Rochester Institute of Technology RIT Scholar Works
Theses
4-29-1992
On black-and-white paper image-stability enhancement
Christopher Gmuender
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Recommended Citation Gmuender, Christopher, "On black-and-white paper image-stability enhancement" (1992). Thesis. Rochester Institute of Technology. Accessed from
This Thesis is brought to you for free and open access by RIT Scholar Works. It has been accepted for inclusion in Theses by an authorized administrator of RIT Scholar Works. For more information, please contact [email protected]. ON BLACK-AND-WHITE PAPER IMAGE-STABILITY ENHANCEMENT
EFFECTIVENESS OF TONING TREATMENTS ON SILVER GELATIN PRINTS DETERMINED BY THE HYDROGEN PEROXIDE FUMING TEST
by
Christopher Gmuender
THESIS REPORT
Submitted in partial fulfillment for the
MFA DEGREE IN IMAGING ARTS Rochester Institute of Technology School of Photographic Arts and Sciences Rochester, New York
Mr. James M. Reilly, Chair Associate Professor School of Photographic Arts and Sciences Director, Image Permanence Institute
Mr. Elliott Rubenstein Associate Professor School of Photographic Arts and Sciences
Dr. Peter Z. Adelstein Scientific Consultant Image Permanence Institute ON BLACK-AND-WHITE PAPER IMAGE-STABILITY ENHANCEMENT
EFFECTIVENESS OF TONING TREATMENTS ON SILVER GELATIN PRINTS DETERMINED BY THE HYDROGEN PEROXIDE FUMING TEST
TABLE OF CONTENTS
REPRODUCTION RIGHTS 1
ABSTRACT 2
INTRODUCTION 4
SCOPE OF PROJECT 6
CAUSES FOR SILVER IMAGE DEGRADATION 8
MECHANISMS OF SILVER DEGRADATION 10 Redox Blemishes 10 The Poisoning Effect 11 Direct Oxidation 12
SAMPLE PREPARATION 14
TONERS 16 IPI J-Toner 16 Kodak Rapid Selenium Toner 16 Kodak Polytoner 17 Kodak GP-1 Gold-Toner 17 Kodak GP-2 Gold Toner 17 Kodak Sepia Toner 18 AgfaSistan 19
THE TONING PROCESS 19 Toning by Fixation 20 21 Types of Toners & Toning Mechanisms
DIRECT SULFIDE TONING 24
SELENIUM TONING 25
GOLD TONING 26
INDIRECT SULFIDE TONING 28
HYDROGEN PEROXIDE FUMING TEST 29 History 30 Test Description 31 Post Incubation Development 32
POTASSIUM DICHROMATE BLEACH 33 35 %-Density Retention vs. Silver Conversion 35 Importance of high density retention HIGH TEMPERATURE - HIGH HUMIDITY INCUBATION (50C./80% RH) 36 The Plumming Effect 36 Other causes for print discoloration 37
REPORTING 38 Density Readings 38 Tables / Density Readings (Appendix A) 40 Graphs (Appendix B) 41
DISCUSSION OF RESULTS 43 Untoned Controls 43 AgfaSistan 45 Kodak Gold Protective Solution GP-1 46 Kodak Gold Protective Solution GP-2 47 Kodak Sepia Toner 48 IPI J-Toner 49 Kodak Polytoner 51 Kodak Rapid Selenium Toner 51 Split-Toning 53
CONCLUSIONS - RECOMMENDATIONS 54 Hydrogen Peroxide Fuming Test 54
Incubation 50C./80% RH 54 Blue-Density Readings 55 %-Density Retention 55 Dilution of Toners 56 Rating of Toners 58 Aesthetic Considerations 59 Tone Change 59 Suggestion for future study - Double Toning 59 BIBLIOGRAPHY 61
ACKNOWLEDGMENTS 65
APPENDIX A - TABLES 66 Agfa Brovira 66-82 Agfa Multicontrast 83-109 llford Galerie 110-125 llford Multigrade 126-141 Kodak Elite 142-168 Kodak Polycontrast 169-195 Oriental Seagull 196-222 Oriental VC-RC 223-238
APPENDIX B - GRAPHS 239 Agfa Brovira 240-255 Agfa Multicontrast 256-282 llford Galerie 283-298 llford Multigrade 299-314 Kodak Elite 315-341 Kodak Polycontrast 342-368 Oriental Seagull 369-395 Oriental VC-RC 396-411 REPRODUCTION RIGHTS
I, Christopher Gmuender hereby grant permission to the Wallace Memorial library of Rochester Institute of Technology to reproduce my thesis,
ON BLACK-AND-WHITE PAPER IMAGE-STABILITY ENHANCEMENT: EFFECTIVENESS OF TONING TREATMENTS ON SILVER GELATIN PRINTS DETERMINED BY THE HYDROGEN PEROXIDE FUMING TEST
in whole or in part. Any reproduction made must not be for commercial purposes or profit. All other copyrights remain with the author.
Rochester, April 29, 1992 Christopher Gmuender -2-
ON BLACK-AND-WHITE PAPER IMAGE-STABILITY ENHANCEMENT
EFFECTIVENESS OF TONING TREATMENTS ON
SILVER GELATIN PRINTS DETERMINED BY
THE HYDROGEN PEROXIDE FUMING TEST
ABSTRACT
The photographic image is by nature fragile. Most photographic print images are supported by
paper and most commonly employ silver as the light sensitive material. The finely dispersed
silver filaments in a photographic emulsion are sensitive in that they are relatively easily oxidized
by airborne pollutants, thereby destroying image information - be it data or pictures.
The purpose of this project was to investigate protective treatments that would render a black
and white image sufficiently stable in order to withstand long exposure to adverse conditions.
This could only be achieved by employing a reliable test-method, jointly developed by the Image
Permanence Institute and Eastman Kodak Co.
Toners were used ever since photography's inception. In the beginning they were mainly utilized
to alter images aesthetically. Although their protective qualities were recognized at the time, this
concept neither found wide acceptance nor was toning for permanence greatly practiced. Only 25
years ago, several research projects got under way to investigate the benefits of such
treatments. Although many scientific papers were published since and the concepts of silver
image oxidation reasonably well understood, little information is available on the practical
implications of toners, i.e., an identification of treatments and their applications that truly protect the silver image. Commercially available toners are still marketed for the aesthetic qualities they impart on photographs. The limited suggestions regarding image permanence were found to be inadequate or faulty. A ranking of toners is given at the end of this paper in the section
Conclusions/Recommendations. Test data is provided in Appendices A and B. These show the marked improvements in image stability that can be accomplished by toning. The optimum toner treatment and concentration is dependent upon the particular brand of photographic paper.
However, the polysulfide toners offer advantages over the others that were evaluated. INTRODUCTION
The benefits of toning treatments on photographic prints have been known for almost as long as
photography exists. As early as 1841, gold toners were applied to Daguerreotypes in order to
improve both color and contrast of the image. Upon the introduction of albumen papers, gold-
"red" toners began to enjoy broad application, changing the image color from to a more pleasing
"brown". This was a much sought after aesthetic effect especially with silver chloride papers of
the printing-out variety; permanence was less of a concern.
By the mid-1 850's, a variety of different toners were available to photographers and the number
of formulas continued to grow throughout the remainder of the century. The main purpose for the
development of new formulas was the concern to obtain a wider range of image-tones in silver
prints.
In 1 854, the London Photographic Society appointed a committee to study the "Fading of Positive
Paper" Photographic Prints on as the lack of permanence of paper prints had already become a
pressing issue. The culprit was identified as residual thiosulfate which had decomposed over time
and caused the images to fade. At the same time, it was recognized, that high humidity in the
degradation.1 ambient storage environment accelerated this type of image
Although the above committee did not come forth with any recommendations, it was soon
recognized by practicing photographers and photo chemists that toned photographs discolored
much less (or not at all) over longer periods of time as compared to untoned images.
Nevertheless, the idea of toning for permanence did not catch on until much later (with the
prevailing attitude that toning was primarily an aesthetic alteration of the silver-image). Although,
Permanence" in 1879 an article with the title "Toning for was published in the British Journal of
Photography. The appearance of this article leaves no doubt that the beneficial effects of toners
had been known even back then.
- Today, we have ample proof of the advantages of some of these toning treatments partly
because a great number of 19th century toned photographs have survived the test of time. Many
of these prints are still in almost pristine condition.
HAIST, Grant: Modern Photographic Processing, Vol. 1, 1979, pg. 655 -5-
It was not until the mid-1 960's, however, that any meaningful research was undertaken to precisely explore the effects of toners upon silver. Until then, comparatively little was known about the actual protection from oxidation toners could impart on silver. Likewise, research data or documented recommendations were either not accessible or not available at all.
Moreover, our world is increasingly burdened with pollution which is taking its toll on photographs. These are mainly airborne peroxides (from curing paints, solvents, adhesives, furniture, varnishes) and other oxidizing substances such as nitric oxides, ozone, etc. As they proliferate in our environment, they have become a major threat to the silver Image. Concern
"photographic" over the stability and longevity of our cultural heritage is mounting. Therefore, the permanence of photographic images and records has assumed new importance.
As very little is known about the long-term stability of electronic (magnetic or optical) media silver- based photographic images seem to be an excellent alternative. They are relatively cheap in terms of hardware and keeping requirements and according to latest research, extremely stable under favorable storage conditions. These advantages make the silver image a prime candidate for a safe long-term storage medium of valuable information. In addition, questions of hardware compatibility are unlikely to arise for retrieval and viewing of photographically stored data. One's own eyes and perhaps a magnifying glass are required. Artistic works deserve preservation to the same degree as art illustrates and instructs us about our history, the cultural heritage of generations preceding ours.
Considering all the above issues, the research currently conducted at the Image Permanence
Institute and this project in particular seem more than warranted and necessary. -6-
SCOPE OF PROJECT
The Image Permanence Institute has devoted much time and resources to the research of a pressing problem: the deterioration of microfilm (formation of redox blemishes or red spots - being the result of silver oxidation) in various archives around the country. This research produced, amongst other things, the formulation of a standardized testing procedure known as the Hydrogen Peroxide Fuming Test. Its purpose is to discriminate between toning treatments that do or do not provide protection for silver-images against oxidation.
Hydrogen peroxide has long been known to adversely affect silver images. Hence, researchers
have widely used this substance in their quest for stabilizing treatments for the silver image. Yet,
until today a standardized and reliable technique had never been formulated and laboratory
experiments employing this substance produced varying and non-comparable results.
It was strongly felt that this test had great potential and far reaching implications and could prove
to be very useful for general-purpose testing of toner-effectiveness and image stability. In recent
years efforts were made both by Kodak and I PI to formulate a precisely specified test method.
Consequently, it seemed appropriate to have the proposed procedures written up in an American
review.2 National Standards Institute-Standard (ANSI) that is currently under preparation and
Apart from investigating the effects of various toners and toner-dilutions on a variety of popular
black and white photographic papers (both, fiber-base and polyethylene-coated), it was the
objective to demonstrate whether or not this testing-procedure is effective in discriminating
between treated and non-treated samples and whether the results would be reproducible and
consistent.
Besides the hydrogen peroxide fuming test, a potassium dichromate bleach bath was employed
silver-conversion on photographic print materials. to qualitatively assess the (toner dependent) temperature high incubation Furthermore, part of the project involved a high / humidity
(50C./80% RH), designed to produce information regarding long-term stability of both, toned and
untoned black-and-white papers.
- The 2 ANSI - IT-9.15: DRAFT American National Standard for Imaging Media (Photography), - Methods for Effectiveness of Stabilizing Treatments for Silver Images Measuring -7-
As mentioned earlier, toners enjoy relatively large popularity and numerous kinds are commonly
used by the photographer. Furthermore, black-and-white photography is enjoying growing
popularity again and a plethora of different photographic papers are available to the consumer.
To account for this variety, it appeared necessary to test several different papers, all of which
having different inherent characteristics. Likewise, numerous different toner-formulations were
included, all of which are known or claim to protect the silver image of a photographic print. The
ultimate goal was to identify one or several toners and their respective optimal application that
would produce the desired protective effect as measured against the harshness of the Hydrogen Peroxide Fuming Test.
However, it needs to be pointed out that it was not the objective of this project to pass
qualitative judgments on the individual photographic papers. They merely constituted the
"medium" in the testing of toners.
Eight different papers were selected for this project - four of the resin-coated variety, four of the
fiber-base type. The choice was rather arbitrary but reflects a sensible sampling of commonly
used photographic materials.
These different papers were all exposed to a step-wedge of 21 increments and subsequently
toned with different toners at different dilutions. Due to the large number of toner, dilution and
paper combinations, totaling @ 170, combined with the three tests each sample underwent
(resulting in a total of @ 20'000 density readings) it becomes apparent that only one test-run per
sample could be performed. Despite the absence of replicate testing, the results were very
consistent and clearly established trends. The findings provided a good indication of how well
toners can protect papers against adverse conditions.
In toning, treatment time and temperature are very important factors. Both determine how much
time- silver is being converted to a more stable compound. Hence, an almost indefinite number of
temperature combinations is conceivable. Obviously, the tests had to be limited to a manageable
number. Therefore both, treatment time and temperature were kept at a standard level, unless
otherwise indicated.
The various aesthetic effects toners can produce were also of interest. Amongst other things it
was the hope to find a treatment that would leave the image color unchanged. For commercial
operations, this might be a much desired feature. CAUSES FOR SILVER IMAGE DEGRADATION
As many roads lead to Damascus, there are many different causes for silver image degradation.
Apart from mechanical damages, such as cracks, tears, etc., there is microbiological degradation
such as fungus attack and its associated gelatin decomposition. Development of fungi is mainly
caused by high humidity and the gelatin in photographic materials represents a ready food
source. Since spores are omnipresent, fungus growth can only be prevented by humidity control.
In conjunction with film, high humidity cause severe deterioration in most acetate based support-
materials. Such degradation occurs by hydrolysis. Cellulose acetate supports can react in the
presence of moisture and release acetic acid which in turn causes polymer chain cleavage. This
process is autocatalytic. Once it has begun, the released acetic acid causes by itself further
degradation which advances at an ever increasing rate. The symptom is typically the smell of
vinegar. At advanced states, delamination of the emulsion-layer from the base occurs.3
Although it is possible for high energy radiation of very short wavelengths (UV, X-rays, gamma
rays) to remove electrons from silver atoms thereby causing oxidation, this specific form of
deterioration is of little concern. However, prolonged exposure to relatively high levels of direct
sunlight or any other strong irradiation results in the unpleasant discoloration of the gelatin and
causes the paper fibers to become brittle.
Early generations of resin coated (RC) photographic prints (1970's) fell victim to oxidation upon
prolonged exposure to sunlight. Titanium oxide (Ti02), a pigment, is commonly embedded in the
polyethylene coat to make the paper appear bright-white. High energy radiation (UV) caused the
titanium oxide to emit peroxides which in turn attacked the silver image. This manifested itself in
what today are referred to as red spots or redox blemishes. Yet, as reported by various authors, this flaw has long been overcome by the addition of antioxidants to the titanium oxide layer, a 4/5/6 technique first patented by Eastman Kodak Co.
of Archival Cellulose Triacetate Base EDGE, M. et. al.: The Deterioration Characteristics Cinematograph Film, Journal of Photographic Science, Vol. 36, 1988 PARSONS, T.F., GRAY, G.G., CRAWFORD, I.H.: To RC or Not to RC, Journal of Applied Photographic Engineering, Vol. 5, 1979, pg. 110-117 FELDMAN, Larry H: Discoloration of Black-and-White Photographic Prints, Journal of Applied Photographic Engineering, Vol. 7, Number 1, 1981, pg. 105 REILLY, James: Archival Aspects of Resin-Coated Papers, Kodak Publication ED3-24-2, 1991, pg. 30 -9-
A number of chemical reactions can generate various effects of deterioration. Inadequate fixing of the image as well as residual silver-thiosurfate complexes (exhausted fixer) cause the development of colloidal silver upon interaction with light. Excessive amounts of residual
thiosulfates in both gelatin and support lead to the formation of sulfides. Hydrogen sulfide,
another pollutant of both natural and artificial origin attacks the silver image in that this gas forms
silver sulfide in a photograph (like in toning) and causes silver-mirroring and the staining of
photographs.
Nitrogen dioxide and sulfur dioxide form nitric and sulfuric acid respectively when combined with
oxygen and water. They have become very prominent in our atmosphere and can easily be
traced back to the burning of fossil fuels. Obviously, such aggressive substances impart very
detrimental effects upon the finely dispersed grains of the silver image.
Frequently harmful contaminants can also be found in the more intimate environment of
photographs, for instance in enclosure materials, boxes, storage cabinets, etc. These emit acidic
fumes, hydrogen sulfide, peroxides and the like. Their sources are many: adhesives, wood-lignin,
residual chemicals used in the manufacture of products, paints, varnishes, printing inks, etc.
Susceptibility of silver filaments to oxidative attack is partly linked to their shape. It has been
known for some time that silver ion reduced to metallic silver by chemical means (i.e. developer)
is filamentary in shape. These filaments are like bundles of intertwined, long irregular threads.
Such an arrangement makes for a large surface-to-volume ratio and correspondingly, for high
large surface area and high surface covering power or light absorbency. However, the resulting
and increases the possibilities for surface reactions on energy lead to thermodynamic instability
the silver-grains. However, in a letter to Mr. J.M. Reilly of the Image Permanence Institute,
Brandt7 distribution nor size of image particles have an effect convincingly argues that neither
particles are upon image deterioration as oxidants attack silver indiscriminately. Smaller simply
larger surface-to-volume ratio. Compared to more readily oxidized because of their inherently
overall mass to begin with and therefore wither larger grains the smaller particles have much less
away faster.
September 1983 BRANDT, E.S.: Letter to Mr. J.M. Reilly/lmage Permanence Institute, -10-
easier For reference a crude rendition of typical silver filaments is given below so that the reader might acquire a better idea of what this particular species looks like.
m-w m V-~4
typical silver filaments after development
MECHANISMS OF SILVER DEGRADATION
Oxidation generally refers to an reaction whereby an element or compound, upon interaction with an oxidant, loses negatively charged electrons. The atom of the original element has thus become an ion of positive charge. Such silver ions are colorless and can migrate from their original sites. This is greatly aided by the presence of moisture, as will be explained later.
Redox Blemishes
In certain cases, oxidative attack occurs locally. Adjacent grains of elemental silver are
oxidized and silver ions form. Then they migrate from their original site and are reduced
again to colloidal silver by a reducing agent. However, these ions do not move far. Instead,
"arranges" the colloidal silver formed itself in concentric rings around the original site of
corrosion.
Therefore, under magnification, redox blemishes have the appearance of Saturn's rings - the
center being the clump of elemental silver grains gradually being eaten away by oxidizing
substances, the surrounding rings being the reformed colloidal silver. The diagram below (by
Fuji Photo & Film Co. Ltd.) graphically displays the oxidation of elemental silver as it occurs
in the hydrogen peroxide fuming test and in real life. -11-
Oxidative Disintegration of Developed Silver - Formation of Redox Blemishes
Colloidal Silver Silver Ions ilver Ions (yellow / brown)
- Oxidizing Oxidizing Reducing _ Atmosphere Atmosphere
Developed Formation of Silver Ions migrating Silver Ions reduced during Silver Grains Silver Ions from away from the deve Dispersion Formation of developed loped Silver Grains Silver Atoms Receding Silver Grains and Dispersion Ions recombine in the Silver Atoms Reduction For mation of Colloidal Silver
Atmosphere" In the diagram above, the section labeled "Oxidizing marks the onset of hydrogen peroxide attack. The subsequent areas display the resulting damage to clusters of silver grains or filaments.
The Poisoning Effect
Hydrogen peroxide and metallic silver react in a somewhat peculiar fashion with each other.
As the chemical notation for hydrogen peroxide (H2O2) suggests, there are two strongly
bonded oxygen atoms attached to two hydrogen atoms. In order for the hydrogen peroxide to
oxidize silver, this oxygen-oxygen bond needs to be broken. Metallic silver proves to be an
ideal catalyst for this reaction to occur. -12-
An adsorbate such as selenide or sulfide electrochemically alters the surface of metallic
silver. Inhibition of the oxygen-oxygen bond cleavage is the consequence and silver oxidation
"poisoning" is effectively restricted. This effect is called and refers to adsorbates preventing
oxidation caused by peroxides. The chemical notation below illustrates how catalytic
hydrogen peroxide decomposition at silver procedes, if not poisoned.
Ag+ OH_ H202 + Ag- + OH +
As mentioned in the paragraph on gold toning, potentially reactive sites which have not
adsorbed addenda such as sulfides or selenide will much more easily be subject to rapid
catalytic decomposition with the introduction of peroxides. As Brandt points out, "the situation
is similar to the greatly accelerated rusting that occurs at a break in the chrome plating of
bumpers."8 objects such as automobile Although this statement seemingly refutes the notion
of the poisoning effect, Brandt clarifies the issue by stating that a "submonolayer coverage
of the silver is sufficient to effectively passivate the entire silver surface toward hydrogen
peroxide caused oxidation".
Direct Oxidation
The mechanisms of oxidation are altogether different with substances such as ozone or
sulfur dioxide. The silver surface no longer functions as a catalyst but is directly oxidized
instead. Neither does partial toning inhibit oxidation as with peroxides. When sulfur dioxide
(SO2) reacts with ozone/oxygen and water, sulfuric acid (H2SO4) is formed. The nuclei of
sulfuric acid molecules are of strong positive charge. To compensate for this imbalance they
accounts for the exceptional of sulfuric constantly seek to acquire electrons which reactivity
required electrons from shells of silver acid. This need is easily satisfied by removing the the
atoms.
8 BRANDT, E.S.: Mechanistic Studies of Image Stability. 3. Oxidation of Silver from the Volume 31 September/October vantage point Corrosion Theory, Journal of Imaging Science, , 1987, pg. 207 -13-
Apart from oxidants interacting with silver, strong silver ligands, such as sulfides might
disrupt the constant equilibrium that naturally exists between silver metal and silver ions. The
"oxidation-reduction" disruption of this constant cycle of within the silver grains is in effect the
"draining" result of sulfides and/or other reducing contaminants continuously away silver ions,
therefore gradually dissolving the silver grain. Of course, the ions lost to the silver grain
would eventually be reduced again to silver sulfide or a similar substance.
Kleinert9 According to a paper by McCamy and Pope, the researchers Marraccini and
discovered that measurable amounts of peroxides form in the natural aging of enclosure
material made out of commercial pulp papers. This formation of oxidant gases was greatly
Pope10 aided with humidity increase. McCamy and confirmed these findings and
"environment" demonstrated that high humidity accelerated the diffusion of oxidants into the
emanating from storage containers. The same is certainly true for any other enclosure
directly surrounding photographs, such as cabinets, closets, boxes, etc. Acids, peroxides,
formaldehyde and a host of other substances may be emitted over time with the aid of
humidity.
Therefore, relative humidity (RH) can play a double-role in silver image oxidation. Not only
does it facilitate the release of harmful substances into a micro-environment but it also
increases the rate of diffusion into the gelatin of a photographic product. When gelatin
absorbs water from its environment a significant increase in volume or swelling can be
observed. This produces a corresponding increase in the diffusion rate of mobile species
within the gelatin matrix. In other words, oxidants such as gases diffuse much more easily in
and out of the gelatin, to and from reactive sites.
Moisture provides an almost ideal vehicle for substances such as hydrogen peroxide to travel
comprehensible to the silver grains embedded in the emulsion. Consequently, it is easily why
role in the deterioration of silver images. high levels of relative humidity play a very important
and Colour Reversion of Bleached Paper 9 MARRACCINI, LM. and KLEINERT, T.N.: Aging Jan./June 1963 Pulps, Svensk Papperstidning, Volume 66, Number 189, pg. 167 10 McCAMY C.S., POPE, C.I.: Redox Blemishes, Their Cause and Prevention, 1970, -14-
SAMPLE PREPARATION
one-third- Sheets of photographic paper were exposed in contact to a 21 -step grayscale having
stop increments of 0.10 density units. The enlarger light-source was a diffused cold-light
ensuring density-uniformity across the sheet. After exposure, the polyethylene coated (RC)
papers were machine processed. By contrast, the fiber-base materials were processed in trays.
"archival" An wash of @ 60 minutes in a Kostiner archival print washer followed a hypo-clear
bath. All fiber-base prints were air-dried.
The following photographic materials were employed in this project:
POLYETHYLENE (RC or PE): AGFA Multicontrast, glossy
KODAK Polycontrast, glossy
ILFORD Multigrade III, glossy
ORIENTAL VC-RC, glossy
FIBER-BASE: AGFA Brovira, DW, Grade 2, glossy
KODAK Elite, DW, Grade 2, glossy
ILFORD Galerie, DW, Grade 2, glossy
ORIENTAL Seagull, DW, Grade 2, glossy
Note: All the above papers are D.O.P. silver-bromide papers. Thus their silver is filamentary in shape which generally appear as neutral-black.
coded. Each The processed sheets were then cut into strips of 2 inches width appropriately
visual11 consisted of 5 strips to produce both and category (i.e. paper-toner combination)
numerical results for:
Control: untoned, untreated sample
Toning: toned paper sample
Permanence c/o Rochester Institute 11 All actual test-samples are on file at the Image Institute, are available for of Technology, Rochester, NY, 14623-0887, where they viewing -15-
Hydrogen Peroxide: test strip to undergo the hydrogen peroxide fuming test at 2000 part per million of H2O2 at 50C./82% RH for 18 hours
Potassium Dichromate: gray-scale/image to be bleached for @ 1 minute to
remove all metallic silver and to determine the
"silver-conversion" approximate or rather the %-
density retention
Incubation 50C./80% RH: samples to be incubated for 30 days under high
temperature and high humidity (artificial aging)
Density readings were taken of all samples (21 steps per strip). Subsequently, the samples of the above listed papers were toned according to the following schedule:
:200* IPI J-Toner: 1:4*/ 1:10*/ 1:25/ 1:50/ 1:100/ 1 / 1 :400
1:4* 1:10* :50* :200* Kodak Polytoner: / / 1 :25 / 1 / 1:100/ 1 / 1 :400
Kodak Rapid Selenium Toner: 1:4*/ 1:10 / 1:25/ 1:50*/ 1:100/ 1:200*/ 1:400
Kodak Sepia Toner: 1 Minute in Potassium Ferricyanide Bleach followed by
redevelopment in Sepia Toner for @ 1 Minute
Agfa Sistan: 3 Minutes at 1:20
Kodak GP-1 Gold Toner: Stock Solution for 5 Minutes
Kodak GP-2 Gold Toner: Stock Solution for 5 Minutes
constant. The temperature of the toning-baths NOTE: All samples were toned in trays. The agitation was manual and the time was 3 Minutes. was @ 25C./80F. (with minor fluctuations). Unless otherwise specified, toning
* llford Above treatment-dilutions were not applied to the following products: Agfa Brovira, llford Multigrade III,
Galerie and Oriental VC-RC. -16-
TONERS
IPI J-Toner
Liver of Sulfur 498.0 grams
Borax 20.0 grams
Distilled Water to make 1 .0 Liter
J-Toner12 is a formulation developed by Kaspars Cupriks of IPI. It is very similar to Kodak's
Brown-toner. However, the addition of borax (sodium tetraborate) renders the concentrate
much more stable and improves the shelf-life dramatically. It also makes the toner stable
once diluted for use, making it suitable for commercial applications. Like Kodak's proprietary
Brown-Toner, J-Toner is based on polysulfides as active agents.
Kodak Rapid Selenium Toner
According to the Photo Lab Index, Kodak Rapid Selenium Toner is identical with Kodak's
published formula for the T-55 Selenium toner:
Water 700.0 ml
Sodium sulfite, desicc. 150.0 grams
Selenium metal, powder 6.0 grams
Ammonium chloride 190.0 grams
Water to make 1 .0 Liter
For use, dilute 1:5
aware of how the T-55 concentrate compares Note: The dilution given above might be misleading as I am not Selenium Toner. to the proprietary and pre-packaged Rapid
12 J-Toner has been IPI's laboratory name for this formula. It has recently been trademarked as since the development IPI SilverLock. There are no restrictions on the use of this technology grants of this treatment had been funded with NEH and NHPRC -17-
It should be added that throughout this project Kodak's commercial Rapid Selenium Toner concentrate has been used and was diluted according to the toning-schedule given earlier.
The recipe above is merely given to list the constituents.
Kodak Polytoner
Proprietary recipe, hence formula not available.
The basic ingredients consist of selenium and polysulfides. However, a number of other
chemicals must be present to render the solution stable. A variety of brown tones can be
achieved on bromide papers, ranging from slight sepia tones to very distinctive cold-brown
tones. According to Kodak, this is accomplished by varying the dilution.
Kodak GP-1 Gold-Toner
Water 750.0 ml
Gold chloride 10.0 ml (of 1% Stock Solution)
Sodium Thiocyanate 10.0 grams
Water to make 1 .0 Liter
The sodium thiocyanate is dissolved separately in 125 ml. of Water.
thiocyanate solution. The gold chloride is added to the water, followed by the sodium
Kodak GP-2 Gold Toner
Water 750.0 ml
Gold chloride 0.5 gram (assay 50% Au)
Tartaric acid 1 .0 grams
Thiourea 5.0 grams
Sodium sulfate (dessic.) 15.0 grams
Water to make 1 .0 Liter -18-
Both gold-toner formulas given above include gold chloride as their main ingredient
responsible for image protection. The GP-2 formula also incorporates thiourea which has
been found to afford some protection when used alone. The GP-2 formula produces a white
or pale yellow sludge of sulfur upon preparation. It has been reported that this is a normal
reaction caused by the interaction of gold and thiourea.13
The prepared GP-2 toner should be left standing over night and the harmless sludge be
filtered off to avoid sulfur residue on papers or film. Gold-toners have a tendency to produce
bluish tones on silver bromide emulsions.
Kodak Sepia Toner
Bleach:
Potassium ferricyanide
(10% solution) 0.5 Liter
Potassium bromide
(10% solution) 0.1 Liter
Sodium carbonate
(10% solution) 0.2 Liter
Water to make 1 .0 Liter
Toning Solution/Redeveloper:
Sodium sulfide 45.0 grams
Water to make 500.0 ml
For use, dilute 1 :8
Kodak's formula. In this project, Kodak's Note: The recipe given above is a substitute for proprietary
prepackaged product was employed.
involves a bleach-bath after which a Sepia toning is somewhat elaborate a technique as it bleach oxidizes the metallic silver which is brief wash is required. The potassium ferricyanide
Vol. pg. 13 HENN, R.W. MACK, B.: A Gold Protective Treatment for Microfilm, PS&E, 9, 1965, 380 -19-
subsequently reduced again by toning (redeveloped) to form silver sulfide. Sodium sulfide is
responsible for the resulting image-color. The degree of tone-change or silver conversion is
controlled by the bleaching time. The subsequent toning step affects only those sites where
silver has been rehalegonized by the bleach. An image is said to be fully toned within about
30 seconds after immersion into the sodium sulfide bath.
Remark: A very weak solution of the bleach was prepared so that the image tone change be less pronounced. The density loss the prints experienced during bleaching was negligible and hardly perceptible. Kodak recommends full bleaching, to the point where only traces of the image are visible. Naturally, this produces a very strong sepia tone that may be objectionable.
Agfa Sistan
Proprietary formula, hence a list of ingredients is not available.
Supposedly, Agfa Sistan is a silver-stabilization treatment aiding in the prevention of image
deterioration. This product does not alter the image color at all. It comes as a clear and
odorless liquid concentrate to be diluted for use. Because the manufacturer warns of the
formation of white crystals if prints are not thoroughly washed after treatment, suspicion
arises that sodium sulfite is a major constituent of this product. As sodium sulfite can be
found in most washing-aids, it is assumed that Agfa Sistan acts much in the same way as
hypo-clearing agent. This point shall be further elaborated in the discussion of the results.
THE TONING PROCESS
The term toning implies more than what is commonly assumed. In a broad sense, toning alters the color of a photographic image and it can impart image stability.
The more general photographic literature consulted is rather evasive when it comes to toning techniques and their effect on the permanence of black-and-white images. Although it is true that
inception of and a many studies were published on the topic (ever since the toning treatments) large number of different recipes put forth, these accounts mainly pertain to aesthetic considerations. Most authors of the consulted sources (Haist, Mees, Neblette, Clerc, Mutter, -20-
Formstecher, and others) are aware of the fact that silver, when combined with selenium, sulfur or gold - produces a very stable compound. However, they fail in most instances to explicitly point out that an additional toning step is necessary to render the silver image permanent.
McElhone14 suggests that more recent changes in the manufacture of emulsions might have brought about the need to additionally protect the image from oxidation. In order to use less silver in an emulsion, the filaments had to be made finer to achieve the same covering power.
As a result they became more prone to oxidative attack. This statement implies that silver oxidation is a new phenomenon and directly linked to modern manufacturing processes.
McElhone's assumption is somewhat questionable as the initial research of silver-image oxidation was fueled by field reports of degrading microfilm dating back to the 1940's. Additionally, many photographic images of the last century underwent severe deterioration.
Earlier literature emphasizes the importance of the complete removal of thiosuffates from the base & emulsion. To this end, solutions oxidizing the remaining thiosulfates, such as the Hypo-
Eliminator HE-1 formula (containing ammonia and hydrogen peroxide) were suggested and often used. Such recommendations directly imply that residual processing chemicals were chiefly regarded responsible for image deterioration.
Toning by Fixation
In photographic images produced from emulsions containing no iodide, the thiosulfate is so
cannot be removed strongly adsorbed to the image-silver that the thiosulfate entirely by
HE-1.15 alkaline peroxide hypo such as prolonged washing or by oxidation with eliminator,
According to Pope16 the silver sulfiding of photographic papers by fixation is approximately Haist17 25% in a Dmax area and considerably higher than with microfilm. states that this type
problem image permanence. of sulfiding during fixation does not present a regarding
14 McELHONE, John: Selenium Toning and Chemical Washaids, (publication date not available) pg. 30 15 Formation of Sulfide LEVENSON, G.I.P- and SHARPE, C.J. : "The Role of Thiosulfate in the Stains during Bleaching", Journal of Photographic Science and Engineering, Volume 4, 1956 16 poPE, Chester: Formation of Silver Sulfide in the Photographic Image during Fixation, Journal of Research of the National Bureau of Standards, 64C:65, 1960 17 HAIST, Grant: Modern Photographic Processing, Vol. I, 1979, pg. 646, -21-
However, he cautions to keep residual thiosulfates in gelatin and base at a minimum (by
means of thorough washing) to curb highlight discoloration.
James18 demonstrated that adsorbed thiosulfate from the fixing bath or possibly sulfide
formed by decomposition exerts a significant stabilizing action on the silver filaments formed
in normal processing of silver chloride, chloro-bromide and bromide emulsions. Hence,
depending on the definition for toning one uses, it could be argued that the process of fixation
"tones" also the image ever so slightly and thereby exerts a protective effect upon the
elemental silver.
Mack19 Henn & had discovered that trace amounts of iodide in the fixer prevent the sulfiding
of the silver image. It is also reported that an iodide layer imparts a protective effect upon the
silver grain. However, more recent evidence indicates that the iodide layer is insufficient a
shield in our modern-day environment. In fact, not long ago it was suggested by Minagawa
Torigoe20 and that the complete removal of thiosulfates from untoned prints and negatives
might not be desirable after all.
Types of Toners & Toning Mechanisms
Processing" In "Modern Photographic Haist21 provides a summary of the various toning
methods which he has summarized as follows:
which the color of the silver image is determined 1 . Toning during image development, by
composition of the developer. by the nature of the photographic emulsion and by the
silver such as 2. Toning by conversion of the metallic silver image into a colored compound,
the formation of brown silver sulfide.
Science and 18 JAMES, T.H.: The Stability of Silver Filaments, Photographic Engineering, Volume 9, Number 2, March/April 1965, pg. 121 Treatment for Photographic 19 HENN, R.W. and MACK, B.D.: A Gold Protective Microfilm, November/December pg. 47 Science and Engineering, Vol. 9, Number 6, 1965, Black-and- 20 MINAGAWA Y., TORIGOE, M.: Some Factors Influencing The Discoloration of at SPSE White Photographic Prints in Hydrogen Peroxide Atmosphere, Presentation the International Symposium: The Stability and Preservation of Photographic Images, Ottawa,
- pg. 43-44 1982 from SPSE advanced printing of Paper Summaries, 21 HAIST, Grant: Modern Photographic Processing, Volume 2, pg. 90 -22-
3. Toning by deposition on, or by partial or complete substitution for, the silver image of an
insoluble metal compound, or compounds, that are colored. This method of toning is
probably the most commonly used for changing the tone of a silver image, formed either
by developing or by printing out the image.
4. Toning by replacing the silver metal of the image by a colored dye which is permanently
attached to a metal salt that has replaced the image silver.
5. Toning by color development during which the oxidized developing agent (produced from
the development of the image silver) reacts with a chemical compound contained in the
developing solution, to deposit a dye image in the same areas as the silver image.
Over the years, many photographic toners have been formulated and described in the
literature. Several of these are listed below though only a few are of practical purpose:
1 . Gold Toners (gold chloride)
2. Platinum Toners
3. Colloidal Sulfur Toners
4. Hypo Alum Toners
5. Sulfur Toners - including sulfide and sulfur complexes
6. Selenium and Tellurium Toners
7. Organic Toners - including Thiourea
8. Copper Toners
9. Vanadium Toners
10. Uranium Toners -23-
Toning by development merely affects the shape and size of the silver grains in a given
emulsion and thus only changes the refractive properties of the silver (and thereby the
appearance or color of the print).
"Toned" images, in which the silver has been (partly or wholly) substituted by organic dyes or
pigments22 (color photographs, iron and copper toning) lie outside the realm of this study.
The dyes in a dye-toned photograph fall outside the scope of providing a protective effect
al.23 upon silver. Although copper and iron toning also alter the image chemically, Lee et
have pointed out that the actual amount of silver in the image is reduced. The structure of the
silver filaments has been changed and considerable amounts of silver replaced by ferric-
ferrocyanide and cupric-ferrocyanide that are much less stable than silver itself. It should be
obvious that substitution of silver by metals of lesser oxidation potential, such as iron or
copper, has a detrimental effect on image permanence.
Hence, only chemical processes which directly convert silver to a more stable compound will
be spoken of. The toning processes for silver gelatin prints can be divided into two groups:
direct and indirect toning. In direct toning, the metallic silver of the image reacts upon the
element or compound available in the toner to form a new compound. In indirect toning, the
metallic silver is first bleached to form silver halide which subsequently bonds with the
solution. is rather effective with element present (usually sulfur) in the toning Indirect toning
tone" "hard to papers and can be employed in conjunction with substances other than sulfur,
the Sepia toner (bleach- e.g., selenium and tellurium. Of the toners used in this project, only
was applied in this way. redevelop method) belongs to the second category and
22 lead to the formation of iron-ferricyanide Iron and copper toning, which employ ferricyanide, both of which are pigments (Prussian Blue) and cupric-ferricyanide (Hatchetfs Brown), Photographic Images to 23 LEE, W.E., WOOD, B., DRAGO, F.J.: Toner Treatments for June pg. 125 Enhance Image Stability, Journal of Imaging Technolgy, 1984, -24-
DIRECT SULFIDE TONING
emulsions24 When metallic silver of paper is treated with sulfides, the resultant silver sulfide is brownish in color (due to the alteration of the shape of the silver filaments), of great stability and low solubility.
$V: * *
untoned silver filaments toned silver filaments (irregular shapes, large surface (much more rounded and regular to volume ratio) shape, smaller surface to volume ratio)
Liver of sulfur (or sulfurated potash) is a ready source for sulfides. It comes in yellowish-brown
Index25 lumps and is easily dissolved in water. The Merck states that these lumps contain a
"mixture of potassium polysulfides, chiefly trisulfide, and potassium thiosulfate, containing no less
sulfide." than 12.8% sulfur as
Index26 Sulfur is a highly reactive element and has a great affinity with silver. The Merck also indicates that sulfur bonds with almost any metal but does not react with gold, platinum, iodine, nitrogen, tellurium and iridium. Therefore, most silver-based papers tone very readily in a polysuffide-toner.
24 It is reported that microfilm with a 60 % density retention does not exhibit such color change upon toning. This is probably due to the fact that film emulsions contain rounder silver particles to start with and are hence less affected by the shape alterations due to toning. 25 MERCK & CO., INC.: Merck Index, 7th Edition, Merck & Co., Inc., Rahway, NJ, 1960, pg. 836 26 MERCK & CO., INC.: Merck Index, 7th Edition, Merck & Co., Inc., Rahway, N.J., 1960, pg. 1002 -25-
According to A. and L. Lumiere and A. Seyewetz27, the sulfiding of silver possibly proceeds according to the following reactions:
S + H2O - H2S +0
2Ag + 0 - Ag20
AgzO + H2S - Ag2S + H2O
Silver sulfide, being the ensuing compound of the above reaction is extremely stable and very difficult to oxidize. It has been postulated that the very low solubility product of Ag2S (Ksp 1 .6 x 10*49 @ 18C.) indicates its inertness for dissociation and subsequent oxidative attack.28
SELENIUM TONING
Toning with selenium has been practiced for at least 80 years. It was in 1910 when a German
McElhone30 patent29 was granted for a selenium formula. states that following their introduction,
selenium-toners were chiefly regarded as a color altering toner and their protective effect was not
appreciated until some years later.
McElhone31 mentions that the study-reports published by Lee, Wood and Drago in 1984 (see
selenium in the bibliography) were the first instance of Eastman Kodak to include toning 1991 that llford incorporates selenium for processing procedure. Incidentally, it is only in toning Sequence!32 fiber-base papers as a general recommendation in their llford Archival Processing
27 HAIST, Grant: Modern Photographic Processing, Volume II, 1979, pg. 97 28 LEE, W.E., WOOD, B., DRAGO, F.J.: Toner Treatments for Photographic Images to pg. 124 Enhance Image Stability, Journal of Imaging Technolgy, June 1984, 29 Rheinishe Emulsions-Papier-Fabrik A.G., Dresden, German Patent D.R.P. No. 238513, September 21, 1910 30 on pg. 17 MCELHONE, JOHN: Selenium Toning and Chemical Washaids: Effects .... 31 ibid., pg. 17 32 N.J. Vol. pg. 5 PLACKO, John: llford Newsletter for Photoeducators, Paramus, , 3/1991, -26-
According to C.E.K. Mees33, "selenium and tellurium, occurring as they do in the same group and
subgroup of elements as sulfur, form equally stable compounds with silver".
Seyewetz34 Haist refers to an article by A. and quotes: "it is thought that the toning action of
selenosulfate (formed by the reaction of selenium in sodium sulfite solution) with silver of the
image involves the reaction:
Ov ONa Ov ONa V Ag2Se + V O SeNa CT Na
Sodium Silver Silver Sodium
Selenosulfate Selenide Sulfite
Howell35 believes that silver selenide (as obtained on bromide papers) is in itself black. Any
reddish-brown tone produced is due to the deposition of elemental red selenium onto the black
silver selenide.
GOLD TONING
Gold toners have been known for a long time and have found wide application in photography.
first to invent a gold chloride toner which Fizeau36, a French contemporary of Daguerre's was the treatments been he introduced in 1841. Although, other efficient metal toning had developed,
exorbitant cost. Amongst these were platinum they have ceased to be utilized because of their the cost of gold might nevertheless be and palladium toners. Being slightly less expensive,
applications. prohibitive for most commercial or other large-volume
Revised Forth the 33 MEES, C.E.K.: The Theory of the Photographic Process, Edition, Printing, Macmillan Company, NY, 1963, pg. 761 Journal of 34 SEYEWETZ, A.: The Chemistry of Selenium Toning, British Photography, 77, 1930
- Number 1943 35 HOWELL, Edward T.: Brown-Blacks: 2. Selenium Toning, J. PSA, 9, 36 FIZEAU, M.H.Louis: Compt. Rend., 11:237, 1841 -27-
Mack37 Henn and found that the deposition of gold upon silver is directly related to the gold
content of the solution - the toning composition of the rest of the solution does not markedly affect the rate of as as the toning, long bath is being kept acidic. Furthermore, they suggested that temperature has only a very slight effect upon gold deposition.
Agitation proves to be crucial in this system and the formation of a gold-silver compound is
elevated greatly by augmented agitation. Treatment time has a likewise effect and Henn &
Mack38 point out that these two factors are more critical than in conventional development. The
formation of the gold-silver amalgam proceeds according to the diagram given below:
+ 3Ag+ 3Ag + Au3 - Au +
metallic auric metallic silver
Silver Gold Gold Ions
Au+ Ag+ Ag + - Au +
metallic aurous metallic silver
Silver Gold Gold Ion
This amalgam of gold and silver was found to be very effective in the prevention of oxidative
attack, provided that sufficient gold is introduced to form a monolayer on the grain surface. Gold
toning has long been recommended as a general post-processing treatment for microfilm.39 The
gold content of a typical gold-toner is very small. Since the quantity of gold deposited upon the
silver directly depends on the amount of gold in the solution, the bath itself is rather quickly
exhausted and adequate replenishment is a necessity (see GP-2R formula given by Henn &
Wiest).40
37 HENN, R.W., MACK, B.: A Gold Protective Treatment for Microfilm, PS&E, Vol. 9, 1965, pg. 380 38 ibid, pg. 381 39 ibid, pg. 382 40 HENN, R.W., WIEST, D.G: Properties of Gold Treated Microfilm Images, PS&E, Vol. 10, 1966, pg. 22 -28-
In contrast to the other toning-processes mentioned in this paper, Gold is chemically plated onto the silver filaments, whereas sulfides and selenides are adsorbed.41 Brandt also explains that defects in this gold-coating lead to increasing silver oxidation at such sites as an oxidant can only satisfy its need for electrons at sites where silver is exposed.
INDIRECT SULFIDE TONING
As pointed out earlier, indirect toning involves an extra processing step in which the silver image
is first bleached. The silver halides thus formed can more readily bond with the substance in the
"sepia-tone" toning bath (typically sulfides). This technique is useful for two reasons: firstly, the
can be varied according to the quantities of bleach constituents and secondly, this indirect toning
method is effective with photographic papers which are inherently difficult to tone.
The proportions of the ferricyanide and potassium bromide are somewhat crucial in terms of
image color obtained. As a rule of thumb, the more ferricyanide present in relation to the
potassium bromide, the yellower the print color. Similar image-tones can be obtained by
substituting the potassium bromide by potassium chloride.
Haist42 Many different bleach-baths have been suggested to oxidize the metallic silver. points out
that the most successful and most commonly used bath employs a combination of potassium
ferricyanide and potassium bromide. This bath is said to have little or no reducing action, does
action differ somewhat and some not stain and has a long useful life. Opinions on the bleaching
compensate the loss. sources suggest that the print should be made slightly darker to for density
from the 41 BRANDT, E.S.: Mechanistic Studies of Image Stability. 3. Oxidation of Silver Volume September/October vantage point Corrosion Theory, Journal of Imaging Science, 31, 1987, pg. 206 42 HAIST, Grant: Modern Photographic Processing, Vol. 2, pg. 108 -29-
The reactions involved in indirect sulfur toning with the above bleach bath are as follows:
Oxidation of the metallic silver Image
+ 4Ag 4K3Fe(CN)e -* 3K4Fe(CN)e + Ag4Fe(CN)e
Conversion of the silver into a bromide salt
Ag4Fe(CN)8 + 4KBr - K4Fe(CN)e + 4AgBr
Sulfiding the silver bromide
2AgBr + Na2S -+ 2NaBr + Ag2S
The important feature of the above chemical reactions is the transformation of metallic silver to
silver sulfide. Again, this compound has extreme stability and is rather difficult to oxidize. This
implies excellent image stability (even under adverse conditions) provided that adequate levels
of conversion were achieved in toning.
HYDROGEN PEROXIDE FUMING TEST
The ultimate reason for the harsh hydrogen peroxide fuming test is rather simple. If an
investigator chooses to study the benefits of a protective treatment he has to establish parameters first against which one can measure the behavior of the test-object.
The Hydrogen Peroxide Fuming Test accomplishes exactly that. An untoned silver image normally deteriorates severely when exposed to the aggressive fumes of H2O2. The silver oxidation achieved in this way manifests itself in various ways, the most common of which are: redox blemishes, overall discoloration (colloidal silver) and silver mirroring. In the first step of image degradation, metallic silver is always oxidized to silver ions. Once these ions are formed,
Hendriks43 they are mobile and can travel with the aid of humidity. As an example, states that there is evidence of ions migrating into the baryta layer where they can form a ghost image upon
43 HENDRIKS, K.: The Stability and Preservation of Recorded Images, Chapter 20, Neblette's Imaging Processes and Materials, Eighth Edition, Van Nostrand and Reinhold, New York, 1989, pg. 647 -30-
combination with silver sulfides. The other route for ions to take is upward, to the surface of the image where once combined with airborne sulfides, a blue metallic sheen forms, commonly
referred to as silver mirroring.
History
The oxidative potential of Hydrogen Peroxide has been known since the turn of the century
and researchers used the substance widely. H2O2 has also been suggested as an oxidant
for sodium/ammonium thiosulfate (HE-1 Hypo-Eliminator), a recommendation which is no
longer in place.
Since the early 1 960's, when first reports of redox blemishes of archived microfilm surfaced,
hydrogen peroxide was employed to simulate this form of silver deterioration in laboratory
experiments. Notably Henn & Wiest pioneered this method. Later on, Pope and others modified both the procedures and concentrations of H2O2 applied. Although these researchers were all successful in demonstrating the susceptibility of silver to hydrogen
peroxide, their results and the degree of attack differed from laboratory to laboratory. Until
recently, hydrogen peroxide tests were widely used in internal quality control and research
facilities of the industry, but no two companies were apparently in agreement over technique
and results.
As Adelstein44 has pointed out, the establishment of a reliable and reproducible test that
accurately measures the behavior of silver oxidation is a prerequisite for any such study. The
"benchmark" which results can be compared is necessity for a reliable or gauge, against to,
self-explanatory. The goal then was to find a method that would cause deterioration of the
a Kodak and kind produced by real life conditions with any untoned material. In joint-effort,
the Image Permanence Institute devised a test that built on the experience of the earlier
test- researchers. A great premium was placed on the reproducibility and consistency of the
results.
44 Formation on ADELSTEIN, P. et al.: Hydrogen Peroxide Test to Evaluate Redox Blemish Processed Microfilm, Journal of Imaging Technology, Volume 17, Number 3, June/July 1991 -31-
The hydrogen peroxide test, as will be described below, is in itself very severe and hardly
resembles real-life conditions. The combined deterioration of long-term exposure to airborne
peroxide is expected to be much less harsh than the erosion caused by this fuming test.
However, if a treated sample withstands such severity of attack it seems reasonable then to
assume that the protection of the silver image is nearly absolute. Although it is true that no
exact life-expectancy predictions can be made, a passing of this test is indicative of high
silver image stability. Hence, the hydrogen peroxide fuming test represents an ideal means to
analyze the advantages toners can impart on a silver print.
Test Description
The Hydrogen Peroxide Fuming Test is described in much more detail elsewhere in the
literature.45 Nevertheless, a brief account of this particular test method and the proceedings
involved shall be given below.
A two-liter desiccator jar constitutes the primary testing vessel within which a relative
potassium chloride a petri dish. humidity of @ 82% is maintained by a saturated solution of in
The test-samples are mounted inside a Plexiglass collar, emulsion side facing away from the
collar-wall towards the center of the jar. This collar is then placed inside the dessicator,
square of Whatman filter paper with separated from the petri-dish by a Coors plate. A piece
1"x1" the dimension of @ is fit onto the Coors plate.
peroxide solution is applied to the filter paper Immediately prior to incubation a 2% hydrogen
micro pipette. This calculates to a total in two charges of 0.120 ml each with an Eppendorf
concentration in the desiccator of 2000 parts per million.
reagent grade 30% hydrogen peroxide The 2% hydrogen peroxide solution is prepared from
volume of 100 ml and diluted with deionized solution (6.7 ml of 30% H2O2 on a total solution)
or distilled water.
a fan-fitted lid. For the entire Following the first charge of H202, the desiccator is sealed with
chamber heated to which makes for duration of the experiment, the jar is placed in a 50C,
50C. and @ 82% RH. an incubation environment inside the desiccator of
Evaluate Redox Blemish Formation on 45 ADELSTEIN, P. et al.: Hydrogen Peroxide Test to Volume Number 1991 Processed Microfilm, Journal of Imaging Technology, 17, 3, June/July -32-
The fan is powered by a 12 Volts DC motor running at 2500 rpm. The total fanning time is set to 60 minutes. After the elapse of the first 30 minutes, the second charge of hydrogen peroxide is applied and fanning continued for the remaining 30 minutes.
The duration for the incubation is set to 18 hours. This time has been chosen somewhat arbitrarily but is very convenient since the experiment can be done over night. Shorter incubation times, ranging anywhere from one to several hours have produced less consistent image oxidation.
This fanning time of a total of 60 minutes appeared to be crucial and deserves special
mention. Early experiments with stagnant air inside the jar resulted in lack of uniformity and
reproducibility of deterioration. It was concluded that the even distribution of hydrogen
peroxide fumes within the jar is an important factor. Hence, the fan inside the desiccator jar.
Although the blower distributes the fumes uniformly within the jar, constant air movement
inhibits the formation of redox blemishes. Instead, overall formation of colloidal silver
(discoloration) is the result. Because photographic materials are seldomly stored in
environments with constant air movement, a compromise had to be found that would
guarantee even dispersion of the oxidant as well as a reasonable period with stagnant air.
Upon completion of the experiment, the samples are removed from the desiccator and collar
and undergo post incubation development.
Post Incubation Development
of negative Oxidation of the metallic silver image results in invisible and mobile silver ions
metallic silver is oxidized and charge. Over time, discoloration increases as more and more
these silver ions travel reduced again to silver sulfide at new sites. Aided by humidity, away
can take in real life from their original sites. Both, oxidation and reduction considerably long
eye quite some time. It has and signs of deterioration might not appear to the unaided for
peroxide. But the hydrogen been explained above how silver is oxidized by hydrogen
deterioration can be made visible at once peroxide test is only meaningful when the degree of
incubation the silver ions need to so that it can be measured. Hence, following the oxidizing -33-
be reduced to colloidal silver again. To this end, the test-sample is simply redeveloped in a
common print-developer; redevelopment makes visible the latent image.
Redevelopment of oxidized silver results in the formation of sphere-shaped colloidal silver. Its
light absorbency and refractive properties differ markedly from the filamentary structure of the
previous grain. Essentially, colloidal silver is yellow-orange as compared to gray-black/black
of filamentary silver. It follows that any yellowing of the print or the formation of yellow spots
and stains is a clear indication of image deterioration. As a consequence, it is the
densitometric increase of yellowing that is significant and of interest for purposes of
qualitative evaluation.
The performance assessment is fairly stringent because a toning-treatment should
completely protect the image. Only samples with a blue-density increase of -/< 0.05 density
units after redevelopment are considered to pass the test. This tolerance-level will be
recommended in an upcoming ANSI-Standard currently (IT-9.15).
POTASSIUM DICHROMATE BLEACH
convert the So far, it has been pointed out a number of times that the purpose of toning is to the metallic silver of the image to a more stable compound, such as silver-sulfide. Aside from
amount of silver that has been tone change of the print, little can be said about the actual converted.
determined unconverted silver An estimate of the amount of silver converted is by removing any
powerful oxidant. It dissolves metallic silver by means of the TC-1 bleach. TC-1 bleach is a very the development process removes unexposed and altogether much in the same way as fixer in
converted (or silver remains undeveloped silver halides from the emulsion. Likewise, the toned)
bleached print is therefore comprised of the unaffected by the bleach. The image of a entirely silver-compound produced by the toner. -34-
The constituents of the TC-1 Bleach (Kodak Tray-Cleaner 1 Formula) are the following:
Potassium Dichromate 90 grams
Sulfuric acid, 98% 96 ml.
Water to make 1 liter
Potassium dichromate bleach is of a prominent orange color. It is very reactive, extremely poisonous and corrosive. Increased potassium dichromate content in the bath reduces the bleaching times but it also makes a proper clearing bath imperative. A typical bleach as used in reversal processing of film (such as R-9R) contains only 22 ml./liter of concentrated sulfuric acid.
By contrast, the 96 ml. used in the above formula assure complete dissolving of the silver. High sulfuric acid content is responsible for highlight stain. These stains are often difficult if not impossible to remove. A more thorough discussion on the potassium dichromate bleach is given by Zuidema.46
Upon immersion in the potassium dichromate bleach, prints are tinted yellow. Treatment time in the bath was typically 1 minute. After removal from the bleach bath, the samples were quickly rinsed in running water whereupon a clearing bath, consisting of @ 10% solution of sodium sulfite, was used to remove any remaining orange stain. A higher sodium sulfite content clears the sample faster and the bath is less quickly exhausted.
The oxidation process of silver to a soluble salt complex by the above bleach proceeds according to the formula:
6Ag + K2Cr207 + 7H2S04 -
3Ag2S04 + K2SO4 + Cr2(S04)3 + 7H20
The silver and chromic sulfates thus formed are usually sufficiently soluble to be dissolved in the bleach, in the subsequent wash or in the clearing bath.
46 ZUIDEMA, J.W.: The Sulfuric Acid-Potassium Dichromate Bleach in the Black-and-White Reversal Process, Journal of the SMPTE, Vol. 72, June 1963, pg. 485-487 -35-
%-Density Retention vs. Silver Conversion
It should be noted that the silver content of a print is very difficult to assess either before or
after treatment. Direct quantity correlations derived from density readings of untoned prints
vs. toned and bleached prints are by not absolute. The silver filaments have sufficiently
changed their shape in the toning process to alter their light-absorbency. Density readings
are nevertheless very useful, but they need to be interpreted appropriately.
Density readings taken before and after treatment can be expressed as a percent (%) ratio.
Such a %-value indicates how much image density is retained after bleaching the image.
Consequently, in the graphs of the Appendix B reference is always made to %-density
retention, which is used to approximate the extent of silver conversion in an image.
Importance of high density retention
It has been pointed out that good resistance in the peroxide fuming test does not necessarily
oxidation.47 guarantee complete protection against image Highly reactive species, such as
than nitrogen dioxide, ozone and other such substances attack silver in a different way
peroxides do: they oxidize silver directly.
"poisoning" the catalytic While only partially converted silver might well resist oxidation by
decomposition of hydrogen peroxide, the same level of change to a compound of higher
ozone. order oxidation resistance might prove to be inadequate when exposed to In to fully
silver-conversion be achieved. this protect an image, it is crucial that high levels of Hence,
the assessment of the approximate bleach test is a particularly useful technique for
such as silver sulfide. conversion of silver to a compound of higher oxidation potential,
bleach test will also form part of the Like the hydrogen peroxide fuming test, the dichromate
preparation. It has been established in this aforementioned ANSI-Standard currently under
retention should be achieved to and other projects that levels of -/>65% density completely
oxidative attack. safeguard the silver image from any type of
ANSI Standard IT 9.15 (in 47 ADELSTEIN, P.Z. and REILLY, J.M.: Appendix B of preparation) -36-
HIGH TEMPERATURE - HIGH HUMIDITY INCUBATION (50C./80% RH)
In the section on silver degradation it was pointed out how humidity greatly aids in the corrosion of silver images by making possible the diffusion of alien substances in and out of the gelatin.
This is often the primary reason why accelerated aging tests involve high humidity levels as this
generally accelerates chemical reactions taking place. The additional introduction of heat
quickens the reactions. The effects obtained are much more pronounced than at humidity levels
resembling a normal environment.
Artificial aging also amplifies flaws of the initial processing steps (fixing-washing) since residual
thiosulfate complexes break down much more swiftly to form sulfides. These in turn cause silver-
mirroring, stains and density loss.
An incubation at high temperature and high humidity is intended to simulate a natural aging
process, however, in a compressed time frame. Obviously, studies conducted in real time and
under real life conditions are not practical. Accelerated aging indicates, although perhaps with a
certain margin of error, how a specific material is likely to behave over long periods of time. Can
objectionable changes in image-density (a loss in most cases) or signs of deterioration be
expected to occur or can we anticipate a print to discolor over time? These are the questions an
incubation is likely to answer.
James48 corrode. found In the absence of strong oxidative substances, silver is very unlikely to
that even an atmosphere of pure oxygen did not have a discernible effect on density readings. have detrimental However, ionization of oxygen from the air at very high temperatures may
consequences.
The Plumming Effect
of silver are nevertheless Despite the absence of oxidants, changes in the morphology likely
known as and the associated to occur, regardless of toning. This effect is plumming density
James49 untoned samples. loss has been observed in this project for both, toned and
48 Photographic Science and Engineering, JAMES, T.H.: The Stability of Silver Filaments, Volume 9, Number 2, March/April 1965, pg. 123 49 ibid, pg. 121-122, 125 -37-
reported a thickening and breaking up of the filamentary structure of the developed silver
upon exposure to heat and humidity. He also noticed that these adverse effects were greatly
suppressed by adsorbed sulfides or iodide.
Hendriks50 reported that the silver-filaments rearrange themselves in most cases under the
influence of heat and humidity such as to form larger clusters with gaps between them.
Usually, this spawns a certain density loss. James51 has demonstrated by means of electron
micrographs that the originally long strands of the filaments simply contracted during
exposure to high humidity and thereby became thicker and shorter. Many of the filaments
were reported to break up into smaller segments and the formation of nearly spherical
filaments' particles was likewise observed. Again, the net effect is a loss of the covering
power and a change in image tone.
Other causes for print discoloration
Regardless of morphological alterations, most images, whether toned or not, do nevertheless
discolor upon such exposure to heat and humidity. Yet, this overall yellow stain is not
attributable to oxidation but can in most cases be ascribed to the discoloration of the gelatin
upon prolonged exposure to heat.
paper-manufacture to incorporate Today it appears to be common practice in photographic
of the product. A optical brighteners in the baryta/titanium oxide and/or support layer
wash. Excessive considerable amount of these is dissolved and carried away during the
can expected to decompose wash times are therefore not advisable. These brighteners be
the print begin to appear over time or are otherwise rendered ineffective. Consequently may
areas. This phenomenon is perceptible to the eye (an to be slightly yellow in the highlight only image deterioration. illusion, so to speak) and has little to do with
densitometric measurement. However, Yellowing of this nature is detected by blue-density is indicative of the filaments having the generally observed decrease in blue-density
Preservation of Recorded Images, in 50 HENDRIKS, K.: Chapter 20, The Stability and Van Nostrand & Reinhold, New Neblette's Imaging Processes and Materials, Eighth Edition, York, 1989, pg. 647 Photographic Science and Engineering, 51 JAMES, T.H.: The Stability of Silver Filaments, Volume 9, Number 2, March/April 1965, pg. 124-125 -38-
undergone considerable rearrangement. Morphological changes, such as in oxidation, are
normally linked to an increase in blue-density. The modified shape of the filaments changes
their refractive properties. This further complicates matters as these remarks contradict each
other. Therefore, need arises to address this point again in the section Conclusions/Recommendations: Blue Density Readings.
REPORTING
Density Readings
In this study, density readings were taken of all samples that underwent evaluation in the
three described tests. An X-RITE Transmission/Reflection densitometer, Model 310, was
used. The density readings reported in the tables of Appendix A reflect Status A, blue density
readings only. The significance be explained:
As yellowing of a print or negative is generally an indication of deterioration, it is the degree
of yellowing that should be measured for. In cases of severe deterioration, it was observed
that the visual-density of a print did not markedly differ from readings taken before oxidation
"yellowness" had occurred. However, the increase in relative was significant and visible to the
unaided eye. Thus, despite oxidation having occurred, visual-density measurements may not
reflect such a change. It follows that visual-density measurements are not a suitable method
for the evaluation of image degradation.
Blue being the complementary color of yellow it is easily understood why blue light is
reflected or transmitted to a degree corresponding to the yellowness. Therefore, increasing
"yellowness" levels of blue-density represent an increase in of the sample.
The same principles apply in the evaluation of toned vs. untoned samples. Most toners
change the silver morphologically besides forming a new silver compound. Thereby the
refractive/reflective properties are altered. Again, the measurement of blue-densities allows
for the detection of minute toner induced in- or decreases of yellowing. -39-
While it is conceivable to directly correlate blue density change to the degree of toning or
deterioration, it is altogether inadvisable to attempt such interpretation. It is possible to attain
very high levels of toning without the expected density increases occurring. This makes it
difficult to anticipate or to determine how shape, size and spatial distribution are affected by both, toning and oxidation.
An acceptable blue-density increase has been set to -/<0.05 units. An augmentation
exceeding that of 0.05 units becomes perceptible to the unaided eye (highlights) and points
to the fact that serious silver corrosion of the image has occurred. -40-
Tables / Density Readings (Appendix A)
Since the objective of the study has been to investigate the behavior of metallic silver in
"noise" black-and-white photographic papers, any needed to be filtered out. Therefore, discoloration of the gelatin had to be compensated for. Typically, a Dmin area of a processed
print does no longer contain metallic silver. Consequently, discoloration of a Dmin area is due to gelatin or paper support stain as opposed to silver oxidation or toning.
It has previously been pointed out in the section on bleaching how increased sulfuric acid
content of the bleach bath may produce discoloration of the highlight areas of a photographic
print. Although resin coated papers were never affected, all fiber-base materials displayed
such discoloration, notably in the Dmin areas. Because RC papers were not stained in the
bleach-bath, emulsion staining can be dismissed as a factor. It is concluded that rather the
baryta layer and perhaps even the underlying paper support were affected. Although the
wash and clearing bath removed the stain for the most part, a slight yellow residue was
observed upon drying of the prints.
Necessarily, the density readings taken after bleaching needed to be adjusted accordingly to
account for this baryta and support stain. Such an adjustment was accomplished by the
following simple computation:
Dmin density reading of toned sample: 0.07 units
Dmin density reading of bleached sample: 0.13 units Difference (or Dmin density increase) 0.06 units (Difference to be subtracted from all density readings of the bleached sample)
"Corrected for Dmin". These were Any such corrections are reflected in the columns marked
graphs. A sample-table of the same also the density-values used in the generation of the
given overleaf: format as the data is reported in Appendix A is -41-
Product ORIENTAL SEAGULL
Toner/Treatment Kodak Rapid Selenium Toner Concentration: 1200 TreatmentTlme: 3 Minutes at 25 C.
Stop* Control Toning Potassium Dichromate SDensay Peroxide Peroxide Peroxide Incubation kicubaeon Incubation (untoned) M Dichromate Bleach Retention Fuming Corrected Net Density SO/80 Corrected Net Density above Bleach Corrected SO/80 torDMIn Change far DMIn Change Density Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue Blue 1 0.07 0.07 0.13 0.07 100 0.12 0.07 0.00 0.15 0.07 0.00 2 0.06 0.08 0.13 0.07 88 0.14 0.09 0.01 0.16 0.08 0.00 3 0.06 0.07 0.13 0.07 100 0.12 0.07 0.00 0.15 0.07 0.00 4 0.10 0.08 0.14 0.08 100 0.16 0.11 0.03 0.17 0.09 0.01
5 0.11 0.11 0.14 0.08 73 0.21 0.16 0.05 0.18 0.10 -0.01 6 0.16 0.14 0.13 0.07 50 0.29 0.24 0.10 0.22 0.14 0.00
7 0.24 0.22 0.13 0.07 32 0.37 0.32 0.10 0.28 0.20 -0.02
8 0.35 0.33 0.13 0.07 21 0.41 0.36 0.03 0.37 0.29 -0.04
9 0.50 0.47 0.14 0.08 17 0.50 0.45 -0.02 0.50 0.42 -0.05
10 0.68 0.65 0.15 0.09 14 0.68 0.63 -0.02 0.65 0.57 -0.08
11 0.87 0.83 0.15 0.09 11 0.85 0.80 -0.03 0.83 0.75 -0.08
12 1.09 1.04 0.17 0.11 11 1.05 1.00 -0.04 1.02 0.94 -0.10
13 1.32 1.27 0.18 0.12 9 1.27 1.22 -0.05 1.23 1.15 -0.12
14 1.57 1.50 0.22 0.16 11 1.63 1.58 0.08 1.44 1.36 -0.14
15 1.77 1.69 0.25 0.19 11 1.77 1.72 0.03 1.61 1.53 -0.16
16 1.90 1.83 0.26 0.20 11 1.85 1.80 -0.03 1.72 1.64 -0.19
17 1.99 1.92 0.33 0.27 14 1.93 1.88 -0.04 1.77 1.69 -0.23
1B 2.05 1.98 0.34 0.28 14 1.98 1.93 -0.05 1.86 1.78 -0.20
19 2.09 2.02 0.36 0.30 15 2.01 1.96 -0.06 1.83 1.75 -0.27
20 2.12 2.04 0.38 0.32 16 2.02 1.97 -0.07 1.89 1.81 -0.23
21 2.12 2.05 0.38 0.32 16 2.03 1.98 -0.07 1.90 1.82 -0.23
Note: All comparisons and calculations in the table above refer to the densities of the toned samples.
Relations to the densities of the untoned samples cannot be considered in this format, nor will they be
shown in the graphs.
Graphs (Appendix B)
In order to be properly interpreted, the graphs in Appendix B require some explanatory
remarks. Due to computer-program inherent limitations, for reasons of practicality (but
are placed to the right as opposed to contrary to customary practice), the Y-axis and its scale the left edge of the graph.
"overlay" The plots presented here are of an type, comparing two different sets of data. This
effort was made to ensure means that the curves shown are running off different scales. An
compared that all graphs in Appendix B use identical scale-values so that they can be directly to each other. All data-points shown refer to blue-density readings only. -42-
The baseline or X-axis (zero-value) represents the original densities of the sample after toning. Throughout, comparisons and calculations made invariably refer to the toned samples. The two curves fluctuating around the baseline represent the change in density as compared to the baseline and are measured densities. If densities of untoned samples should be of interest, reference is made to the tables in Appendix A.
The %-density retention curve deserves special mention. Each data point is obtained by
comparing it to the original density of the toned sample and expressing the change as a
percentage. Since each data point is labeled individually, there is no need for showing the
respective scale. This allowed for the separation from the other curves, improving the
legibility. The spatial separation was accomplished by using an independent Y-axis, which is
not shown. The Y-axis shown refers only to the curves for the peroxide and high
temperature/humidity incubations.
The data points of the %-density retention curve are in most cases 100% or more in the low
density areas. This is a small but inevitable flaw. Dmin densities are generally very low,
"non-image" typically between 0.06 and 0.12 units. These figures represent areas of the print
where no silver is present in the emulsion. Accordingly, no conversion of silver can have
taken place for steps in the Dmin region. Therefore, the %-density retention values become
attributable to silver presence. only significant in areas having considerable density
Consequently, the first couple of data points can be discarded altogether since they are
irrelevant and misleading.
densitometer Slightest differences in the order of 0.01 density units, attributable to error,
translate into an increase of 20% density unevenness of the sample-step, etc. can easily
compared. For if 0.06 marked when toned vs. bleached samples are numerically instance,
Dmin corrected with the subsequent the original density of the untoned sample, a density
over the original which of course is value of 0.08 units is equal to an increase of 33% value,
excess of 100% should be disregarded. misleading. Thus, low density values in -43-
For easy reference, a sample graph is shown here, being the analogous counterpart to the
data in the preceding table.
ORIENTAL SEAGULL in Kodak Selenium Toner 1 :200 I
? -10O>JM-'1O&.1OO 0.60 ? 88 "?.73 0.50 '?50 -rj '?32 J- 0 40 ? "?*U-17^.i4*.1.1*.1.1>a.^.1.1*.11^-n-14+-14^-16>-16-160"30 tS ::0.20 t O {0.10 8 0.00 C w ;-0.10 2 s 0.20 Q Q 0.30
e e o Original Density
Peroxide 2000 ppm * Incubation 50/80 % Density Retention/Bleach
DISCUSSION OF RESULTS
the large mass of data compiled in Appendices A It is virtually impossible to adequately discuss
endeavors highlight the more important issues and and B. The exposition to follow, which to
unimportant in this findings, is inevitably incomplete. Because product specific behavior is study, that is toners. the comments are organized by treatment categories, by
Untoned Controls
expected that most if not all untoned samples Due to similar studies performed earlier, it was
exposure to hydrogen peroxide fumes. This would present symptoms of deterioration upon
formed fixation affords far too little protection clearly indicated any silver sulfide during
hydrogen peroxide test. Kodak's Elite paper against oxidative attack, such as in the fuming little discoloration. The was the exception to the rule and exhibited comparatively %-density
retention for all untoned samples was quite low. -44-
The behavior of Kodak Elite appears to be somewhat irregular as compared to the other products. It is suspect that significant amounts of antioxidants are incorporated in this paper, rendering it practically inert to peroxides. Secondly, the support layer is of extra thickness and much heavier than a double-weight stock of a regular fiber base paper. Both of these properties might account for Elite's relatively good resistance to peroxides.
The properties of the support materials deserve commentary. In the fuming test, it was observed that RC papers discolored more severely and more readily than fiber base materials. The fibrous support is suspected to absorb a considerable quantity of the oxidant, thereby inhibiting some of the oxidants to reach the silver grains. It is also conceivable that
part of the H2O2 permeates from the gelatin into both, the baryta layer and support, leaving
the silver filaments unaffected. This behavior is unimaginable for RC materials due to the
polyethylene coating on either side of the paper support.
During the heat/humidity incubation, all materials experienced a general loss of density; up to
0.30 density units for Dmax in some severe cases. These losses are largely the result of
plumming and not attributable to image deterioration. As the incubations of toned samples
indicate, all black-and-white print materials may exhibit a certain density loss over time,
regardless of storage conditions or protective treatments applied. However, under less
severe storage conditions, this does not present a practical problem.
The data gathered from an incubation run at only one condition does not warrant predictions
regarding the real-life/real-time behavior of photographs. Only Arrhenius plots can
accomplish that.
The hydrogen peroxide fuming test can be said to represent a "worst case scenario".
Nevertheless, the test clearly demonstrates that all untoned photographic papers can sooner
or later be expected, with a high degree of certainty, to suffer from irreversible deterioration in
"archival" of prints is does not provide an oxidizing atmosphere. So called processing simply
adequate enough a protection. It merely removes residual processing chemicals, which can
be another cause for image degradation. Although archival processing is a widespread
print outside practice with uncontested advantages, it accomplishes little to protect a from
influences.
controlled storage environment for Most individuals cannot afford the luxury of a
command over the constituents of photographic photographs. Moreover, they have even less -45-
enclosure materials. The most logical conclusion then is to tone black-and-white prints for permanence. It is the most inexpensive way to safeguard photographs against the detrimental impact of pollutants and ensures a dramatic improvement of their life-expectancy in less favorable environments.
Agfa Sistan
Agfa describes Sistan as a silver-stabilization treatment. It is alleged to aid in the protection of silver against adverse environmental influences. The contents of this product are not
disclosed and therefore one can only speculate on the mechanism by which image protection
is supposedly brought about. The suggested dilution of 1:50 for papers was mdre than
doubled in these experiments, using a 1 :20 dilution. The increased concentration did not add
to the performance of Sistan.
Sistan failed completely to render silver more stable. Of the series of samples treated with
Sistan, only Kodak's Elite and Oriental's VC-RC did not discolor in the peroxide test. These
two papers demonstrated good resistance to oxidation and behaved similarly in the peroxide
test when toners (at high dilutions) did inadequately protect the image. VC-RC's only flaw in
these experiments has been its gelatin deterioration upon exposure to head, humidity and
peroxides in particular. Adhesion failure and an overall dulling of the gloss was often
observed.
conceivable that Sistan functions While not converting silver to a more stable compound, it is
required post-treatment as an antioxidant additive. However, this would make need for the
samples treated with Sistan wash rather doubtful. Interestingly enough, some of the
can thus deteriorated more than their untoned counterparts. The antioxidant theory be
print surface if the dismissed. Since the manufacturer warns of a crystalline build-up on the
present as a constituent of the required wash is insufficient sodium sulfite is suspected to be
aids which helps remove residual concentrate. It is the primary agent found in wash
similar that of a thiosulfates. Therefore, it is postulated that Sistan's effect is to hypo-clearing
of the image silver and the complete agent. This additionally inhibits protective sulfiding
peroxide decomposition. removal of thiosulfates further suppresses poisoning of hydrogen -46-
There is no evidence of treatment related silver conversion having taken place. Clearly, the overall low %-density retention, (typically being 20-30% for the Dmax areas of a print) illustrates this point. The measured density retention is likely due to partial sulfiding during fixation. These values are incidentally in keeping with Pope's findings about silver conversion during fixation (see paragraph on Toning by Fixation).
For many samples treated with Sistan, considerable density losses of up to 0.30 units in the
Dmax areas were noticed in the high temperature/high humidity incubation. In several cases, these density losses were more pronounced as compared to the untreated controls.
Kodak Gold Protective Solution GP-1
Gold toners enjoy a good reputation as safeguards against deterioration and this study is in
agreement with the data published for other research projects. Henn & Wiest recommended
a toning time of 1 0 minutes. It was decided that such a long treatment time was not feasible
and has subsequently been shortened by 50% for reasons of general practicality. Otherwise
the recipe remained unaltered.
Henn & Mack had pointed out that both agitation and treatment time are of utmost
importance in achieving gold deposition (see section on gold toning). Thus, the lack of
density retention in the bleach test could be attributed to the reduction of the treatment time.
gold- Yet it also looks as if the GP-1 formulation is simply less effective in achieving
deposition.
The observations from data and graphs can be summarized as follows: The density changes
for Dmax between the untoned and toned samples are not very significant. Kodak
Polycontrast marks the extreme with a loss of 0.20 units upon toning. Oriental's Seagull
remained unchanged. Other products lost about 0.10 units in density, which is not of great
concern. The mid-tone regions indicate negligible changes of @ 0.05 units.
Polycontrast papers discolored beyond In the peroxide test, Agfa Multicontrast and Kodak
poor the 0.05 unit tolerance (note: both are RC papers). The conversion levels are relatively
compared to fiber base papers: @ 60% for for all samples, yet significantly higher for RC as
RC vs. @ 30% for fiber base papers. -47-
The following conclusions can be drawn from the data supplied in Appendix A: Since the
conversion levels (%-density retention) are rather low, silver image protection cannot be
guaranteed for more aggressive oxidants, despite the fact that reasonable resistance to the
peroxide fumes was achieved (except for Agfa Multicontrast and Kodak Polycontrast).
rather Aesthetically, blue-black image color might be attractive to photographers while the
toner adds some protection to the silver image. However, the rather high cost involved in the preparing toning solution may be a supplementary factor to be considered. It appears that
the chemicals involved in the preparation of the gold-chloride solution (as well as the
subsequent disposal of the toner itself) may present problems with regard to environmental issues.
The incubation at 50C./80% RH did not reveal any irregularities. All samples suffered from
an overall loss (plumming effect) over the original (toned) densities. This reduction is most
noticeable in the Dmax areas and least perceptible in the highlights. On average, the
deviation constituted @ 0.20 units for a shadow area.
Kodak Gold Protective Solution GP-2
The GP-2 toner is a more successful recipe than GP-1. In spite of the shortened treatment
time, sufficient amounts of gold were deposited to virtually eliminate all signs of deterioration.
No blue-density increase indicating oxidation was detected in any density-step for any
material.
It should be cautioned, however, that a passing of the peroxide fuming test does not
necessarily constitute total safeguard against oxidative attack, notably with regard to ozone
and strong acids. By implication, fiber base papers ought to be toned slightly more in order for the %-density retention to be raised a few percentage points as compared to the values
obtained above. Although it is preferable to attain as high as a conversion as possible this will
inevitably produce a quite noticeable image tone shift.
In most cases, toning by itself did not produce dramatic density changes. Multigrade (-0.08) and Polycontrast (-0.15) were affected in the Dmax areas by a slight loss. Oriental VC-RC gained some 0.15 units for the corresponding step. All other five papers experienced losses or gains too small to be mentioned. It is the opinion of the author that density shifts in a -48-
Dmax area ought not to be of great concern. Even if they were rather substantial, they cannot be easily perceived by the eye. Only a direct comparison to other photographs could reveal such changes. More important to the eye are density shifts in the highlight and upper
mid-tone areas of a print which are easily noticed.
The %-density retention curve confirms ample deposition of gold. The %-density retention
was found to be approximately 70% for RC papers and about 50-60% for the fiber base
variety. This seems to be further proof for RC's greater susceptibility to both oxidation and
toning. Such levels of %-density retention are also very close to the forthcoming ANSI
recommendation of 65% to assure adequate protection.
The 50C./80% RH incubation resulted in a general blue-density loss which gradually rose to
approximately -0.10 units for Dmax. Ilford's Galerie lost 0.20 units for the same step.
Interestingly enough, Agfa Multicontrast's curve for this incubation slumped in the midtones
by -0.15 units but retained its original density in the shadows.
Aesthetically, the noticeable blue-black hue created by the GP-2 toner might be of special
interest for certain pictorial applications. Gold-toners, if used over any sulfide toner (such as
in double-toning) will shift the photograph's tint to a very distinct pinkish-red which might not be desirable.
Kodak Sepia Toner
In spite of having altered the toning method for Sepia Toner as well (see Toning) the
obtained results are very satisfactory. None of the samples displayed symptoms of
deterioration after the hydrogen peroxide fuming test. The %-density retention curves are
consistently high over the entire density range. Kodak's Elite paper appears to be the most
difficult to tone as the 65% density retention for Dmax marks the lowest value measured.
Despite the relatively high degree of conversion, the overall tone-change is not as dramatic
as one might expect from a Sepia toner, llford Multigrade and Agfa Multicontrast both remain
almost neutral in tone. All other materials assumed a slight to moderate sepia tone, which is
not offensive or overly pronounced. -49-
Exposure to heat and humidity affected the two Agfa papers most. Oddly enough, in toning both papers gained density. The incubations amply compensated for this gain and left the
samples with a net loss of @ 0.20 units for Dmax.
This is not "warmer" utterly surprising. Both papers make a significantly print which is
suggestive of a chloro-bromide as opposed to a pure silver bromide emulsion. A tentative
conclusion is that the toner has a more prominent effect on the slightly rounder particles of
the chloro-bromide emulsions.
IPI J-Toner
The J-Toner presents the photographer with a very viable alternative over any other toning
treatment. Its contents are relatively inexpensive and the stock solution can easily be
prepared from raw chemicals. Recent tests at IPI have demonstrated that J-Toner has
excellent keeping properties as a stock solution, which is largely attributed to the added
borax. Once diluted, it keeps rather well at high concentrations of 1:25 and higher but
oxidizes more readily at high dilutions (1:400), causing precipitation.
Consistent with the expected behavior of polysulfide toners, I Pi's J-Toner is rather effective in
delivering oxidation resistance. Highly dilute toner concentrate (1 :400) was unable to provide
the desired protection and some of the samples (Kodak and Agfa RC papers) discolored in
the peroxide test. At the lower dilution of 1:100, the toner activity seems to be effective
enough to prevent image degradation. However, on some of the samples, silver-mirroring
had formed - an indication of incomplete protection.
The comparatively high degree of conversion for all samples at the 1:100 dilution combined
with signs of silver mirroring is paradoxical and troublesome. This phenomenon only comes
to bear at high dilutions. Such weak toner-solutions are rather unstable and toner activity
increases dramatically as the toner is slowly being oxidized by oxygen found in water and air.
This extra activity would explain the high conversion rates but it remains unclear as to why the same samples discolor in the fuming test and manifest signs of silver-mirroring.
While density retention in the shadow areas has been very high for the Kodak Polycontrast sample at 1 :400, an unacceptable rise in blue-density for the same part of the image was observed in the peroxide test. -50-
Kodak Elite has largely resisted toning over the entire range of dilutions. The graphs clearly show how the %-density retention curve decreases quite dramatically in the higher midtones/highlights and falls short of the recommended threshold of 65%. By contrast, the conversion in the Dmax areas is consistently high. It was noticed that the transformation of elemental silver to silver sulfide is further restrained by very high concentrations, that is at
1:10 and 1:4. Oriental's Seagull has responded similarly, although to a lesser degree.
Generally, all materials profit from increased toner-concentration. Density retention after bleaching approaches nearly 100% for Dmax with some samples. (For more detailed
information, please refer to the attached graphs and data sheets).
Aesthetically, all papers took on a rather pronounced cold-brown tone. This was especially
the case when very strong dilutions such as 1:4 and 1:10 were employed. The RC materials
were slightly less affected in this regard. The tone change on resin coated papers diminished
more and more as the dilutions were increased. At 1:25 these prints all appear to be just
up" "warmed somewhat, an effect which is not at all objectionable and similar to the print
color of a warm-tone paper. The fiber base papers retain the colder brown tones which also
become less noticeable as the dilutions are increased.
Densitometric evaluation after the 50C./80% RH incubation indicates a blue-density loss of
common response for all samples at all dilutions. roughly 0.20 units (Dmax) which is a However, the initial density gain due to toning has often been significant enough to
compensate for the subsequent loss in the incubation.
elemental sulfur upon dilution in wastewater. As an effluent, J-Toner quickly decomposes to because it has low biochemical and In terms of environmental considerations, sulfur is benign
pungent smell of rotten eggs might chemical oxygen demands (BOD5 and COD5). Its (H2S)
be objectionable to the darkroom operator.
perhaps a threat to untoned images, if adequate The emitted hydrogen sulfide poses
store other photographic materials in the ventilation is not available. It is advisable not to any
unprocessed performed. Hydrogen sulfide will cause fog on vicinity where sulfide toning is
silver on processed images. photographic materials and can possibly lead to mirroring -51-
Kodak Polytoner
Kodak Polytoner appears to be a highly effective post-processing treatment and is
comparable to IPI's J-Toner. It performs well even at very high dilutions and the silver
conversion appears to be relatively high. Kodak Polytoner is alleged to contain both,
polysulfides and selenium. This mixture is said to make possible a wide variety of image
Wood52 tones while giving a photograph resistance to oxidation. However, Lee, Drago and
found, by means of X-ray fluorescence, that photographic papers and plates toned with
Kodak Polytoner did not contain any (or only trace amounts of) selenium. Instead, the silver
was entirely converted to silver-sulfide. This claim suggests competing chemical reactions, in
which the polysulfides are the more reactive species.
At 1 :400, Agfa Brovira and Oriental VC-RC exhibited slight silver-mirroring upon exposure to
hydrogen peroxide fumes. As the concentration was stepped up to 1:100, none of the
samples manifested any signs of oxidation damage. The %-density retention curve is
fiber- consistently high for all polyethylene coated materials, although slightly lower for the
base counterparts. Kodak Elite presents a special case again in that it is notoriously resistant
to toning. Agfa's Brovira is similar in this respect and also fails to attain high conversion
concentrated solutions that both materials levels. It is only at toner dilutions of 1 :25 and more
are on equal footing with the other papers.
50C/80% RH is a For most samples a considerable blue-density loss upon incubation at
units over the disturbing fact that was observed. Frequently, decreases of @ 0.30 density
toned controls were registered which are clearly visible in a print.
Kodak Rapid Selenium Toner
lengthier discussion because it has Of the toners discussed so far, selenium merits a
popularized late Ansel Adams become the favorite toner for many photographers. Partly by
toner can be found in almost standard (his all-time favorite), references to selenium any
for Photographic Images to 52 LEE, W.E, WOOD, B., DRAGO, F.J.: Toner Treatments Number June pg. Enhance Image Stability, Journal of Imaging Technology, Vol. 10, 3, 1984, 122-124 -52-
photo magazine or book. However, it is believed that there is a great deal of misconception concerning its benefits. The two major reasons why selenium enjoys such broad acceptance are the following: it is alleged to have little effect on image tone and is said to boost print contrast by means of Dmax density increase. As a side-effect it is believed to render the image inert to oxidants.
The findings of this study do only partially confirm the above assumptions. The collected data refutes significant blue-density increases in the Dmax areas for any materials used in the experiments - even at a high concentration of 1:4. Moreover, tone-change cannot be circumvented if image permanence is the objective. While slight toning does not appreciably change image color, it has virtually no merit in regard to image protection. The hydrogen
peroxide test revealed that only strongly toned prints resisted oxidation. Heavy toning goes
hand in hand with tone-change.
Selenium and sulfur both belong to the same group in the Periodic Table. Accordingly, their
solubility should be equally low. The main reason for selenium toner's inferiority over a
polysulfide treatment is the fact that selenium is less readily adsorbed to silver.
At any dilution greater than 1 :25, selenium failed to poison hydrogen peroxide decomposition
and subsequent silver oxidation. With the exception of Kodak Elite and Oriental's VC-RC, all
papers consistently manifest signs of oxidation severe enough to be readily visible. At the
1 :25 dilution considerable progress is made while Agfa Brovira and Oriental Seagull are still
plagued by attack. It was only upon rising the concentrations to the levels of 1:10 and 1 :4 that
all materials passed the hydrogen peroxide test.
The observations made in the above paragraphs are echoed in the data for the %-density
retention. The silver conversion for dilutions of 1:400 / 1:200 / 1:100 / 1:50 is not very high.
affected. in some cases the Neither portion of the gray scale was appreciably In fact, density
their untoned counterparts. retention is lower for these toned samples as compared to
must therefore be present in Metallic selenium can only be dissolved in sodium sulfite which
earlier that sodium sulfite happens to be the comparatively large amounts. It was pointed out
aids. another constituent responsible agent for thiosulfate removal in washing Yet
of the bath. When gelatin is (ammonium chloride) makes for a strong alkalinity toning
swells as a subjected to an alkaline substance, it is softened, considerably and,
sodium sulfite and consequence, any emulsion hardening is reversed. Furthermore,
thiosulfates from emulsion and ammonium chloride both help in the extraction of residual -53-
"poisoning" paper support. As a result, the near complete absence of thiosulfates inhibits of hydrogen peroxide decomposition and in the case of inadequate conversion, oxidative attack occurs more readily.
The performance of polyethylene coated papers is sound at concentrations of 1:25 and higher. They all attain >65% density retention. Generally, fiber base papers adsorb selenium less well, llford Galerie and Agfa Brovira are especially difficult to tone, judged by the mere
20% of density they retain after bleaching. Not even the highest concentrations yielded adequate results. In like manner, highlight densities of Kodak Elite barely pass the 50% mark.
Split-Toning
Split-Toning generally refers to an aesthetic effect. It is achieved by prematurely
removing a print from the toning bath - precisely at the moment when the shadow-areas
of the print have taken on color while the rest of the image still remains largely
unaffected. This suggests, that selenium is toning is density dependent. Only after
excessive treatment selenium starts to show its effects in the lighter areas of a print.
Therefore, split-toning should more appropriately be referred to as partial toning since the
highlights remain largely unprotected against oxidation according to this method.
Contrary to popular belief, selenium has failed to provide adequate protection. While it is
true that tone changes can be minimal, so are the safeguarding effects. Only strong
concentrations have proven to afford complete image protection - perhaps at the
expense of print appearance.
For reasons of pollution control and cost, the following suggestion would be in order. In
discarded before exhaustion. This is small batch processing solutions are often
powerful baths are prepared. the particularly true when very Furthermore, keeping it to properties of diluted selenium are unlikely to be very good, making necessary
Should selenium be chosen as a prematurely discard the toner. post-processing
compromise. The lack of silver conversion treatment, a dilution of approx. 1 :25 strikes a
increased temperatures and/or at this concentration can be offset by processing by
appropriately adjusted treatment times. -54-
CONCLUSIONS - RECOMMENDATIONS
Hydrogen Peroxide Fuming Test
The hydrogen peroxide fuming test has been found to be very successful in evaluating
resistance to peroxide attack. The results obtained by this method are consistent and
repeatable in that they regularly show the same degree of protection or lack thereof. It can be
said with confidence that the test method is reliable. In short, the data supplied is ample proof
for this claim.
Incubation 50C./80% RH
It has been observed in this study that all paper samples, toned and untoned and regardless
of brand or type suffered a density loss in the incubation. A visual tone shift from neutral
black to slightly brownish image tones was observed. Whether this is solely a matter of
filament contraction, i.e. plumming, the result of gelatin-discoloration or a combination of both
cannot easily be answered. Since no micrographs could be made for this study, the claims of
James and Hendriks (as mentioned earlier) cannot be verified.
As concerns the plumming effect, all papers seem to be similarly affected by high
temperature and high humidity, both in the incubation and the peroxide fuming test. For
samples that did not discolor in the peroxide test, the two curves run fairly parallel to each
effect" other. This suggests that the "plumming sets in after a brief period of exposure to
heat/humidity. It is also apparent in the graphs, that the more profound changes can
invariably be found in the high-density areas of a print. In other words, the plumming effect is
by virtue density dependent.
The observable discoloration of the highlight/DMin areas are attributable to overall gelatin
discoloration. Such a claim is further hardened by the fact that neither the toned nor the
untoned samples revealed any symptoms of silver oxidation, such as silver-mirroring or
yellow stain upon post-development. -55-
The findings also suggest that all papers, regardless of brand or type may experience gelatin discoloration and density loss over time. The extent to which this will occur can impossibly be predicted from this study. To this end, Arrhenius relationships needed to be established.
Although not directly part of this study, the 50C./80% RH incubation implies that storage
conditions are an important factor for the life of a photograph. As a general recommendation,
prints and negatives should be stored in a cool and dry place (@ -/<15C./40% RH). To
prevent shock-effects, both temperature and humidity fluctuations ought to be avoided or
kept at a minimum.
Blue-Density Readings
The rationale behind blue-density analysis ought to be clear from the earlier discussion.
However, it now appears that there is merit to expand the analysis to all four densitometer
bands, i.e. visual, red, green and blue. Indeed, one is presented with a problem when
attempting to undertake an analysis of blue density data only. The reason is one of conflicting
reactions. Blue-density readings are affected by both, losses in density due to the effects of
"plumming" blue- and increases in density, due to yellowing of a print. To put it differently; a
density reading measures different phenomena which have a tendency to interfere with each
other.
%-Density Retention
A print with a comparatively low level of toning/conversion might not be adversely affected in
the peroxide incubation at all. It is nevertheless preferable to attain relatively high levels of
threshold-value is on this silver conversion, in the order of 65% density retention. This based Image Permanence Institute. It has been study as well as independent investigations at the
found in countless experiments on both film and paper that a high conversion safeguards
photographic images against a variety of strong oxidants, peroxides, ozone, etc. -56-
Dilution of Toners
Less concentrated toners might be more economical in small batch processing but they do pose other problems. Oxidation and decomposition of the solution is one of them and applies particularly to polysurfide toners. Upon oxidation, their activity increases considerably and tone changes are often more pronounced than with strong solutions. Tone change alone is
not a sure sign of image protection. Moreover, depletion of the bath is much more quickly
brought about by toning in weak solutions and consistency of the results is less easily
achieved. Exhaustion of the bath is difficult to judge and assess. Any exhausted toner inhibits
the successful protection of silver.
Even comparatively weak solutions of polysulfides proved rather effective in the protection of
the image. This was not the case for selenium toner. Its behavior was very different and the
protective benefits are directly dependent upon concentration. Most samples discolored in
the peroxide fuming test when high dilutions were used. Correspondingly, the conversion of
silver to silver-selenide was very low. The overall performance improved considerably as the
toning solution became more and more concentrated. Along with higher silver conversion,
signs of deterioration diminished as the graphs below illustrate. They are both based on the
greatest blue-density increase measured due to oxidation in the hydrogen peroxide test.
While the application of stronger toning-baths has generally improved image stability it is
believed that the performance of Sistan would not benefit from such concentration increases.
discoloration decreases with The graphs shown on the following page illustrate how
increasing concentration of the toner. They were generated by using the respective density
pronounced readings (from the hydrogen peroxide incubation) exhibiting the most
discoloration (blue-density increases). -57-
KODAK SELENIUM TONER - EFFECTS OF DILUTION ON PRINT DISCOLORATION
1:400
D AGFA MULTICONTRAST KODAK KODAK EUTE ? ORIENTAL SEAGULL POLYCONTRAST
KODAK SELENIUM TONER - EFFECTS OF DILUTION ON PRINT DISCOLORATION
1:400 1:100 125 1:10 Dilution
MULTIGRADE ? ORIENTAL VD-RC ? AGFA BROVIRA ILFORD GALERIE ILFORD -58-
Rating of Toners
It is important to note that ALL PAPERS BEHAVE DIFFERENTLY in toning solutions.
Although there is a certain resemblance in their response to protective treatments, it is difficult to make blanket recommendations. While it is true that J-Toner is generally a very effective treatment, it has not yielded the desired density conversion for Elite paper. Similar comments can be made about any of the other paper-toner combinations.
Apart from issues relating to image permanence, aesthetic considerations might have to be
"preferences" looked at as well. One could at best speak of and these differ from individual to individual. Selenium has a tendency to form a neutral/red/pink image while gold frequently
imparts a blue hue. However, the precise effects of each toner differ from paper brand to
paper brand and are furthermore dependent upon the technique used in applying them.
This is largely due to inherent differences in the manufacture of these emulsions; the
sensitization, size, shape and distribution of silver halides, chemical make-up (silver bromide,
chloride or iodide and any combination thereof), the gelatin itself, etc. Furthermore, the
developers used in processing most certainly affect the shape and size of filaments in
different ways which in turn can lead to distinct image colors.
are rated in However, from experience with these different toners and papers, the treatments
were also taken into the following order. Effectiveness, cost and environmental strain
requirements successful image consideration. The dilutions which are deemed to fulfill the for
protection are given in brackets.
Polysulfide treatments: IPI J-Toner, Kodak Brown-Toner (1:10/ 1:25/ 1:50)
Polysulfide treatments: Kodak Polytoner (1:10/ 1:25)
Selenium toner: Kodak Rapid Selenium Toner (1:4/1:10)
- Solution Gold toners (where the GP-2 formula is preferable) Stock
to convert metallic silver to a Not Recommended: any treatment lacking the capacity
than silver itself (such as Agfa Sistan compound having a higher oxidation potential
and similar products). -59-
Aesthetic Considerations
The aesthetic component of this project cannot be negated. No single toning-treatment could be identified would that leave the image color unchanged while fully protecting the
photograph. While tone change of a photographic print might not be desirable for some
applications, toning for permanence combined with the possibilities for aesthetic effects might
be of interest for some individuals.
Tone Change
Image tone change on photographic papers is inevitable when meaningful protection of
"permanent" the photographic image is the concern. Why should one disapprove of a
image that happens to have a sepia tone? One should be reminded that a hundred years
ago papers came with a sepia-tone right built into them, due to the colloidal silver in
printing-out-papers. Between the 1920's and 1950's, sepia tones were in high fashion
and liked by everybody. Notions of old age and nostalgia nowadays associated with
sepia-tones should certainly not stand in the way of toning. The color-changes imparted
by toning of photographs are a small price to pay in return for the assurance that an
image will last.
Some of the more technical issues, such as contrast, tone rendition, etc. can surely be
overcome and compensated for, much in the same way as one calibrates for film-speed
and the like. Certain adaptions in lab procedures might have to be made. However, this
constitutes much smaller an adjustment than having a whole collection discolor or fade
away some time in the future.
Suggestion for future study - Double Toning
can be argued that for Addressing the artistically inclined photographer, it toning
permanence with its associated hues, colors, etc. makes for an extra opportunity to
"personal" produce photographs of distinction. Although singly applied polysulfide toners
have been found to be very effective in protecting photographic print materials, double or
even triple toning with different toners might make for intriguing aesthetic results. Indeed, -60-
this technique is somewhat arduous but it could full well compensate for some of the
"inefficiencies" aesthetic (as well as protective) of toners.
For reasons unknown, selenium has a tendency to affect the high-density areas more than the highlights. The graphs supplied in Appendix B clearly show this. By contrast,
any polysulfide toner works its way in the opposite direction, instantly converting all the
silver in a highlight area. By applying both toners, perhaps to lesser degrees, each end of
the curve conceivably be properly protected and an adequate overlap in the midtone
section is almost certain. -61
BIBLIOGRAPHY
1. ADELSTEIN, Peter Z. Preservation of Microfilm, Journal of Micrographics, Volume 1 1 , Number 6, July/August 1 978
2. ADELSTEIN, Peter Z. Hydrogen Peroxide Test to Evaluate Redox Blemish REILLY, James M. Formation on Processed Microfilm, Journal of Imaging NISHIMURA, Douglas W. Technology, Volume 17, Number 3, June/July 1991 CUPRIKS, Kaspars M.
3. DRAFT - American National The Effectiveness of Stabilizing Treatments for Silver Standard for Imaging Media Images - Methods for Measuring, proposed Standard, (Photography) 1991/1992
4. BRANDT, E.S. Mechanistic Studies of Silver Image Stability 1: Redox Chemistry of Hydrogen Peroxide at Clean and at Adsorbate-Covered Silver Electrodes, Photographic Science and Engineering, Volume 28, Number 1, January/February 1984
5. BRANDT, E.S. Mechanistic Studies of Silver Image Stability. 3: Oxidation of Silver from the Vantage Point of Corrosion Theory, Photographic Science and Engineering, Volume 31, Number 5, September/Octo-ber 1987
6. CLERC, L.P. Photography, Theory and Practice (English Edition) Third Edition, Sir Isaac Pitman & Sons, Ltd., London, New York, Toronto, 1954
7. EDGE, M. The Deterioration Characteristics of Archival Cellulose ALLEN, N.S. Triacetate Base Cinematograph Film, Journal of JEWITT, T.S. Photographic Science, Vol. 36, 1988 APPLEYARD, J.H. HORIE, C.V.
8. FELDMANN, Larry H. Discoloration of Black-and-White Photographic Prints, Journal of Applied Photographic Engineering, Volume 7, Number 1, February 1981
9. FORMSTECHER, Felix Zur Geschichte und Theorie der Selentonung, Photographische Industrie, Volume 34, 1936
10. HAIST, Grant Milford Modern Photographic Processing, Volumes I & II, John Wiley & Sons, New York, Chichester, Brisbane, Toronto, 1979
11. HENDRIKS, KLAUS The Stability and Preservation of Recorded Images, Chapter 20, Neblette's Imaging Processes and Materials, Eighth Edition, Van Nostrand & Reinhold, New York, 1989 -62-
12. HENN, R.W. A Gold Protective Treatment for Microfilm, Photographic MACK, B.D. Science and Engineering, Volume 9, Number 6, November/December 1965
13. HENN, R.W. Microscopic Spots in Processed Microfilm: Their WIEST, D.G. Nature and Prevention, Photographic Science and Engineering, Volume 7, Number 5, September/October 1963
14. HENN, R.W. Properties of Gold-Treated Microfilm Images, WIEST, D.G. Photographic Science and Engineering, Volume 10, Number 1 1 966 , January/February
15. JAMES, T.H. The Stability of Silver Filaments, Photographic Science and Engineering, Volume 9, Number 2, March/April 1965
16. KEEFE, Laurence E., Jr. The Life of a Photograph - Archival Processing, Matting, INCH, Dennis Framing and Storage, Focal Press, Butterworth Publishers, Stoneham, MA, 1984
17. LEE, William E. Toning: It's Invention and Expanding Role in Photography, unknown publisher and publication date
18. LEE, William E. Review of the Effects of Processing on the Image DRAGO, F.J. Stability of Black-and-White Silver Materials, Journal of Imaging Technology, Volume 12, Number 1, February 1986
19. LEE, William E. New Procedures for Processing and Storage of KODAK DRAGO, F.J. Spectroscopic Plates, Type Illa-J, Journal of Imaging RAM, A. Tulsi Technology, Volume 10, Number 1, February 1984
20. LEE, William E. Toner Treatments for Photographic Images to Enhance WOOD, B. Image Stability, Journal of Imaging Technology, Volume DRAGO, F.J. 10, Number 3, June 1984
21. LUCKEY, G.W. The Effect of Various Pretreatments on the reaction of JAMES, T.H. Hydrogen Peroxide with a Silver Image, Photographic VANESLOW, W. Science and Technique, Technical Quarterly, November 1955
22. McCAMY, C.S. Redox Blemishes - Their Cause and Prevention, Journal POPE, C.I. of Micrographics, Volume 3, No. 4, 1970
23. McELHONE, John Selenium Toning and Chemical Wash Aids: Effects on the Stability of Modern Black-and-White Photographic Prints, Art Conservation Program, Queen's University, Kingston, Ontario (unknown publication date)
24. MEES, C.E.Kenneth The Theory of the Photographic Process, Revised Edition, Fourth Printing, The Macmillan Company, New York, 1954/1963 -63-
25. MERCK & CO., Inc. The Merck Index, 7th Edition, Merck & Co., Inc., Rahway, New Jersey, 1960
26. MINAGAWA, Y. Some Factors Influencing The Discoloration of Black- TORIGOE, M. and-White Photographic Prints in Hydrogen Peroxide Atmosphere, presented at the SPSE International Symposium: The Stability and Preservation of Photographic Images, Ottawa, Canada, 8.29-9.1, 1982
27. MUTTER, Edwin Kompendium der Photographie, Volume I, 2nd Edition, Verlag fuer Radio-, Photo-, Kinotechnik GmbH, Berlin, 1963
28. NEBLETTE, OB. Photography, It's Materials and Processes, Fifth Edi tion, Fifth Printing, D. Van Nostrand Company, Princeton, New Jersey, 1952, 1959
29. PARSONS, T.F. To RC or Not to RC, Journal of Applied Photographic GRAY, G.G. Engineering, Volume 5, Number 2, Spring 1979 CRAWFORD, I.H.
30. POPE, Chester I. Blemish Formation in Processed Microfilm, Journal of
Research of the National Bureau of Standards - A. Physics and Chemistry, Volume 72A, No. 3 May/June 1968
31. REILLY, James M. Care and Identification of 19th-century Photographic Prints, Kodak Publication No. G-2S, Eastman Kodak Company, Rochester, NY, 1986
32. REILLY, James M. Archival Aspects of Resin-Coated Papers, Photo Educator International, Kodak Publication ED-3-24-2, Eastman Kodak Company, Rochester, NY, 1991
33. REILLY, James M. Polysulfide Treatment for Microfilm, Journal of Imaging NISHIMURA, Douglas W. Technology, Volume 17, Number 3, June/July 1991 CUPRIKS, Kaspars M. ADELSTEIN, Peter Z.
34. REILLY, James M. Stability of Black-and-White Photographic Images, with NISHIMURA, Douglas W. Special Reference to Microfilm, Microfilm Review, CUPRIKS, Kaspars M. Volume 17, Number 5, 1988 ADELSTEIN, Peter Z.
35. SHAMIS, Robert Toning for Image Stability Enhancement, unpublished paper, 1989
36. STROEBEL, Leslie Photographic Materials and Processes, Focal Press, COMPTON, John Butterworth Publishers, Stoneham, MA, 1986 CURRENT, Ira ZAKIA, Richard -64
37. STURGE, John Imaging Processes and Materials, Neblette's Eighth WALWORTH, Vivian Edition, Van Nostrand Reinhold, New York, 1989 SHEPP, Alan (Editors)
38. WALL, E.J. Photographic Facts and Formulas, American JORDAN, Franklin I. Photographic Publishing Co., Boston, 1947
39. WEYDE, Edith A Simple Test to identify Gases which destroy Silver Images, Photographic Science and Engineering, Volume 16, Number 4, July/August 1972
40. ZUIDEMA, John W. The Sulfuric Acid-Potassium Dichromate Bleach in the Black-and-White Reversal Process, Journal of the SMPTE, Volume 72, June 1 963 -65-
ACKNOWLEDGMENTS
I wish to express my sincere gratitude to the members of the Image Permanence Institute for their continued generous support, the use of equipment, materials, facilities and library without which this project and its completion would have never been possible.
Furthermore, I would like to thank the following individuals and particularly my thesis board members for their guidance, assistance, insightful comments, criticism and their passing on of knowledge, all of which was indispensable for the successful realization of this thesis-project:
Dr. Peter Z. Adelstein, Image Permanence Institute
Kaspars Cupriks, Image Permanence Institute
Douglas Nishimura, Image Permanence Institute
Prof. James M. Reilly, Director, Image Permanence Institute
Prof. Elliott Rubenstein, Rochester Institute of Technology
Christopher Gmuender Rochester, April 29, 1992 66
APPENDIX A - TABLES
Agfa Brovira 66-82
Agfa Multicontrast 83-109 llford Galerie 110-125 llford Multigrade 126-141
Kodak Elite 142-168
Kodak Polycontrast 1 69-1 95
Oriental Seagull 196-222
Oriental VC-RC 223-238 67
Agfa Brovira - Tables
Control No Treatment 68
Kodak GP-1 Gold Toner Stock Solution - 5 Minutes 69
Kodak GP-2 Gold Toner Stock Solution - 5 Minutes 70
Agfa Sistan 1 :20 - 3 Minutes 71
Kodak Sepia Toner 1 Minute Bleach / 30 Seconds Toning 72
IPI J-Toner 1:25/ 1:100/ 1:400 - 3 Minutes 73-75
Kodak Polytoner 1:25/ 1:100/ 1 :400 - 3 Minutes 76-78
Kodak Selenium Toner 1:10/ 1:25/ 1:100/ 1:400 - 3 Minutes 79-82 00 co
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CO CM o o o o O O i> o o o o o s tn tl o O O o o o o o O o o o o o o o ? c 3 1 1 * IB g C ffl CL o in in m CO T- 00 00 CM CM en T- rx. in in CT) co nr> o o * ? c o o o o T T CO in * fx. 8 to fx. m in co CO IX. fx. 2 tl o o o o o o o 8 Q 3 ^ ffl o 0- o en en en CM in CM to to CO in , en en 00 o CM o o o ~ *~ St - in m fx. rx. fx. in to co fx. fx. rx. rx. 2 ? o 81 3 CO 3" 3 o O o o o o O in ffl O rx. 00 CO CM CO CO o o o CO CO t- * 8 CM CO in CO CM CM CM CM CM CM CM CM CM 8181 CM CM CM s T T T~ <2 s tl c 3 t ffl s? rr m to [X. fx. fx. 00 en O CO co o CO rx. , CM rx. fx. Q O CO o o o O o o o o T T- CM CM CM CO CO CO CO ^ Tf CO ^ o o O o o o o O O o o o O O o O o o o o o 1 u II o 8 3 \j fa. fa. < 2 ffl ffis 0 cc 10 o CM a u > ** C CO ix. en in en CD co en en (x. o CO ^ in CD to to CO CM IT CO p 81 CM CM CO CO 5 3 5? sr 'it * tn o ffi 2 o O o o o O O o o o o o o o o i II o o O o o o (0 3 o 3 < S II ffi LL. o 0 o ffi O 0) en fx. fx. o in CM in T o en cn CO fx. CO 00 o m rx. o CO *t CO 00 en T- S m CO fx. fx. 00 s 00 CO s o o 81 tl o o o o o o O o o o O 3 e o I SJ ffi o i 2? "*^ t= c g 2- * 3 ^- a M o ~ CM CO in to fx. 00 en ,_ rx. en g g S u e CM CO * in CO 00 CM CM 2 ti CO Q Q. r- O H CM ix. 1-COfx.pCMCOCMCMfx. 888oSS8^8S8g t-i-i-CMCMCMCMCMCM dddddddddddd u lllll ddddddddd 3 iiiiiiii ffi corx-oocn^i-cMCD TTTcT'cd'^F qoooT-wn^iosoir co^mmcototocoto II ddddddddddd-r- 3 ffi enOf-CMfx.'^rincnm-r-cnrx. ini-oocM^cocoT-ix. Ot-T-T-T-cgnttDoocriT- cq in in to to to cq fx. to II 3 ffi Qt-QQ-i-t-CMCMt-CMt-t- i-CMCO^COQCMCOCM oooooooooooo oodoooodo dddddddddddd ddddddddd II iiiii i i i iii 3 ffi CDCOOOOLOCJCOOO ^Tf^wT ^eneninocDinrx.cn ^- O O O t- -r- CJ CO ^t CD 00 O coooocMfx.'d-mocorx.mm coT-i-rx.cMaofx.cni- oo^^i-;CMcqintqooocM ^f to fx. (x. en tl oq oq oq cq 3 ffi QtDcogoorx.oom^T-cn tocMi-ocncno->-T- OOOOOOOOOOOOCOCOOOOOfx. Ix.|x.|x.|x.cOtOIx.|x.rx. T T tl 3 ffi % (OIOSO^OOOQIOOQIO 00C0CMtDfx.O)i-^;in u ooO'-'-NN^insaio) o-r^cMCMCMCMcqcqcq E II dddddddddddd O H 3 c ffi < o -C DC o CO > .2 O 5. coco^fx.T-fx.inrx.cMfx.oco incoenco^ttoco-r-CM OQ i- 1 CO 1 ^ DC V T^T--ri-T-CMCMCO,*tOfx.cnO CM CM CO CO CO ^ to > m tl 3 < IS i ffi u. ~ <3 o < * *- cofx-coococoinQincocMCMcoi-CMcncocorxOT- ooo^^CMcointoooqcM'Ttorx.rx.oqcooqcncn tl o't-t-t-t-t-t-t-t-t-t-t- 3 do dddd odd ffi ossowwojirjT-ooio) in to fx. rx. cq oq oo oq c .. cu ooo'-'-Nn^qqqr ^ 1 ddddddddddd-r- T T T T T T TT T 3 " ffi "Bl|~ 2? He o * g 3 J) E co^mtofx-oocnpT- o a M 0 g c S C o tl o to a I- O H CO lx. T CM m CO CO o - CM CO T in 4 CM CM CO CD CO CD 8 o o o o o o ? O) o o o o o o o o o o o o o o o O O O O O O 1 c 3 IB Is ffi u c z rx. IX. rx. 00 T- rx. CO 00 o en 00 en fx. rx. cm m m fx. co o o T T rx. * rx. ix. rx. ix. rx. 0 || c o o CM CO 8 00 o CM 8 co 2 tl o o o o o o o o o o o 2 Q 3 3 t ffi O 0 o o *- tj- CO CO CD fx. o CD m IX. CM CT) 00 rx. 00 CO CD to i- co rx. 1 5 T o ?- T- CM CM CO ffi CM CM to 4 CM CO ^- in m to to rx. 8 o o o o O o o o o o ci o o o o o o o o 2 g O) o o o o o O o o o o o o o o o o o o o o o c 3 IB S J ffl a. u o rx. rx. en T- 4 i o fx. fx. rx. en 00 in en co m rx. rx. c o o o ? T CM CO in fx. en CO to fx. fx. 00 00 00 00 S .t! i a 8 2 II o o o o o O o o o o o O 3 is = ^ ffi 3 T~ CO in CO m 4 CM en co rx. en t- t- ^ CM to GO o CM IX. S 00 CO CO O) O) I ? o $ $ 09 S" 3 o o o o o o o o o o m ffi Q o CO CO CM o 4 m CD 00 rx. to m co fx. co co rx. en * O CO o 00 fx. fx. rx. 00 CO CO 00 CO 00 00 00 00 00 00 00 00 00 s ^~ ^~ ^~ 2 tl c 3 "-1 ffi u S? ffi fx. 00 oo oo T- CD CO rx. CO CO rx. co "^ CO en o in ^ fx. co o o o o o T T CM CO in to 00 o CM s in in to co co co fx. * c o o o o o o o o o o o o tl o a 3 o . < fa. m o ffi 0 DC O CM a > CD o fa. CO fx. rx. rx. o in CM CD CM 00 CD in CO en CM oo en ^t co to cm > T T CM CO * CD rx. en T- CO * to to co rx ix. rx. oo cc CA E s CM S > o o o o O o o o o o o ffl S fi 2 a 3 < ffi LU t in = 3 0 O ffl =- ^ s a. q < ^ ^- fx. CD 00 o m CM to T T- T CM 4 en ^ oo i co ti o o o 1 T CO ^t 2 CO o CM 3 CO fx. fx. oo oo en en en > II 81 3 o o o o O o o o o o 1 ffi IB to fx. fx. o in CM en en to fx. co oo o co m fx. o o o T 81 CO 3 to 8 en 5 m to fx. fx. 00 00 00 00 C .. II o o o o o o o o o o o 3 c o " ffl isj'-C o c IS o 2? ^^ o H c g * & 3 T" in o CM CO *t in to rx. oo en t- a. T- fx. 00 en p o 7- e e CM CO >* in to o ti s CO a Q. H O r- 4 rx CMcocorxcocnT-cM co rf co co in oo t- ti Ol ii d o d d ci d d d d d d d d d d d i i i i i i c 3 IB ffi o CO CO CO OOi-tDLONT-SNNSCO CD CM in CO CM t- t- c o o o o-r-;T-c\Jcoin in in in r^om^fcootocotococvj in t- rt fx. i- o o t-;C\jCNjC0^t ^- r-i-CMCOCO^CMinCOi-m in in rf m m fx. ooooooooooo o o o o o o o II 0) d d d dddddddd d d d d d d d II i i i i i i i i i i i i i i c 3 IB ffl o co to 00 en co o en cm to To^^TnTo^oT rf CM ID Q cm 5 in C o o o qT-c\jt\j*inr>.o)T-coio to tx. rx. 65 oq cq oq 2 II odd Q 3 m S o O CM COS^CO(DOOCOO)WtO oo co o ^ co oo en 1 T- T -r--f-C\iC0^"tO00O)i-;Tj-LO to fx. oo oo oo oo o ii cq 00 S" 3 odd m ffi o in in Oi-^cMcoo-r-cMinrx-co co rx. rx. co oo rx. ix. o rx. ix. oorx.torx.fx.rx.ix.rx.fx.rx.fx. rx. ix. rx. fx. rx. ix. rx. 11 3 ffi % OOO'fCOCOCMtOi-OOrx.cO cm to o m in co rx. to to to rj- o o o Oi-T-cMco'^i-mrx.coocM cq cq rj <*; rr rf tj odd o tl t) 3 u fa. < ffi o o DC CM o > o rx.fx.rx. 3" CU t- I to in LO DC CVJ CM CO LO C0 CO OTit; CO Tf ^J; LO Ifl j odd ffi o I! IB 3 < 1) ffi U. 111 ffi 0 fX < ;j eo i- rx. CD 00 00 OrfCMCMlOOOOCOCOCOrx. co to ^f en cm II "* to fx. co r- co in co rx. co oo oo oo co II o o o ^ ^ cm co as 3 odd dddddddd-r^-r1-^ 1 ffi a fx. in rx. co fx. rx. omcMCMm-r-ocncnQtD co oo o co ^- t- ^- t- ix. ix. o o o cm co to co ^; in to oq oq oq oq = .. 4) oq dddddddd^-:-<--r: 1 ?- T 1 T ?- T~ II odd 3 " ffi In|*= 2? tS He g * & 3 - fx. oo en M in to o "D a. t- g c e CM CO 2 o u to a a H O r- m fx. CO m to CO CO fx. fx. 00 o t- CO CM CO CO IO rf 888 o o o o o o o o o y i Ol II o o o o o o o o o o o o o o o o o o o o o e 3 1 1 1 ( 1 H IB Is ffl o c > = z T T- 00 00 o> rf en o 00 CO CO CM CO 00 T- CO fx. O o o o O u c CM CO r? m 00 en CO m to CO fx. fx. fx. ix. 00 ? 2 tl o o o o o o o o o o o Q 3 t m O O 0 o "fa. fx. fx. e TT rf m o fx. en in CO CM on CO rf rx. CM CO to 'T T~ rm 1 o CM CM CO rf to 00 CM rf in CO fx. fx. 8 00 00 CO v e u o o o o o o o o o o 3 ffi CM CO m CO CM CM CM CM t- CM 4? 88 o o o o o o o o o o o 88 o o 8 o o Ol II o o o o o o o o o o o o o o o o o o o o o s s ' 1 ' * ' 5 c 3 S IB 2 o ffl CL 4) o 00 00 o CO CO 00 CO CM CO in ,_ rf t- in to en t- CM e o o 1 ? * CM CO r? co 00 o CM CO fx. 00 00 00 CO en en 8 2 i 2 II o o o o o o o o o o 8 g Q 3 S ffl o- o fi CM CM rf fx. CM rx. CM CO 00 rx. CO in oo in en o CO m co ?- s 1 1 ^ 8 CO 00 in CO CO o CM r? to fx. 00 00 en en en en ? II eo S" 3 o o o o o o o o o o in ffi CO 00 co in CO to in in CO in 8 T" 8 00 CO 00 00 00 00 00 00 00 00 2i 00 00 00 00 00 0 rj ^ T~ T" 2 s II S c 3 S ffi s? rr oo en o CM in T o rx. IX. o IX. rT to in cm in LO co cm m o o o ?- CM CO i m rx. CO o CM CO rf in in in in to to ti 2 o o o o o o o o o o o o II O IB 3 fa. ffi o ffl o Q o o> o , CO co CM T in 00 00 1 00 in rx. CD CO CD to rx. co to E 1 CM CM CM CM CO rf in to 00 o 1 CO rf in to to to to rx. rx. 3 o o o o o o E II o o o o 8 2 3 I ffi o o a a- 5 m m O) CM fx. co rx. T fx. IX. m to CO rf -r- IX. CO CM rfr ti in CO CO CM rf rx. oo 00 CO en en e II o o o CM CO o s 8 * s 0 3 o o o o o o o o o o 0 11 ffi r- to rx. rx. o in CM en CO CO CO m fx. o o o 81 CO r? to 8 en s m tO lx. fx. 88 00 00 s s ? II o o o o o o o o o o o 2 S 3 e o ffi ISj c O 3 fi c H C tS g 2> 3 at a H o T- CM CO rf in to fx. 00 en ,- fx. en g c u c CM CO rf m to 00 CM w s o II o fi CO a Q. I- O H CO fx. i CM to o> 2> CO to on O 00 O CO to e 88 o 8 O o o o CM CM ct CM CM CM 0 81 81 n o o o o o o o o Tii Ol tl o o o o O o O o o o o O o ti c 3 a 3 Q ffl o tl u Z 1 1 (x. 00 o in IX. rf in CD in CO ^_ in to CO ^~ ?- i 0 c o o ^ 81 CO # in IX. en T CO in to rx. [X. ix. fx. 00 a o 2 II o o o o o o o o o o o u a 3 fa. ffl u o o e u ^ in to 00 en CO o O) CM in CM CM CO CO CM tn en CO en T- T 1 ^ 0 ^ tM CO CO in to 00 o CM ^ to fx. ix. fx. 00 CO 00 00 a e tl o o o o O o o o o O 3" 3 m ffl o c CM CM CM CO CO in to IX. CM CO CO CO 2- O O CO CO CM 88 o 8 O O o o o o o o 1^ o i* Ol o o o o O O o o o o o o o o O o o o o o o 1 1 1 1 1 ' ' ' 1 ' ' 1 ' ' * ' X c 3 o IB fa. Q ffl 0. II u Z rx. oo 00 ^* CO rx. CO co t- rx. co CO en o rf CM rf CO m tl C rx. rx. fi o o o 81 CO rf 8 00 q CM rf to s CO oq CO oq o 2 II X 3 d d d d d d d d d d 0 II a ka ffi 0 0 u ^T i- CM CM in CO to rx. y to oo rx. o in T ix. en o CO CO T T- rx. rx. "O 0) CM CO in CO o CM 8 00 00 00 en CO en c CO 3 o o o o o O o o o o E S" fa. ffi II 3 in Q. U. <7> T_ in t- co 00 CM in rx. en o CM CM T y CM CM o '& 88 00 en rx. fx. CO co r-. IX. ix. fx. 00 CO 00 00 00 00 00 00 T V w c tl e e 3 a fi ffi S5 cc fx. 00 on o CM rx. CO CM in CO CM CO rf CO i in |x. o CO in i T ? to ** o o o o CM CO rf CO 00 O CM CO in in m to to to ti o o o O O o o F II o o o o 0 IB u 3 - O _ II < "> o ffl 0 DC c u o 5 > o If m co to CO o in o T CM fx. en in 00 CO y T 1 jx! en in to to ix. fx. to DC O u F fi CM CM CO r?S CO rf 8 Q. 3 o O o o O O o o ffi F II o o o .* 3 o IB 3 < CO c II LU a ffi o to s o ffl o cm S 0 o 0, a < * ^ rx. en fx. 00 m ^ CO rf in O co fx. o to CO o in CM CM T" Ol II y 00 U) fx. en en en en o C_> II o o o CM CO in to 8 T M 3 o T ' " T- CM CM c IB o o o o o O o o o 1 ffi IB fx. fx. CO fx. fx. o in CM m O) en to CO co in IX. IX. o o o 81 CO rf to 8 o> r? in CO 88 00 CO y- T- - - i~ t- - "- ,,_ F f II o o o o o o o O o o o ^ a e 3 e o isi o ffi (0S "Si o 3, fi c o 3 f t) E T- (x. O) a. w o CM co rf in CO CO o t- rx. CO o> = CO c CM CO rf in to 8 CM 0 II .o Pi CO a I- O H fx. fx. m CO to fx. O) CO CO O) en CO o - t- cm in 2f 8 o o o o o o o o o o O o O o s 1 II Ol ti o o O o o o o o O o o o O o o 1 1 1 1 1 1 o o o o o o c 3 1 i 1 i 1 I 1 1 1 1 s IB 3 Q ffi O u o z 00 00 en fx. c o CM 00 en CO in to m co oo TJ T- 0 c o o o OJ CO at IX. en CO to fx. fx. fx. 00 CO fi 8 CO s t) o IB 2 o o o o o o o o o o Q 3 3 fa. ffi U 0 o E u fx. ,_ C CO CO rf in CO CM CO to 00 o 00 o co m co co T" T T I- 0 ' tM CO r} in rx en CM rf m rx. fx. CO 8 00 00 00 e II o o o o o O O O o o IB 3 O 3 m ffi U c T- CM 1 rf in rx. rx. fx. on to in CO m 00 to fx. O rx. rx. co i- tl * 8 o O o O o o o O o O o O o o O O o o o TJ i o> o o O o o o o o O o o o O o o O O O o o o 1 * ' ' * ' ' c -) 0X. IB fa. Q ffi a. u o z 00 00 00 o CM 00 to 00 CM rf to 00 rx. CO rf en en rf CD fx. T- y II c o o o ?" CM CO IX. co CO in to rx. IX. IX. 00 CO 00 o 2 II X 3 o o o o O o O o o o o 0 II O fa. fa. m o o a. o m in m rx. CO in 2 m , en , CO LO CO ^_ co to t- CO rf o 01 *~ y ,_ ~ T~ CM CO rf co rx. o CM rf fx. 00 00 CO en co en c o 00 3 o o o o o o O o o o 8 E 5" fa. 3 m u m Q. U. T i T ^ rx. , 2> Q o in CM CM rf 00 00 o CM CM o O O CO en r- CO in in CO rx. IX. rx. fx. rx. CO 00 CO 8 on co on ^- 1 to a ti ^ e c 3 ti a ffi S? DC 00 en CO o CM rx. CO 00 |x- CO CM IX. en y- fx. io en to T ** TJ o o CM CO in fx. CO CM CO r? in m in in in o o o o o o o o o o O o F tl II 0 IB 3 w tl < t> fa. LO o 01 o CC c o o CM a > o in CO o (X. en o LO en to CO co to CO II DC O CO F CM CM CM CO rf 00 8 rf in LO CO co to co ffi a 3 o O O o O o O F II o o o o 3 < X 0 IS 3 CO C ffi u. "0 0 = fi ffi O 2 o U o t: a. Q < * ^ n m rn o co CO in ., o T CM rf O to en t- CO CO II y to rx. CO 00 00 co en co II o O CM 8 rf to 00 8 CM i M 3 c IB o o o o o O o o o o 0 i ffl r- CO IX. fx. o in T- o en CO CO fx. CO oo g co in ix. IX. fx. 00 00 00 CO ^ o o O 81 CO r? 10 CO en m to s f tl o o O o o o o o o o o a e 3 c o 1 0 ffi o 8 2 ,3, tS a- 3 * t- ~ fx. a. M o CM CO rf in CO 00 O) O y- lx. ti C CM CO rf in to CO o> 2 II to a a i2<3 CO fx. CO fxT to rx. 00 00 fx. T CO 00 m rx. fx. 00 fx. s * 8 0 O 0 O 0 0 0 0 0 O 1 01 II 0 0 O 0 O 0 0 0 0 0 0 O O t 1 1 1 O O 000 000 c 3 1 1 1 1 1 1 1 1 1 1 IB ffl O c - z 1- en O) t- O rf cn 00 CO 0 CO cn fx. m cm co cn O rf 0 0 ^ y~ ^ T~ rx. O u e CM r? m CO O CM r? in to to CO fx.fx.rx. 3 o 2 II 0 0 O O O O O O 0 0 0 fi O 3 t ffi U O 0 O rx. rx. N. 1 T c CO O) CO 00 to fx. in CO ^^>*^^ 00 en cm y T ? y O 81 tM CO r? CO fx. en 1 CO m to fx.fx.rx. rx- rx. 00 S3 O II O O 0 O 0 O 0 O 0 0 O ffi O 1 y- T T ,_ CM CM CO ^^ CM tO CT) co to m O ti * O O 8 0 O 0 O 0 O O 8 0 0 000 000 2 01 O O O 0 0 O 0 O 0 O O 0 0 0 0 000 000 c ' 1 1 1 ' 1 ' 5 c -1 S IB 2 Q ffl 0. tl O CO en rx. 1- "O O CM CO in CO to rf to m co in CO CD tl e O 0 81 CO rf in fx. co CO 8^ IX. |X. 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M I c fl C o 41 2 o fi co a a H o h 223 Oriental VC-RC - Tables Control No Treatment 224 Kodak GP-1 Gold Toner Stock Solution - 5 Minutes 225 Kodak GP-2 Gold Toner Stock Solution - 5 Minutes 226 Agfa Sistan 1 :20 - 3 Minutes 227 Kodak Sepia Toner 1 Minute Bleach / 30 Seconds Toning 228 IPI J-Toner 1:25/ 1:100/ 1:400 - 3 Minutes 229-231 Kodak Polytoner 1 :25 / 1 : 1 00 / 1 :400 - 3 M inutes 232-234 Kodak Selenium Toner 1:10/ 1:25/ 1:100/ 1:400 - 3 Minutes 235-238 xf CM CM T CM CM CO CO fx. OT T O i- s ^ 8 o O o 8 o o 8 o 8 O O o o o o O Ol 41 o o o o o o o o o o o O o o o O o 1 1 1 1 o o o c 3 1 i q 1 1 1 1 i 1 1 1 IB ffl o r Z% rx. 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IX. i- e 00 00 00 OT CM o to 00 CO 00 CO 0 o o o O o o o O CM 8 co 8 CO s IX. ss CO 00 a o 41 o o o O o o o O o O is en 3 o o o m 1 CO in fx. rx. o 4 |x. rx. OT O CM * 8 o o o 8 o o O s O o o o 1 i i CM CM Ol 41 o o o o o o o o o O o o o o o o o o O O O S 1 1 1 ' 1 1 3 c 3 IB 2 Q ffl a. ai CJ in xf xf xt CO 4 in co OT CO rx. 00 CM rx. ._ CO ^^ o O OT fl C o o o o o o o o o T" CM # CO O CO co fx. 00 00 00 fx. 1 41 "x tl S o o o o o o o o o O o o o T" T - T" *- >- T 1 8 a 3 * ffl 1? * n ft. o < ro fx. rx. rx. to (x. 00 OT CM OT o rx. in OT CO CO CM o o o O o o o O CO xf fx^ o IX. 00 00 00 2 9 o 3 3* OB 3 o o o o o o o O o O o o o" o Ul ffl o o o o o -T in rx. OT rx. rx. |x- CO co (x. Ol o CM CM * 8 00 00 00 00 00 8 rx. in CO CM CM CM CM CM CM CM CM CO CO CO s T T <2 s 41 S = 3 a" a m 41 S* OC LO xt xf 5 xf co in to rx. OT CO OT 00 m CM fx. S TJ o o s o o o o o o o o 8 CM CO LO in to CO CO f fl o o o o o o o o o o o o o O O o O o o o o i tl 41 o 0 A 3 fa. 41 cc d fa. in O ffl 0 6 CM a o > c a 1 IX. T fx. _i fx. co to CO to CO CD CO 00 CM CM in O LO CM 00 OT Q o o o o o 8 CO s fx. xf IX. OT OT OT OT O E * o o o 41 o o o o o o o o o 3 o o o o 1 SJ c o e ffl O 3 fi S He fi O "c- 2- j> E * 3 T- T CM CO xt in CO fx. 00 OT O TJ a in fx. o c CM CO xf in to 00 OT CM CM 0 * 41 o I fi to a H O H o o T" CM CO CM 4 to co CM in to xt Tf in * 8 8 5 o o o o o s 41 85 8 o o o Ol 41 o o o o o o o o o o o o 1 d c 3 1 q 1 q 1 1 1 1 1 9 9 IB ffl CJ c fl - z in lo rx. T- cn m in in 00 o in CM CD OT in C o o o o ir O 41 o o o o CM CO 00 m rx. OT 8 o z 41 s o o o o o o o o o o *- "- *- T" 3 o o o CM CM CM CM 3 = ffl O 0 o fl o |x. (x. fx. rx. fx. c 00 Ol o CO rx. CO 00 IX. to tO o o LO o o o o o o a CO in s 00 OT 8 o o o 41 d d o o o o T T 3 o o o o o o CM CM CM CM ffl CM CM LO CM in OT CO fx. xf LO , 888 o O 5 o o o o o o T 4? 41 888 5 Ol 41 o o o o o o o o o o o o o o o o o o o o 1 q 1 1 1 1 t c 3 1 1 1 1 1 1 1 IB S3 CL 41 CJ m "O in m xf in co 00 CM CM m CO o rx. CM to 41 C o o o O o fi o o o o CM CO in s CM m 00 OT 8 o o-8 41 3. o o o o o o o o o o o o o T T" T T" CM CM CM CM o 3 Ss - ffl i? o O 0. o rx. rx rx. to co fx. ro o 4 xf fx. ro in CM OT co CM ID LO o o 1 T- o o o o o o CM CO m 00 CM in OT o 8 o o 00 T" *" T T~ S" 3 o o o o o o o o o o o o o CM CM CM CM Ul ffl a. in OT o CO xt in xf rx. co 00 m rx. s 888888S |x. CO IX. rx. fx. fx. fx. to co co rx! s rx. rx. > 41 5 c 3 a ffl 41 S5 CC in in in LO m lo in CO OT to rx. CD o Ol CO xt OT ft) 41 T TJ o o o o o o o o o CM x? CD OT o CM 9 LO in to CO E = 2 41 o o o o o o o o o o o o o o ft) o H 0 3 c p 3 cc fa. m I o o fflfl O o s CJ > CO "5. ffi rx. ix. ix. ix. rx. fx. fx. 00 T 00 OT LO ro CM T- 00 in to T-. CO Ol ft) O o T- 1 CM t CO OT 1 CM xf in co to to E a o o o o o O to ftj o o o o o O O o o o o o o o S F it 3 3 M 0 IB 41 LU CO c ffl "O fl ffl QC ^ o o ft- 5 o y lo in in m in w to 00 CO CO fx. 00 CO CM 1 o to 00 00 00 41 in 00 to y T- 1 T 1 c 41 o o o o o o o o CM CO a OT 3 o o o o o o o o o o o o o ~ ~ " CM CM CM CM CM ffl a to to CO CO co CO CO 00 CM o CM m o in CM rx. CO OT Q o o o o CM CO s (X. T" fx. OT OT OT Ol o E o o o o 41 o o o o o o o o 3 o o o o o c 0 0 ffl isj c O 3 U fa. C x H S O i- 3 | % * Q. in o T_ CM CO xf in to fx. 00 OT O i- TJ s t- fx. ? c ja 41 c CM CO xf in CD 00 OT CM CM 0 41 o fi CO a H O H OT T CM CO to to rx. o CO OT * o S 8 88 5 o o o o o o o o RI CM CM CM o Ol 41 o o o o o o o o o o o o o 1 1 I 1 1 1 O o O O O O c 3 q 1 1 1 1 1 1 I 1 IS ffl CJ c > z IO in in in CO OT fx. IX. m cn in CM to rx. OT OT c o o o o 1 r^ 41 o o o CM xf o * rx. OT OT OT OT OT 2 41 o o o o o o o o o o O o o Q 3 3 C ffl O 0 0 fl CJ . 00 fx. 00 fx. fx. e 00 00 Ol CM o O CO xf OT rx. m in rn CM CM o o o o T- o o o o o CM CO xt rx. O xt rx. OT OT 8 o o a o 41 IB OB o o o o o o o o o o O o o CM CM CM ffl o CM CM CO CO co ro CM 00 * 8 o 8 o 5 o 5 5 o o O o o o o CM RI CM CM 2 Ol 41 o o o o o o o o o o o o o o o o o O O O O g 1 ' 1 ' ' c 3 ' - 1 I 1 IB 2 Q ffl 0. 41 CJ m in in xf in to OT CO OT IX. IX. 41 "O o o CO OT Q OT c o o o o T T rx. 8 t o o o CO ^ xt Ol OT OT O OT 41 2 o o o o o o o o o o o o o CM i- Q 3 = ffl -o .? o ft- 0 fa. 00 CO 00 fx. fx. rx. CO OT CM T CO 1 ix. CO CM o co CM CO CM o o o o o o o o T CM CO m IX. in 00 OT O O O fl ? o 8 00 i T S" 3 o o o o o o o o o o o o o CM CM CM CM Ul ffl o o o CO in IX. CO in CM ro OT CM CO CO fx. tO * s 8 CM CM o 88S 00 s to CO CO to rx. |x- fx. 00 00 00 00 00 <2 a 41 = 3 4)S Q fa* ffl ss rr m co co in in in in CD rx. CO CM CM y CO CM OT CO rx. 7 CM O -k* TJ o o o o o o o o o CM CO m 00 CM xt rx. 00 OT OT OT 41 -= ** c 41 o o o o o o o o o o O o o o 0 IB 3 fa. fl ffl m o Q 0 o CM Q ** fa. n 1 Ol o o cn OT OT OT o 1 (X. to to in ix. CO CO ix. in CO xt ft) CO T- T CM CO in 00 CM Ul rx. OT OT Ol Ol E *! o o O O o c ft) 0 **: 1 F o o o o o o o o o o O o o o H 3 2 o IB 3 c 41 "s fl m in o CO w & o a*r 0- Q ^ CO m m in in in in cn rx. T 00 to ix. at 00 Ol 41 m rx. 1 m 00 y CM CM CM 41 o o o o o o o o ^ 83 s " 3 T i T CM CM CM CM CM " o o o o o o o o o o O o o ffl rS IB co CO co CD CO to to 00 CM CM in o 00 m CM rx. 00 OT Q IX. c o o o o o o o o a CO g fx. xf OT OT OT OT O .. ft) 41 o o o o o o o o o o O o o c o isi ffl a o i fi i -e > "sr j) E * ^" fx. in o CM CO xf in co 00 OT a. T rx. g c c CM CO xf in to 00 OT CM CM o 41 o fi co Q H O H T So- fi" CM CO IX. CM CO in m 1- 88 o 5 5 8 o o o y S 41 8888 5 CM o o o Ol 41 o O o o o o o o o o o o o o o o o C 3 i q 1 1 IS ffl CJ c fl - z rx. CO to to to cn co 00 y O CM OT in OT in m in i- c o o o o o t- O 4) o o o CM 3 in sa LO 00 OT o o o o 2 41 o o o o o o o o o o o o o "- "- "- *" CM CM CM CM a 3 3 fa. ffl tl O 0 fl CJ . 00 ^^ T_ c 00 00 ro 00 OT 00 o CO CM LO in xt IX. lx. |x. fx. CO O o l_> u o o O o 1 t- CM CO CO CM to 00 o O O o o a o 41 o o o o o O o o O O o y- y- ,_: IS CO 3 o o CM CM CM CM CM ffl 1 i 1 i o o o t- CM y CO CM CM rx. T to CM CO i 'i o o T i ,. * 8 o o o o o O O o o o O o CM CM CM CM Ol 41 o o o o o o o o O O o o o O o o o O O O O 8 1 ' 3 c 3 ' s IB 2 a ffl Q. 4) CJ CO to to to CO to co 00 O 00 T rx. in cn OT CO in CO rx. OT i- c o o o o o o o o T" T CO xt rx. ^- xt fx. Ol OT OT OT o fl O 2 41 o o o 3 o o o o o O O o o o o ; fc ffl o ft- o * fx. rx. rx. rx. rx. rx. rx. OT i- OT CM to 4 OT CD IX. 00 o o o o o o o o T" T- CO rx. T IX. OT OT OT 2 ? o 3 8 88 00 5" 3 o o o o o o o o o o o o o CM CM Ul ffl o o o o fx. r- o in o CO T CO in fx. rx. * s o 8 CM CM CM 8 T 8 ot ro fx. rx. rxi rx. S 00 s 00 00 00 00 41 1 ? 3 ii ffl t rr to to to co to m IX. 00 o to xt in m o OT in O IX. t- xt T 1 o o o o o o o O o CM CO in OT CM fx. 00 00 OT OT 41 e -= ** o o o o o o O o o o o o o o O 41 o O IB 3 u fa. 41 cc fa. I m O ffl o o o CM a > rn rn rn cn Ol 00 o y CO OT fx. ro 00 CO CM fx. ro CO O * rx. *> co T T 1 CM CO in OT CO in rx. 00 OT OT OT < E *s o O o o o o o o O F o O o o o o o o o o o z 5 1 10 3 ffl SH " fl -b8| O O ffl cc - s ft- Q O 9: y CO T fx. C- 3 ft) E * T" fx. 00 a M o CM CO xt in to OT j. *- ca CM CO xt in co fx. CO rn c c CM CM ir cu 41 O o S co a HO H CO CM T 2" o CO CM xf in to m 00 CM fx. CO OT S 888 o 888 o o o o o o o o CM CM CM i- Ol 41 o o o o o o o o o o 1 o o O O O c 3 q q 1 q 1 1 1 q q 1 q i i IB ffl CJ r * z 1 y- to to IX. i- CO co co to 00 OT OT CO o [X. CM in tn IX. o l_> l_> o 1 T 3 C o C_) o o co * rx. xf rx. OT Ol OT OT O 2 41 o o o o o o o o o o o o o a . 3 3 c ffl O 0 o fl o i IX. fx. rx. IX. rx. IX. c CO OT CM o CM o xf co tn ro cn CO CM to rx. OT o CO o CO CO i- > 41 8 5 5 5 O 5 8 5 o o o o o CM CM CM CM CM CM Ol 41 o o o o o o o o o o o o o o o o O o O O O S ' 1 ' ' 1 ' 1 1 c 3 ' IB 2 a ffl a. > CJ to LO in in in in rx. 00 T- OT y- CO CM to in OT in to |x. Ol c o o o o o o o o 1 1 co * rx. o Ti 00 OT OT OT OT S fl s 2 41 o o 3 o o o o o o o o o o o o a !K - ^_ m 0 ft. 0 i Ol 00 00 00 00 00 o y xf xt 1 m Ol ro tn CM 00 OT o o o o o o 1 Si CO in rx. o xt co OT OT OT 8S 09 o o o o o o o o o o o o o CM CM 41 Ul 3 a m o o lx. 00 OT to o LO OT to CM CM O * o o sss T 8 ix. rx. 00 00 00 00 00 00 00 00 00 ro oo s ^ T T- 1 y T s fl 41 = 3 "-1 ffl 41 s? rr to co co to in rx. fx. rx. 1 ro 00 5fi o OT i i 00 CO m ro 1 T ix. |x- IX. fx. fx. ** TJ o o o o o o o o CM ** OT 8 in CO = c fl 41 o o o o o o o o o o o o o o o 0 IB 3 6 fa. 41 OC = III 1 in O ffl O o CM O CJ > ** v T i Ol i- -J rn rn a> rn ro o o o xt OT CO CM CO xt xt 00 T <* fx. rx. < fl o o o o O CM CO rx. o CO in CO 00 CO O o o o o o o o o H O o o o o Z H * 1 O c fl. 2 41 LU IX l ffl 41 OC ir" fl .2 3 O Q O 9: y CO a. ffl co to co CO cn co IX. OT 4 in OT in in to OT to OT 41 o o o o o o o o CM CO fx. in 00 O 88 Ol > O o o o o o o *" *" T" CM CM CM CM CM fl s 41 o o o o O o o 3 o IB r- CO rx. to co CO to co CO to CO CM o CM in o m CM 00 OT Q fx. rx. OT OT OT OT C o o o o o o o o CM CO 8 9 O .. ft) 3 ? r. o o o o o o o o o o o o o isi -- fl 0 c 41 o 3 10 "2 g j= = ffl O H C 3 Tr ft) E 2? o CM CO xt in to IX. 00 OT O y a T TJ "S in CM CO xf IO to fx. to Ul CM CM O g g fl c o o fi CO 41 H O H a CM CO CM CM CM CM CO xt to OT 00 CO CM 01 xf CM CM CO i 8 o O o 5 5 o o o o o Ri CM CO CO CM CM CM CM CM o o O 3 Ol 41 o o o o o o o o o 0 0 O O O O O O O 1 3 1 1 1 1 1 I rg IcS ffl o c fl Z to xt m 4 xt m in to OT to CO CO n f\l O ro xt O o o o o 1 0 41 C o o o o o CM CO OT CO CO 00 OT OT OT OT 41 o o a ti 2 o o o o o o o o o o 0 O Q 3 ffl U 0 0 fl CJ o 00 OT 00 00 OT OT o CO o o in rx co in IX. 00 ^t 0 y o O o o O o 1 T CM CO i tn 01 CO co 00 01 OT OT OT a o 41 o o o o o o o o o o o o 0 IB 00 3 0 ffl CM xf in to 0 in ,_ 01 CO rx. m CO CD * 8 o o o o o o o o o o o 1 1 CM CM CO CO CO CO CO Ol o o o o o o o o o o o o 0 0 O 0 0 0 0 O O 8 ' 1 ' 1 * 1 1 1 c 3 IB 2 a ffl a. CJ co m in m m to 00 T- 00 o CO CO CM in co 00 0 O O a * e o o o o o o o T" T CO 9 fx. 0 xt co IX. fx. 00 00 00 2 41 o o o o o o o o o o o o 0 O 3 ft = ffl i? o o Q- o * o OT OT OT 00 OT o CM in CM rx. 0 co OT 0 CM 00 1- T" o O o o O T~ T- T CO in rx. 1 xf CO 00 00 rx. rx, to 2 ? o a 00 S" 3 o o O o o O o o o o o o 0 Ul m o CO CO o CO to Ol Ol xf o co in -r cn 00 CM CM CM 1- CO T* o 00 S3 CO o oo 00 00 CO to cn to cn rx. IX. 00 OT OT OT OT OT S T T <2 a 41 S = 3 "-1 ffl 41 S? CC "5" co in in in m in CO 00 OT 4 T xt CO 01 0 CO rx. ro rx. ,- ? rx. TJ o o o o o o o o o CM co m 00 CM OT 01 01 01 0 41 * ** 2 41 o o o o o o o o o o o 0 O 0 O 0 1 n cn cn cn in CO rx. OT CO tn CO Ol LO m CO CO T- T" "" T~ Ol T 41 o o o o o o o o RI CO S3 CM to Ot O 1 7 S 6 3 o o o o o o o o o o o 0 0 1- T CM CM CM CM CM o ffl r- IB IX. CO to CO co cn co co 00 CM CM 0 in O Ul CM 00 OT Q o o o o 8 CO in (X. x? IX. Ol OT OT OT O E *> s ? o o o o 41 o o o o o o o o 0 0 g 3 o o o isi C 0 0 e ffl 2 .. fi * = E 2- 3 1- fi T- rx. III o CM CO xt 10 co 00 OT O a. fx. OT e CM CO xt m to 00 CM CM ** o 41 8 o fi CO a a h o H T in o CM OT o xf 00 in CO fx. 8 5 5 88 o 8 5 5 o o T~ T T T s 41 s t O O o o o ? 01 41 o o o o o o o o o o o o o o o o 1 3 1 1 1 1 1 1 IB Is ffl CJ c fl = z rx. cn to to to cn to fx. o CO rx. 00 00 CM CO OT OT C o o o o o o o O 41 o CM 3 CO o s 00 5 J o o o 41 T- 2 o o o o o o o o o o o o o T- - CM CM CM CM CM Q 3 3 = ffl O 0 o fl u 00 e 00 OT ro 00 00 00 OT CM 00 OT o o CM CO to o O o o O o o o o o CM X* IX. in o o ^ T^ 33 O 41 T ,_: o o o o o o o o o ? IS 03 3 o o o o CM CM CM CM CM ffl o 1 T o CM CM m CO CO (X. CM in LO CO co rx. T T T 41 8 5 8 o o 5 o 8 o o o o o o o o o o o o 2 ? Ol 41 o o o o o o o o o o o o o o o o c 3 IB d* ffl Q. 4) CJ CO CD co to in to rx. 00 T- m o rx. xf TF CO T lx. o OT OT fl e o o o o o o o o 1 CO xt lx. in CO 8 o o o fl 41 2 o o o T_ T- ^- 3 o o o o o o o o o o CM CM CM CM CM o a s t ffl o ft. o y- 00 ro ro 00 fx. 00 OT o CO o CM OT to co in CM OT CM , y o o o o o o o CM CO xf ix. T" m o o T 1 2 ? O 00 3 o o o o o o o o o o o o o T CM CM CM CM CM Ul m o o o o o o (X. 00 , o ro rx. CO "xf^r o tn to to tO CM * S o o o o o CM 1 00 OT 00 00 00 OT OT OT OT oo 00 00 00 CO 23 41 c 3 S fl ffl s* rr to in to co co to rx. |x. o CD 00 xt o CO in CM CM xt tO T 1 1 TJ o o o o o o o o CM x? fx. 8 fx. 00 OT OT OT 00 41 e -= ** o o o o o o o o o o o o o o O rg 3 "- o cc ft) fa. LU I "> u ffl O o e u o Q > % % m rx. CO 00 CO 00 OT OT CM 00 o rx. co CM CM in rx. xt 5 to ro 1 fx. 1 in fx. 00 OT OT OT 00 0 co c c o o o o o o o o CO xf Q. o o o o o o o o o J F 41 o o o o it 3 1 IS 3 (A P LU CO o c ffl O = fl TJ 0 O ffl cc or.2 ft- 5 o it. t- co IX. CD CO co CO co CO CD 00 CM CM in o in CM 00 OT Q IX. x? fx. OT OT OT OT O *> O o o o o o o o 8 CO s E Oo ?41 41 O o o o o o o o o o o & e 3 o o e o 0 c ffl o i fi ^ w o o 2> 3 "f tl E * * o 1- CM CO xf in CO fx. 00 OT TJ in IX. CO e CM CO xt in to 00 OT CM CM 0 ft> 41 M CO Q rScSn t- CM to CO o xt OT 00 in O T- * 8888 o 5 O O o o o T" 1" T CM CM g 41 88 Ol 41 d d o o o d d d d d d d d O c 3 i 1 i 1 1 i i i i i IB ffl U fa* CJ C fl z IX. fx. rx. rx. rx. rx. rx. 00 o CD in CM o rx. IX. CD T~ CM t- O O o o o o i i O 41 e o o CM co OT CM q 00 OT o O O 41 T 1 2 d d d d d d d d d d d ^ ^ CM CM CM a 3 3 E . ffl O O O fl o j. c OT OT OT OT OT OT OT o CM 00 rx. CM 4 CM Ol OT CO 00 CO O T T 1 o O O O O O O CM xf CO OT CM in 00 OT o s a o 41 i y-1 d d d d y^ IB 00 3 d d d d d d CM CM m O CM CO CO xt T in CO rx. CO rx. 4 OT OT T t 4. * 88 5 5 88 O 8 O o o O o o o o 41 3 Ol 41 d d d o d d d d d d d d d c i 1 d c 3 i I i i i 1 1 IB 2 & ffl CL V o ix. rx. to (x. IX. [x. -. "h CO to to 00 OT m to CM xt in CM 4 CM CO CO fl e o o o o o o o o o i CM xf to Ol CO Ol O o o fl 41 q q 2 ^ T- T 3 d d d d d d d d d ^ CM CM CM o a !K i_ ffl i? CL 0 fl OT OT ro 00 00 ro Ol T rx. ro IX. 41 _ o co to OT OT in in o O o o o o o T- i CM 5 CO OT OT C^ o o 2 ? o 41 . q q 00 S" 3 d d d d d d d d d d d d CM Ul ffl to co CO CO CM CM CM o o rx. 00 00 O t- CM 88 00 00 888 00 IX. rx. rx. ix. ?^ rx. rx. to to co rx. rx. ix. T- T ^~ ^~ ^~ 2 s 41 a 3 X ffl 41 S? CC rx. rx. to co co CO rx. rx. 00 CO Y CO 00 o CO LO LO to CM 00 OT TJ o o o o o o o o o i CM CO xt IX. OT 1 41 q 5 q q q 41 d d d d d d d d d d d d o 0 IB 41 3 tj OC 7 fl ffl m u ffl O o c CJ 0 CM o > ** CD IX. rx. y _l OT OT 00 00 00 00 OT OT o in CO in o CM 00 00 O o CA F O O o o o o O O i CM CO m rx. OT T- ft) fl q 5 q q a *- 2 d d d d d d d d d 2 I 41 d z it 3 o is 3 5 o III CO p C fl fl ffl o ffl cr s o o ^ ft- o o It. y CO fx. fx. [X. fx. CD co rx. 00 i 00 OT co 00 00 T- xf tn CM CM 41 O O o o o o o o T- t CM xf tn 8 rx. 8 T~ T- CM CM c > 41 q i S O 3 d d d d d d d d d i- T^ r^ CM CM CM CM CM ffl 2 IB to to to CD co CO CO CO CM o CM o in o LO CM fx. 00 OT Q o o o O o o o o CM CO in rx. 1 rx. OT OT OT OT O u Oo ^ E ?41 41 6 C d d d d d d d d d C 0 i ii*~ 0 ffl IS ~ HC fi 5 = He 2* "t ft) E = T" rx. i- a. i o CM CO xt in tn 00 OT O TJ 1- fx. OT c 41 c CM CO xt in CO 00 CM CM O g o 41 o fi CO a H O H in co CM 1 T- o CM o CM in IX. in T- to CO CO fx. fx. Ol * 8 o 88 o o o o o O o O CM i g 41 CM o Ol 41 o o o o o o o o o o O O O O o O o O O c 3 1 1 1 q 1 1 1 1 i i IB m " CJ z5 cn CD to to IX. to IX. OT CM 00 00 OT CO OT 00 fx. 00 ot rx. o o o O 41 c o o o o o CM $ CO o CO CO 00 00 00 00 2 41 o O o o o o o o o o O o O a 3 3 s ffl l) 0 o fl o - OT T y- 1 e OT OT OT o OT O CM in CM to CM tn O CM O t- O l_> y 1 1 T o O O CM co 3 IX. o xf fx 00 OT Ol OT OT a o 41 O O O o O o o o o IB OO 3 O o o O ffl i T O i 1 1- 1 T CM CO CO in to O tn CM CM CM * O u o 8 o o o o O O o o o o i 1 41 o o o r Ol 41 o o o o o o o o o o o O o O O o O O ' 1 - ? c 3 ' 8 IB 2 Q ffl 0. a> CJ to rx. fx. CO co to IX. IX. y- 00 o OT in Cxi 00 Ol CO CO CM CM fl S c o o o o o o o o 1 1 CO Sf fx. T" 8 n. 00 OT OT OT Ol 2 41 o o 3 o o o o o o o o o O o o a m i? ft- 0 fl oo OT OT 00 00 00 OT OT CO o CM ""^ IX. CM o y in in xt Tf o O O o o o o o CM CO m fx. LO 00 at OT OT OT Ol 2 9 o 00 S" 3 o O O o o o o o o O o o O Ul ffl o O CO o o 00 co o CO CO 00 ro co rx. 4 in to to ^t * o o 8 ro a 8 o ro 00 00 fx. ix. fx. rx. 00 00 OT OT OT OT OT s T ^ ^ ^ T^ ^ 2 *- 41 u c 3 c ffl o H s? rr E co CD co m in in to rx. O CD xf 00 CM CM fx. 00 OT in [x. rx. co 4) 1 i * TJ o O o o o o o o CM CO CO Ol CO CO 00 OT OT OT OT fa* o O o o o o o o o o O o O o 'E tl 41 O o a 3 J. y* fa. a. fa. CC ft) 2 m fflfl to Ul o 0 o CM 5 o > TJ "5. CO 00 00 rx. rx. rx. 00 OT CM 00 CD Q xt xf OT o i ix. OT ot in co CO F o o o o o o o o 1 CM 5 OT CO rx. OT OT OT OT OT cc ft) fl ** -^ o o o o o o o o O O O O 1 41 o o Jr. 3 o IB 3 2 41 LU CO C ffl 00 = fl ffl E 2 O t) O T. ft- Q o is. -^ CO cn ^- 2" > _ * '- fx. i- a - VI O CM CO xt IO CO 00 OT O to y- CM CO xt in to IX. 00 OT g g 41 c CM CM o 41 o fi CO a H O H CO CO CM i CM in 00 in in CO co to 8888 o 8 o 5 O O o T CM CM CM CM CM CM 41 8 o o Ol 41 O o o o o o o O O o O o O o o O O C 3 1 1 q 1 q i i 1 1 i IS ffl CJ c fl z in fx. in in m co m in o CO OT cn CM xf rn en m co rx. "o <_) u o T O 41 C o o o o o CM xt fx. O CO 00 00 00 00 00 2 41 o o o o o o o o o o O O o a 3 3 E ffl O 0 O fl u ,_ C 00 CO 00 00 OT 00 00 o CO CM OT m rx. CM fx. xt en ,_ y O 1 1 0 t_> t_> o o O o o CM CO xt rx. o xf to 00 00 OT OT OT fa* o 41 o o o o o o o o o O O O IB 09 3 o ffl 1 1 1 o T- 1 CM CO 1 in m T CD 4 o oi in CO CM o 1 41 * 8 o o o o o O o o O o o CM CO CM CO CO CO 41 2 Ol o o o o o o o O o o O o o o o O o O o o o g ' ' ' 1 1 1 ' 5 c 3 IS 2 Q m 0. 41 o in in xf xt ix. ,_ 1 1 "8 xf Tf LO in 00 00 in CM in in CM OT 41 c 1 fl fl o o o o o o o o o CM xf rx. o xf to fx. 00 rx. 00 00 2 41 o o 3 o o o o o o o o O O o o Q = ffl ft- o Ol OT ro 00 ro ro OT at CM CM T- OT to CO in OT OT co in in rj" o o o o o o o o T CM CO fx. o xt CO rx. 00 S3 CO 00 41 00 5" 3 o O o o o o o O o O o O o Ul III o o o o o o rx. , CO in 00 ro OT O in in cn CM i- o 00 ro 00 00 CO tn rx. s in in in to to ix. rx. IX. 00 OT 00 R T 2 A 41 o c 3 c Q ffl o fl H S? OC E in xt xt 4 4 in |x- o ix. OT at 00 00 CM CO 00 cn cm T 3 fl TJ O O o o o o o o o CM xt rx o CO m in ot rx. 41 fa. o o o o o o o o o o o o o o C O 41 o J o 3 6 fa. 41 cc u fa. I O ffl o "' CJ o CM a > TJ *. a rx. (0 tn co co to co rx. OT CM OT 1 i o o xt in o to 00 xt T T CO CO F fl o o o o o o o o o i CO in 00 CO LO CD 00 ot rx. oc o o o o o o o o o o o o o o i f z JC 3 IB 3 2 41 UJ CQ C 3 ffl TJ U> i= ffl OC CM 5 0 ft- Q o is. y CO 1 in ID in m in in to IX. 1 OT 1 o rx. LO rx. OT in xf T- T- 1 T Ol 1 i T- 41 o o o o o o o o CO LO fx. in 00 o > 41 S > 0 3 o o o T- i T CM CM CM CM CM " o o o o o o o o o O ffl rS IS rx. en cn en t- CM Q CM 5 CO oicMLoorx-oiooco 88 5 5 8 5 8 o o o o o o Oi-t-CMt-t-t-CM Ol 41 o o o o o o d d d d oooooooo q 1 c 3 iii 1 1 1 1 1 1 1 IB ffl 2 o - z2 TB^^Tn^S" in in CD CO OT OT OT IO OT ococorx-mincocM "o t- c o o o o o o O O O CM xt CO ocotoix-ooooooco *" SB 41 o a t) 2 o o o o o O O O O O O O a 3 t m O O 0 fl o fa. OT OT O 00 OT O O O CO CO CO OT CO '^Qrx.i-OIOTOIO i i T t- o O O O O t- CM CO xt ix. 05C00000000100 a o 41 d o o o o O O O O O O O 3 ffl "" QQQQqqt-cmcococo rx.aicorx.cofx.tDOT ooi-t-1-t-t-t- 4. * 85 ooooooooooo 2 oi o o o o o o O O O O O O O oooooooo g lllll 1 1 1 I I 1 1 1 c 3 IB 2 Q ffl ft. 41 CJ m co in in in in CD rx. rx. ro co CMOimocorx.roco "O o cm 41 c i- i- rx. fl fl o o o o o o O O CM xf qqqq q q q q 2 41 3 d d d d d d d dddddd o ffl is s m n o CL o ? [x. 00 rx. rx. rx. rx. m OTCMOToroxt'rfi-rx.cMrooioro fl 2> o o o o o o o o i- t- co xf rx. 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Ol 41 o o o o o o o O y y CO xt Oxtr-oioooo 1 s O 3 o o d d d o dddddd 1-1-1-1-CMCMCMCM o ffl r- IB in cn tn CD CO CD CO CO ro cm o cm q oroiocMrx.ooOTQ t- fx. * o o O O O O o o cm co in i-5rx.OTOTOTOTO e .. ft) 75 O T T-T-1 41 41 dddddd T-T-TCM 4 e o o d d d o c 0 "" ffl !|35 ? c IS o fi 2^ T5 H c g 2 3 xflOC0rx.00OTOT- n - > a i fx. TJ Z r- COm CM co xt m tn oo ot 2 $2 fl 41 9 o o fi CO a Q. H O H CO CM xt IX. OT rx. e CO in cn in LO co 2 T 8 5 5 5 o T T T T- o 5 8 5 5 O o O o Ol o o o o o O o c 41 i I o O o O o o o o IS q 1 1 i 1 1 1 o d d 41 c 3 1 1 1 q i i 1 i i i IB 3 Q ffl O CJ c 41 z m m m in c xf m m to OT CO CD o in CM CO CM in TJ o o o 41 e o o o o o o o CM 5 OT CM m fx. 00 CO 00 00 fa* 41 o o IB O 2 o o o o o o o O O o o O 41 Q 3 3 fa. ffl O O O o oo rx. e 00 CO 00 00 00 OT CM OT OT CO 00 m co in 00 rx. ix. o o o 0 o o o o o CM 3 OT CM m fx. 00 00 00 00 41 IB 00 o o o o o o o o o O O o o O S" 3 3 Ul ffl 11 C o in in T 1 in T xt CO 00 OT tn m 4 ^t i i i 1 T in in to ro xt CO ^ 41 Tl CM CM CM OT in CO in ro <_> T~ TJ o o o o o o o o CM <* cn OT CM xt to fx. fx. rx. fx. tf 41 O 2 o - T" T T~ T" T- T" X 3 o o o o o o o o o O o o O 0 41 Q fa. m 0 0 CL o 1- 41 o to CD to to to o CO OT y- to rx. fx. ix. o m fx. OT CO TJ T o l_> o o o T T- i 1 co * tn OT CM IX. fx. fx. CO fx. 01 00 S" 3 o o O o o o o o o o o s E o o O fa. m 41 3 Ul Q. LL o to CO CO CO ro rx. in - rx. C o O xf in 00 CO cm 2 r^ n o 00 00 00 88 00 3 CM CM CM CO ^~ ^~ ^~ i a 41 ft) c 3 4) c a m 0 41 H nt OC E m m in in m in in in in LO m rx. ro o xf CO OT in in CO LO 3 fl TJ o o o o o o o o o o O o o T CM CM CO xt in to IB o o o o o o o o o o o o o o o O O o o o o C F tl 41 o 0 IB 3 fa. cc ft) fl fa. ffl "> O 01 0 CO' o CM Q CJ > TJ *- y -J '5. OT OT OT OT OT OT OT OT OT Ol OT CM xf ro rx. OT OT (x. Ol < CO CO E fl O O O O O o O O O o O 1 i CM 3 CO *f in to OC 3 H F O O O O O o O O O o O o O o o O o o O o o Z -* 3 0 IS 3 III CO o c ffl s ffl CC ^x?i o tl 0. Q o SC co in cn cn CO in in cn rx. CM 00 O fx. o 1 ro rx. OT fx. Q O i- 41 T xt fx. CO to 00 OT c 41 o o o o o o o o CO o O O O M 3 C 0 o o o o o o o o O o o O o CM CM CM XI ffl >2 IB en cn co CO tn tn cn 00 CM o CM O in o CO in CM fx. 00 OT TJ' *a- Q C O o o o o o o o CM CO in fx. T" rx. OT OT OT OT O .. d 0 41 o o O o O o o b c 3 O o o o o o c 0 ii o ffl c CJ 3 fi 2? x-* He =" g E * 2 fi i- 0 T CM CO xf in co rx. 00 OT O TJ t- o CM CO xf in en fx. 00 OT O g c c CM CM o o fi . Q H O H 239 APPENDIX B- GRAPHS Agfa Brovira 240-255 Agfa Multicontrast 256-282 llford Galerie 283-298 llford Multigrade 299-314 Kodak Elite 315-341 Kodak Polycontrast 342-368 Oriental Seagull 369-395 Oriental VC-RC 396-411 240 Agfa Brovira - Graphs Control No Treatment 241 Kodak GP-1 Gold Toner Stock Solution - 5 Minutes 242 Kodak GP-2 Gold Toner Stock Solution - 5 Minutes 243 Agfa Sistan 1 :20 - 3 Minutes 244 Kodak Sepia Toner 1 Minute Bleach / 30 Seconds Toning 245 IPI J-Toner 1:25/ 1:100/ 1 :400 - 3 Minutes 246-248 Kodak Polytoner 1:25/ 1:100/ 1 :400 - 3 Minutes 249-251 Kodak Selenium Toner 1:10/ 1:25/ 1:100/ 1:400 - 3 Minutes 252-255 xt CM a6uei|Q Aiisuaa papajjoo uj|/\iq 98' I- ^8-r m E81 o c CD 08 l CU CC 2> 14 8Zr C EZr cS Z9I- ? 9SI- * 0171. CA e 6rt- o n 00 8" "co c c '5) 660 o fa. "3 O .a 3 080 o c 3 CM a6ueu.o Aiisuaa paioajjoo uj|/\ia O O to in x? d h I r wv in CM a ? 911 to in "c? CM o ? 9LI c CD m CM "5 ? VLl rr >. .fa in to CM c ? vrv t5 Ul 19' ^ CM V ? 19 V ? 6fr'r rx CM 2EI- ? co c ft) o CM Err- oo ? a o CD in o C c 5? '5 t-6'0 o &. *m O .O -4- 3 PI WO O ? Ol m 9S0 ? 1 1-fO CM 630 CM Ul WO H ? rx ZOO ? 1 900 !f I 8 SOO ? 9 CM a6uei|Q Ai;suaa paioajjoo uj|/\ia o o o o o o o o CM CO CO in CO CM T- o o o o o o o o H i r- ^ h H h 8 ? 681- 98' o r co CD m "c? ? S8'r o c a> oo -- CD o r8r rx Ol CO -- ai 8Z'r c rS 2Z'r S9 I* CM * ES'r ? > ZE'l- Ul IX ? oo 03 lx ? cn -- Or S CM 3 ? CM 9 Ol 8' ? s ? CM a6ueqo Aijsuaa paioajjoo ui|/\|Q o o o o o o CM CO S w x? CO CM o d 6 6Z'r 9ZI- 8 m ? SZI- o 1 CD ZL'i "5 QC to OZ'r c CD Q S9I- 6S'r 6fr'r EE'r "5 c ft) frl-l. o Q 00 "3 S c c "a WO o to O 3 SZ'O O c 9S0 Efr'O 620 E 61.0 Q. Q. ZVQ CM CD g 800 1 CD Q. 900 CM SO'O SO'O in xf CM a6uei]Q Aijsuaa paioajjoo Uj|/\ia o o o o o o o o T- CM CO to in CO CM o o o o o o o o 1- --d 1 1 h H lx 1-6' ? I- 06' V 1- co CD m O rx ? Z8I- o c oi CD 981- CD rx Ol 10 E8'r c 2 CD rx ? tx ? 4> C CM o H Q co 6- "a. J Wl > Ol rx Q- o .Sr. ? oo (0 "O ? o c ? o c 13 S 3 ? O < c > o 5? OC CQ o < u. O o < oo ? f 8' -3 ? CO 5? 8/ ? x? CM d6ueqo Aijsuaa paioajjoo ui|/\ia o o O o o o o CM CO CO LO x? CO CM o d d d i i i i Ol A h H I h H I oo ? W, tx o 5? E61- co CD m S 1-6' c ? 1- o *- c CD 881- CD rx rx to Wl c CD a 01 00 ^ ? 6ZI- W, 4 I Z9'l rx * Efr'1- M C ft) o ? 1-3-1- 00 n s~ "3 ID c 9 '5> Wl o 13 O SI Ul ao 3 ? I-80 O C o CO 5 co o 8. S3 8 ? fx. xf CM a6uei|o Aijsuaa paioajjoo ui|/\ia o O o o o o CM CO to S x? CO CM o d d H 1 1 1 1 h H 1 h S 26 1- S 68 I 8 CO oo rx I? ? IV V o *-> c 01 CD Wl rx rx 10 5 IV I c lx rx ? 911 03 69' I 00 IS'V rx 5? 6EI- Ul rx ? 5? IX ? 5> co CM I 5? o f Ul 5 Ul ft 8. ? x? CM aBueqo Aijsuaa paioajjoo ui|/\|Q o o O o o o CM CO S LO CO CM o d A I h H I I oo ? i 261- 13 J. to. s 68' & ? I- o 1 CD f IV I "5 rx Ul CO 81- c 2 s 1-8' ? I- i Ml CO C9"l. I . 9PV "w in 92' co I- o ? r 00 "3 ? to c :l sov g " o .o. COSi 3 ? Z80 O c Ul Z90 I WO ? ZE'O s 920 ZI-'O 8" 2 l-'O * 600 800 8 800 ? at xt CM aBueqo Aijsuaa papajjoo ui|/\ia o o o o o o o o T- CM 3 CO LO 5 CO CM o s o o o o o o o 9 9 H 1 h ? 202 CM 202 s m CM 00 t ? 661- 'e1g CD "5 $ IV V OC CO ? c CM CM W'l ezi- Ol & 9SI- IX o X ESI- 00 sr Ul c O '^ .? CM rx 3 ? O c I * E Q. 5 a. Ul 5? CD g 9 1 CD 0_ on 8' ? 8 ? CM aBueqo Aijsuaa paioajjoo uj|/\ia o o o o o o o CM CO to s x? CO CM s d d d d d d 9 9 H h H ^H 961- CM CO' ? I- \\ m CM & IV V .2 c f 681- CD rx to 5? 981- c fa? CO ? 081- 00 29' I. oo rx ? CO c It o l-2'l- 00 ? fa$ a 8 c c 001- O 13 O SI rx 3 ? 080 o c W0 Sfr'O EEO E 5? 20 a. a. Ul. 5 910 CD "O H-'O X * 2 CD 0. oro 8 600 ? 8 800 ? LO CM a6ueqo Aijsuaa paioajjoo uj|/\ia o o o o o o CM CO 8 LO I? CO CM o d d d I h H 1 1 1 1 1 h H i I Wl 68' k c3 !f CD m "cT Z8I- O *^ c CD Ul 981- "5 rx Ul CO IV1 c 2 m SZI- ut 891- ? Wl |x * 8EI- '3 c ft! 9I-I. 5? Q s "3 8 CO c c 960 O 13 O .a rx 3 8Z0 O c $ a y> $ Ul. 5? 8.-' ? 8 ? CM in CM aBueqo Aijsuaa paioajjoo ui|/\ia o o o o o o 8 to m 3 CO CM o o o o o o o o H i h s ? 961- CM j= 61- CD CO c ? 61- O c CD 06' 1. CD f rx $ to ? IV I c <3 CM oo 28' ? I- ? LL'l m 9 91- I Eft co CM c 5f & 221- S CO 5> 5? 9 If ,? e*i . 5" -o Ul 5 8. ? 8 ? 8 ? s CM a6ueqo Aijsuaa paioajjoo uj|/\ia o o o O O O CM CO 8 8 xt CO CM o d d d d 3 m g (D 15 cc to c 2 9I-I- 8 sr c O CO o c CM aBueqo Aijsuaa paioajjoo uj|/\ia o O o o CM CO 8 8 x? CO CM s d d d d 9Z't CO CD m Pl'V o *^ c CD UV CD rx CO 691- c 2 m in CM aBueqo Aijsuaa paioajjoo uj|/\ia 256 Agfa Multicontrast - Graphs Control No Treatment 257 Kodak GP-1 Gold Toner Stock Solution - 5 Minutes 258 Kodak GP-2 Gold Toner Stock Solution - 5 Minutes 259 Agfa Sistan 1 :20 - 3 Minutes 260 Kodak Sepia Toner 1 Minute Bleach / 30 Seconds Toning 261 IPI J-Toner 1:4/1:10/ 1:25/1:50/ 1:100/1 :200 / 1 :400 - 3 Minutes 262-268 Kodak Polytoner 1:4/ 1:10/ 1:25/ 1:50/ 1:100/ 1:200/ 1:400 - 3 Minutes 269-275 Kodak Selenium Toner 1:4/ 1:10/1:25/ 1:50/1:100/ 1 :200 / 1 :400 - 3 Minutes 276-282 m CM aBueqo Aijsuaa papajjoo ujifla o o o o o o o CM 8 8 LO CO CM o d o o o o o o 9 9 9 \ I I 002 661- CD CQ IVV o c CD <-* CD WV OC to 881- c 2 91' V 19' V ? "r & S21- CO c ft) 20' 1- a & "3 &r c c '5> r8'0 o 13 o .a 3 90 o c ZfrO 00 LO CM aBueqo Aijsuaa papajjoo uj|/\ia o o o o o o o CM CO CO LO x? 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CD 8 TJ ZOO ? 1 CD 8 0- 900 ? 8 900 ? 90'0 CO Ol CM a6ueqo Aijsuaa paioajjoo uj|/\ia o o o o o o o o CM CO CO LO x? CO CM T- 8 o o o o o o o 9 9 CM' H tf IX ? 9 8 si CQ rx ? o CD 5 rr Ul 9 2 o 9 '? -- o 9 at oo CM ? LU CM 9 o 9 800 8 ? 8/ ? 4 Ol CM aBueqo Aijsuaa paioajjoo uj|/\ia o o 8 m 3 CO CM d d d d d d I 1 h H i I i I i h rx s: 9 8 si CQ "5- Ul ? o CD s ? cc co c 2 rx ul ? o o 9 xt rx 9 ft) c o ** . >l o CM OL Ul ? 8 .if CO H o c o g ""8 Si 3 3 O UJ c CC fx LU _l < CM o Q CC O * ul. rx E ? a Q. 2c- 5? CD g ? 1 CD 8' CL Tt> ? 8 ? 8 Ir" ? m oi CM aBueqo Aijsuaa paioajjoo uj|/\ia o o 8 8 3 CO CM d d d d -^j-+ H 1 h IX ? 22 W3 8 J2 co s 222 1*- c CD 9 8L'2 | rx 80'2 c. 2 261 * 5? OZ'L ? 00 9 2tr'L > EL'L .Ul co ft) ? o Q 880 00 a~ CO . m JL c ? "at Z90 O 13 co O Si 3 ? OSO O c a ? co 9 9 8-' ? I' Ul Ul rx ? ui 5 8. wo co Ol CM a6ueqo Aijsuaa paioajjoo uiyya o o o o o o o o p o CM CO m CO CM o d o ai o o d 9 9 9 I 1 h i I I I I I I H 1 1 1 1 1 rx ? ? ? rx ? rx ? LO T"" ? 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CD Q CC 9 O LL ' rx. 9 t 8/' ? 8 ? 8 ? rx. at CM aBueqo Aijsuaa paioajjoo uj|/\ia o o o o CM 8 in CO CM 8 d d d 9 JC EL2 8 CD CO & LL2 o c CD 5 Z0'2 CC CO 661 c 2 LU 00 Ol CM aBueqo Aijsuaa paioajjoo uj|/\ia o o o o o o CM CO 8 in 3 CO CM o d d I I L I i H h LL2 CM y- ? 0L2 8 CQ CM "c? ? 602 O 1 CD Wl IS rr 96' L c 2 28' L WL CM ? 8EL 9 -- o 2LL ? 9 LU y rx, CM ? 3- $' 5? ffi 8. ? 299 llford Multigrade III - Graphs Control No Treatment 300 Kodak GP-1 Gold Toner Stock Solution - 5 Minutes 301 Kodak GP-2 Gold Toner Stock Solution - 5 Minutes 302 Agfa Sistan 1 :20 - 3 Minutes 303 Kodak Sepia Toner 1 Minute Bleach / 30 Seconds Toning 304 IPI J-Toner 1:25/ 1:100/ 1:400 - 3 Minutes 305-307 Kodak Polytoner 1:25/ 1:100/ 1:400 - 3 Minutes 308-310 Kodak Selenium Toner 1:10/ 1:25/ 1:100/ 1:400 - 3 Minutes 311-314 aBueqo Aijsuaa paioajjoo uj|/\ia o o o o CM CO 8 8 3 CO CM 8 d d d d d 1 I h^H i 1 I 1 i 1 i f i i i i i i 9 002 .c 86' i : L 8 si CQ 8 "i* ? 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CM CO aBueqo Aijsuaa paioajjoo uj|/\ia o o o o o o T 8 LO 3 CO CM T- 8 CM 8 o o o o o o o 9 9 9 h i CO H H I 55 LO'2 I 002 CO CD 00 "c? 55 Z6L o c Ul CD 9 PVl CD rr rx 06' CO 9 L c 2 co 28' 55 L CO 55 LZ'L CO 9 8fr'L 02' 9 2r L CO Ul c 9 n S60 8 8' "3 Ul L. c 9 'cn SZ'O o 13 co O 3 9 6S'0 O c CT 55 9 Ul 9 IX ? 8. ? 8 ? 8 ? 8 60'0 ? 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