Types of Fatliquors

Saponification Value

Saponification value (or "saponification number"/"Koettstorfer number

also referred to as "sap" in short) represents the number of milligrams
of potassium hydroxide required to saponify 1g of fat under the conditions
specified.
It is a measure of the average molecular weight (or chain length) of all
the fatty acids present.
As most of the mass of a fat/tri-ester is in the fatty acids, it allows for
comparison of the average fatty acid chain length.
The long chain fatty acids found in fats have a low saponification value
because they have a relatively fewer number of carboxylic functional
groups per unit mass of the fat as compared to short chain fatty acids.
If more moles of base are required to saponify N grams of fat then there
are more moles of the fat and the chain lengths are relatively small, given
the following relation:
Number of moles = mass of oil/relative atomic mass
 Iodine Value

The iodine value (or "iodine adsorption value" or "iodine number" or

"iodine index") in chemistry is the mass of iodine in grams that is
consumed by 100 grams of a chemical substance.
Iodine numbers are often used to determine the amount of
unsaturation in fatty acids.
This unsaturation is in the form of double bonds, which react with
iodine compounds.
The higher the iodine number, the more C=C bonds are present in the
fat.
It can be seen from the table that coconut oil is very saturated, which
means it is good for making soap.
On the other hand, linseed oil is highly unsaturated, which makes it
a drying oil, well suited for making oil paints.
 Acid Value

Acid value (or "neutralization number" or "acid number" or

"acidity") is the mass of potassium hydroxide (KOH)
in milligrams that is required to neutralize one gram
of chemical substance.
The acid number is a measure of the amount of carboxylic
acid groups in a chemical compound, such as a fatty acid, or in
a mixture of compounds.
In a typical procedure, a known amount of sample dissolved in
organic solvent (often isopropanol), is titrated with a solution of
potassium hydroxide(KOH) with known concentration and
with phenolphthalein as a color indicator.
 Hydroxyl Value

Hydroxyl value is defined as the number of milligrams of potassium

hydroxide required to neutralize the acetic acid taken up on acetylation
of one gram of a chemical substance that contains free hydroxyl groups.
Hydroxyl value is a measure of the content of free hydroxyl groups in a
chemical substance, usually expressed in units of the mass of potassium
hydroxide (KOH) in milligrams equivalent to the hydroxyl content of one
gram of the chemical substance.
The analytical method used to determine hydroxyl value traditionally
involves acetylation of the free hydroxyl groups of the substance
with acetic anhydride in pyridine solvent.
After completion of the reaction, water is added, and the remaining
unreacted acetic anhydride is converted to acetic acid and measured by
titration with potassium hydroxide.
 Objective of Fatliquoring

Softening
To prevent the fibre structure resticking during
drying
Softening
Lubrication
Reduce the friction between the fibres
 The Concept of Fatliquoring

The charge on the leather (neutralization) can affect fatliquoring

effectiveness (charge of the leather and fatliquor should be same
for penetration)
Penetrating power depends on emulsion stability
Particle size distribution an emulsion is a variable that influences
stability and penetration
Sulfonation (to make partially sulfited oils) imparts more stability
than sulfation (to make partially sulfated oils)
Softness depends on the ratio of emulsifier fraction to neutral oil
fractions
Softening is influenced by the viscosity and interfacial tension of
oils
 Mechanism of Fatliquoring

The neutral oils is transported into the pelt as an

oil-water emulsion
The emulsifying agent interacts with the leather,
reducing or eliminating its emulsifying power
The neutral oil is deposited over the fibre
structure- the level of hierarchy of structure
depends on the degree of penetration
The water is removed by drying, allowing the
neutral oil to follow over the fibre structure
 Factors Affecting Lubrication

Distribution
Diffusion
pH
Particle size
Viscosity (higher the viscous better the lubrication)
 Factors Affecting the Application of Fatliquor

High Temperature
Heating the fatliquor to the same temperature as the
water, allows the oil to break up into small drops due
to the decreased viscosity (practically 60C-especially
for vegetable tanned leathers)
Mechanical Action
For mixing the fatliquor into water, mechanical action
must be maximised, because this the way the oil is
dispersed into drops (motorised stirrer, broom handle)
Water
Formation of water in oil emulsion
 Particle Size

The particle size of the emulsion is determined by the degree

to which the oil is converted into the sulfo derivative
The bigger the sulfo to neutral oil ratio the more solubilised
the oil becomes and the particle size is reduced
Most fat liquor formulations contain about 50% neutral oil,
25% sulfo fraction and 25% water
 Difference between Sulfated and Sulfited
Fatliquors
Sulfated Sulfited
Stability Less More
Reactive More Less
Penetration Less More
Affinity More Less
SO2-4 SO32-
strength strength

Stress softness
Chemical softness

softness softness
 Anionic Fatliquors-Sulfated

For sulfating the oil must be unsaturated with

a minimum iodine value of 70
The iodine values is defined as the number of
grams of iodine absorbed by 100 g of oil or fat
Oils that have used are castor, neatsfoot, soya,
groundnut, cod (sperm oil)
 Preparation of Sulfated fatliquors

Conc sulfuric acid 10-20% added slowly to the oil with constant stirring
The temperature of the exothermic reaction must be controlled to less
than 28C (otherwise the oil can char results in darkening and the
triglyceride oil may be hydrolysed to release the fatty acids
The release of fatty acids leads to the formation of spue when the long
chain carboxylic acids migrate from the internal structure of the leather to
the grain surface, visible as white efflorescence
Altenatively mixture of sulfuric and phosphoric acid (0.8:1.0)-this process
is expensive but fast
Brine wash: Excess free acid is removed by washing the partially sulfate oil
with brine, which also separated the oil fraction from the aqueous fraction
Brine is used to avoid creating an emulsion which would happen if only
water is used
Alternatively, sodium sulfate, ammonium chloride or sulfate could be used
Neutralization: Bound and free acids are neutralised with alkali
Sulfating Reactions
 Properties of Sulfation

Anionic charges increases, hence greater affinity for cationic leather

Lubrication decreases due to the lower concentration of neutral oil
Emulsion particle size decreases
Stability of the emulsion to coagulation by acid or metal salts increases
At high sulfation, the oil functions more like wetting agent than lubricant,
hence the leather becomes more hyrophilic
The leather becomes looser in terms of break, possibly due to the
damaging effect of the sulfate species on collagen
Hydrolysing the oil to create free fatty acids increases thereby creating the
possibility of chrome soaps, fatty acid spue, poor wetting back, uneven
dyeing and poor finish adhesion
 Low level of sulfation:
Low stability of the emulsion to coagulating by acids or
metal salts.
Typically used to lubricate the outer surfaces
Drum oiling of vegetable tanned leather
Medium level of sulfation
More stable to coagulation, therefore greater potential for
penetration
Used for surface neutralized chrome leather
High level of sulfation
Used for complete neutralized chrome leather for gloving,
clothing, softee leathers
 Sulfited Oils

The requirement for the oil is unsaturation for sulfating

Preparation
Sulfitation/oxidation
Air is blown through a mixture of 100 parts of oil (COD)
and 50 parts of sodium bisulfite solution, with stirring at
60-80C
Alternatively, hydrogen peroxide may be used instead of
air
Brine wash: Washing with brine remove axcess sodium
bisulfite
There is no pH adjsutment required, due to the use of
bisulfite rather sulfur dioxide or sulfurous acid
 Properties of Sulfited Fatliquors

No charring or darkening
Higher emulsion stability to acids, hard water salts, metal ions (Al,
Cr) due to the presence of sulfonate and hydroxysulfonate groups
and the low level of free fatty acids or soaps,
The fatliquor may be formulated with non-ionic detergent, to
increase emulsion stability, to promote better penetration, to make
the leather softer and fuller
There is a danger of giving the leather loose break
Softness and strength for all leathers by deep penetration
Woolskins and furskins in mineral tanning baths
In shrunken grain production, to minimise loss of tensile strength in
the acidic tanning bath
 Soap Fatliquors

Raw oil (neatsfoot oil) is emulsified with soft soap e.g. potassium
oleate
The emulsions have a large particle size, due to their tendency to
have low stability to water hardness and acid
The formulation typically has pH 8.
At pH less than 6, the soap is increasingly converted into free fatty
acid which does not act as an emulsifier and so the emulsion
coagulates
The uses of soap fatliquors are limited to the low emulsion stability
They have traditionally been used for surface fatliquoring calfskins
for shoe upper and formaldehyde tanned sheepskins for gloving
leather
 Cationic Fatliquors

Raw oil is emulsified with a cationic agent

The hydrophilic group is typically straight chain, aliphatic C10 to C18
Low affinity for cationic charged leathers e.g. chrome tanned
leather
High affinity for anionic charged leathers e.g. vegetable tanned for
lubricating the outer layers
Incompatible with anionic reagents e.g. anionic dyes, fatliquors,
retans
High stability to acid, but unstable to alkali
Good stability to metal
Poor shelf life
Emulsion stability can be improved by formulating with non-ionic
detergents (e.g. alkyl ethylene oxide condensates)
 Non-ionic fatliquors

These fatliquors are emulsified with compounds made

by condensing ethylene oxide in the presence of an
aliphatic alcohol
CnH2n+1-(OCH2CH2)x OH
The properties of the emulsifying agent depend on the
value of n, the aliphatic carbon chain length and the
value of x, the degree of polymerization of ethylene
oxide
These compounds are not very good emulsifying
agents because the hydrophilic end, the ethylene oxide
chain, does not have a high affinity for water relying on
hydrogen bonding via the ether oxygens
 Properties

High stability to metal ions, salts, hard water and wide pH

tolerance
Miscible with cationic and anionic reagents
Little or no affinity for anionic or cationic charged leathers
The non-ionic emulsifier increases the hydrophobicity of
leathers
Used for fatliquoring Zr and Al tanned leathers which are
highly cationic charged
As a crusting fatliquor for suedes splits i.e. merely to
prevent fibre resticking on drying to aid rewetting
May be formulated with anionic or cationic fatliquors to
improve stability
 Multicharged Fatliquors

These fatliquors are formulations of non-ionic, anionic

and cationic fatliquors in which the presence of the
non-ionic species prevents precipitation of the anionic
and cationic species
They are more stable to a wider pH range than singly
charged fatliquors and hence more stable to variations
in leather charge
The proportions of the constituents can be varied
depending on the leather properties required
Depth of penetration
Surface lubrication
Ease removal from paste drying plates
 Amphoteric Fatliquors

Raw oil is emulsified with an amphoteric reagent i.e.

one containing both acidic and basic groups
The point of neutrality, the isoelectric point, depends
on the numbers of acidic and basic groups
A typical IEP for this type of structure is pH 5
At pH>5, the emulsifier is negatively charged
At pH<5, the emulsifier is positively charged
The choice of pH of the fatliquors depends on the
charge of the leather and the requirement of surface
reaction or penetration
 Solvent Fatliquors

These are typically anionic fatliquors, containing a high boiling

point, polar petroleum solvent with minimum flash point 60C
and preferably odorless
The function of the solvent is to replace the water as it is
removed during drying
With lesser affinity for the leather than the polar triglyceride
oils, it can spread further and deeper