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 Table of Content
Sr# topics Page#
STEPS IN LEATHER PROCESSING
Neutralizing, Dying, Fat Liquoring
1 Introduction 3
2 NEUTRALIZING 3-7
2.1)Definition
2.2)Purposes
2.3)Observable Defects on the Leather Due to Neutralization
Errors
3 DYEING 8-11
3.1)Definition Of Dyes
3.2) Leather Dyeing and Its Purposes
3.3)Methods of Dyeing
3.3.1)The Leather is Dyed by Soaking the Leather in big Barrels of Dye
3.3.2)Dip Leather Dyeing:
3.3.3)Brush and Sponge Leather Dyeing:
3.3.4)Spray Leather Dyeing

4 FATLIQUORS AND FATLIQUORING PROCESS 12-14

4.2)Sources Of Oils/Fats/Waxes
4.3)Fatliquoring.
4.3.1) Purposes
4.3.2)Chemistry of fatliquoring
4.4) Classification of fatliqouring agents
4.4.1)the emulsion type fatliquoring
4.4.2)the non-emulsion type fatliquoring

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 STEPS IN LEATHER PROCESSING
Neutralizing, Dying, Fat Liquoring
1)INTRODUCTION
Leather is a durable and a flexible material created by converting animal raw hide and skins. It is
created through a process known as tanning where the raw hide and skins are converted to non-
putrescible material which resist bacterial attack, chemical degradation and resist mechanical
deformation. The material gains hydrothermal stability, good breathability, durability, high
strength among others characteristics. The leather stability is attributed to the strong interlocking
of the collagen fibers with the tanning agent which can either be organic or inorganic.The
processing of hide and skin involves different process and operations such as preservation stage,
pretanning operations, tanning operations, post tanning and finishing to get the desired features of
the leather. I have discussed the following highlighted steps.

International Journal of Scientific and Research Publications, Volume 9, Issue 12, December
2019 213 ISSN 2250-3153

2)Neutralizing:
2.1)Definition:
Chemical neutralization is relatively a more thorough deacidification of mineral tanned leather
with mild neutralizing salts than the simple surface flooding off of the free acids, unbound basic
chromes and acids attached with them. If we need our ultimate leather to be softer, level dyed, well
lubricated, inner fibers are full and round, relatively complete neutralization is a must.

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2.2)Purposes:
 To remove collagen bound and some free acids which still reside on the skin surface (even
after washing) and which are found in the inner fibers.
 To remove unfixed chrome and the acid groups associated with it.
 To reduce the acids and unbound chromes that adversely affect the uniformity of the main
processes of dyeing, retanning and fatliquoring etc. as we usually use anionic nature of
such chemicals.
 To improve the aesthetic value of the ultimate leather, i.e, the physical properties of leather
such as grain character, surface feel, fullness, strength and dye take up can be adversely
affected if the acids are still there.
 the excessive positive charge must be removed for smooth reaction with any anionic
substances to come.
 To make the users and the leather itself safe from acid damage or rot.
 To improve the quality and character of the final leather. These mild neutralizing salts not
only neutralize the free acids and basic chromes from the leather but also replace or
substitute the aquo and sulphato groups /ligands/ in the collagenchromium complexes. That
is, there will also be reaction between the anions of the neutralizing agents and the
chromium in the leather by the introduction of the fairly complex organic groups into a
chromium compound in displacement or substitution of the acidity (sulphuric) in the
leather.
This improves the physical properties and processing behaviors of the leather (feel, grain
character, level dyeing, improved take up of fats and tannins). These mild alkaline salts give anions
that able to enter into the complex of chrome tanning compounds displaying masking effects. The
anions such as acetates, formates, lactates, phthalates, adipates, diglycolates etc. have very mild
alkalinity on the grain. In addition, they can modify (reduce) the affinity of the leather towards the
anions of the dyes, synthetic or natural tannins, anionic emulsifiers etc. This results in deep
penetration and even or uniform distribution of these chemicals.

Table 1: Selected Commercial Mild Neutralizing Salts and Their Properties

Product Properties Remark

Soda ash(Na2CO3) Danger of excessive Seldom used, except for some

neutralization, because of type of suede
superficial action and have
detanning effect

Sodium bicarbonate(NaHCO3) Good penetrative power. Danger Don’t use more than 2% based
of excessive neutralization only on shaved weight
when large amounts are used.
Don’t dissolve above 35ºC,

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 because otherwise soda
formation.

Borax(Na2B4O7.10H2O) Danger of excessive Don’t use for overnight

neutralization is similar to use of neutralization
soda. Acts somewhat milder at
the beginning but on the
prolonged treatment the alkaline
effect can be higher than that of
soda.

Sodium sulphite(Na2SO3) Mild neutralizing agent with Don’t use for pastel shades as it
uniform penetrative power has greenish effects

Sodium thiosulphate(Na2S2O3) Has poor neutralizing power. Mainly used for white and light
Thus used in large amounts. colors, as golf glove
Besides, it can lighten leather
colors by deposition of
sulphur(bleaching out)

Sodium formate(HCOONa) Rapidly penetrative and mild Mostly used in conjunction with
neutralizing agent. No excessive NaHCO3
neutralization even if large
amounts are used

Calcium formate((HCOO)2Ca) Mild neutralizing agent. No May produce CaSO4 stain

excessive neutralization. But
there exists interference by
formation of CaSO4

Tanigan PAK-S(Bayer synthetic Strong neutralizing and Use in conjunction with

product) buffering synthetic salt. It has HCOONa &NaHCO3
also retanning effect

Neutrigan(BASF synthetic 7.5-8.0 Mild neutralizing agent Use in conjunction with

product) with masking and buffering HCOONa &NaHCO3
effect. No excessive
neutralization problem.

All neutralizing agents mentioned above and other plain alkalis like caustic soda can remove
collagen bound acids fairly quickly, raise the PH of the leather.
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a)Alkalinity of Neutralizing Salts: Higher acidity of tanned collagen (whether it be free,
bound with collagen or the basic chrome itself) prevent the subsequent processes such as deep
penetration, even dyeing, emulsion of fats and selective deposition of organic retanning materials,
if especially anionic species, in and on the leather. These problems can occur if the PH of the media
is usually less than 4.3. On the contrary, if we use high alkaline media or if we neutralize with
plain alkalis like soda ash or caustic soda that results in sudden PH rise, detanning effect can result.
That is, the collagen— chrome complex is sensitive to rush PH change (especially to PH higher
than 5.0—5.2) and to a higher PH even if gradual PH change in the presence of buffering agents.
Thus, if we treat chrome tanned leather with some plain alkali, as the PH of the leather rises, the
free acids and the radicals outside the chrome complex are neutralized. In parallel, the acido groups
(SO4 --or HCOO-) inside the chrome complex are started to be replaced by the hydroxo (OH-)
groups. But don’t forget that the tanning effect of the chrome salt depends up on the optimum
proportion of the hydroxo groups in relation to the acido groups in chrome compounds, which is
known as basicity figure. But if the PH rises still higher (because we have stronger base), the bond
between collagen—chromium acid complex is affected due to the rapture of the bond which results
in detanning or chrome precipitation in the form of Cr(OH)3, due to the replacement reaction.
Over neutralization due to high concentration of OH-(and hence higher PH) can result in detanning
in the neutralization bath. Due to higher replacement of acid radicals like acetate, formate, or
sulphate by hydroxyl groups, the leather character can change (becomes hard, loose or empty,
coarse and brittle or weak grain). E.G: Neutralization of wet blue especially by soda or borax
particularly for soft nappa type can over neutralize the outer layer leaving the inner zone least
affected which in turn result in zonal difference in retanning, dyeing and fatliquoring, and hence
affects the fullness, softness, levelness etc. of the final leather.

b) Temperature: If the temperature of the neutralizing bath is above some limits, say above
35ºc,the neutralizing salts shall be over-activated (E.g. NaHCO3 can be changed into Na2CO3)and
hence results in superficial and over-neutralization .Cold neutralization doesn’t help the process
effectually as the solubility of the neutralizing salt, especially the organic base, is reduced.
Practically, the temperature range of 33--40ºc is important and especially at the higher extreme
range, hydrolysis of chrome salt is increased and hence accelerating diffusion of acids formed by
the hydrolysis. Besides, the neutralizing salts(formate, acetate, phthalate, glycolate etc.) which
involve no precipitation with chrome solution penetrate into the chrome-leather complex faster
(within 30 minutes) and attain equilibrium at a PH of about 4.5—5.0. But as mentioned above, this
elevated temperature is only suitable for aliphatic and aromatic complexing or neutralizing agents,
not for borax, soda ash or ammonium bicarbonates which should be <35ºas otherwise causes
chrome precipitation or over neutralization.

c) Chemicals: Generally, simple acid radicals or plain alkalis with less buffering and masking
capacity tend to break down the chrome complexes. On the contrary, too much masking or chrome
complexing and hence excessive stability can pose/create other difficulties such a reduction in
affinity for dyes, vegetable and synthetic retanning agents , difficulties in exhaustion of fatliquors
and ultimately production of loose and spongy leather with higher water absorption which in turn
resulting in difficulty of finishing . Hence, it is recommended to use a combination of radicals
that give stable chrome complex, mild alkalinity and optimum masking and buffering:
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 Organic neutralizing salt/ formate +NaHCO3 or Organic neutralizing salt/formate +NH4CO3 or
Organic neutralizing salt/formate +synthetic neutralizing agent +NaHCO3 etc. Note also that those
anions of monocarboxylic acids (acetate, formate etc.) can form stable complexes and have good
masking effect; but relatively with less filling effect.
However, anions of polycarboxylic acids (phthalates, diglycolates) have both filling and masking
effects. Besides, neutralized synthetic tanning agents , either naphthalene base or based on highly
aggregated aromatic sulpho-acid condensation products are used for neutralizing, buffering and
filling agents as they have tanning effects as well as grain tightening and dye leveling power.
These neutralized syntans or salts act as neutralizing agents as the possible carried over strong acid
(H2SO4) from chrome leather is consumed by the syntans to release the weaker tanning sulphonic
acid with the by-product of Na2SO4; Na + comes from the neutralized syntan salt, H+ goes to the
amine group of collagen to form__NH3+ and then the anion group sulphones will react to __NH3+
of the collagen, and as result, the overall acidity of the leather is reduced or consumed, hence
neutralization.
After processing, cut off a small piece of leather from a section of denser texture (usually from
neck area).Then let a 0.1% indicator solution of bromo cresol green /BCG/ (dissolved in 50%
alcohol), drip on to the cross section. Interpretation: If the color of the cut shows pure blue, the
PH of the crosssection is expected to be about 5.5 and above and this range of neutralization is
suitable for products such as softie nappa garments, gloves, suede, upholstery and some pastel
shades. - If the color of the cut shows bluish –green, the PH is expected to be about 5.0 with
intermediate range of neutralization which is especially suitable for box side upper type. - If the
color of the cut indicates pure green or yellowish green, the PH is about 4.0 and neutralization is
not good, and needs corrective measure.

2.3)Observable Defects on the Leather Due to Neutralization Errors:

a) Inadequate Deacidification: Results in the middle zone of the cross section remain
unneutralized .Thus, clearly the following problems are observed in the process or on the leather:
Astringent retanning agents diffuse only with difficulty into this middle zone (You can have a look
at a white streak on the leather, especially in dyeing).Fat emulsions crack in this zone and cause
smudging/staining and fat stain. In the leather the free acid migrates into the outer zone, causing
corrosion at metal parts of final products. Fatty spew may also occur to a greater extent.
b)Over Neutralization and over masking: Results in detanning of the grain zone and thus result
in loose grain, strawy, brittle grain or in unfavorable cases even crackiness of the grain.
Furthermore, it may lead to uneven, pale and thin dyeing.

3)DYEING

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The concept of dye and dyeing is directly related to the concept of light and color. Color is simply
a reflected or composite reflected light rays.

3.1)Definition Of Dyes: Dyes are complex, natural or synthetic, inorganic or organic solvent
soluble, colored organic compounds having the property of imparting their permanent color to
other substances such as collagen, wool, cotton fibers etc. From the definition one can recognize
that every colored compound can’t be called a dye, like beet roots. Thus, specifically, for a colored
compound to be called a dye, it must be:
 organic compounds=>not inorganic, unlike pigments
 colored compounds=>not colorless or white, unlike pigments
 capable to fix chemically by itself to other fibers permanently=>not as easily washable as
beet root nor physically coated as paint/pigment
 complex and larger in molecular size so that it can be inert or fast to be resistant for the
action of light, solvent, abrasion etc.=> not as simple as picric acid. natural origin, e.g.,
wood log dye or synthetic dye, e.g., mauve or aniline dye synthesized by Perkins from coal
tar or petrochemicals
 Soluble in a given solvent /aqueous or organic solvents/=>not insoluble.

3.2) Leather Dyeing and Its Purposes

As mentioned above dyes can impart colors to some substrates such as collagen fibers, cotton and
wools. Thus dyeing of leather is the process of imparting color to the leather fibbers. Nowadays,
many types of leathers, except some heavy leathers and some corrected leathers, are drum or spray
dyed. Dyeing of leathers has several purposes, if properly done.
1. To improve its appearance or aesthetic appeal, as color or dye can enhance the beauty of leather
or divert the psychological tendency / choice of the users towards some color of the leather/ and
then you can make your products competent in the market.
2. To make the leather adaptable to fashion style. For instance, aniline dyed leather has elegant
appearance and long lasting fashion in the leather market than heavy pigmented finish.
3. Dyeing is one of the well known value adding process steps in leather processing. The marginal
price markup after dyeing is clearly higher than the intrinsic cost incurred due to dye consumption.
4. To fulfill leather properties and customer requirements, i.e. color properties rank equally with
different leather properties such as feel, break, temper etc. factors by which most leather types are
evaluated /inspected by customers as quality parameters.
5. To upgrade leather by covering of defects.
Normally pasting refers to dissolving a dye in a little cold water until thoroughly wetted and then
further dissolving it 90OC in 1:10 or 1:20 ratio of dye to water.
=>As a result, the Secondary valence force of attraction between molecules decreases.
=> Aggregation of dye molecules decreases.

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=> Solution can be formed /the higher temperature, the lower the aggregate of dye molecules
will be. The lower the aggregate of dye molecules, the higher penetration of the dye and the
lower surface fixation will be.

3.3)Methods of Dyeing
Nowadays, the common dyeing methods include:
3.3.1)The Leather is Dyed by Soaking the Leather in big Barrels of Dye

3.3.2)Dip Leather Dyeing:

most frequently used methods for processing deep shade and drum used to not only to keep or
maintain the temperature but also develop heat as mechanical action.Usually its speed is ~ 16 – 20
RPM during dyeing. Dip dyeing can be considered as one of the traditional methods. And as the
name conveys, it consists of dipping the raw tanned leather into a bath of dye. The leather is left
to stay submerged in the bath of dye for sufficient retention time so that the dye binds itself to the
leather on the molecular level. This technique is employed by both small and large scales, though
with different approaches.

3.3.3)Brush and Sponge Leather Dyeing:

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Conventional dyeing methods can sometimes damage delicate and expensive leather, they require
gentle dyeing strategies, and that’s where this process kicks in. The process typically is done by
Brushes and Sponges, depending primarily on the sensitiveness of the leather.

Normally, brushes are used to apply the dye effectively on the leather smoothly and evenly. The
leather is spread out on a slightly convex surface to expose more surface area to cover.

For fine and delicate leathers, sponges are used to coat the dyes and solutions for a uniform and
even finish, as the brush fibers are prone to scratch off the sensitive leather.

This technique of leather dyeing is efficient in terms of minimal solvent and dye wastage, and a
relatively lower amount of paint and binders are required as compared to the conventional dyeing
methods.

3.3.4)Spray Leather Dyeing

Spray dyeing technique uses a whole assembly of machines to produce a finished product, and as
the name indicates, this method uses small nozzles to squirt the solvent directly onto the surface
of the leather evenly and smoothly. Of all the leather dyeing techniques, spray dyeing stands out
prominently because of its speed of dyeing operation, a minimal amount of dye usage, and
efficiency.

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This method uses spray guns with rotating small nozzles to apply the color and solvents to every
edge of the raw tanned leather rapidly, continuously coating the leather from every possible angle.
This efficiency of operation makes it time-saving and saves a lot of paint and solvents. This method
minimizes the need for labor by using computer precision soft wares. But the more the machinery
is used, the more frequent maintenance is required.

Out of the many stages in leather manufacturing, leather dyeing is said to have the utmost
importance in prolonging the leather’s lifespan and gives it more appeal aesthetically.

Suede is a high-quality form of leather, made from the underside of the animal hide. It’s
characterized by a soft smooth surface, and it is popular for fashion items, like shoes,
accessories, and jackets.

4)FATLIQUORS AND FATLIQUORING PROCESS

4.1)Introduction
One of the main natural constituents of the raw or untreated skins is oils & fats that make the
former flexible, heat resistant and energy source. But, these natural fats & oils should be removed
mechanically (fleshing, scudding) and chemically by degreasing for the following reasons:
 The Presence of them can accelerate skin degradation/rancidification/in storage of pickle
or wet blue
 They are not the components of the ultimate leather structure
 The fat layers prevent chemical penetration during tanning, retanning, dyeing etc
However, the undesired consequence of removing of these natural fats /oils is that the leather can
become stiff after drying, due to sticking/gluing or adhesion of fibers. Thus in order to make the
skins or leathers flexible, less stiff or soft after tanning, retanning & dyeing, artificially applying
of fats & oils (technically called fatliquoring is important.
Definitions: Fatliquors are oils, fats and waxes, synthetic or natural, plus associated products,
prepared in some way so that they become emulsifiable in water and suitable for use on leather in
a water float.
4.2)SOURCES OF OILS/FATS/WAXES:

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Natural Fatliquors/Fats & Oils:
There are a lot of natural fatliquors/fats & oils/ , such as: -
Vegetables: e.g. nut oil. Olive oils, coconut fat, carnua wax etc. - Animals: e.g. neats foot oil,
mutton tallow, lecithin oil from egg yolk or protein.
- Fish: e.g. Sperm whale oil, cod liver oil.
Synthetic oils: e.g. paraffin waxes, mineral oils, hydrocarbons of acyclic and cyclic petroleum
origin treated with chlorine or sulphochlorinated ones. If we become more specific, mineral and
synthetic oils are quite different, chemically, from fats and waxes. Synthetic oils are artificial oils,
not analogous of natural oils/fats, usually hydrocarbons, chlorinated or sulphochlorinated,
distinguishable from mineral oils by the fact that they don’t fluoresce under UV rays; and usually
detected by the presence of chlorine/copper wire test/. However, mineral oils are obtained from
petroleum crude, wholly unsaponifiable or alcohol insoluble aliphatic hydrocarbons/not aromatic
as it may cause yellowing in light rays/, before the treatment of them by the associated groups.
4.3)FATLIQUORING. - It is a process of coating the surface of fibers (or including the interior
fibers for soft leathers) of leather with a thin layer of oil/ fats or oil-in-water emulsion of oils. - It
is a treatment of leather fibers with fatty substances emulsifiable in water which are introduced
into interfibrilar spaces in an aqueous float.
4.3.1) Purposes The main objectives of fatliquoring processes include:
 To give the leather the desired softness/ to avoid hardening by drying / & handle i.e. full
and round /properties at the same time
 Correction & control of the physical properties (Additional strength) like tensile, tear splits
strength & elongation, extensibility /run or stretch/ abrasive resistance.
 Wetting properties or water repelling capacity, water proofness (oils /fats & waxes are
generally, water repellent products)
 Permeability to air & water vapor, water absorption & moisture storage capacity by
splitting of the fibers
 Resistance of thermal & electrical conductivity & chemical attack
 To make slide fibers one an other as the leather made flexed and avoid breakage in bent
 Reducing of leather density (by splitting or separation of leather fibers)
 For producing light weight leathe ,roundness property ,fluffy effect
Proper lubrication or fatliquoring gives the leather perfect physical properties like stitch tear,
tensile strength, and comfort of leather. Over lubrication will results in excessive softness and
raggy leather.Under lubrication or improper penetration ,results in a hard bony leather that may
cack in use.
4.3.2)Chemistry of fatliquoring: To allow a small amount of oil to be spread uniformly over the
large surface area of the leather, it is necessary first to dilute the oil. In an emulsion with water,
the oil is dispersed in microscopically small droplets. It is important that the drops of oil in the
water remain as an emulsion until they penetrate the leather, and not separate out as large drops or

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as a layer of oil, which could not penetrate the leather fiber and result in merely a greasy surface
layer.

4.4) Classification of fatliqouring agents

The fatliqouring agents are roughly classified in as emulsion type and non-emulsion type.

4.1)The emulsion type fatliquoring agents include anionic, cationic, amphoteric and
nonionic ones.

These oils need to be emulsified to reach inside the leather in water medium. For these purpose,
there are a wide variety of emulsifier available in the market. They are a means of dispersing the
lubricants very finely in water to enable it to penetrate into the leather. Such emulsifier should
have the desired property of allowing the emulsion to break at a point predemined by the tanner to
give him the required penetration and complete uptake of the applied lubricate. In order to do this,
they must be the anionic or cationic. Although non- ionic emulsifiers are used, it is primarily as an
adjunct to other systems.
The fat liquor consists of aqueous liquid containing oil in a state of fine dispersion. It is a three-
phase system:
a) The dispersed i.e. the oil which lubricates the leather
b) The water which is dispersion medium is the carrier of oil droplets into the leather.
c) The emulsifier which is the disperses the oil and stabilises the oil-in-water emulsion

4.2)The non-emulsion type fatliquoring agents include natural oils such as fish oil, beef
tallow oil, vegetable oil (olive oil), animal oil (beef tallow, lard and mutton tallow), wool grease,

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mineral oil, wax, paraffin wax and the like. The optimum softness is achieved by a penetrating as
well as surface fatliquor.

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Refrences:
(1) Smiechowski, K., & Lament, M. (2017). Impact of Corporate Social Responsibility (CSR)
reporting on pro-ecological actions of tanneries. Journal of Cleaner Production, 161, 991-999.
(2) Sarkar, M. Q., & Akter, N. (2008). Environmental, health and safety guidelines for small and
medium enterprises of BRAC Bank Limited. Dhaka: BRAC.
(3) Jian, Z., Shuxiang, H., Ya-Nan, W., Qiang, H., Xueping, L., Wenhua, Z., & Bi, S. (2012).
Release of Chrome in Chrome Tanning and Post Tanning Processes. Journal of the Society of
Leather Technologists and Chemists, 96(4), 157.
(4) Appiah-Brempong, M., Essandoh, H. M., Asiedu, N. Y., Dadzie, S. K., & Momade, F. W. Y.
(2020). An insight into artisanal leather making in Ghana. Journal of Leather Science and
Engineering, 2(1), 1-14.
(5) Maina, P., Ollengo, M. A., & Nthiga, E. W. (2019). Trends in leather processing: A Review.
(6) Merrill, H. B., & Niedercorn, J. G. (1929). Effect of Neutralization of Chrome Leather upon
Fat Absorption. Industrial & Engineering Chemistry, 21(4), 364-366.

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