Add Kodak Brown to KRST?

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

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


Mike wrote:

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 wrote:
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


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

"Mike" wrote


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.


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 wrote:

"Mike" wrote


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.



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


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

"Mike" wrote

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?

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.

Francis Mitner wrote:

... 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 potash (aka liver of sulfur,
potassium trisulfide) as a contaminant ...

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, Cleveland, Ohio
Consulting Engineer: Electronics; Informatics; Photonics.
psst.. want to buy an f-stop timer? nolindan.com/da/fstop/

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

....
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.

....

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 wrote

"Nicholas O. Lindan" wrote:

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.

apr2604 from Lloyd Erlick,

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

I searched for an amount of sulfide I could put into
my selenium toner...

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

"Francis A. Miniter" wrote in message ...
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


Mike wrote:

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



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

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


Richard Knoppow wrote:

"Francis A. Miniter" wrote in message ...


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


Mike wrote:



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





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