85

Van Dyke Brown

Historical and Alternative Photography

You can purchase the book at Amazon.com.

Learn about other books on the Authors page.

Peter Mrhar

Peter Mrhar
Van Dyke Brown
Historical and Alternative Photography
First edition: June 2015. All rights reserved. No part of this book may be in any way
reproduced, stored, or copied without the prior written consent of the copyright
owner.
Copyright 2015 Peter Mrhar; Graphic design: Peter Mrhar
Downloadable files and other information can be found online at
www.petermrhar.com/alternative.
Available from Amazon.com and other book stores.

Contents
Preface

About Van Dyke Brown and chemicals

About Van Dyke Brown prints

Materials and accessories

The general workflow

10

Home-made emulsions

12

Making a modern emulsion

13

Some older recipes

16

Problems with emulsions

24

Developing water

25

Fixing photos

28

Neutralizing the fixer

29

Final rinsing

30

Getting ready to print

31

Paper used in Van Dyke Brown

32

Sizing paper

34

Application of sensitizer

40

Border problem

44

Number of layers

49

Contact frames

51

Problems and corrections

53

Problems during development

54

Problems due to the paper

61

Coating problems

63

Printing and digital negatives

65

About digital negatives

66

Standard printing time

69

Finding bright tones

71
3

Creating a colored negative

73

Advanced techniques

77

Adding contrast

78

Reducers

84

Improving density of tones

88

Toners and toning

93

A brief description of toning

94

Selenium toner

96

Platinum toner

98

Palladium toner

100

Golden toners

103

Iron blue toner

107

Creative techniques

111

Local and double toning

112

Hand colored photographs

114

Colored paper

116

Printing on fabric

118

About varnishes and coatings

120

Preface
The present book is one in a series about Historical and Alternative Photography and is
devoted to a historical process which was known as Brown and Sepia Paper in the past,
but today is better known as the Van Dyke Process or Van Dyke Brown.
Basically, this is a process in which we mix an emulsion of ammonium ferric citrate
(which is used for cyanotype) and silver nitrate (which is used in the salt print process)
with a small amount of acid.
Although Van Dyke Brown is a fairly popular technique due to the easily available and
low-priced chemicals required, quite a few fans of old and alternative processes often
avoid it, because of the significant number of factors that lead to failure.
But with the correct initial preparation and proper knowledge, these first difficulties
are overcome rather quickly, so that we are soon able to produce beautiful photos
with the characteristic deep, dark brown color, with almost no trouble.
Like in the other books in this series, all procedures are described in an extremely
comprehensible manner, step-by-step, and have been thoroughly checked and tested.
At the beginning of the book, we will describe how to produce some of the most
popular recipes of light-sensitive emulsions for Van Dyke Brown prints. We will then
learn about digital negatives, discover how to print and tone photographs, and
towards the end of the book we will get acquainted with somewhat more advanced
techniques for enhancing the contrast, bleaching photos, printing a photo on fabric,
etc...
In this book, solutions for a significant number of problems that can occur in the
photographic process are, for the first time, extensively described also. Thus, a user
who closely follows the instructions will be able to produce high-quality photos
without major problems.
But enough of the introduction...

Peter Mrhar

Warning and disclaimer

Any use and handling of chemicals poses a potential threat to health and life. As a result,
every user must, prior to beginning to work with such chemicals, learn all about the
dangers, warnings, safe work methods, protection techniques, and procedures in case of
accidents. This information can be found online in the form of documents, MSDS (Material
Safety Data Sheet), and in books specialized in this area.
The author assumes no liability for any damage, injury, or loss arising from the use of the
information in this book.

About
Van Dyke
Brown and
chemicals

About Van Dyke Brown prints

The photographic technique that we describe in this book was known as Brown or
Sepia Paper or Sepia Printing in the 19th century. But at the beginning of the last
century, someone renamed it, the Van Dyke Process, even though this was already
the name reserved for describing the so-called photo-lithographic process, invented
by F. Vandyke (Cassells cyclopaedia of photography, 1911).
Today, it is widely believed that the Van Dyke Brown technique is probably named
after the color shade which is often seen in paintings by the Baroque painter Anthony
van Dyck (1599 - 1641), because a photo formed by mixing ammonium ferric citrate
and silver nitrate is recognized directly by this typical dark brown color.
The inventor of Brown Print is supposedly the English scientist John Frederick William
Herschel (1792 - 1871), although similar research and results were also written in 1839
and 1841 in the book Researches on Light, by Robert Hunt (1807 1887). But whoever
the inventor was, the first, second, or some third scientist, the initial procedures of
those inquisitive people were almost identical. When Herschel discovered that iron salts
are sensitive to light, he started with a series of tests which are described in the early
publication, Philosophical Transactions of the Royal Society of London in the year 1842.
The descriptions show that Herschel coated paper with ammonium iron citrate, tartrate,
etc..., and he exposed the paper and coated it with various additional compounds. He
came to surprising results. He first mentioned cyanotype (Philosophical Transactions
of the Royal Society of London, 1842, p. 210) as follows: The varieties of cyanotype seem
to be innumerable, but that which I shall now describe deserves particular notice, not
only for its pre-eminant beauty while in progress, but as illustrating the peculiar power of
the ammoniacal and other persalts of iron above mentioned to receive a latent picture,
susceptible of development by a great variety of stiumuli. This proces consist in simply
passing over ammonio-citrated paper on which such a latent picture has been impressed,
very sparingly and evenly, a wash of the solution of common yellow ferrocyanate (prussiate)
of potash.
The number of options with which we can make a photographic image on the basis
of ammonio-citrated paper is not limited to cyanotype. Thus, on the same page, the
author also describes the photographic process of chrysotype (printing using gold
chloride) and the use of silver nitrate, If paper prepared as above recommanded for the
chrysotype, either with the ammonio-citrate or ammonio-tartrate of iron, and impressed,
as in the process, with the latent picture, be washed with nitrate of silver instead of a
solution of gold, a very sharp and beautiful picture is developed, of great intensity.
In short, if the paper is impregnated with ammonium iron citrate, exposed and washed
in various compounds, a photo of various shades, or better said, a photo of different
currently-known photographic techniques, is obtained.
8

Materials and accessories

The modern process of making Van Dyke Brown Print is carried out in a number of
stages. The paper is prepared for exposure in an enclosed space with an ordinary,
somewhat weaker lamp of power of 20-40 W. Then it is exposed in the sun or by UV
lamp and fixed in sodium thiosulfate.
The basic materials and accessories that we need for making Van Dyke Brown prints
are as follows:
1. a bottle with a light-sensitive emulsion
2. a syringe
3. a container with water to clean syringes and brushes
4. paper
5. a brush or other device for applying a solution onto the paper
6. paper towels for cleaning brushes
7. a negative
8. a hair dryer to accelerate the drying of paper
9. a contact printing frame or glass plates
10. at least two trays for the development of the image in a water
11. a tray for fixing the image and, optionally, an additional tray for toning the pictures

The general workflow

Here we will only briefly describe the general process of making pictures with the Van
Dyke Brown process; the entire process is presented on the pages that follow.

Preparation of materials
On the work table, we set out all materials and tools that we
will use in the work. These depend on the way in which we
want to make a photo.

Application of light sensitive emulsion

For the production of Van Dyke Brown Print, we need
emulsion. This is applied onto the paper by any of a variety
of techniques.

see Making a modern emulsion on page 13

see Application of sensitizer on page 40

3 min.

Drying of the paper

The paper is dried for about 3 minutes in air, so that the
emulsion is absorbed into the paper. Then it is thoroughly
dried with a hair dryer or some other device.

Exposure
The negative is placed on a sheet of paper which is covered
with a light-sensitive emulsion. The task of the negative is to
block or transmit light through the negative. The negative
and paper are then placed in a contact frame for exposure.
The photo is exposed according to the selected standard
printing time.

see Getting ready to print on page 31

see Contact frames on page 51

see Standard printing time on page 69

10

Developing photos

3 min.

The photo may be developed in one tray, but more often

two trays are used, with slightly acidic water. In this case,
the photo is first developed for 3 minutes in the first tray
in slightly acidic distilled water and then for 2 minutes in
the second tray filled with normal tap water or sometimes
slightly acidic tap water.

2 min.

see Developing water on page 25

Toning
After developing, the photo can be toned in any toner.

see Toners and toning on page 93

Fixing
After exposure or toning, the photo is placed in a
photographic fixer for 3 minutes.

see Fixing photos on page 28

Neutralizing the fixer

Since Van Dyke Brown is quite an unstable process, any
residues of fixative must be removed from the paper with
the help of sodium sulfite.

3 min.

3 min.

see Neutralizing the fixer on page 29

Final rinsing
At the end of the process, the photograph is rinsed in tap
water for 15 minutes. The photo is then dried and optionally
protected with the desired protective coating.

see Final rinsing on page 30

see About varnishes and coatings on page 120

11

15 min.

Home-made emulsions
Like in all old photographic techniques, also in the Van Dyke Brown process we can
observe quite a few different formulas being used. In our book, we will, of course,
describe only those formulas that provide the highest quality and stability. First, we
will describe the so-called modern formula, and then a few of the formulas of the old
masters.

Preparation for the production of emulsions

Before making the solutions, we must first read the instructions and warnings about
working with the selected chemicals. Then we adequately protect ourselves, prepare
the working environment, and collect up all the necessary material and tools. We will
need the following:
1. a pair of protective, latex gloves
2. a plastic spoon and a number of sheets of paper of size A6 to be used to weigh
chemicals
3. the relevant chemicals
4. distilled water
5. a precision or kitchen scale (this is used only to weigh photographic chemicals)
6. a funnel
7. a brown glass bottle for storing the emulsion
8. plastic cups for mixing chemicals, and a variety of other tools, which will be
described for each process separately

12

Making a modern emulsion

Below is described a recipe for a modern emulsion that, among the considerable
number of solutions that I have tested, gives the best results. Tones in the photo are
clean and saturated (see photo on next page), and most importantly, the photos we
make with this solution are quite stable. For the production of this emulsion, we need
the following chemicals:

10 g
1.5 g
4 g
100 ml

ammonium ferric citrate - C6H8O7 . x Fe3+ . y NH3

tartaric acid - C4H6O6
silver nitrate - AgNO3
distilled water

Method for producing the solution

Making the emulsion is quite simple. To begin with, we need three empty plastic cups.
1. Into a cylindrical vessel, we pour 100 ml of distilled water (1). Approximately one
third of the water is poured into each of the three plastic cups (2), so that in each
cup there is about 33 ml of distilled water.
2. On a precision scale, we place a sheet of paper and weigh 10 g of green ammonium
ferric citrate (3). We pour this into the first glass of water. The contents are dissolved
well with the help of a glass rod.

Warning

3. Then we weigh 4 g of silver nitrate (4), which is dissolved in the second glass

Prior to each production and use of solutions,

it is best to read the instructions and warnings.
Information on safety, the so-called MSDS (Material
Safety Data Sheet), can be found online or in
relevant manuals.

13

Warning

Silver nitrate is toxic and causes severe skin burns

and eye damage. When inhaled dust damages the
respiratory system. Before each production and
use of chemicals read the relevant instructions and
warnings. Properly protect yourself.

4. Using the precision scale and paper, we weigh 1.5 g of tartaric acid (5) and dissolve
it in the third glass.
5. Then the mixing of the solution follows. We pour the dissolved tartaric acid (6) into
the first glass of dissolved ammonium iron citrate. We mix the solution well.
6. To the solution we have just prepared, we add the content of the second glass, i.e.
the solution of silver nitrate, slowly, drop-by-drop, while stirring continuously
(7).
7. The resulting light-sensitive emulsion is poured into a brown bottle, tightly sealed,
onto which a label with the relevant information about the compound and the
date/time of production is glued. The solution cannot be used until the next
day, when the compound has fully ripened.

Warning

Tartaric acid causes skin, respiratory tract and severe

eye irritation. Before use, we must read the warnings
and adequately protected ourselves.

14

15

Some older recipes

In this chapter, we will learn about some older recipes from the last century, which
were some of the best, according to the old masters. Of course, we will notice that
among them there are no very big differences, but maybe we will find a formula that
is adequate for our way of working and desires.

Arndt and Troost

One of the first and most popular emulsions in the last century was patented by
Arndt and Troost in 1894. As mentioned by George E. Brown, the author of Ferric
and Heliographic Processes, Arndt and Troost manufactured paper called Sepia BlitzLichtpaus papier. For making this recipe we will need the following:

10 g
2 g
2 g
100 ml

ammonium ferric citrate - C6H8O7 . x Fe3+ . y NH3

tartaric acid - C4H6O6
silver nitrate - AgNO3
distilled water

We notice that this one is just a little different from the modern recipe, since only
slightly less silver nitrate is used and there is a quarter of a pinch more tartaric acid.
Since the method for making this emulsion is the same as the production of modern
emulsion just described, this will not be explained again here.

Sepia (Cassell) recipe

This recipe is also similar to the above-presented recipes: however, this time the ratio
of chemicals is somewhat different. Unlike before, this time citric acid is used in place
of tartaric acid.

22 g
5 g
5 g
100 ml

ammonium ferric citrate - C6H8O7 . x Fe3+ . y NH3

citric acid - C6H8O7
silver nitrate - AgNO3
distilled water

The emulsion does not display the image with the right sepia tones, but rather creates
a gentle, somewhat softened drawing. In the book Cassells Cyclopaedia Of Photography
(1911), in which this formula is written, it can be read that it is advisable to apply two
layers of emulsion before exposure. However, the reality is somewhat different. When
applying the two layers, there is a fairly strong leaching of the pigment, so it is better
to apply only a single layer.
16

17
Arndt and Troost recipe - 2 layers on Fabriano Artistico HP paper

18
Sepia (Casell) recipe - 1 layer on Fabriano Artistico HP paper

Sepia paper
The recipe for this emulsion was known in the last century as sepia paper.
Although the basic ingredients are still ammonium ferric citrate and silver nitrate, this
time, unlike in the previous recipes, diluted gelatin and acetic acid are added to the
emulsion.
The emulsion for sepia paper shown in the photograph is the once quite popular sepia
tone, which is no longer so greatly appreciated.
For the production of this emulsion, we need the following chemicals:

20 g
3 g
0.25 ml
1.5 g
500 ml

ammonium ferric citrate

silver nitrate
glacial acetic acid (or 5 ml of vinegar)
gelatin
distilled water

Making a gelatin solution

The gelatin used in this technique is a simple kitchen gelatin. This is made according
to the manufacturers instructions or according to the procedure described below. We
need the following:

20 g of gelatin
100 ml of water

Most often, gelatin is made as follows:

Warning

1. From the above-mentioned half-liter of distilled water, 100 ml of water is poured

into a small beaker into which we slowly pour 1.5 g of gelatin while constantly
stirring.
2. We wait 15 minutes for the gelatin to swell.
3. We place the bowl with gelatin in a pot of water heated to about 45C.

Glacial acetic acid accelerates combustion and causes

skin burns and eye damage. Eye protection must be
worn and care taken when using other mild acids,
too.

19

4. When the gelatin liquefies, we stir it slowly for a few minutes. We have to be very
careful to avoid bubbles.
5. Bubbles generated during mixing can be removed with the edges of a paper towel.
Method for producing the emulsion
Once we have prepared the gelatin solution, we can make the remaining part of the
solution.
1. With precision scales, we weigh 20 g of ferric ammonium citrate (1) and we pour it
into the 400 ml of water that remains from the preparation of the gelatin.
2. The ammonium ferric citrate is stirred until completely dissolved.
3. We measure 3 g of silver nitrate (2), which is poured and stirred into the ammonium
ferric citrate that was just dissolved.

4. Using a syringe, we weigh 0.25 ml of acetic acid (3), which is added to the solution.
All of the components are now again mixed together well.
5. Finally, we pour hot gelatin into the 400 ml of solution previously prepared (4).
This is stirred slowly, so as to create as few bubbles as possible.
6. We slowly pour the liquid into a brown bottle and label it with the appropriate
data.
This emulsion also shows a much nicer sepia tone if the surface of the paper is coated
with only one layer of the emulsion.
20

21
Sepia Paper recipe - 1 layer on Fabriano Artistico HP paper

Reducers
To lighten photos which are made with the Van Dyke Brown process, dozens of different
recipes can be used, which are useful both for brightening silver prints as well as for
lightening the cyanotypes. Here we will, of course, mention only a few of the reducers
that are easy to produce, and are especially suitable to the Van Dyke Brown process.

A general description of the process

1. Lightening, brightening or bleaching the image is almost always done on
produced, fixed and washed-out images.
2. If the image is dry, it is best to immerse it for a few moments in tap water. In this
way, the chemicals of the reducer will be more evenly distributed throughout the
surface of the paper.
3. The image is then placed in a tray with the reducer for the chosen amount of time,
where it is most often continuously shaken.
4. We stop the act of bleaching by submerging the photo in a greater amount of
tap water for a few minutes, and then, if necessary, the photo has to be fixed and
washed in water.

Recipe with potassium ferricyanide

Potassium ferricyanide is one of the most powerful chemicals used to bleach silver
images, but today it is much better known as a basic component for making cyanotype
emulsion. As a reducer, it is also used in so-called Iron blue toner (see Iron blue toner
on page 107).
Years ago, bleaching took place in two steps. The first step was bleaching and the
other was fixation. Of course, we can also make a one-component solution composed
of fixer (see Fixing photos on page 28) and reducer. For the production of our two-step
reducer, we need the following:

0.2 g
1000 ml

potassium ferricyanide (K3Fe(CN)6)

water

The production is quite simple. We pour 0.2 grams of potassium ferricyanide into 1
liter of water and mix well. The reducer can be used immediately. If we want consistent
results, we use the reducer only once.
1. Brightening takes place by first slightly soaking the image in water and then
immersing it in the reducer for the desired time, usually for 1 to 2 minutes.
2. When the image is bright enough, it is quickly transferred to a larger amount of
84

plain water and washed for a few minutes.

3. The image is then transferred to the fixer, where it is fixed for 3 minutes.
4. Finally, the picture is washed for 25 minutes in plain water
On the next page, we see that a previously rather deep brown photo (1) lightens on the
entire tonal range after two minutes of weakening, while colors become slightly cold
(2). If the weakening time is extended, the image, under the influence of potassium
ferrycianide, became increasingly light blue.

Recipe with potassium permanganate

The next group of reducers in traditional photography represents reducers which have
been prepared on the basis of potassium permanganate and one of the acids. In our
case, we will use the formula that I compiled from a number of recipes. Instead of
conventional sulfuric acid, we will use citric acid.
As this reducer first brightens the bright tones, it can also be used to clean the whites
on a photo. A brightened photo gets a slight green-brown hue (3).
As in the production of reducer, we use a very small amount of potassium permanganate;
we will first make a 5% potassium permanganate solution for our recipe. This is
made by dissolving 5 g of potassium permanganate into 100 ml of distilled water.
The solution of the reducer is made by mixing 0.2 ml of a 5% solution of potassium
permanganate into 1.5 liters of water.

0.2 ml
1500 ml

5% potassium permanganate (KMnO4)

water

Warning

The process of weakening with potassium permanganate is similar to the previously

described procedure. A moistened photo is immersed in reducer for the desired
time and then washed for 25 minutes in the water. There is no need to fix the photos

Potassium permanganate diluted in water is a

common disinfectant, but, undiluted, it is toxic by
ingestion and accelerates combustion. Therefore,
great caution is necessary.

85

86

bleached with this reducer, but some authors recommend a short washing in sodium
sulfite (see Neutralizing the fixer on page 29).

87

84