KISS BOB bobkiss at caribsurf.com
Thu Oct 25 10:59:37 GMT 2012

      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!

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 
> <alt-photo-process-list at lists.altphotolist.org>
> Sent: Thursday, October 25, 2012 9:10 AM
> Subject: [alt-photo] Re: ANYONE? CYANO TONER WITH 
> Must your answers always be so short and dismissive??? 
> 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 
> fantastic, I continue my search for a toner (which I 
>thought contained
> copper) to turn Cyanotypes more green.
> -----Original Message-----
>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 
> 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 
> 4) ferricyanide oxidizes copper(I) to copper(II) and the 
> 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 
>                             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 
> 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.
> 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 
> 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 
> 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?
>>            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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