mong a number of experiments with mineral tannage in the middle decades, one of the most

promising was that conducted by Prof. F. L. Knapp, a German chemist who in the I 85o's
demonstrate
the chemical feasibility of substituting mineral for vegetable tannage. Not until
i877 did Knapp produce a satisfactory chromate-tanned leather, but it was not
successful commercially. In I88o another chemist, Dr Christian Heinzerling,
patented a similar process in the United States using a different combination of
mineral inputs,6 but it was not until I 884, when the American, Augustus Schulz,
patented the "two-bath" chrome-tanning process, that the chrome-tanning industry began to develop

. In Britain it was the Eglinton Chemical Company Ltd

of Glasgow which took up the British patent rights for the manufacture of bichromate of potash used
in the chrome-tanning process. Prof. Hummel of the Department of Textile Industries at the Yorkshire
College was consulted on the problem of "fixing" the chrome. Even so, the company struggled unsuccessfully to persuade either
merchants, manufacturers, or the public of the quality and value of chrometanned leather. The firm's venture into the production of
chrome-tanned footwear proved a failure.

A commercially satisfactory chrome-tanned leather possessed several important features. The product
possessed a greater elasticity and resistance to water
than vegetable-tanned leather, and its flexibility and lightweight characteristics
made it particularly suitable for upper and a few specialist leathers.4 The process
required less labour, though with greater skill, than did vegetable tanning, and
its rapidity-taking hours rather than days-diminished working capital requirements. Because the
process was more subject to scientific control a greater degree
of precision was introduced to that part of leather production, and it was also
possible to produce leather of various colours and with a wider variety of finishes,
an important advantage to those American footwear manufacturers who at that
time were seeking to stimulate the element of fashion in the field of leather goods.5
The spectacular upsurge in imported dressed leathers from America to the 'nineties was directly
related to the progress of chrome tanning in that country, for
even by i900 three-quarters of the upper leather produced in the United States
was chrome-tanned.6 This innovation was introduced to Britain in the late 'nineties in response to a
lecture given by H. R. Proctor, head of the Leather Industries
Department at the Yorkshire College, on his return from the Chicago Exhibition
in I895,7 when he was able to describe the scientifically simpler "single-bath"
chrome-tanning process patented in America by Martin Dennis in i893

Chrome Tanned Leather Conservation

Leather is a strong, supple material that can be a pleasure to work, but due to
acids that are created as most
leathers age, it can deteriorate and cause the deterioration
of adjacent materials such as paper, sometimes penetrating through several
layers. Leather produced since the
early nineteenth century tends to deteriorate at a faster rate
than older leather, leading some to believe that either the
tanning processes since the nineteenth century were faulty
or the animals were inferior

--
The
leather samples embedded in the covers were placed there
in 1905a naturally occurring aged leather sample. The
chrome tanned leather is the only sample that has not discolored the paper
adjacent to it.

he discovery of the element chrome came in 1766,

and it was used in the preparation of red, yellow, orange,
violet, purple, maroon, and green pigments. It was given
the name chromium, from the Greek word for color.
Robert Warington patented a process for the use of chrome
in leather production in 1841. Several similar patents were
granted in various European countries, although none was
a commercial success until 1878. In that year, Christian
Heinzerling patented a leather tanning process using alum and zinc salts, chromic
acid, potassium ferrocyanide, and
barium chloride. Augustus Schultz, a salesman for a
dyestuffs company, became aware of a problem in the manufacture of womens
corsets. Because of cost, whalebone,
the traditional material for making corset stays, was giving
way to steel. The acids in the leather that cover the stays
reacted with the steel and made ink. Chamois smells of
fish, and the alum salts wash out of tawed leather with perspiration. How Schultz
came to be interested in and able to
create chrome tanned leather remains a mystery, but he
took out a patent in 1884 for a two-bath chrome process
that most consider the foundation of chrome tannage

The chrome forms strong bonds with carboxylates on

the side chains of the collagen molecules. The result is a
supple greenish-blue skin. In vegetable tanning, the large
gallotannin molecules allow for movement in the interstices of the collagen fibers.
There are no residual tannins
in the chrome tanned skin (Erickson 1998). The chrome
ions are much smaller than the gallotannin molecules and
become tightly bound with collagen. This is the cause of
both the desirable and undesirable qualities associated with
chrome tanned leather: its chemical stability as well as its
tough, spongy quality. It may prove possible, however, for
the tanning processes to be altered to create more desirable
qualities for conservation purposes.

Because of the sponginess of the material, the cut resembled a tiny ragged cliff
the edge was
feathered and there was a steep angle upwards resembling
a shelf. This is not peculiar to chrome tanned leather, but
means that the material must be pared in stages. The
shelf that is created can be taken down in two to three
passes of the knife. Because long cuts are difficult if not
impossible, the process of shaving this down can be
tedious.

. Chrome tanned leather does not mold as easily as a vegetable tanned leather,
so thinness is important.
Other than the fact that the leather was too thick, the result
was a satisfactory reback. The color and sheen of the new
leather matched the old and the adhesive did not darken
the old leather. The new leather was pared thinly enough to
blend in unobtrusively under the old leather.

The improvement in the performance of leather from 1930

onwards was brought about
rgely through the studies made by Faraday Innes of the
B.L.M.R.A. in collaboration
ith the then library of the British Museum. In 1924 Innes
began a series of investigations
hich extended over 10 years. He confirmed that
absorption of sulphur dioxide from the
mosphere accelerated decay and rotted leathers were
found to contain as much as
0-80 per cent sulphuric acid.
He was able to show which tannages gave the most
durable leathers and which tannages
hould be avoided. The salts naturally present in vegetable
tanning materials increased
urability and this in turn led leather manufacturers to
incorporate buffer salts in leather
ntended to be used for bindings.

After 1850 mineral tanning salts based on chromium

sulphate became available.
Chromium salts are widely used today and these form co-
ordination compounds with the
skin protein to form a leather with a shrinkage
temperature of 100 ""C or above. Today
there is the possibility that binding leathers will be tanned
firstly with a vegetable tan and
then retanned with a mineral salt. Retannage with
aluminium sulphate or chloride has
produced a more durable leather than retannage with
chrome. The mechanism of this
is not understood but recent work has indicated that close
control of the molar ratio of
aluminium and phenolic hydroxyl is important for optimum
effect

Skins that contained no tanning material at all, that is

vellum, parchments, and acetone
dehydrated skin showed no sign of deterioration at the
end of the storage period nor had
67
they accumulated significant amounts of sulphuric acid.
Chromium tanned leathers were
equally resistant
The most common form of mineral tanning in more recent times uses chromium salts.
Beginning in 1884, the chrome tanning process began to be used on a large scale. The
adoption of chrome tanning methods revolutionized the leather manufacturing industry
since it decreased the amount of time it took to process leather. What took days to
vegetable-tan could be done in a matter of hours with the chrome tanning process. Today,
over 80% of leather is produced using variation of chrome tanning (Thomson 1991a).
Chrome-tanned leathers are hard-wearing, supple, stable, not subject to the ravages of red
rot and can withstand hot, even boiling water. In fact, the chrome tanning process produces
leather that can be used under conditions that would be damaging for leather produced
using any other tanning process (Haines 1991b). Unfortunately, the resilient, open texture
of chrome tanned leather carries with it less desirable qualities. For this reason, chrome
tanned leather holds water, feels clammy and does not hold its shape as well as vegetable
tanned leather. Generally, chrome tanned objects are pale blue in colour and can not be
made pure white (Waterer 1971).

Vegetable Tanned
Collagen in tanned leather is more resistant to mold growth than in
untanned leather. Chrome-tanned leathers are relatively impervious,
vegetable-tanned leathers considerably less so. Book leathers are,
unfortunately, vegetable tanned, chrome leathers being used primarily
in shoes, luggage and other such items. Studies indicate that mold
growth does not affect leather in the same way that it does
cellulose. The mold apparently does not attack the hide-tannin
complex itself. The components of leather which support mold growth
are the lubricants, the conditioning materials and the finish. It
would seem from the literature cited 12. Mold / Fungi, page 8 above
that high ambient relative humidity rather than mold damage is the
primary cause of deterioration of leather. Special book binder's
leather is now available tanned with non-hydrolyzable vegetable
tannins. (MLF)

--

A consequence of this confusion via the literature regarding new bookbinding leather has encouraged the use of alternative materials.
For example, the practice of replacing degraded vegetable tanned leather components of a binding with large strips of Japanese
repair paper or alum tawed (semi-tanned) leather for rebacking. This is similar to the issue of using Tyvek to replace the spines of
vellum bindings. While these alternative materials are being used with confidence within the conservation profession there are two
problems. Firstly, both materials require further research into their long term chemical and physical properties such as that observed
by Vest (1999) in the analysis of the deterioration of white tawed leather. The second problem is the permanent alteration of the
character of the binding due to the different physical properties of these materials in conjunction with the original covering material.
The aesthetics and mechanics of the binding are being changed by the use of alternative materials that can not always be easily
reversed. Using the example of the conservation of 19th century vegetable tanned leather bindings it is difficult to find published
evidence against using some of the modern vegetable tanned bookbinding leathers for book conservation repair. Coupled with
improved storage and handling when returned to the collection, the longevity of the conservation work done using modern leathers is
a vast improvement from previous repairs undertaken in the 19th and early 20th century.

Leather treatments are another area of confusion within book conservation literature. There is a documented history of now
inappropriate leather consolidants and surface coatings that leave the book conservator unsure of which treatments to trust (see
Haines, 2002). The newest leather treatment has been developed by Dr. Anne Lama (2012) at The Leather Conservation Centre,
Northampton in co-operation with Dr. Jeffry Guthrie-Strachan of The Institute for Creative Leather, University of Northampton. This
should be another option for the treatment of acid decay damaged vegetable tanned binding leather available to the book conservator.
This like any leather treatment can only be used if the constituents of the treatment are understood by the conservator for its short and
long term effect on the physical and chemical properties of the leather. Only through clear and concise literature and training in correct
use can this, or any leather treatment, be used by the conservator with confidence that they are slowing the rate of deterioration in
leather.