LEATHER

LEATHER - any animal hide or skin that has been processed for use by man.

Animal skin that has been processed to retain its flexibility, toughness, and waterproof
nature is known as leather.

Large animals are said to have HIDES, while small animals have SKINS. In either
case, the hide or skin is composed of water and proteins and unless preserved, decays
quickly.

Fresh hides are (by weight)

60-70% water,
30-35% proteins (both fibrous and non-fibrous),
2% lipids,
0.5% carbohydrates,
1% mineral salts and other substances (i.e. pigments).

Main Steps of Processing of Hides:

The four steps of processing hides and skins are

1. Curing
2. Beamhouse Operations which wash and soak the hides or skins and remove
the hairs
3. Tanyard processes in which the tanning agent reacts with and stabilize the
proteinaceous matter in hides or skins
4. Finishing or post tanning processes.

1. CURING is the process of dehydrating the hide without disturbing the skin structure.
This is necessary because within hours of slaughter, decay begins. The hides contain
about 60-70 % water and such a high quantity of moisture help the bacteria and mould
to grow which leads to decomposition of protein. Hides need to be protected against
excessive heat, humidity, rain and pests.

For long-term preservation (up to six months)

A. Air Drying - proceed with caution, this produces a bony flint hide
B. Salting
1) Brined - treating the hide with a saturated solution of salt
2) Wet Salted - rubbing the flesh side with salt
3) Dry Salted - Air drying after doing B1 or B2
 C. Pickling (Salt and Alum)
1) Brined - soaking the hide in an Alum/Salt Solution
2) Wet Pickling - rubbing the flesh side with salt and alum (2:1 ratio)

Methods for short-term preservation (2 – 5 days) are cooling, using crushed ice or
refrigerated storage, and biocides. Sod. Metabisulfite, boric acid and naphthalene (1 – 2
% of salt weight) are also added to prevent from bacteria attack. Biocides are also being
used as an alternative to salt. Some insecticides are also sprayed to prevent attack from
insects and beetles.

BEAMHOUSE OPERATIONS:
1. SOAKING

The main objectives of soaking the hide are

 To restore it to its natural condition as on the living animal with water content of
approximately 65%.
 To clean up of the surface of the hide. Manure, urine and blood generally
contaminate the typical hide. Animal skins are naturally contaminated with soil,
dust and sand from normal activities of the animals during grazing and on the
feedlot.
 To remove salt some of which adheres to the outside of the hide and the rest
that is well penetrated in the entire cross section of the hide.

Salted hides, fresh hides and chilled hides all require several washings with fresh water
under strong mechanical action for proper cleaning. Drums, mixers and paddles can be
used and the wash float should be changed at least twice with fresh water after 30 to 60
minutes of drumming. The drum is turned intermittently during the normal soaking
period.

The process is mostly carried out in two steps: a dirt soak to remove the salt and dirt,
and a main soak. The duration of soaking can range from several hours to a few days.
Salted hides need about 5 hours of drum soaking and dried hides and skins may need
24 hours or more.

The soak water removes the salt, some proteins, some loose fat, blood, dirt, and
manure. The effect of washing can be followed by observing the color of the wash float.
The first wash float is brown and appears to have a high content of solubles and solids.
The color comes from blood and from manure. With each change in float it becomes
clearer and more colorless.

Full rehydration of fiber structure is most important precondition for all of the
beamhouse operations. Liming cannot substitute for insufficient soaking. The hide has
to reach as nearly as possible the state of suppleness it had when it was freshly flayed
from the animal.
Soaking in the final rehydration float is currently enhanced by adding either 0.3%
sodium hydroxide, (NaOH), or surface active agents and sometimes proteloytic
enzymes. In many cases small amounts of bactericides are added.

The addition of NaOH has to be made properly. The purpose is only to adjust the float
to a slightly alkaline pH. Addition of too much alkali and/or poor mixing may result in hair
immunization. Elevated temperatures up to 32 °C speed up the soaking. The warmth
helps to make the fiber structure more flexible however water uptake is somewhat less
than it would be at 15 °C.

2. UNHARING AND LIMING

The process of unhairing is the first major step in leather making. The pelt has to be
freed of the epidermis and hair, including the hair roots, and the keratinous material
filling the hair follicles before proceeding with the next step. The majority of leathers
produced are treated in order to remove the hair or wool to leave the characteristic
pattern of the grain surface.

The S-S bridges of the keratin can be split by reduction or oxidation quite selectively
without influencing the collagen fiber network. The keratin structure may partially break
down forming a pulp or dissolve completely, leading to a clean pelt surface with the
assistance of mechanical action on the hides that can suspend the hair sludge and
empty the hair follicles completely.

Reduction can be performed by almost any kind of reductive agents, preferably under
alkaline conditions. The most widely used compounds are reductive sulfur- or thio-
compounds. They act by exchanging with one of the sulfur atoms in the disulfide bridge
of cystine. The most widely used unhairing agents in the leather industry today are
sodium sulfide (Na2S) or the half neutralized form sodium hydrogen sulfide (NaHS).

Alternatives to inorganic sulphides include organic compounds such as Mercaptan or

sodium thioglycolate in combination with strong alkali and amino compounds.
Enzymatic preparations are sometimes added to improve the performance of the
process. Fats are hydrolyzed due to the increased pH and the skin structure swells as
water is drawn into the fibre network to form a dull, open-structured, translucent, jelly-
like material.

The unhairing process is usually not separated from the liming process. It is generally
done in a rotating vessel such as a drum or mixer in a float containing 3 to 4 % lime
hydrate (Ca [OH]2) and 1 to 3 % sodium sulfide technical grade.

Unhairing is done in some tanneries in a paddle using an even higher float, because it is
easier to drain. The combined unhairing and liming operation requires from 14 to 24
hours at room temperature to complete. The mechanical movement of the hide during
the process rubs off the pulped hairs and helps to free the hair roots from deep within
the hair follicle. At the same time the structure undergoes swelling and opening.

The conditions of unhairing with respect to time, temperature and concentration

of sulfide and alkalinity have a strong influence on the unhairing and the opening
effect on the collagen fiber structure.

Removal of the intact hair is facilitated and the process is referred to as a hair saving
process. Hair saving processes results in a cleaner grain than in the destruction, hair
burn process, because the hair roots remain more or less intact and are removed by
mechanical action.
The limed and dehaired hide is now called pelt. Soaking and liming are carried out in
one process, which typically lasts from 24 to 36 hours.

The extent of swelling, measured by increasing thickness and uptake of water (which
means an increase in weight) depends greatly on the given structure.
Hides from older animals are much more cross linked and may swell much less than a
hide of a young animal under the same conditions

3. TRIMMING AND FLESHING:

The limed hides not fleshed before curing are usually trimmed and fleshed at this point
in the production.
In the fleshing, excess flesh and fatty tissue from under the pelt is removed
mechanically. The fleshing is done on a multi roller machine that pulls the hide over a
rotating blade, similar to rolling machine that cuts off the flesh from the inside of the
hide. The machine includes a rubber roller that holds the hide near the rotating fleshing
blades.

Afterwards, the defleshed pelt is trimmed. During this process, the sections of the root
of the tail, the navel, the kneecaps, and other unwanted parts of the hide are cut off.
The trimming is done by hand to remove any portion of the hide that could interfere with
the subsequent machine processes, e.g.: the shanks, ears, and snout.
 4. SPLITTING:
In splitting the hides are cut to the desired thickness with a horizontal belt knife. The
hides are fed in to the machine grain up. The clearance between the grain and the
blade is maintained by a series of narrow rollers supported by a rubber roller
underneath the spacing rollers. The grain layer is then cut to the thickness desired to an
accuracy of about 0.1mm.
The grain layer is most valuable part of the hide and serves as the outside of the shoe.
Splitting allows the grain layer to spread to the maximum area yield and also allows an
efficient use of the valuable tanning chemicals.

5. DELIMING

The limed hides have a pH around 12. Because chrome tanning is done at pH 2-4 , the
lime must be removed for pH adjustment After liming in strong alkali the alkalinity has to
be reduced to neutrality, what is called deliming operation. The aims of deliming are
eliminating swelling and the removal of mechanically deposited lime, chemically bound
lime and of capillary lime by conversion into readily soluble salts.

For deliming, ammonium salts and acids are used. The proportion of ammonium salts to
acids and the type of acids employed is a matter of tanners’ choice. The acid
neutralizes the lime, Ca (OH) 2, there by adjusting the PH. The ammonium salts have
two functions: to buffer the solution to a pH required for bating and to form calcium
ammonium complexes. The acidity and the complexes’ formation solublize the calcium
and serve to bring the hide to the desired pH.

The extent of deliming to be achieved depends on the type of final leather; a thorough
deliming results in softer leather, whilst partial deliming gives firmer leather. At this
stage, the hides and skins are ready for vegetable tanning but, for chrome tanning, the
delimed hides and skins have to be further processed by bating and pickling. Delimed
skins must be taken to the next process immediately, as once the alkali has been
removed, putrefying bacteria can thrive.

TANYARD OPERATIONS:
1. PICKLING

The purpose of pickling is to acidify the pelts to a certain pH before chrome tannage and
thus to reduce the spoiling of the chrome tanning agents. Pickling is also used for
preserving. Chemicals include 5 - 10 % of common salt (sodium chloride) or sodium
sulfate and 0.6 -1.5 % acid (sulfuric, hydrochloric, acetic or formic, or mixtures).

During neutralization of the pelts in the pickling unit, the pH of the collagen has to be
shifted to the isoelectric point and the state of swelling has to be changed.

Reversing swelling is much more difficult, because a hide swelled in sodium hydroxide
cannot be reversed by offering strong acids. Therefore weak acids or acidic salts are
used. Boric acid, ammonium sulfate, sodium bisulfate, and very recently sodium
bicarbonate or carbon dioxide has been proven in practice. They can be offered in
excess without causing acid swelling. A most important point is, that the float should be
as short as possible, to obtain the highest concentration possible of the neutralizing
agents.

2. BATING

Bating is a part of the deliming step in cattle hide leather production. The hides contain
some elastins proteins which are very inert to the action of acids and bases and react to
tanning chemicals in a limited manner if the elastins are not broken down sufficiently.
The leather may be firm and stiff for the desired use, and the grain may not be as
smooth as desired. The bating enzymes and the pH adjustment disperse much of the
degradation products from the unhairing. The resulting hides are clean and flaccid

Bating is an enzymatic process which has the purpose of further loosening and
peptizing of the fiber texture of the skin and elimination of alkali-swelling.

Enzymes are biological catalysts which accelerate the reactions without themselves
being modified. They act specifically on proteins called proteases. Current enzymatic
treatment employs 0.5 % bating material for 30 minutes up to 12 hours. The bating
material is typically composed of 50 % wood flour or other carrier, 30 % deliming agent
(ammonium chloride), and 1 - 5 % pancreatic enzyme.

Temperature influences the bating effect. The rate of enzymatic reaction increases with
rising temperature. Bating temperatures used in practice are about 30 - 37 °C.

Deswelling is enhanced by higher temperatures in the bath. Here it is wise to take

advantage of the inverse temperature dependency of swelling. The enzymatic bating
process completes not only the deswelling of the hide but also the process of deliming
liberating additional calcium ions.
The following signs appearing on the bated pelts will indicate the effect of proper bating:

 The grain of bated pelt should feel like silky and slippery
 The thumb impression should be retained on the grain when pressed
 The pelt should be white, clean and porous
 The pelt should be perfectly fallen and flaccid
 The flesh should come off easily when scratched from finger nail

3. PICKLING
The bated pelts are finally treated with acid (commonly sulphuric and/or formic acid) to
obtain the desired pH for optimal penetration of the tanning agent, and with salt, to
suppress swelling when the acid is added. Delimed and bated pelts have a pH of 7.5 to
8.5. If they are treated with chrome tanning agent at this pH then the acidity of chrome
will be used to neutralize the alkalinity of pelt, making the chrome tanning agent basic
and which precipitate at this neutral pH and deposit on the surface of the pelt thus
nullifying the tanning action. When the hide has reached a pH-value of about 3
throughout its full width, it is ready for the adding of the tanning agent.

TANNING OF LEATHER

The process of tanning is to retain the skin's natural properties, to stabilise its structure
and at the same time to chemically process it so it will no longer be subject to
putrefecation. Thus leather is animal skin that has been treated such that its natural
properties are retained.
In addition, the process of tanning imparts the advantage of resistance to heat. This is
an important factor in many of the uses of leather. In conjunction with chemical
processing, the tanner imparts colour, texture and finish to the leather, to enhance its
appearance and suit it to today's fashion requirements.

Hides and skins are primarily composed of water, protein and fatty materials. The most
important protein in the production of leather is collagen, which makes up approximately
29% of the mass of a freshly flayed hide. The collagen desirable for tanning is found in
the grain and reticular layers where it is "intimately woven" in a three-dimensional mesh
that is think and tightly woven in the grain and coarser and stronger in the reticular
layer.

The main objective of tanning is to convert animal skins or hides into commercial
product termed leather. Hides and skins have the ability to absorb tannic acid and other
chemical substances that
 prevent them from decaying,
 make them resistant to wetting, and
 Keep them supple and durable.

During tanning protein is altered in chemical composition so as to make it more resistant

to heat and hydrolysis. Until it is tanned, the hide is perishable. Only by tanning is the
hide preserved and made durable.
Tanning is essentially the reaction of collagen fibers in the hide with tannins, chromium,
alum, or other chemical agents.
The materials used for this purpose are called tanning agents.
The majority of tanning agents fall into one of the following groups:

 Mineral tannages e.g. chromium, titanium, aluminium, zirconium

 Vegetable tannins (extracted from specific tree barks)
 Syntans (Synthetic Tanning agents or Retanning agents)
 Aldehydes
 Oil tannage.
In the vegetable tanning process, the concentration of the tanning materials starts out
low and is gradually increased as the tannage proceeds. It usually takes 3 weeks for the
tanning material to penetrate to the center of the hide. The skins or hides are then
wrung and may be cropped or split; heavy hides may be retanned and scrubbed. For
sole leather, the hides are commonly dipped in vats or drums containing sodium
bicarbonate or sulfuric acid for bleaching and removal of surface tannins. Materials such
as lignosulfate, corn sugar, oils, and specialty chemicals may be added to the leather.
The leather is then set out to smooth and dry and may then undergo further finishing
steps.
CHROME TANNING
Chrome tanning is the most widely used tannery system worldwide. It has the
advantages of light color, speed of processing, low costs and great stability of the
resulting leather. Chrome tanned leather is so stable that exposure to boiling water for
short (<2-3 minutes) periods of time usually shows no adverse effect.
Tanning refers to a specific reaction of the tanning chemicals combining with the hide or
skin to stabilize the protein and make it resistant to bacterial degradation. Tanned
leather is so biorefractive that leathers even centuries old found under adverse natural
storage conditions are often in almost usable condition.
Chrome tanning is done in a drum similar to that used for deliming. The salt solution
from the pickle is present and the solution is at about pH 2.0. The chrome tanning
material is usually a basic chromium sulfate. The general formula for the most common
commercial chrome tanning product is 2Cr(OH)SO4,Na2 SO4.After the addition of the
chrome tanning salts, the pH of the solution rises to about 2.5. At this PH the chrome
salt is taken up by the hide and the tannage begins.
At a pH > 3.0 the reactivity of the hide to the chromium complex is greatly increased.
The pH is therefore raised gradually to the desired point by addition of a mild alkali,
usually sodium bicarbonate. The chrome tanned leather is removed from the drum and
wrung to remove the absorbed tanning solution. The leather is then inspected for quality
of the grain and other characteristics of importance for the leather being made. In large
tanneries where very uniform hides are worked, the leather may be trimmed and split to
the desired thickness. Hides split before tanning need no splitting at this point.
Chromium is the most widely used and the most eco-friendly tanning agent available.
Chromium is a natural, non-toxic element and is actually a micronutrient found in our
food. Chrome-tanned leather tends to be

 Softer and more pliable than vegetable-tanned leather,

 Has higher thermal stability,
 Is very stable in water, and
 Takes less time to produce than vegetable-tanned leather.
 It produces leather that combines to the best advantage, most of the chemical
and physical properties desired by the end user.

Chrome tanning is performed using a one-bath process that is based on the reaction
between the hide and a trivalent chromium salt, usually a basic chromium sulfate. In the
typical one bath process, the hides are in a pickled state at a pH of 3 or lower, the
chrome tanning materials are introduced, and the pH is raised.

Following tanning, the chrome tanned leather is piled down, wrung, and graded for the
thickness and quality, split into flesh and grain layers, and shaved to the desired
thickness. The grain leathers from the shaving machine are then separated for
retanning, dyeing, and fatliquoring.
Chromium tanned hides or Wetblue are often retanned - during that process the
desirable properties of more than one tanning agent are combined. Synthetic tanning
agents in retanning of wet blue leather help to modify the physical properties of leather
with respect to its strength, softness, fullness, weather resistance, dye penetration,
levelness and brilliance of dye shades, grain characteristics etc. towards meeting
the end use of leather for use as shoe-upper leather, garment leather, bag leather,
furniture upholstery leather, car upholstery leather etc.
POST TANNING OPERATIONS
This stage includes preparing the retanned material for finishing by processing through
to dried crust.
1. Retanning, Coloring and Fatiliquoring
Chrome-tanned leather is light blue in color. The fibers are only stabilized against
microbial action and do not have feel of leather. If the leather were dried at this point
only a stiff unattractive product would result. The characteristics of desired leather result
from the retanning, coloring, and fatiliquoring.

Dyeing
Leather that is not subject to scuffs and scratches can be dyed on the surface only. For
other types of leather (i.e. shoe leather) the dye must penetrate further into the leather.
Typical dyestuffs are aniline-based compounds that combine with the skin to form an
insoluble compound.
Chromium tanned leather is blue in colour and must be dyed to obtain the desired
colour. The dye acts as a base colour for finishing, and the depth of dye penetration and
leather colour are of great importance.

Fatliquoring

Chromium tanned material dries out hard and crusty and is unsuitable for most
purposes. Small quantities of oil, present as emulsions known as fatliquors, make a
significant difference to the handle, i.e. the fullness, softness and flexibility, among other
factors.
Fatliquoring is the process of introducing oil into the skin before the leather is dried to
replace the natural oils lost in beamhouse and tanyard processes. Fatliquoring is
usually performed in a drum using an oil emulsion at temperatures of about 60 oC to
66oC for 30 to 40 minutes.
 2. Drying
The retanning, dyeing and fatliquoring chemicals are allowed to penetrate and distribute
within the collagen fibre structure before the pH is lowered and the astringency causes
them to "fix" to the tanned material. The final binding of chemicals is encouraged by the
drying process. Batches of leather are commonly toggle dried on frames in heated
tunnels for four to six hours or are vacuum dried individually for two to ten minutes.
Drying is usually followed by buffing, conditioning and staking or milling. The resultant
curst material is resistant to microbial attack and contains all the leathering properties
desired of leather and is ready for finishing.

3. Finishing
A finish process and finishing chemical must be carefully designed and "married" with
the production of the curst to ensure compatibility. The finish may be required to hide
defects, to contribute to the leather beauty and properties and to provide fashion effects.
Resins, pigments, dyes, handle modifiers, fillers, dullers and other chemicals are added
in layers to the surface of the leather by spraying, roller-coating, curtain-coating or by
hand. Heated hydraulic or roller presses are used to produce smooth or patterned
leathers, depending on customer requirements. Finishing finally completes the leather
manufacturing process and the area is then measured and the leather sent for dispatch
to a product manufacturer to be turned into shoes, clothing or upholstery.

Vegetable tanning agents

Extracts from different types of trees, bark and fallen fruit contain tanning agents used
for vegetable tanning. In particular, the mimosa and quebracho trees, along with the
fallen fruit of the tara tree in South America, make up some of today's principal tanning
agents. Vegetable tanning agents make for full, robust and compact leather.

Synthetic tanning agents

Synthetic tanning agents do not occur naturally in the environment, but are
manufactured using chemicals. Synthetic tanning agents like formaldehyde,
glutaraldehyde, phenols, uric acid and its derivatives as well as acrylates are highly
effective in the tanning process.

As a general rule, synthetic tanning agents are not used on their own, but often give an
interesting result when used together with chrome or vegetable tanning agents. This is
called combination tanning.