Add Kodak Brown to KRST?

Discussion in 'Kodak' started by Mike, Apr 24, 2004.

  1. Mike

    Mike Guest

    I've googled this group and found numerous posts saying that KRST at 1:20
    doesn't provide adequate archival protection because it won't tone the
    highlights.

    Would adding 1:200 of Kodak Brown Toner to the 1:20 of KRST help without
    changing the overall tone?

    Thanks,
    Mike
     
    Mike, Apr 24, 2004
    #1
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  2. Hi Mike,

    I think so. Research done at the Image Permanence Institute in
    Rochester and published in the Abbey Newsletter (available on line)
    indicated that at one time KRST was more effective at providing archival
    results than as currently sold. The research found that the earlier
    KRST had a small amount of sulfurated postash (aka liver of sulfur,
    potassium trisulfide) "contaminating" the product. The active
    ingredient in Kodak Brown Toner is potassium sulfide. Both potassium
    sulfide and potassium trisulfide have toning properties. The latter is
    also said to be able to remove silver complexes. So, using the Brown
    Toner may not get you all of the benefits of using the sulfurated
    potash, but it should get you at least some of them. I do know that
    some contributors to the group experimented with various ratios of Brown
    Toner. I cannot remember if all of the results were published, but I
    think that I recall that 1:200 was yielded satisfactory results for
    those who tried it.


    Francis A. Miniter
     
    Francis A. Miniter, Apr 24, 2004
    #2
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  3. Mike

    nicholas Guest

    Not sure about the nitty and the gritty of toning permanance issues. But
    the standard thing to do is to tone with more than one toner. Here is an
    article on it. Remember that there is an order to the toning...
    http://unblinkingeye.com/Articles/Double/double.html
     
    nicholas, Apr 24, 2004
    #3
  4. Mike

    Dan Quinn Guest

    I think the silver in the highlight areas accepts selenium as readily
    as the silver in the shadow areas. If they are truly less archivaly
    protected then some other mechanism must be at work.
    I think it may be a purely precieved lack of tone rather than an
    actual non-reaction twixt the selenium and highlight silver.
    In other words, I'm not a subscriber to the "split tone" school
    from the chemistry's view point. Dan
     
    Dan Quinn, Apr 24, 2004
    #4
  5. Sorry, Dan, but Mike is right on this.


    Selenium affects shadows before highlights.


    First, I want to clarify a couple items from my previous post. In my
    previous post in this thread I had referred to research done at the
    Image Permanence Institute at the Rochester Institute of Technology.
    The work was done by Dr. Douglas Nishimura, a research scientist at the
    IPI. In fact, I had occasion to inquire of him in and for a while he
    posted to this news group some superb summaries of his research into
    image permanence. This was back in year 2000. I had also mentioned
    research done by participants in this group. One such was undertaken by
    Lloyd Erlick who summarized his results in a post started September 14,
    2000, and entitled: "T-8 Brown Toner and Selenium Toner in
    Combination". Dr. Nishimura, Richard Knoppow and I were contributors to
    that discussion. I also at some point posted a chart of tonal changes
    resulting from selenium toning in various papers after development in
    several different developers.


    As to the affect of KRST on shadows and highlights, it definitely
    affects shadows first. I have myself done extensive testing (noted
    above) to determine which papers exhibit what tonal change with
    selenium, and in the course of those tests, I observed, consistently,
    that tonal changes occur first in shadows, and only many minutes later
    in the highlights. I also have regularly engaged in split toning
    (selenium/brown toner), toning first in selenium and second in brown
    toner. The result is that black tones remain black and highlights go
    brown, while the affect on mid tones depends on the amount of time in
    selenium.


    This is not just my observation, however. I refer you to Dr. Tim
    Rudman's most recent book "The Master Photographer's Toning Book: The
    Definitive Guide" (Argentum, 2003), where on page 42 he states:

    "Prints that have been fully selenium toned robustly resist attacks
    by most image destroying chemicals. However, not all the commonly
    recommended archival toning regimes are valid. This is a reflection on
    the advice given rather than on the toner, because selenium toner
    initially affects the shadow areas before the mid tones and highlights
    and short toning times in highly diluted toner do not allow toning to
    proceed far enough for all the image-silver to be converted. The
    highlights and possibly the mid tones may therefore be unprotected. "


    Dr. Rudman also sites the IPI research. See page 158 of his book. On
    page 159, he further explains that the shadow values have the finest
    grains and that is why selenium tones them first.


    The problem is that the color shift accompanying full selenium toning is
    often unacceptable. This is why many people try to selenium tone to a
    point before the tonal shift occurs. And this is why confusion arose
    because KRST used to have a modicum of sulfurated potash in it. The
    potash provided protection in the highlights that the selenium was not
    providing. But with the "purification" of KRST, this subtle protective
    affect was lost. Thus, we have to deal now with the problem of how to
    achieve protection without an annoying tonal shift. Mike is on the
    right track. On further reflection, it may be better to use Kodak
    Polytoner rather than Kodak Brown Toner, to get some potassium
    trisulfide into the mix.


    Francis A. Miniter
     
    Francis A. Miniter, Apr 25, 2004
    #5
  6. Kodak Polytoner was a mixture of brown and selenium toner,
    it is no longer made.

    You can make your own mix. I don't know the ratios -- I bought
    a few quarts of PT before stocks disappeared and still have some on hand.

    To ask the obvious: why not add a pinch of "Liver of Sulfur" to KRST?
    Available at most arts & crafts stores -- around $15-30/lb, $8/4oz.
    UPS doesn't like to ship the stuff.
     
    Nicholas O. Lindan, Apr 25, 2004
    #6
  7. Mike

    Lloyd Erlick Guest

    On Sun, 25 Apr 2004 16:59:35 GMT, "Nicholas O.

    ....
    ....

    apr2604 from Lloyd Erlick,

    I think this could literally be done, and I'd
    guess it is being done by many darkroom workers.

    If you want a weight of potassium polysulfide
    (liver of sulfur) to use, I'd say pinch your thumb
    and index finger in a container of table salt and
    weigh that. Weigh out that amount of sulfide for
    each liter of selenium toner working solution. In
    fact, this may be a bit too much.

    The problem I had was the smell of the sulfide. It
    gave off hydrogen sulfide (rotten egg gas). I
    searched for an amount of sulfide I could put into
    my selenium toner and not smell it, and also not
    get a 'brown toner' toning result. I found a very
    small amount of solid potassium polysulfide in
    water could really stink the place up. But in view
    of the fact that only a very small concentration
    of sulfide in the toner will (apparently) provide
    archival protection qualities, I think the
    literally-a-pinch amount should do the trick.
    Frankly, I'd be inclined to use a pinch per
    gallon.

    regards,
    --le
     
    Lloyd Erlick, Apr 26, 2004
    #7
  8. Mike

    Dan Quinn Guest

    IIRC, The Abbey Newsletter to which Mr. Miniter refers in an earlier
    post this thread, reports that sodium sulfide at a 1:9,999 dilution
    confers very good archival qualities to microfilm. IIRC, microfilm
    is the principle subject of that article and if I'm not mistaken,
    a priority item at the RIT's IPI reaserch facility.
    BTW, Mr. Miniter provided an interesting link. I thought your work
    with brown and selenium and in combination very interesting. Also, the
    IPI director if I'm not mistaken, provided valuable information with
    regard to gold, platinum and sulfur preservation. He did not discuss
    selenium. Dan
     
    Dan Quinn, Apr 26, 2004
    #8
  9. AFAIK, the research at IPI never determined what the change in
    KRST was. Do you know of later research on this? There was
    speculation that there was some sulfide or polysulfide as an impurity
    in one of the ingredients. Kodak claims that the formula and method of
    manufacture have not changed.
    Full toning with any sulfide or polysulfide toner, or with
    Selenium or Gold toners, provides full image protection. The problem
    with KRST is when it is used as long recommended, i.e., at a 1:20
    dilution. According to personal communication with Dr. Nishimura, KRST
    will provide full protection when used at a dilution of no greater
    than 1:9 and for not less than 3 minutes at 68F.
    Polysulfide toner made so that the concentrate has high order
    polysulfides, will tone all densities uniformly so will provide full
    protection even when only partial toning is done. Kodak Brown toner,
    at the recommended dilution works fine as does T-8. Agfa Viradon
    should work as well. Kodak Polytoner, and the older version of
    Viradon, were combinations of Polysulfide and Selenium. These toners
    provide full protection but were less desirable for microfilm because
    they affect the crystaline structure of the silver to a greater extent
    than either polysulfide alone or KRST. This is of no consequence for
    pictorial negatives or prints.
    I have never seen any formal testing of KRST with added sulfide
    or polysulfide.
    Kodak had a formula for making a combination toner from KRST and
    KBT, I've posted it to this group a couple of times. Ryuji Suzuki
    tells me he has tried it and found that it caused strong orange stains
    on prints. Polytoner was discontinued some time ago but Kodak
    maintains the secrecy of the formula.
    Gold toner provides very good image protection but does cause
    some shift in image color for printing paper. The shift is toward blue
    so may be desirable for some papers. The problem with Gold toner is
    that it is expensive even at the relativly low concentration of Gold
    used in protective toners.
    It appears that stabilizers, like Agfa Sistan, are effective
    in preventing oxidation of the image silver. Sistan, in particular,
    has not been fully tested. A test of a similar (but not identical)
    Fuji products, called Ag-Guard, suggests that the effectiveness is not
    as great as toning but is nonetheless significant. These products do
    not affect density, image color, or crystaline structure.
    Highly diluted Polysulfide toners can cause serious staining.
    Polysulfide has the peculiar property of toning faster as it becomes
    exhausted or more diluted. For this reason the use of highly diluted
    toner of this type is not recommended. In fact, the use of a 10%
    solution of Sodium Sulfite is suggested as a sort of stop bath
    following toning in Kodak Brown Toner or Agfa Viradon to prevent
    staining from the toner remaining active in the wash bath. Washing
    after toning should be quite vigorous even when this bath is used.
    I am skeptical of toning in a simple solution of sodium sulfide
    since it does not affect silver directly. In fact, sodium sulfide is
    used as a test of unfixed halide. It tones the halide very effectively
    causing a stain if fixing is not complete. It does not significantly
    affect metallic silver.

    Richard Knoppow
    Los Angeles, CA, USA
     
    Richard Knoppow, Apr 28, 2004
    #9
  10. Hi Richard,


    I just re-read the article: Nishimura et al "Stabiality of
    Black-and-White Photographic Images, with Special Reference to
    Microfilm", Abbey Newsletter July 1988 vol 12 No. 5


    You are right. They do not specify which sulfide they thought was the
    problem. They wrote:

    "It is our strong feeling that the changes in formulation that suddenly
    rendered dilute selenium toner ineffective relate to the sulfiding
    action of minor constituents. Although the formula for Kodak Rapid
    Selenium Toner is proprietary, it is known to contain both sodium
    sulfite and hypo (sodium thiosulfate), both of which may be contaminated
    with small amounts of highly active sulfiding agents. Apparently
    insignificant manufacturing changes may have caused this active agent to
    be no longer present; it would still form silver selenide and achieve a
    toning action (in the sense of color change), but would no longer
    protect against peroxide. In any case, the surprising ineffectiveness of
    Kodak Rapid Selenium Toner, together with many other signs of the
    potency of sulfiding agents, pointed the way to a much different
    analysis of image stability and how to achieve practical protection
    against red spots."


    Later on, in discussing sulfiding treatments is where they took up Kodak
    Brown Toner. They wrote:

    "There is great promise for sulfiding treatments as a way of protecting
    microfilm against oxidative attack. Once we had determined that the
    sulfiding ingredients were in fact responsible for most of the
    protection imparted by dilute selenium and gold toners, we began to
    explore the effectiveness of various compounds which might form a layer
    of silver sulfide at the surface of developed silver grains. This work
    is still under way, but already at least one simple, extremely effective
    approach has been identified: the use of polysulfides, as found (for
    example) in the commercial product "Kodak Brown Toner." This product
    gives complete protection in our severe hydrogen peroxide test (2000
    ppm), even when used in quite dilute solution (for example, 1 part toner
    to 200 parts water).

    "It is characteristic of the sulfiding approach that only a small amount
    of the sulfiding agent is needed. For example, sodium sulfide solutions
    of 0.1 grams per liter (about 1/100th of a percent) are completely
    effective. However, for reasons of diminished odor, toxicity of the bulk
    substance, and shelf life of the solution, the polysulfides are
    preferable in practice to straight sodium sulfide. We have shown that
    Kodak Brown Toner does its work of protecting the image silver without
    significant change of density or image hue. The method of treatment is
    simple: processed microfilm of any age can be immersed in the solution
    for a few seconds (shorter immersion times require slightly higher
    concentrations than longer times), then washed and dried. Conventional
    processing equipment can be readily used for post-treating, with
    throughput rates comparable to normal processing."


    Francis A. Miniter
     
    Francis A. Miniter, Apr 29, 2004
    #10
  11. Dan

    The difference has to do with the size of the grains.
    Finer grains have a larger surface to volume ratio than
    larger grains so there is more surface to work on. This
    seems to be at least part of the explanation. For some
    reason polysulfide toners, where the polysulfides are of
    higher orders, do not have this effect. Highly concentrated
    stocks have lots of high order polysulfides.
    Sulfiding toners of other kinds can produce split toning.
    For instance the old Hypo-Alum toner split tones. Indirect
    toner split tones but that is due to the effect of the
    bleach, not the toner. Both KBT and T-8 are concentrated
    enough to tone evenly when used for partial toning. Agfa
    Viradon is currently a simple polysulfide toner like KBT and
    has the same properties. I am not sure the simple addtion of
    sodium or potassium sulfide to KRST would cure its problems,
    maybe so, but I am not a good enough chemist to know. I am
    sure Dr. Nishimura, and his associates at IPI, must have
    thought of this.
    I will also point out, that from personal communication
    with Dr. Nishimura, that simple sulfiding is NOT as
    effective as gold toning with Kodak GP-2. GP-2 remains the
    standard of protection for microfilm. Diluted KRST was not
    better, just a lot cheaper. (I've resisted calling GP-2 the
    gold standard of protection, but I DID think of it).
     
    Richard Knoppow, May 3, 2004
    #11
  12. Mike

    Dan Quinn Guest

    The following are extracts I believe important. More of that article
    can be seen from Mr. Miniter's post. The entire article can be found
    via Google.
    " ... completely effective." There it is, the 1:9,999 dilution I've
    mentioned. Contrary to Mr.Knoppow's assertion, Mr. Nishimura states
    that
    sodium sulfide does react with silver.
    Mr. Nishimura is likely speaking of 5 to 55 gallon drums. I've
    worked with sodium sulfide and never noticed any oder. I've used it
    in the sulfer for silver test to confirm complete fixing.
    Dan
     
    Dan Quinn, May 4, 2004
    #12
  13. Mike

    Dan Quinn Guest

    RE: (Dan Quinn) wrote
    Pardon me, sulfur is correct sulfer is not. //
     
    Dan Quinn, May 5, 2004
    #13
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