THE MANUFACTURE OF LEATHER

R. K. CARLETON
Rhode Island State College, Kingston, Rhode Island
From time immemorial, man has been making use of the
skins of animals for protective purposes. Any knowledge of the
change occurring in animal skin during its conversion into
leather is made doubly interesting by the possibilities which it
presents for preserving one^s health and beauty through a better
knowledge of the skin and its functions.
Most of the solid matter of what we know as hide consists of
substances termed proteins. A protein is familiar to all in that
much of our foodstuffs are of protein nature, such as beans,
peas, etc. A protein is a complex type of substance, being made
up principally of four chemical elements namely, carbon, hydro-
gen, oxygen and nitrogen. The skin also contains oily sub-
stances, blood and inorganic salts.
COMPOSITION OF THE SKIN
The skin is divided rather sharply into two parts differing
both in origin and structure: the derma, or true skin, which
forms by far the greater portion of the whole, and the epidermal
system comprising the epidermis, hair and glands. The latter
system, namely the epidermal consists entirely of reproducing
cells which rest on the surface of the derma and draw their
nourishment therefrom. The portion of the epidermis in contact
with the derma is a layer of living cells, rather elongated in
shape.
The outer surfaces of the skin are constantly changing and
are worn away. This scaling is often very noticeable on the
scalp in the form of dandruff, which in itself is not the result of
a disease, but rather is evidence that the epidermal cells are
functioning normally.
To the naked eye the hairs appear to pierce the skin, but
actually they do not do so. The epidermis dips down into the
derma here and there, forming follicles or pockets, in which
hairs grow. At the bottom of each follicle there is a projection
from the derma known as a hair papilla, which is supplied with
both nerves and blood vessels. Lining the space around the pa-
pilla are numerous epidermal cells, which derive from the blood
the nourishment necessary for their production. As new cells
are formed, the older ones are pushed outward. In uniting to
840
 THE MANUFACTURE OF LEATHER 841

form the hair, they assume the shape of the follicle; if this hap-
pens to be curved the hair will be curly.
Unlike the epidermis, the derma is fibrous in character in-
stead of being composed of cells. Furthermore, these fibres are of
two kinds: the large, white fibres of collagen which make up the
great bulk of the derma; and the thin, yellow fibres of elastin
which occur only in the region of the upper and lower surfaces of
the derma. In some types of skin, fat cells replace some of the
collagen fibres. However, the greater the proportion of fat cells
to collagen, the less valuable is the skin for leather making,
since the collagen is the leather-forming part of the skin. The
derma is also transversed by complex systems of nerves and
blood vessels.
The derma divides itself rather sharply into two layers, the
dividing line occurring at the lower extremities of the hair roots,
or about one-fifth of the distance from the upper surface to the
flesh. The lower, fibrous region of the skin is often referred to as
the reticular layer because of the network appearance of the
collagen fibres. The upper layer has been referred to as the
"thermostat layer^ for reasons which will become apparent
shortly.
It is possible to account for numerous characteristics of the
leather by a consideration of the properties of the two layers of
the derma. The structure of the reticular layer determines the
physical properties of the leather, such as tensile strength, solid-
ity, resilience, etc., while the upper or thermostat layer deter-
mines more especially the appearance of the leather. In making
the finer grades of leather, much attention is paid to the thermo-
stat layer. A very important fact which should be noted in pass-
ing is that this layer is practically as thick in the skins of very
small animals as it is in larger ones, and even in the thinner por-
tions of the same skin, this layer occupies a greater proportion
of the total thickness.
The reason for the name "thermostat layer" is explained as
follows: Attached to the base of the hair follicle and weaving its
way upward to the right is the erector pili muscle, one being at-
tached to each hair. Just above this muscle and emptying into
the hair follicle is a group or cluster of sebaceous or oil glands.
The muscle and glands make up what is essentially a most re-
markable thermostat, which tends to keep the temperature of
the whole body constant.
The muscles are controlled by the pilo-motor nerves which are
842 SCHOOL SCIENCE AND MATHEMATICS

sensitive to temperature changes. If the surface of the skin is

cooled, the muscle is made to contract. The visible effect is that
phenomenon known as ^gooseflesh." The contraction of the
muscles puts a pressure on the sebaceous glands, causing the
cells to give up their oil to the hair follicle, through which it
flows to the surface of the skin. In this operation the flow of
water from the sweat glands to the surface of the skin is stopped
or retarded, thus preventing loss of heat through the evapora-
tion of water. Enough of the heat generated by the body is thus
conserved to maintain the body temperature constant.
TANNING OPERATIONS
Since the same fundamental operations are followed in general
in the conversion of any skin into usable form, namely leather,
the following description of tannery operations will be a rather
brief survey of a specific series of operations in actual use for
making shoe upper leather. In making the leather described,
calfskins are used.
One of the most dangerous enemies of hides is bacteria since
the inner surface of the skin from the moment of flaying or
separation from an animaPs body provides an ideal medium for
bacterial growth. Therefore, even though the inner surface of
the living animal may be free from bacteria, it acquires them
rapidly from the air from the moment it is flayed.
In order to guard against damage by bacteria, it is customary
to apply dry sodium chloride which is the ordinary salt most of
us eat regularly, to the skins until the solution retained by the
skin is nearly saturated with salt.
This application of salt does more than simply protect the
skin, it lowers the water content of the skin from about 65 to 45
per cent. As long as the solution wetting the skin contains more
than 6% salt, there is little danger of putrefaction, provided the
temperature remains fairly low. On the other hand, if the
strength of the salt solution falls below 1% the bacteria may be
more active than if no salt had been used. The process of salting
is generally known as curing.
The first tannery operation is that of soaking in vats of water
in order to cleanse the skin and to restore the water lost through
partial drying. As soon however as the skin has absorbed enough
water to restore its natural size and shape, it is fleshed. In this
operation, the flesh side of the skin is forced against a revolving
roller set with sharp blades, which cut away the adipose or fatty
 THE MANUFACTURE OF LEATHER 843

tissue. The purpose of this adipose or fatty tissue is to connect

the skin loosely to the rest of the body. It consists mainly of fat
cells and loose strands of connective tissue and is of practically
no value in leather making. With the trimmings it is used in the
manufacture of a familiar product, gelatine.
After fleshing, as the foregoing process is termed, the skin is
soaked again until freed from most of the soluble protein matter
normally present in the blood vessels and lymph spaces. The
skins are usually given a change of fresh, cold water each day for
three days. In order to make certain that no dangerous increase
in bacteria is occurring, bacterial counts, so called are made of
the soak water.
The cleansed skins are next put into a vat, equipped with a
paddle wheel to keep the liquor well stirred, and treated with
limewater, commonly called ^milk of lime," whose chemical
formula is Ca(OH)2 and which contains a small quantity of
sodium sulfide, Na2S..An excess of quicklime, CaO is used in
making the limewater, in order that the liquor be at all times
saturated. This liquor slowly destroys any epidermal layer and
effects a complete separation from the true skin.
From the lime liquor the skin is transferred to an unhairing
machine wherein the hair side of the skin is forced against a re-
volving roller set with blades which scrape off the loose hair and
epidermis. The skin is then thrown over a convex, wooden slab,
called a beam, and a man pushes a specially designed, two han-
dled knife downward over the skin and to the left and right,
forcing out the loose material from the hair follicles and pores.
This operation is known as scudding and the operator as a beam-
ster. Following the scudding process, the skins are washed with
running water in an open, revolving drum in order to remove the
free lime. The skin is now practically free from the various parts
of the epidermal system and is ready to be bated.
After the treatment which removes the last vestige of hair,
the skins are transferred to a paddle vat containing a very di-
lute solution of pancreatic enzymes and a salt which neutralizes
the caustic alkalinity of the skins. An enzyme is a tiny micro-
organisim which is capable of bringing about a specific type of
chemical change, for example, fermentation. The lime treatment
previously mentioned causes the skins to swell up and become
rubbery, but the bate liquor counteracts this effect and the
skins quickly lose their resilience and become flaccid. At the
same time the enzymes act upon the elastin fibres of the skin,
844 SCHOOL SCIENCE AND MATHEMATICS

dissolving them to a greater or lesser degree, depending upon

the amount of enzyme used and the time and temperature of the
digestion.
It is essential that the elastin fibres be removed since they
have a tendency to prevent an extension of the surfaces of the
skin; their removal makes the grain surface of the skin more
readily extensible, which is sometimes though not always, ad-
vantageous. The extent to which the bate liquor is permitted
to dissolve elastin is governed by the specific properties desired
in the leather.
The bating operation has another purpose, aside from render-
ing the skin flaccid and removing the elastin. It is to cleanse the
skin, freeing it from any scud and partially decomposed pro-
teins not previously removed. A half century ago, bating was
done almost entirely with warm infusions of the dung of dogs or
fowls. It was then a most disgusting process. However, with the
advent of scientific methods, this disgusting process has been
relegated to the past.
The bated skin is now composed almost entirely of fibres of
the protein collagen and it is now ready to be tanned. Up to this
point the operations have been conducted chiefly with the ob-
ject of removing constituents of the skin not wanted in the
leather.
THE CHEMISTRY OF TANNING
Two very different methods are employed generally for con-
verting the raw skin into leather: vegetable tanning, which is a
very old process; and chrome tanning which has been in use less
than half a century. Skin which has gone through the bating
process is highly putrescible, that is, more or less sensitive to
putrefaction, but when brought into contact with materials
known as tanning agents, it assumes new properties, one of
which is resistance to putrefaction.
In the former tanning process, that is, vegetable tanning, the
bated skin is suspended from a stick, head down, into a vat con-
taining a weak infusion of barks, woods, and leaves containing
tannin. The first liquor into which the skin is put is the weakest
and one which has been used many times before. Each day it
is transferred to a stronger and fresher liquor until fully tanned,
which takes about ten days.
During the time the skins are in the tan liquors, the tannin
diffuses into the interior of the skin and then into the very sub-
 THE MANUFACTURE OF LEATHER 845

stance of each fibre. The chemical compounds collagen and tan-

nin then combine to form a new material, leather, which is
neither collagen nor tannin, but a quite different substance hav-
ing the properties of neither of the constituents which combined
to make it. When the tanning is complete, each collagen-tannin
fibre appears under the microscope like a transparent rod of
brown glass. In actual practice about sixty parts of tannin com-
bine with one hundred parts of collagen.
In the newer method of tanning, the bated skins are first
pickled in a bath of sulfuric acid and sodium chloride (common
table salt) and then treated with a solution of basic chromium
sulfate, having the chemical formula CrOHS04. This chromium
solution or "chrome liquor^ as it is called diffuses rapidly into
the skin substance and a combination occurs between the col-
lagen and chromium, forming the substance known as chrome
leather. When collagen is brought into contact with boiling
water, it is rapidly converted into gelatine and as such passes
into solution. Chrome leather on the other hand remains unaf-
fected by boiling water. A test very often employed in a tannery
to ascertain when a skin is fully chrome tanned is to keep it in
boiling water for five minutes. If it has not curled up at the end
of this time, it is considered tanned. Of course, the combination
of chromium with collagen is not always stopped at this point;
for some kinds of leather it is desirable to carry the tanning
further.
The protein material also combines with sulfuric acid during
the operation, free acid always being present in solutions of
chromium sulfate ((^2(804)3). This acid appears to be necessary
to the leather, for when it is removed by neutralization the
leather becomes brittle. Under the microscope each chrome-
tanned fibre looks like a transparent rod of green glass. If the op-
eration is properly performed, there is no precipitation of chro-
mium on the surfaces of the fibres, but only a direct combination
of chromium with collagen, which is practically uniform through-
out the substance of each fibre. Ordinarily, 100 grams of collagen
combine with about 7 grams of chromic oxide (Q^Os). In
chrome tanning the collagen fibres combine with only 11 per
cent as much material by weight as in vegetable tanning, which
explains the greater fullness and solidity of the vegetable-tanned
leather.
If leather is permitted to dry without further treatment, im-
mediately after tanning it becomes very stiff. In order to make
846 SCHOOL SCIENCE AND MATHEMATICS

the leather soft and pliable, oils are incorporated in it by tum-

bling the tanned skins in a warm emulsion of oil-in-water. The
tiny oil globules cover the surfaces of the leather and during the
subsequent period of drying, the oil slowly diffuses through the
leather, lubricating the fibres so that they slip easily over one
another. This results in the leather being pliable and increases
its strength. The leather is then dyed to give it the desired color
This is usually done by putting the skins into a revolving drum
and pouring the dye liquor on them through a hollow axle in the
drum.
The skins are finally treated with a sizing material, that is a
filler, such as gelatine and casein in order to give them the de-
sired lustre. This operation is referred to commercially as finish-
ing. Incidentally, the skins are subjected to a score of mechan-
ical operations designed to adjust the many physical properties
of the finished leather and these demand the attention of highly
skilled artisans.
, In the tannery wherein the above described processes are car-
ried out, a rather large staff of chemists is ordinarily employed.
As in every other industry it has been necessary during the
past several years to carry on these processes under the supervi-
sion of considerably curtailed chemical staffs. One group of
chemists usually analyzes all incoming material in order to in-
sure constancy of composition; another analyzes all liquors and
skins at the various stages in order to control and guarantee uni-
formity of operation; and a third group is constantly seeking
new ideas and experimenting in order to improve the processes.
There are undoubtedly few industries which present to the
chemist, problems which are so complicated as those of the
leather industry. This very fact however makes the leather in-
dustry one which offers unusual promises of reward to the
chemist who is outstanding in the fundamental knowledge of his
profession.
OPPORTUNITIES FOR THE RESEARCH CHEMIST
Before bringing this paper to a close it might be advantageous
to point out briefly some of the opportunities for research that
are to be found in the leather industry. For example there is a
problem of why so long a time is necessary to bring about the
combination between collagen and tannin. The apparent answer
is that the tannin must come into contact with the collagen be-
fore it can combine with it and that tannin diffuses throughout
 THE MANUFACTURE OF LEATHER 847

the substance of a hide ever so slowly. It has been discovered

however that this rate of diffusion can be changed by adjusting
the acidity of the tanning liquor or by adding certain non-tan-
ning substances. But not a great deal of information is availa-
ble. There still remains much work of an investigative character
for the chemist to do.
In the beamhouse too, the time required to get rid of the un-
desirable portion of the hide is too long. Some substance should
be found to quickly dissolve all material except the collagen
fibres used in making the final leather.
These are but two of many problems confronting the chemist
in the leather industry. What a rich field for the chemist with an
investigative mind!
LITERATURE CITED
1. Adcock, K. J. Leather: From the Raw Material to the Finished Product.
Sir Isaac Pitman and Sons, London.
2. Howe, H. E. Chemistry in Industry, Vol. I. H. E. Howe, Editor. The
Chemical Foundation, Inc., New York.
3. Proctor, H. R. The Making of Leather, Cambridge University Press,
London.
4. Proctor, H. R. Principles of Leather Manufacture. D. Van Nostrand
Company, New York.
5. Proctor, H. R. Leather Industries Laboratory Book, Spon and Chamber-
lain, New York.
6. Wilson, John Arthur. The Chemistry of Leather Manufacture. American
Chemical Society Monograph. The Chemical Catalog Company, New
York.

AMERICAN MATHEMATICAL SOCIETY

The Forty-eighth Annual Meeting of the American Mathematical So-
ciety will be held at Lehigh University, Bethlehem, Pennsylvania, Monday
to Wednesday, December 29-31, 1941, in conjunction with meetings of the
Mathematical Association of America, the Association for Symbolic Logic,
and the National Council of Teachers of Mathematics.
The sessions of the Society will begin Monday afternoon and continue
through Wednesday afternoon.
The sessions of the Mathematical Association will be held Thursday
morning and afternoon. The Association for Symbolic Logic will hold its
meetings on Wednesday, one of which will be a joint session with the So-
ciety.

The history of science shows, that the greatest advances have always
been made by men who undertook their inquiries into Nature without
thought of proximate or ultimate practical application or pecuniary re-
[Link] Gregory.