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DISCUSSION OF ALTERNATIVE CHEMISTRY

     Another quick look into the chemicals of the traditional Noble print reveals that combining solutions of ferric oxalate (Fe2(C2O4)3) . 6 H2O, along with an approximately equal molar volume solution of platinum salt in the form K2PtCl4 and/or palladium salt in the form  Na2PdCl4 ,  yields a solution that is sensitive to ultraviolet light.  But are these the only forms of these reactants that will work together to form an image? Further research done over the years has come up with several variations that use it.
 

Ware/Malde process
     Let's first examine the first major scientific study of a platinum printing process.  In Michael Wares’  an “Investigation of Platinum and Palladium Printing “ published in 1986, the ammonium based printing  process was examined quite thoroughly.  When I saw this paper in 1991,  it helped confirm many aspects of the platinum/ palladium printing process that I had been observing in my prior 9 years of printing.  Although I was using the traditional based chemistry, I could see many of my theories being supported by Wares’ research.  Dr. Ware examines the process down to the molecular  level and provides the platinum printing world with its first hard look in many years.  He uses ammonium ferric oxalate  instead of the traditional ferric oxalate that he  describes as being  “ notoriously unreliable .”     Dr. Wares’ scientific research reveals  relationships between relative humidity, speeds of sensitizers,  and the color of prints.  It also covers  the molarities of the different compounds and how they work together, the relative contrast of platinum vs. palladium, what changes the addition of gold chloride and mercuric chloride  to the sensitizer produce, and much more.  It is important to note that Mr. Ware makes no claim that he has invented a new platinum process, just that these new chemistries offer certain advantages that can be applied to the printing of noble prints. 

Ziatype
     The other alternative to traditional chemistry was brought forth in 1994 when the world of the platinum/palladium printer was introduced to the Ziatype  by  Richard Sullivan , of  Bostick & Sullivan. It also uses Ammonium Ferric Oxalate. While the palladium salt Na2PdCl4 is the main metal salt used in Ziatypes,  it also uses the addition of a lithium chloride and cesium chloride in place of sodium chloride.  This allows printers to use palladium to produce prints that have a variety of colors, but in the case of cesium chloride introduce new problems, primarily that of insolubility.  The Ziatype has been reviewed in several photographic publications, most notably in PHOTO TECHNIQUES, July/August 1997.  The article written by Carl Weese , certainly gives the impression that the Ziatype is a brand new 19th century process,  when in fact it is very similar and related to the Ware/Malde process referred to earlier. As with other printing systems, the Ziatype incorporates other components that influence image color ; gold chloride, sodium tungstate, and others.  Sullivan and Weese have come out with a book to promote this printing system, The New Platinum Print.  In their book, TNPP, the Zia system is featured over traditional methods and it does not even go into any detail about the Ware/Malde system.  Even as late as May 1999, Mr. Weese had not even tried an ammonium based palladium solution. 

  The original Ziatype all but eliminated the use of a platinum salt,  although  in its later versions, platinum salts have been reintroduced back into the system. It is hard to see just what the Zia system is.  It has changed rapidly since Sullivan first introduced it to me at a gathering at his home in Santa Fe.   I believe that it is just a clever marketing tool in the B&S line of alternative printing supplies and a chance for Mr. Sullivan to make his mark on the alternative printing scene and on the world of platinum printing.

   Both  the Ware/Malde process and the Ziatype are printing out methods of  image creation.   Also, they both have a reliance on the control of humidity into the paper as a major part of the process.  The Ziatype uses the addition of ammonium dichromate in the developer to help control contrast. In most important ways however, the new methods and the traditional method share a common process; mix the sensitizer, coat the sensitizer onto a piece of high quality paper, dry the paper,  expose it to UV light, and process the exposed paper in several wet steps to produce a finished print. It is these steps that must be done well using any of the printing methods that allow for the creation of beautiful prints. 

ADDITIONAL & HISTORICAL ALTERNATIVES

   There have been many curious attempts made over the years to enhance the images either during processing or by adding different components to the coating solution.  The Palladio company  had ingredients to add to the developer to add warmth to the print.  There are also different ferric oxalates other than the more common ferric oxalate and  ferric ammonium oxalate.  Several early workers with platinum printing had formulas for using sodium ferric oxalate (SFO).  This has also been reborn and commercialized in the Zia formulas with the addition of lithium ferric oxalate (LFO). 

PRINT OUT vs. DEVELOP OUT
     So does the printing out method provide the printer with any substantial advantages vs. the developing out method?  First to take advantage of the inspection of print completion as seen in the printing out effect, the use of a split back printing frame is required.  The frame allows the printer to examine the print during the exposure.  This is accomplished by keeping pressure on a portion of the paper/negative sandwich. That part of the print that is not under pressure, can be inspect and the image can be seen on the exposed paper.  If it does not look like it has received enough exposure, simply shut the back and expose it some more.  Judging the exposure will take some practice as the image will look a little different than when the print is cleared and dried.  When you are well practiced at this step, test stripes will become a thing of the past.  Or will they?  If you use sturdy papers and don't print much larger than 7x 17 or 11x14 ,  you will be able to use the POP method and save yourself time by eliminating  test strips. 

    If however,  you use a vacuum frame or some other contact printing system that does not allow inspection of the print while maintaining registration of the negative /paper sandwich, the POP chemicals will not add any advantage to the printing process.   It also offers no advantage to printers who use fragile papers like Beinfang 360, as any motion of the paper/negative sandwich is not possible. 

     So why use the new vs. the old?  What do these new alternatives offer the noble printer? The POP printing methods allow for quicker printing due to visual inspection over test strips.  Does this make it a better process? For some the answer is yes, and yet for others it makes no difference.  Perhaps the new chemicals just offer a few more tools in the artistic tool box.  While the absolute chemical formula may be more stable for ammonium ferric oxalate, many prints have been made over the years with the traditional ferric oxalate, even with all its slight variations from batch to batch and maker to maker. 

   It should be noted that as you experiment with the combination of oxalates and metals salts, you will find some that work better than others.  Some may work one day, and then not at all the next. For instance, Mr. Ware suggest that by using a lithium palladium chloride with platinum, the lithium cations actually inhibit the platinum chemistry. Some may work today and then not as well several weeks later.  It is important to take good notes and to trust the source of your chemicals.  If you do not have good lab skills that include making detailed notes, than I might recommend that you stay away from too much experimenting, unless you are just trying different looks and will not try to repeat that look again.

   So rather than limit yourself to traditional methods only, I would suggest trying to incorporate some of the new elements into your printing procedure. I have not seen any better prints made with either the Ware/Malde or Ziatype process than have been made with the traditional chemistry. The goal is to make pleasing images.  It is best to start simple and expand your printing techniques as you gain control over the processes involved.  So after getting comfortable with the traditional chemistry; ferric oxalate, platinum salt K2PtCl4 and the palladium salt, Na2PdCl4 ,  move on and expand your capabilities. Soon you will settle in on a process that gives you the type of print that expresses your ideas for each print. 

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