquired this
    substance.}





    Sodium phosphate tri-basic (TSP) reacts with
    the alum in most hardening fixing baths to
    form insoluble aluminum phosphate. Therefore,
    avoid hardener when using this formula.
    Consider the fixer formula for "Plain Fixer"
    published by Ansel Adams in the Appendix to
    his book, "The Print". Using this fixer is
    described in an article on my website
    (www.heylloyd.com).





    *Using 102 Print Developer on Ilford Warmtone
    FB (MGW).

    I used the Potassium version of the working
    solution at first. Believe it or not, I
    actually found it too extreme for my taste,
    which happens to run pretty far to the warm.
    Most of my work with this developer was with
    the sodium version, which is the formula as
    it has always been published.

    The formula is simple and cheap to prepare.
    It also lasts well, giving several days
    service if necessary. I eventually stopped
    storing it even until the next day, because
    although it worked well and continued to
    yield attractive prints, the exposures and
    contrast levels might not remain consistent.
    It just became too much hassle for little
    gain. In fact, the only gain would be to make
    the cost of the Glycin provide more working
    sessions. But in fact it takes diligence and
    hard work to use up 250 grams of Glycin
    before it goes bad in storage. As a dry
    powder, Glycin stores poorly. It gradually
    turns darker and darker and browner and
    browner until it is kaput as a developer, and
    ready for its new life as a fur dye. Paper
    dye, too, if you let it. Glycin should be
    white or off- white or very light gray or at
    worst some significant degree of gray that is
    brighter than medium gray. If there are
    traces of brown it's a danger sign. Glycin
    powder is usually very finely divided,
    texture quite like flour, so watch out for
    dust when handling it. Glycin is not directly
    outright toxic, but nothing is safe to
    inhale, including flour and oven cleaner.
    It's possible Glycin, like many substances,
    is a sensitizer, which means it can cause a
    human to become allergic to it. Thus direct
    skin or respiratory contact is to be avoided.
    To use this or any other developer safely,
    please consider my article about Single-Tray
    Print Processing (published on my website,
    www.heylloyd.com, in the 'technical' area of
    the table of contents). This article outlines
    a practical and rigourous method for using
    conventional black and white print developing
    solutions to make traditional fiber base
    black and white prints -- with no (that's
    zero) chemical exposure for skin or mucous
    membranes.

    For all the cautionary zeal of the foregoing
    paragraph, Glycin is easy and safe to handle
    if the most basic precautions are taken. In
    fact I'd have no problem teaching a ten year
    old to do it, as long as I was sure it was a
    kid who would listen. The powder is about the
    consistency of baking flour, so it won't
    really dust up into the air as long as it is
    handled slowly and gently. I use a teaspoon
    to scoop small amounts out of the container.
    I gently slip the powder onto my scale. I
    gently tip it into my container of water. I
    keep a light shining across the mouth of the
    container while I do this, so I can see any
    trace of a powdery cloud if I slip up. Even
    if I do see some dust in the air, I also see
    it fall quickly and close to the container.
    So I can see it does not travel all over the
    place, and I can also see it's my mistake if
    it's in the air at all. So the danger really
    does not exist.

    102 Developer is relatively cheap, as well. I
    like to use distilled water for most of my
    solutions, so a liter of this developer in
    working solution starts with about twenty
    cents worth of distilled water. The sodium
    sulfite and TSP are very cheap. In fact, I
    buy my TSP at the hardware store, where it's
    considered a degreaser and heavy-duty cleaner
    (good for that stain on the driveway...). The
    sulfite can be found in twenty-five kilogram
    bags for about sixty dollars (Canadian
    prices, current just after the turn of the
    Twenty-First Century). So, except for Glycin,
    the ingredients are cheap. Recently (in 2006)
    I paid about 41 dollars for 250 grams of
    Glycin. Some years ago (late 1990s) I bought
    a pound of Glycin for about USD83. The price
    hasn't changed all that much.

    I'm a little extravagant in the darkroom, and
    I could probably get by with less developer
    in my tray than I actually use. I mix up two
    liters of working solution for my developer.
    So I need twelve grams of Glycin for the
    above formula. That's a bit of an expense,
    but it's offset by the fact that it doesn't
    keep long! So use it up! It's rather like the
    admonition of various elderly aunts and
    grannies in Wartime Europe, and during the
    Depression: "Use it up! It's going bad!" ...
    (well, OK, they said eat it, but I'm only
    making an analogy...).

    Communicating with other darkroom workers
    over the Internet brought a little nugget of
    information my way some years ago. In a paper
    developer, the greater the number of
    potassium ions, the warmer the final result.
    So replacing the ubiquitous sodium sulfite in
    print developers with potassium sulfite makes
    a significant difference in the final look of
    the print, after it has been toned. (The
    relation between developer and toner,
    especially selenium toner, is crucial.
    Controlling potassium vs. sodium in the
    developer manipulates this relation.) Usually
    I like my print as warm as I can get it. On
    Ilford MGW Warmtone FB material, when I use
    Metol as my only developing agent (in the old
    Ansco 120 formula, amended to contain no
    sodium salts at all) I like the degree of
    warmth that results. With the Glycin-only 102
    formula, when I used potassium sulfite, I
    found the result too warm. It struck me as
    too red. People took on a ruddiness I found
    unpleasant. Matter of taste, to be sure; I
    showed people these prints and some like
    them. My perception of red is probably
    different from other peoples'. Anyway,
    playing with these chemicals affords a
    mechanism of control over a very subtle
    aspect of what we could call a final, or
    perhaps, fine print.

    Now, I'm both a cheapskate and lazy. I had
    some luck a few years ago, and found some dry
    powder Potassium Sulfite. It's very nice,
    double-bagged reagent grade material. I got
    what feels like a lot, but I can already see
    the end of my supply and I'm getting jealous
    of using it. Finding it in powder form is
    tough to impossible; usually it's made in a
    beaker of water by reacting some other stuff
    in the right amounts. So I don't fancy going
    about finding this stuff again, at any price,
    let alone my lucky cheap price.

    I began to use the 102 formula with sodium
    salts only. I believe this is a difference
    between these two developing agents (Metol
    and Glycin, that is) -- Glycin yields a print
    that accepts selenium toner in a way we
    interpret as 'warmer', compared to Metol.
    Both of these developer can be controlled in
    the warmth department by the proportion of
    potassium ions present. For Metol, I like all
    sodium salts changed to potassium, for a
    level of warmth I like. For Glycin, I find
    the sodium-only salts (that is, both sulfite
    and phosphate) suffice for a satisfying
    warmth. So I'd have to say I find Glycin a
    'warmer' developer than Metol. But that is
    modified with my observation that the added
    warmth is too red for my taste, so I prefer
    not to make that change in the formula when I
    use it.

    So far untested is the 102 formula with both
    Potassium Sulfite and Tri Potassium Phosphate
    in place of their respective sodium salts.
    I'd expect this to be quite warm, too, but
    whether the tinge of red I perceive (I asked
    others if they saw it, too, and even female
    eyes do so) is present, absent, or altered I
    can't predict.

    Keeping properties for 102 print developer
    are very good. I used the same two liter
    batch of working solution for three
    successive days. Prints were very nice,
    finally becoming not so nice on the fourth
    use. Another strategy I used was to keep only
    one liter of the previous session's
    developer, adding one liter of fresh mix.
    This worked very nicely, too. But frankly,
    just making up a fresh batch each time I want
    to work is fine, no problem, and not all that
    expensive. Certainly not close to the expense
    of the photo-sensitive materials I use. I
    often print on 16x20 sheets, so one sheet is
    probably twice the cost of my working
    solution of developer. One wasted sheet
    offsets anything gained by being a cheapskate
    about the developer. Yes, I'm a cheapskate,
    and yes, I've burnt my nose on account of it!
    School of hard knocks. Just try to take your
    knocks in money, not your body...

    I always use distilled water to make up
    important solutions (and I consider fixer
    important, not just developer, eh?) I think a
    developer will behave more consistently from
    session to session if it's made up with
    distilled water. Municipal tap water can have
    who knows what in it, so why should it act
    the same every time?

    Overall, now I feel like I know something
    about Glycin. The first time I used it on its
    own, when I saw the print before I toned it,
    I was very impressed with the beautifully
    dense black where it contrasted with the
    white paper margin; the black struck me as
    very satisfyingly warm in tone. After toning
    in selenium the densest blacks are deep
    black, enhanced in density by the toner, and
    altered in color slightly toward the brown (I
    suppose I like brown better than red ...).
    The tone is very nice in the mid-tones, or,
    as a portraitist (that's me!) might prefer,
    in the skin tones. Selenium toning must give
    pleasant looking skin or I can't use it. I
    liked the skin tones I saw after selenium
    toning all the prints I made with Glycin.



    *Gold Toning

    On Ed Buffaloe's website (unblinkingeye.com)
    he outlines a method of Gold Toning that is
    very easy and convenient. It is a one-shot
    way of preparing and using the chemicals
    involved.

    Basically, the Gold Toning process uses the
    old DuPont 6-T Gold Toner formula. Ed
    Buffaloe has worked it out so it can be mixed
    as a one-shot, so storage and waste are
    pretty much eliminated.


    For each liter of one-shot gold toner, as
    described by Ed Buffaloe ...

    distilled water 1 liter
    Potassium Thiocyanate 6 gram
    gold chloride 1% solution 2 ml (probably
    this can be varied over a range such as 1 to
    4 ml)

    .... one 16x20 print would need two liters,
    which means a 16x20 would use up 4 ml of gold
    solution. That implies twenty-five 16x20
    prints from the 100 ml of gold solution. The
    gold would cost about a dollar fifty per
    print (cost estimate circa end of 20th
    century, beginning of 21st).

    It would be a good idea to find a spoon or
    scoop that would be appropriate for removing
    six grams of Thiocyanate from the container
    without having to weigh it on the scale. In
    other words, weigh six grams on the scale
    once and see which spoon it fits. The gold
    solution can be measured out quickly and
    easily by pipette. I used to do that with
    Rodinal!

    When the gold solution is released from the
    pipette into the container of water and
    Thiocyanate, it appears as a small dark cloud
    jetting into the water. To my inaccurate eye,
    the color is dark orange or perhaps red/dark
    red. It disperses quickly (and
    beautifully...) into the volume of water. The
    overall solution darkens and colors only very
    slightly (after all, it's only four ml of
    gold solution entering two liters. Pretty
    significant dilution.)

    I bought Potassium Thiocyanate at around
    sixty dollars for 500 grams. Twelve cents per
    gram. Two liters of solution to make a 16x20
    would require twelve grams at twelve cents a
    gram, or $1.44. Basically the same price as
    the gold! Three bucks a print (16x20) for the
    gold toning. Might as well add the cost of
    the distilled water ...

    The gold solution is slightly sensitive to
    light. Direct sunlight will help it degrade.
    Low level interior lighting probably won't
    affect it. But it's easy to store in a small
    dark glass bottle, or a clear bottle inside
    an opaque cover (or cabinet). Basically,
    ordinary darkroom white lighting won't kill a
    gold chloride solution. So double protection
    would be to expose it to a convenient level
    of white light exclusively while it is in
    use, and put it in a dark container or
    cupboard the rest of the time.



    *Using the One-Shot Gold Toner

    My favorite size print is 16x20 inch, and I
    find two liters of solution cover it very
    well. If I decide to switch to 20x24, two
    liters will still be enough, as long as I pay
    attention and permit no part of the print to
    spend significant time sticking out of the
    solution.

    To make two liters of one-shot Gold Toner,
    it's very easy to get two liters of distilled
    water in a plastic jug (I'm squeamish about
    putting toners into a metal container of any
    sort; maybe I'm too conservative) and stir in
    two teaspoons (should be twelve grams) of
    Potassium Thiocyanate. This substance will
    absorb water from the air quite readily, so
    don't leave it's container open too long. A
    ten percent solution could be prepared and
    kept at hand easily for added convenience. A
    hundred grams dissolved in distilled water
    and brought up to one liter of solution will
    be ten percent. The six grams we need for our
    two liters of one-shot toner will be present
    in sixty milliliters of the ten per cent
    solution. It should keep close to
    indefinitely this way.

    It's best to use Gold Toner at slightly
    elevated temperature, so the distilled water
    might as well be warmed before the dry powder
    is dissolved. It will dissolve readily. Using
    a pipette, or a tiny measuring graduate,
    remove four milliliters of one percent Gold
    Chloride from its bottle (remember, this is
    enough for a 16x20 or even a 20x24). Add it
    to the Thiocyanate solution (watch the lovely
    swirls of red eddy around and fade away; try
    to send little donut-rings of red to the
    bottom of the container.)

    I like to process my prints with the
    single-tray method, so I'd say pour the Gold
    Toner over the print in the tray. Maybe some
    would prefer the expression, immerse the
    print in the Gold Toner. In any case, ten
    minutes in the Gold Toner should yield quite
    a noticeable result. Elevating the toner
    temperature, and adjusting the length of time
    in the toner, change the result, although to
    a much slighter degree than I expected.

    I have discarded my Gold Toner after its
    one-shot use. I have not experimented to see
    if results would be acceptable if it were
    used again. Perhaps it will do several
    prints; please have a squad of graduate
    students investigate this immediately.

    Anyway, a gram of Gold Chloride seems to cost
    in the neighbourhood of thirty five dollars
    around the beginning of the 21st century.
    Doesn't seem to matter much whether Canadian
    or US dollars. A little bottle of one percent
    Gold Chloride, 100 ml, will cost thirty five
    bucks, roughly. If each use involves 4 ml,
    that's 25 uses per 35 dollars. You do the
    math.



    *Gold Toner -- Usage with Selenium Toner, and
    Effect on Final Print

    The one thing about all this is that toning
    in gold does not turn the picture gold. I
    would really love it if gold toner turned
    faces and white dresses a lovely, sunny,
    golden glow.

    To achieve that, however, one would best
    follow the advice of innumerable advertisers,
    and try their products until your laundry,
    and teeth, turn white.

    Gold toning black and white fiber base prints
    yields a neutral to blue toned level of
    black. Gold toner has been called Blue Toner,
    too. Another effect is better protection of
    the silver image from atmospheric pollutants.
    This is not visible, however, and is a
    side-benefit as far as this article is
    concerned.

    For the greatest blue effect from this toner,
    apply the toner after rinsing or washing the
    print. To reduce the 'bluish' quality, in
    fact to yield a beautiful, clean neutral
    black that seems to strike the eye as India
    Ink, tone the print in Selenium Toner before
    the Gold Toner.

    This is exactly what I have been doing for
    the last few months. I have always used
    Selenium Toner on my finished FB prints. My
    method has been to dilute the Kodak version
    (KRST, or Kodak Rapid Selenium Toner) 1+5 in
    distilled water, and apply it to the print
    for ten minutes, at around 32-34 degrees C.

    I have been Gold Toning my prints after the
    above Selenium treatment. At first I washed
    them quite extensively, but I tried rinsing
    them with four changes of tap water in my
    processing tray. After this easy and
    relatively quick wash, all my prints have
    Gold Toned with no problems and no staining.

    As they sit in the Gold Toner, I see very
    little change going on. Some workers
    (reported by Ed Buffaloe) like to tone for
    15-30 minutes, and users advise temperatures
    from room temperature to 100 degrees
    Fahrenheit. I couldn't see much difference no
    matter what I did. I think I saw a little
    deeper or denser black after 30 minutes, but
    the difference was so slight I can't say. If
    densitometers are necessary, maybe the
    differences aren't that great...

    I find Gold Toner gives me the option of
    turning a successful warmtone print into a
    beautiful neutral tone print. In fact, I
    really like the ability to do this without
    darkening or bleaching the print. A properly
    done warmtone print will look fine after
    one-shot Gold Toning. The enlarger exposure
    need not be adjusted compared to the exposure
    for a good Selenium Toned print.



    *Gold Toning Problems

    I ran into only one problem while toning my
    prints in gold. As ever, the sheet has the
    strong tendency to float in the solution, and
    push a portion of its surface up into the
    air. In my case, it seems to like pushing the
    top right corner and right edge of the sheet
    out of the solution. I've noticed this 'float
    pattern' many times. Maybe my tray is not
    quite level ...

    Well, I have a lovely Gold Toned print that
    has weird differences in the density of the
    black over its surface. A patch in the upper
    right corner has a distinct 'veiled black'
    quality, compared to the rest of the print,
    as does the whole right edge of the print.

    I'd say one should attend the print while it
    is in process. Pay attention! Make sure all
    of it stays in the solution.

    There are suggestions the Thiocyanate
    solution is capable of bleaching a silver
    print. I doubt this is true of such a dilute
    solution as we are using here, and I
    double-doubt bleaching would occur in the few
    minutes we are immersing the print. However,
    effects that occur where there is some sort
    of air-solution boundary can be very weird
    and unpredictable. Keeping the print
    submerged avoids all this rhetoric and
    unpleasantness.
     
    Lloyd Erlick, Oct 18, 2006
    #1
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  2. Lloyd Erlick

    dan.c.quinn Guest

    Same formula as in Patrick Dignan's Classic B&W Formulas.
    A 1:3 dilution, 60 to 70 F., 3 to 4 minutes. TSP is very caustic.
    In particular speaking of toning. Do you think 'stand' toning
    would work? I 'stand' wash using a Still Water Diffusion Wash.
    I make sure the prints remain separated and stay submerged
    using thin non-woven polyester sheeting.
    A sheet goes on bottom and top of tray with interleaving of
    sheets and prints between. With the proper solution volume the
    top sheet keeps all under the surface. Lengthy still solution toning
    may work. After all the print came from a Glycine developer. Dan
     
    dan.c.quinn, Oct 18, 2006
    #2
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  3. Lloyd Erlick

    Greg \_\ Guest

    Seriously: I going to save this for future
    experimentation-Thanks!
    Less than seriously you should try: "Tie Dyed prints",....
    the density botches will appear less important on those :^)

    Take Care!
     
    Greg \_\, Oct 19, 2006
    #3
  4. This is an interesting experiment. I have not been able
    to find any other print developers using Glycin exclusively
    but Agfa/Ansco has one using Glycin and Hydroquinone, which
    I copy below. Since you have the ingredients it may be worth
    checking out:

    Agfa 115 Glycin-Hydroquinone Developer

    Stock Solution
    Water (at 125F or 52C) 750.0 ml
    Sodium Sulfite, dessicated 90.0
    grams
    Sodium Carbonate, monohydrated 150.0
    grams
    Glycin 30.0
    grams
    Hydroquinone 9.5
    grams
    Potassium Bromide 4.0
    grams
    Water to make 1.0
    liter

    For warm tones dilute 1 part stock with 3 parts water and
    develop about 3 minutes.

    The stock can be diluted further for even warmer tones but
    shadow density will suffer.
     
    Richard Knoppow, Oct 27, 2006
    #4
  5. Lloyd Erlick

    dan.c.quinn Guest

    There has been much talk of alkaline fixers, hca, and
    my mention of and your use of a sodium carbonate hca.
    Mr. Troop has stated that he does not believe a fixer ph
    greater than 10.5 is advisable for emulsions. That is
    an easy ph for a carbonated developer. I'd think the
    ph of your Edwal 102 to be 11.5 or better.
    Tri-sodium phosphate is very caustic.
    Have you checked your emulsions lately? Are they
    peeling off in the wash? Or have you jumped ship
    entirely? Acid stop, acid fix with hardener? Dan
     
    dan.c.quinn, Nov 1, 2006
    #5
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