new vanadium toner

Discussion in 'Darkroom Developing and Printing' started by Wilco Oelen, Jun 21, 2004.

  1. Wilco Oelen

    Wilco Oelen Guest

    Hello, all of you photographers,

    I have done quite some research on toning with different colors and
    could not find a suitable recipe for yellow and green toners with
    common chemicals. I have some knowledge of chemistry, although I'm not
    a professional in that field. Based on my knowledge of vanadium
    chemistry, I have come up with a vanadium toner (yellow base toner
    with lots of variations, allowing greens, olive greens and sepia
    variations). I would like to share the results with other people and
    would appreciate feedback and improvements (no, nothing is perfect in
    this world and everything can be improved...). The toner gives good
    results, but preparation is still somewhat cumbersome and for many
    darkroom hobbyists there may be too much hassle with chemicals,
    although I expect that many others will not have any problems with it.
    If somebody sees a way to make preparation easier, then this would
    really be a nice toner.

    In order to keep this posting short, just a link to a PDF file,
    containing a description of the toner.

    I hope this is interesting for some of you out there.

    Wilco Oelen

    PS: The email address , given here, will be removed
    soon if it receives too much spam. For the definite address replace
    photo by the dutch word foto and I prefer replies on the foto-address.
    Wilco Oelen, Jun 21, 2004
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  2. foto-address.

    This is a very interesting paper. There have been other
    Green toners in the past using Vanadium compounds. I will
    see if I can find some formulae. In some books its only
    mentioned that Vanadium-green toners exist but without
    description or formula. I think I have one or possibly two
    formulas somewhere.
    As you know most published formulas for green toners are
    combinations of Sulphide sepia and Iron-blue toner and are
    not completely permanent.
    Richard Knoppow, Jun 22, 2004
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  3. From my 1924 edition of Wall, "Photographic Facts and Formulas"
    A bath:
    Potassium ferricynaide 50g
    water l liter
    ammonia (enough to smell distinctly!)

    B bath:
    Vanadium chloride - 2 percent solution
    ferric chloride 2 percent solution

    For use: 125cc of A & B
    water to make 1 liter

    There are three other formulas as well using oxalic acid

    It's hard to discover anything new in conventional photography..
    Robert Feinman, Jun 22, 2004
  4. Wilco Oelen

    Tony Wingo Guest

    Tim Rudman gives formulae for two Vandium-based green toners -- GT-16
    and Walls -- in his Toning Book.
    Rudman states that while Vandium based toners are not archival, they are
    "reputed to be very permanent".
    Tony Wingo, Jun 22, 2004
    Richard Knoppow, Jun 23, 2004
  6. Wilco Oelen

    Wilco Oelen Guest

    From my 1924 edition of Wall, "Photographic Facts and
    I agree that really new things in photography are very hard to find.
    What may make this 'new' toner interesting, however, is that only
    common, cheap and easy to obtain chemicals are needed. I have tried to
    find a source of vanadium chloride of any oxidation state and did not
    succeed. Finally I could obtain some vanadyl sulfate pentahydrate,
    which was very expensive ($99 for 100 grams), and which only has a low
    vanadium contents and hence is used up quickly.

    This made me look for more economical alternatives. I have used
    vanadium pentoxide, as stated in the original posting, with great
    satisfaction and this can be obtained at many ceramics/pottery supply
    stores at low cost (some sources are given in the article). It has a
    high vanadium content, so only small amounts of this are needed.

    Wilco Oelen
    Wilco Oelen, Jun 23, 2004
  7. You've now put a bee in my bonnet because I saw somewhere
    a method of making Vanadium chloride. I don't remember where
    but it seems to me it wasn't too difficult. A toner which
    does not use concentrated Hydrochloric is an improvement
    right there:)
    Richard Knoppow, Jun 24, 2004
  8. Wilco Oelen

    Wilco Oelen Guest

    You've now put a bee in my bonnet because I saw somewhere
    I strongly doubt that you had a method for making vanadium chloride.
    Vanadium chloride is very hard to prepare for the average home
    hobbyist/chemist. This compound comes in three oxidation states, of
    which VCl2 (+2 oxidation state) and VCl3 (+3 oxidation state) are very
    prone to oxidation and extremely moisture sensitive and hardly can be
    kept outside the laboratory. VCl4 is more stable, with respect to
    oxidation, but it is even more sensitive to moisture than VCl3 and
    VCl2. It is a brown fuming liquid. This may be the 'sirupy' vanadium
    chloride mentioned in a recipe from the 1940's in this sequence of
    postings, but I'm not sure. Compounds of vanadium, which are easier to
    handle are hydrated vanadYL chloride and hydrated vanadYL sulfate.
    Vanadyl is vanadium in oxidation state +4, very tightly bound to one
    oxygen, hence [VO]2+, which is nice bright blue, when hydrated. I have
    bought some vanadyl sulfate (VOSO4 . 5H2O) at $99 per 100 g, which to
    my opinion is expensive. Vanadyl chloride (VOCl2 . xH2O) is even more
    expensive. Both the vanadyl sulfate and the chloride can be used for
    vanadium toning, but because of the low vanadium content, a fairly
    large amount of this stuff is needed.
    What can be done fairly easily is preparation of a vanadyl-salt
    (either sulfate or chloride) in solution from a vanadium compound in
    oxidation state +5, albeit that some noxious chemicals are needed for

    All recipes, based on vanadium toning mention vanadium chloride, but I
    personally believe these recipes are based on vanadyl chloride. If
    vanadium chloride of oxidation state, other than +4 is used, then
    these will be oxidized at once on addition of ferricyanide solution,
    as prescribed by many recipes.

    I tried my own recipe, as described in the paper, but without the use
    of hydrochloric acid or sulphuric acid, using sodium bisulfate
    instead. My attempt was not succesful, the result was really crappy.
    The toner, described in the paper gives remarkably white highlights,
    while with the bisulfate the highlights were almost as dark as the
    shadows, hence it is virtually useless. I'll try lateron with some
    other ratio's of chemicals, but I do not expect much of it. O.t.o.h.,
    the toner itself does not require concentrated acids, the starting
    concentration is just 10%.

    Wilco Oelen, Jun 24, 2004
  9. This was a vague memory, I nearly always remember anyting
    I've read, but not always where it was. What I saw was
    instructions for making some Vanadium compound that was
    needed for the particular toner but not easily avialable off
    the shelf.
    I think there may be some material on green or yellow
    toners among the papers published on the old three-color
    Cinecolor process. Its been many years since I read these.
    Super-Cinecolor was a process intended to compete with
    Technicolor for motion pictures. It used duplitized film
    (film coated with emulsion on both sides), each toned to an
    appropriate color, with a dye image printed on top of one
    side for the third color. It was not a successful process. I
    don't remember ever seeing a movie made in it. There was an
    earlier Cinecolor process which was two color, it was awful.
    I think only Republic Pictures ever used it for features.
    From what I've seen on Turner Classic Movies Paramount
    evidently tried Super-Cinecolor for a few short subjects. In
    any case, most of the technical papers were published in the
    Journal of the Society of Motion Picture Engineers (now the
    Society of Motion Picture and Television Engineers) c. late
    1940's. Authors are Allan Gundlefinger and possibly others.
    Richard Knoppow, Jun 27, 2004
  10. Wilco Oelen

    Wilco Oelen Guest

    I did some tests with the vanadium toned prints, with respect to
    'fastness' of the colors. Pictures, toned with the toner were kept in
    daylight, directly exposed to sunlight (on sunny days) for two months,
    during spring and early summer. We had a lot of sunshine during the
    testing period.

    All toners, described in the article were stable for at least this
    period, the yellow and green toners, together with their sepia
    versions, were stable from day 1 and did not change color noticeably.
    When the olive green version (no refixing after toning) is used, then
    the image tends to darken somewhat, the amount of darkening being
    proportional to the strength of the color (whites remain white).
    However, after a few days the final color is reached and no further
    changes are observed.

    These tests, of course, cannot be compared to decennia of storage, but
    they indicate that the colors, obtained with the toner, as mentioned
    in the article, are stable towards light. In practice, pictures
    usually are not displayed in full sunlight all the time.

    Wilco Oelen, Jul 10, 2004
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