[alt-photo] Re: ANYONE? CYANO TONER WITH COPPER?
KISS BOB
bobkiss at caribsurf.com
Thu Oct 25 10:59:37 GMT 2012
DEAR DON,
Thanks for that link to some great work but, sorry,
the pecan color is not the green about which I read. The
effect was to shift cyano from the blue-green (cyan) to
green...grass green. But again thanks for your efforts!
CHEERS!
BOB
On Thu, 25 Oct 2012 12:06:45 +1300
"Don Sweet" <don at sweetlegal.co.nz> wrote:
> Hi Bob
>
> Someone posted a link to this exhibition a few months
>ago, and I recalled
> the unusual colour of the pecan dyed cyanotype about 2/3
>of the way down the
> page. Is that close?
>
> http://www.suntomoon.com/pages/ntapg_images.html
>
> Don Sweet
>
> ----- Original Message -----
>From: "BOB KISS" <bobkiss at caribsurf.com>
> To: "'The alternative photographic processes mailing
>list'"
> <alt-photo-process-list at lists.altphotolist.org>
> Sent: Thursday, October 25, 2012 9:10 AM
> Subject: [alt-photo] Re: ANYONE? CYANO TONER WITH
>COPPER?
>
>
> DEAR CHRIS,
> Must your answers always be so short and dismissive???
> JUST
> KIDDING! LOL!!! I really appreciate how thoroughly you
>have replied to
> both this request and my request for additions to my
>chem "wish list"!
> Thanks so much! You are great!
> However, as I walk slowly into the sunset, skipping the
>light
> fantastic, I continue my search for a toner (which I
>thought contained
> copper) to turn Cyanotypes more green.
> CHEERS!
> BOB
>
> -----Original Message-----
>From:
>alt-photo-process-list-bounces at lists.altphotolist.org
> [mailto:alt-photo-process-list-bounces at lists.altphotolist.org]
>On Behalf Of
> Christina Anderson
> Sent: Wednesday, October 24, 2012 3:58 PM
> To: The alternative photographic processes mailing list
> Subject: [alt-photo] Re: ANYONE? CYANO TONER WITH
>COPPER?
>
> Bob,
> It was a version of Obernetter's formula, I think, that
>used copper; a
> formula I shared a long time ago from Jim Patterson.
> Sorry I can't edit right now but this is what was
>posted. No green tho, but
> reddish brown. All my notes from the list, below. Again
>I apologize for
> lengthy.
> Chris
>
> Obernetter (iron based, 1864).
>
> Anybody knows who is the author of the article in
>Popular Photography 1978
> cited in http://pinhole.stanford.edu/cp.htm
>
> Hi Alberto
>
> I have not yet tried this process, but I may argue that
>your blue hue
> developing with time might be prussian blue due to iron
>left by an
> insufficient clearing. This is also in the
>Troubleshooting section of the
> article above.
>
> I also thought it could be a clearing problem and that
>is why I have always
> used freshly made chemicals and doubled the clearing
>time but that didn't
> seem to make a difference. I have also increased the
>wash time in case it is
> the toner that is not being cleared. It still could be
>the clearing time and
> I am just having trouble clearing the Iron out of this
>paper. I was also
> wondering if I have Iron in the wash water. I live in a
>large city and have
> been using tap water for the final wash. I may try
>increasing the clearing
> time and see what happens. I could also shorten the
>clearing time to see if
> it increases the problem. One of the problems is that
>it takes so long to
> find out if it will stain.
>
> perhaps a good reference about this process is in
> http://www.usask.ca/lists/alt-photo-process-l/200710/msg00135.html
>
> As for the chemistry, if the description of the article
>is too complex to
> you, it can be resumed as:
>
> 1) iron(III) is reduced to iron(II) by light;
>
> 2) iron(II) reduces Cu(II) to Cu(I) and
>copper(I)thyocyanate is formed;
>
> 3) iron is removed by thyocyanate (blood-looking
>compound);
>
> 4) ferricyanide oxidizes copper(I) to copper(II) and the
>resulting
> ferrocyanide reacts forming copper(II)ferrocyanide
>(brown). Alberto
>
> So I have now made several attempts at making Cuprotype
>prints using Jim
> Patterson's formula that Christina posted in October. I
>have had varied
> results and a near disaster(that's another story). The
>resulting colour tone
> is a wonderful terra cotta red when I used BFK paper
>and a not quite, but
> still good, colder tone when I used Platine. The dmax
>is good when it is
> wet but is too low when it dries. I have not tried to
>double coat or adding
> ammonium dichromate to bring that up but I have another
>problems that are
> more pressing. The problem is that the print is getting
>an overall light
> blue stain (some times not so light) after as short a
>period of 3 days and
> as long as 3 months. It looks fine after it has been
>dried and than
> after a period of time it quickly goes blue. It tends to
>be relatively even
> over the white paper surface, front and back. In order
>to stop this problem
> I increased the clearing bath from a total of 4 min to
>8 min with 3 baths,
> always with fresh chemistry. I also went from the 3
>changes of wash baths
> as recommended to 30 minute wash time. One of the
>prints that I did I
> washed for 2 hours and it still had a light blue tinge.
>So my questions are
>
> 1) Is anyone else trying this process and have they
>experience and similar
> problems? 2) Could this be the reason that this process
>never caught on,
> that it is not stable? 3) I am not a chemist but can
>some one explain to me
> in layman's terms how this process works. It is not
>like other photo
> processes, with this you coat the paper than develop
>that paper until the
> image disappears, than you "clear" it with the
>developer that has been
> diluted(what's that going to do). The blank paper is
>than put into a strong
> bath of chemicals which is normally used as a bleach and
>a photograph
> appears and than you wash it in water. Is that magic or
>what. Thanks for any
> help Bruce
>
> Hi Chris, Good to hear from you. Here's some info that
>may help.
>
> The first image formed in the developer is copper (1)
>thiocyanate, and the
> citric acid in the developer is to help mobilize the
>iron out of the paper.
> The clearing bath is diluted developer to have a small
>amount of thiocyanate
> to keep the copper thiocyanate insoluble by common ion
>effect, and the
> citric acid helps remove the iron. Adding more citric
>acid to the clearing
> bath will help remove the iron better, but if it is too
>high it may remove
> part of the copper thiocyanate image. I toyed with the
>idea of making a
> separate clearing bath, which may be more effective,
>with a small amount
> thiocyanate and more citric acid, but I was trying to
>avoid more solutions
> and keep it simpler. Example: Clearing Bath: 0.1 %
>ammonium thiocyanate
> and 1 % citric acid. If you don't clear the iron salts
>out of the paper,
> when you add it to the toner (potassium ferricyanide),
>any iron immediately
> reacts with the ferricyanide to cause a permanent blue
>stain. Use distilled
> water for the clearing bath to avoid iron in tap water.
>
> The WASH of dilute acetic acid is to remove the
>ferricyande toner out of the
> paper. If ferricyanide is not removed from the paper,
>it auto- decomposes
> after some time to iron ferricyanide, the blue stain.
> If your tap water has
> iron, use distilled water. Also a 1% citric acid wash
>may work better than
> the acetic acid wash. Thanks,Jim Patterson
>
> ----- Original Message -----
>
>From: "Bruce" <steelbar at shaw.ca>
>
> CUPROTYPE (Obernetter's Process, Ferrocupric Process,
>Copper Print) Jim
> Patterson10-5-07
>
> J. B. Obernetter developed his process in 1864. The
>original formula is
> noted in Jan Arnow's "Handbook of Alternative
>Photographic Processes",
> 1982, page 113.
>
> "Copper Print" is from a 1978 Popular Photography "How
>to" guide. See
> http://pinhole.stanford.edu/cp.htm for details.
>
> GENERAL: A contact printing photographic process
>analogous to Cyanotype;
> full size negative, print frame, UV exposure. The image
>is reddish-brown
> copper ferrocyanide. All solutions are w/v (weight in a
>final volume),
> dissolving each salt completely before the next is
>added, in 10% less water
> than the final volume. Make up to final volume when all
>salts are
> dissolved. Use very pure chemicals and distilled water,
>and plastic or
> glass trays, vessels, stirring rods, etc. Try these
>processes at your own
> risk. The chemicals can cause property damage,
>environmental damage,
> personal injury, or even death. Store the stable
>solutions in brown glass
> bottles, plastic caps, plastic cap liner (corrodes
>metal). Damp coated
> paper (high humidity) may damage negatives. Use kitchen
>plastic wrap
> between the negative and paper if needed. Sunlight and
>florescent light fog
> the coated paper. Agitate trays during processing.
>
> PATTERSON'S modified Obernetter's Process (MO3)
>
> SENSITIZER: 100 ml distilled water
>
>
> (Stable) 12grams ferric ammonium citrate
>(green)*
>
> 12 grams copper sulfate,
>hydrated (CuSO4.5 H2O)
>
> *ferric ammonium oxalate & ferric oxalate do not
>work; precipitate
> with copper.
>
> Light sensitive component; mix in safelight area
>(yellow bug light,
> tungsten)
>
> DEVELOPER: 1000 ml distilled water
>
> (stable) 10 grams citric acid (hydrous
>or anhydrous)
>
> 10 grams ammonium
>thiocyanate (NH4SCN)
>
> (can substitute potassium-
>or sodium-
> thiocyanate)
>
> Or make a 10% C.A, 10% A.T. stock solution and
>dilute 1 part stock :
> 9 parts water.
>
> CLEARING BATH: 750 ml distilled water + 250 ml
>DEVELOPER (1 part
> developer : 3 parts water)
>
> TONER: 1000 ml distilled water
>
> (Stable) 20 grams potassium
>ferricyanide (K3Fe(CN)6)
>
> (or make a 20% stock
>solution and mix1 part
> stock: 9 parts water)
>
> WASH: 900 ml tap water + 100 ml white vinegar, or add
>5 ml glacial acetic
> acid (CAUTION: noxious fumes) to 955 ml water. If your
>tap water has iron,
> use distilled water to avoid blue staining. This is a
>0.5 % acetic acid
> solution.
>
> Coat paper with sensitizer in a darkened room with
>yellow bug light or low
> wattage tungsten lights; no fluorescent or sunlight.
> Dry with forced air
> (fan, no heat) & expose in print frame to UV light until
>an image is
> present. Work out your own exposure time. I have kept
>coated (no
> dichromate) dry paper in a dark, dry place for 3 days
>and it works ok. I
> don't know how long it lasts. I usually coat, dry, and
>expose the same day.
> Adding a drop of Kodak Photoflo to the sensitizer makes
>it coat better.
> Tween 20 might work (I didn't have any) but I'm unsure
>if it's compatible
> with copper.
>
> Tray develop in DEVELOPER until the shadows clear of
>orange color and are
> pale gray. About 3-5 minutes. Highlights may have a
>slight orange stain at
> the end of development. The developer will be slightly
>orange in color
> (iron salts). One shot developer. Do not save or
>reuse.
>
> Place directly into CLEARING BATH, series of 3 tray or
>solution changes,
> until highlight are clear (paper white) and solution is
>clear. If you don't
> get all the orange out (iron salts) the print will be
>blue stained in next
> step. About 5 minutes, longer with thick or unsized
>papers. The image is
> now copper (I) thiocyanate, which is a dye mordant.
> (You can stop at this
> point and dye-tone the image with basic dyes (methylene
>blue, basic brown,
> basic fuchsin, etc) in a 2.5 % acetic acid dye bath
>(0.1% dye). Wash in a
> 2.5% acetic acid wash and dry. 2.5% acetic acid is 1
>part vinegar : 1 part
> water.) Or continue on for the Cuprotype if you are not
>dye toning.
>
> Place directly into TONER until fully toned to reddish
>brown image (About
> 15-20 min). The image is now copper ferrocyanide.) A
>tray of toner can be
> used for more than one print but discard when it slows,
>and do not pour back
> into the stock bottle. The thiocyanate from the prints
>causes it to break
> down. Discard at the end of a work session.
>
> Transfer to WASH, 3 or more tray or solution changes
>until highlights are
> clear and solution is clear. Check the back of the
>paper. About 10
> minutes. Thick papers clear slowly. Thin or dip sized
>papers clear faster.
> See TROUBLESHOOTING.
>
> If your tap water is alkaline or hard, final wash in
>distilled water +
> vinegar as above.
>
> Dry and marvel.
>
> CONTRAST CONTROL: Do NOT use potassium chlorate, as the
>copper chlorate
> that forms is EXPLOSIVE when dry!!! It may be better to
>tailor your
> negative to the characteristic curve with 1 drop
>dichromate to clear the
> highlights. I use 30% ammonium dichromate drops
>(CAUTION: dermatitis,
> carcinogenic; handle carefully), with 0-4 drops in 2 ml
>sensitizer.
> Ammonium persulfate and hydrogen peroxide do not work.
> (Just for your info,
> I tried potassium chlorate in a very safe area and it
>didn't work either.)
>
> PERMANENCE: USDA tests show that copper ferrocyanide
>used as a pigment in
> outdoor fences holds up well. Probably as permanent as
>Cyanotype, and does
> not bleach on light exposure.
>
> AMIDOL TONING: see the Copper Print http reference.
> Works fast. 250 ml
> water, 5 grams citric or acetic acid, 0.2 gram amidol.
> Soak the print for 1
> minute, wash in the WASH and dry. It darkens
>dramatically to a dark warm
> brown as it dries. I think the copper ferrocyanide acts
>as a mordant,
> binding the amidol, which oxidizes to the familiar dark
>brown as it dries.
>
> GALLIC ACID TONING: Brown image, lower Dmax just as
>with Cyanotype.
>
> PAPER: I have used Crane's Diploma Parchment (very
>sharp image, no
> bleeding, & ferricyanide stain clears easily). Arches
>Hot Press Watercolor
> Paper (slight texture) and Cold Press (moderate texture)
>work but are slow
> to clear the ferricyanide stain. (See TROUBLESHOOTING)
> I am sure other
> papers work, but some do not. Don't use buffered paper
>or paper filled or
> sized with calcium carbonate or magnesium carbonate as
>alkalis bleach the
> image. Works on cotton fabric also.
>
> TROUBLESHOOTING: Low Dmax: double coat the paper,
>drying between coats or
> size the paper. Blue Staining: Iron contamination of
>solutions, iron not
> cleared completely in CLEARING BATH, or toner
>(ferricyanide) was not washed
> out of the print. Increase the clearing or wash times.
> If a thick paper
> has a yellow ferricyanide stain after a long wash, you
>can soak it in a
> solution of 500 ml water, 5 grams acetic acid, 5 grams
>zinc sulfate & 5
> grams sodium sulfite, which converts the potassium
>ferricyanide to zinc
> ferrocyanide, a white pigment used in marine paints.
> Then WASH to remove
> excess salts and dry.
>
> ARCHIVAL WASH: Don't! The long alkaline tap water wash
>will dissolve part
> of the image making it fuzzy or weak. Use tray washes
>of dilute acetic
> acid.
>
> MOUNTING & STORING: Don't use buffered mats or papers.
> See PAPER above.
>
> EXPOSURE: I use a homemade UV unit of eight, 18-inch
>black light bulbs from
> Home Depot about 3 inches from the print frame. My
>exposure time is about 5
> minutes with no dichromate added. 30-150% longer with
> increasing
> dichromate additions.
>
> COPPER PRINT: A printing out version. Develops in
>water. See the http
> reference. I get staining of highlights and bleeding of
>shadows, but
> Obernetter's gives sharp prints with clear highlights.
>
>
>
> EXPERIMENTAL NOTES: I tried the original Obernetter's
>formula: Sensitizer:
> ferric chloride, copper chloride, with added
>concentrated hydrochloric acid.
> Developer: potassium thiocyanate with added
>concentrated sulfuric acid and
> some senstizer added (why?). Slow process, very long
>scale and very
> difficult to clear the iron salts. Split tones with
>reddish brown shadows
> and blue highlights were common, due to cyanotype
>reaction in the toner when
> all ferric salts not removed in washing. Almost
>impossible to clear the
> iron with a water wash. The developer is dark blood red
>and can't see the
> print unless you pull it out of the solution. I don't
>recommend it.
>
>
>
> I first modified the formula (MO1) to use 1 % citric
>acid instead of
> hydrochloric acid and sulfuric acid in the sensitizer
>and developer
> respectively, and left the sensitizer out of the
>developer. The clearing
> bath I added to get the iron out and keep some
>thiocyanate ion in the bath
> to keep the copper (I) thiocyanate in the print by
>common ion effect. It
> is also slow (20 min exposure) but clears the iron out
>easily. Very fine
> grained smooth image. The 21 Stouffer step wedge gives
>about 18 steps.
>
> (OM2) I next tried ferric ammonium citrate to replace
>the ferric chloride
> with a great increase in speed and about the same long
>scale on step wedge.
>
> (OM3) is the process above, with ferric ammonium citrate
>and copper sulfate.
> If you have very long range negatives, such as an older
>process with glass
> negatives, the long range of the process without
>dichromate may match well.
> The best print is probably from a long range negative
>with 1 drop dichromate
> in the sensitizer to keep the highlights clear and the
>scale matching your
> negative. Photoshoping the image to match the scale of
>the process will
> probably work great. With very high dichromate levels
>the print is grainier
> and much longer exposure.
>
> The Copper Print is analogous to the New Chrysotype by
>Mike Ware, in that
> the potassium ferricyanide and copper sulfate are mixed
>together as the
> sensitizer and the process is mostly a printing out one
>with washing
> (developing) in water. But without ligands (complexing
>agents) like
> citrate, acetate, etc., the copper precipitates as
>copper (II) ferricyanide,
> just as gold does in chrysotype without the 3,3
>dithiopropionic acid ligand.
> I tried disodium EDTA alone, sodium citrate (tribasic)
>alone, ammonium
> citrate (tribasic) alone and combinations with sodium
>acetate as in the
> reference. The starting weight ratio of copper sulfate,
>hydrated, to sodium
> citrate is 1:4 which is also about the molar ratio.
> Speed is fast, but
> staining of highlights and bleeding is a problem, just
>as with the New
> Chrysotype with low ligand ratios. By increasing the
>ratio to 1:5 and 1:6
> the staining of highlights is reduced and the contrast
>is increased, but the
> Dmax is decreased and exposure is increased, just as
>with the New
> Chrysotype. Also, as with New Chrysotype, the Copper
>Print sensitizer is
> unstable after mixed and must be coated, exposed and
>washed (developed)
> quickly. I never got prints as sharp and clean with
>this process as with
> the modified Obernetter's. I also had great difficulty
>with ammonium
> persulfate causing a precipitate (potassium persulfate
>was worse.) Ammonium
> dichromate worked better for me.
>
> I also coated paper with ferric oxalate 10 % solution
>and exposed. Very
> fast exposure. (1 min.) This can then be placed in TONER
>directly for a
> cyanotype, or transposed to copper ferrocyanide by using
>a reagent of copper
> sulfate, complexed with citrate (1:5 sodium citrate) and
>ammonium
> thiocyanate The reagent is unstable after mixing and
>must be kept in
> separate bottles and mixed just before use. It is slow
>to convert to copper
> (I) thiocyanate, and then it is cleared and toned just
>as for Obernetter's.
> The image tends to be grainy. Obernetter's has stable
>reagents and is
> faster to complete.
>
> The image is redder, grainier, & printing speed faster
>with increasing pH
> of the sensitizer used. I like the color of the
>modified Obernetter's
> detailed above. Lower pH sensitizers respond to smaller
>doses of
> dichromate. Higher pH sensitizers take a lot of
>dichromate to modify
> contrast. GOOD SOUPING! I know you real photographers
>can make great
> images with these processes.
> Christina Z. Anderson
> christinaZanderson.com
>
> On Oct 24, 2012, at 1:42 PM, BOB KISS wrote:
>
>> Anyone? Was it cupric sulfate or chloride?
>>
>>
>>
>> DEAR LIST,
>>
>> I am going bonkers trying to find a formula
>>for a toner that
>> changes cyanotypes to a more greenish color. I seem to
>>recall that it
> uses
>> cupric sulfate but I just can't seem to find the
>>formula. I have looked
> in
>> Christopher James' Alternative Photo Processes and even
>>Googled it. Can
> any
>> of you send me the formula?
>>
>> CHEERS!
>>
>> BOB
>>
>>
>>
>> Please check my website: <http://www.bobkiss.com/>
> http://www.bobkiss.com/
>>
>>
>>
>>
>> "Live as if you are going to die tomorrow. Learn as if
>>you are going to
>> live forever". Mahatma Gandhi
>>
>>
>>
>> "Madonne e fiori, trionfo eterno di gioventù!" from
>>Mattinata Fiorentina
> by
>> Antonella Ruggiero
>>
>>
>>
>>
>>
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