[alt-photo] Re: Trying to understand how ferric chloride reacts with gum arabic

[Mike and Jan Andrews]

Hi Kees
 
Thanks for your reply.  If you would like to join the experiments we are discussing on alternativephotography.com you would be most welcome 
 
I have mainly experimented with gum myself but I have also tried gelatine.
 
You say that you tried adding ferric chloride to the ferric ammonium citrate in Halvor's Chiba system, and it didn't work well.  I'm not sure why it would work.  Certainly adding citrates tends to prevent ferric salts hardening gum or gelatine (oxalates and tartarates do so less).  But it's not obvious to me how the ferric chloride would help in this case.  In my process the ferric chloride hardens the colloid in the unexposed areas, but one would hardly want that to happen in the Chiba system!
 
I am intrigued when you refer to
"... carbon techniques where a coat of dichromate is exposed and pigmented gum is brushed over it. Here the hardening compound is allso diffusing in the colloïd."
 
I can see why this would work if the right amount of ferrous sulphate was added to the gum, for example.  The unexposed dichromate would diffuse up through the gum and be reduced by the ferrous salt.  Then two kinds of hardening would occur simultaneously.  The reduced dichromate would harden the gum in the normal way.  But the ferrous sulphate would also be converted to ferric.  Then it would harden the gum too, as it does in my process.  In fact the whole process is like an 'upside down' version of my process, when it is made to be negative-working.
 
But if unmodified gum was brushed across the dichromate how would it get hardened?
 
Michael
 
 
 
> From: workshops at polychrome.nl
> Date: Wed, 8 Dec 2010 13:58:34 +0100
> To: alt-photo-process-list at lists.altphotolist.org
> Subject: [alt-photo] Re: Trying to understand how ferric chloride reacts with gum arabic
> 
> Hi Michael,
> 
> I saw your articles, and the forum discussion, about this process on alternativephotography.com too. As I am working with Halvor Björngårds ferric approach to carbon printing I also am interested in other ferric (direct) carbon techniques. I experimented too with different mixes of ferric chloride and ferric ammonium citrate. The reason I did that was that I had found a patent that explained a method of mixing a simple and complex ferric salt to better control the hardening of colloids. The advantage acording to the patent was a higher light sensitivety whithout the immediate hardening that occurs when ferric chloride is mixed in the pigmented gelatin for carbon. But.... it didn't work very well. So I continued working with the ferric ammonium citrate alone.
> 
> So I do have some experience with ferric hardening of colloids.
> The direct carbon ferric chloride technique you describe also reminds me of other direct carbon techniques where a coat of dichromate is exposed and pigmented gum is brushed over it. Here the hardening compound is allso diffusing in the colloïd.
> This principle works also with cyanotype itself (but maybe not by diffusion). Coat a paper with solution A, dry and expose and brush (locally!) solution B over it. Fun to do!
> 
> The colour change in the ferric salt/ colloïd mix I also encountered. It is a stain that is very difficult to clear from the paper base. I once tried to make a ferric oilprint paper with a heavy unpigmented gelatin. After exposure there is a serious relief, but also a very dark stain. When I experimented with mixing ferric chloride / ferric citrate mix in a warm liquid gelatin, the resulting mess was also almost brown.
> 
> Kees
> 
> 
> 
> On 6 dec 2010, at 13:51, Mike and Jan Andrews wrote:
> 
> > 
> > I am working on a printmaking process which involves ferric chloride reacting with gum arabic. But I am having some difficulty understanding certain things about it. Can anyone help me with their ideas!
> > 
> > The process starts by making an image on paper with ferric chloride. This can be done photographically or by other means. Then liquid gum is flowed or brushed across the image. The ferric chloride is dissolved by the gum and it diffuses upwards, hardening the gum as it goes. This produces a relief image where the ferric chloride image was.
> > 
> > The relief is very robust. It is probably held together by the ferric ions forming 'bridges' between OH groups in the gum.
> > 
> > The first thing I don't understand is the relationship between the amount of ferric chloride and the thickness of the relief. Each amount of ferric chloride produces its own thickness of relief, and these amounts and thicknesses seem to stay constant however much I try to change them!
> > 
> > Why does a given amount of ferric chloride diffuse just so far and fix a certain thickness of gum?
> > 
> > Can anyone suggest what factors might be at work here? Alternatively can anyone suggest a way to make the ferric chloride diffuse further into the gum? It does't matter if the crosslinking is made less 'dense' because the relief is currently much more robust than it needs to be.
> > 
> > +++++++++++++++++++++++++++++++++++++++++++++++++
> > 
> > The other thing I don't understand concerns the series of events which occur when the ferric chloride diffuses into the gum.
> > 
> > First the gum gets fixed and this occurs before any colour change happens. Then the 'ferric and gum' mixture starts to change colour. It turns light brown, then it darkens and ends up a rich reddish brown. These events appear to happen all at once unless the gum is previously acidified with HCL.
> > 
> > Is there any possiblity that the ferric ions crosslinking the gum could also participate in the subsequent colour changes without affecting the crosslinks?
> > 
> > If this is impossible then additional ferric ions must be causing the colour changes. In that case why do these additional ferric ions get stuck instead of diffusing further into the gum, just as the first lot did?
> > 
> > Any help with these difficulties would be most appreciated!
> > 
> > Michael Andrews
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