new vanadium toner

Thread view:

Enable EMail Alerts

Start New Thread

Thread rating:

Wilco Oelen - 21 Jun 2004 22:24 GMT

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.

http://www.woelen.nl/photo/toner.pdf

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

Wilco Oelen

PS: The email address photo@woelen.nl, 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.

Reply to this Message

Richard Knoppow - 22 Jun 2004 03:09 GMT

> Hello, all of you photographers,
>
[quoted text clipped - 25 lines]
> 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.

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.

Signature

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

Reply to this Message

Tony Wingo - 22 Jun 2004 19:59 GMT

> 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.

Tim Rudman gives formulae for two Vandium-based green toners -- GT-16
and Walls -- in his Toning Book.

> As you know most published formulas for green toners are
> combinations of Sulphide sepia and Iron-blue toner and are
> not completely permanent.

Rudman states that while Vandium based toners are not archival, they are
"reputed to be very permanent".

Signature

-tony

<http://www.shapesandshadows.com

Reply to this Message

Wilco Oelen - 10 Jul 2004 21:22 GMT

> > This is a very interesting paper. There have been other
> > Green toners in the past using Vanadium compounds. I will
[quoted text clipped - 12 lines]
> Rudman states that while Vandium based toners are not archival, they are
> "reputed to be very permanent".

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

Reply to this Message

Robert Feinman - 22 Jun 2004 16:09 GMT

> Hello, all of you photographers,
>
[quoted text clipped - 5 lines]
> with lots of variations, allowing greens, olive greens and sepia
> variations).

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..

Signature

Robert D Feinman
Landscapes, Cityscapes and Panoramic Photographs
http://robertdfeinman.com
mail: robertdfeinman@netscape.net

Reply to this Message

Richard Knoppow - 23 Jun 2004 01:48 GMT

> > Hello, all of you photographers,
> >
[quoted text clipped - 21 lines]
>
> It's hard to discover anything new in conventional photography..

I found the following in the "British Journal Almanac"
for 1940
For Green Tones
Solution A
Potassium Fericyanide 2.0 grams
Distilled water to make 100.0 ml

Solution B
Vanadium Chloride stock solution 3.0 ml
Ferric Ammonium Citrate (green scales) 1.0 gram
Sodium Citrate, neutral 25.0 grams
Ammonium Chloride 2.0 grams
Hydrochloric Acid 14.0 ml
Distilled water to make 100.0 ml

The Hydrochloric Acid is specified as being Specific Gravity
= 1.16

The Vanadium stock solution is made by mixing:
Vanadium Chloride ("syrupy") 28.4 ml
Hydrochloric Acid 18.0 ml
Distilled water to make 62.0 ml

In making up the B solution first add teh hydrochloric
acid to the vanadium solution. then dissolve the ferric
citrate, sodium citrate, and ammonium chloride in 100.0 ml
of water and mix the two. Solution should be dull mauve
blue; not green - until mixed with A.
Both A and B solutions will keep for months at least.
To mix the toning solution take 1 part A and 4 parts
water, and separately, one part B and 4 parts water. Mix the
two diluted solutions together to make the toner.
Prints tone in 4 to 8 minutes. Rock constantly, then
wash in 5 changes of water, each of 2 minutes, give a bath
of hydrochloric acid, 1 part, and water, 50 parts, for 2
minutes, and finally wash for 15 minutes in 7 or 8 changes
of water. Prints should be of the ordinary depth. The green
tone is permanent.

The above is somewhat of the kitchen chemistry type
formula. I suspect, that since part of the toner is
Iron-blue, the final tone may depend on the acidity of the
wash water. Iron toners are bleached by alkaline wash water
so must be washed in water which has been acidified, usually
with a little Acetic acid. I suspect the color of the final
image here is likely affected in a similar way.
I stress that I am posting this for reference. I have
not tried the formula and have no idea of whether it works.
In general, BJA formulas are reasonably reliable.
If you try this watch out for the Hydrochloric acid.
Concentrated Hydrochloric is nasty stuff and very hazardous.

Signature

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

Reply to this Message

Wilco Oelen - 23 Jun 2004 09:11 GMT

> > From my 1924 edition of Wall, "Photographic Facts and
> Formulas"
[quoted text clipped - 14 lines]
> > It's hard to discover anything new in conventional
> photography..

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

Reply to this Message

Richard Knoppow - 24 Jun 2004 01:04 GMT

> > > From my 1924 edition of Wall, "Photographic Facts and
> > Formulas"
[quoted text clipped - 29 lines]
>
> Wilco Oelen

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:-)

Signature

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

Reply to this Message

Wilco Oelen - 24 Jun 2004 21:15 GMT

> 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:-)

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
this.

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

Reply to this Message

Richard Knoppow - 27 Jun 2004 00:52 GMT

> > You've now put a bee in my bonnet because I saw somewhere
> > a method of making Vanadium chloride. I don't remember where
[quoted text clipped - 41 lines]
>
> Wilco

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.

Signature

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

Reply to this Message