Professional Documents
Culture Documents
Baileys Industrial Oil and Fat Products, Sixth Edition, Six Volume Set.
Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.
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2. SOFTENING OF LEATHER
2.1. Drying Skin or Hide
The skin or hide of an animal is an organ whose complex structure can be simplified
for purposes of analysis into two layers: a thin (<1 mm) epidermis and a thicker (up
to 1 cm) dermis. The epidermis, bearing the hair, is removed early in the steps of
leathermaking. The dermis comprises very long fibrils, 100 nm in diameter,
composed mostly of the protein collagen type I. The fibrils are organized into
interwoven bundles. Among the fibrils is a concentrated solution or network of
glycoproteins and, immediately after slaughter, blood plasma. There are also
blood vessels and nerves, which are removed during leathermaking before the
tanning (collagen crosslinking) step, which is the last step before the addition of
fatliquor.
If skin or hide is dried, even minus the hair and epidermis, it becomes a hard
material, like horn. If the skin is thin, this product can be used as a tough parchment, but little else. This behavior is attributed to the proteins and proteoglycans
found among the fibers of the hide, which act as a glue when they dry.
If the skin is agitated with lime-buffered water (pH 12.5), it swells enormously, and most of the gluelike material is extracted. On neutralization, however,
the fibers become flaccid and, on drying, stick together to again form a hard mass.
Before being dried for leather, however, the extracted skin is tanned: the collagen
protein of the fibers is crosslinked to make them stiffer. The resulting product can
be dried to a leathery material that is stiff, but much more flexible than that dried
without tanning. To soften tanned skin, one can mill it by lifting and dropping it in a
large rotating drum or in a staking machine, which pounds it with small hammers.
The result is not satisfactory, however, for a number of reasons, including the effect
on the integrity of the surface of the leather and the inability to rewet the leather
without making it become stiff again.
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Figure 1. Effect of fatliquor on the structure of fibers in leather after drying. (Top) The 100-mm
fiber bundles in the leather dried without fatliquor are intact. (Bottom) They are broken into
fragments when dried with fatliquor, making the leather compliant. Bar 10 mm.
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rather than deeper inside. This allows the leathermaker a means to control deposition of oil stratigraphically. As already described, this permits adjustment of the
mechanical properties and leather esthetics.
A balance of properties of the product can be obtained by formulations based on
natural oils to which sulf(on)ated oils are added. The mixtures can then be optimized statistically with respect to the mechanical properties (7).
Aside from sulf(on)ates, carboxylates (soaps) and phosphates can also be used in
the surfactant. An emulsion based on alkyl phosphate emulsifier is reported to give
an especially soft leather (8). Phosphates are reviewed by Fricke and Haeussler (9).
There is also experience with sulfosuccinic acid amides (10) and other surfactant
formers.
Before the growth of organic chemistry and techniques for sulfonating fats and
oils, tanners emulsified oils for leather softeners with soap and protective colloids.
These mixtures were prepared as water-in-oil emulsions, called mayonnaise in
the trade and added to the water in the drum with the leather. They are still used
but not nearly as frequently as sulf(on)ated oils. On the other hand, salts of naphthenic acid are used with hydrocarbon oils (e.g., 11) to make the reverse forms of
these.
Egg yolk was once commonly used, probably because of its lecithin, to emulsify
oils in leathermaking. Lecithin itself is effective as a fatliquor emulsifier (12). Nonionic emulsifiers have the advantage of forming emulsions that are stable to electrolytes, so they do not interact electrostatically with the chromium or aluminum
tanning ions. Nonionicanionic combinations (e.g., 1% nonionic99% anionic)
are now used to suppress the accumulation of fatty deposits or extrusions at the
surface of the leather. These systems are under active development.
Cationic surfactants are used mainly to treat the surface of the leather, making it
waxy. These are typically C-16 to C-18 alkylbenzyl quaternary ammonium compounds (e.g., 13). Also effective are cationic fatliquors from aminated and quaternized castor oil; other vegetable oils are also used (14).
Oils are frequently chlorinated in addition to being sulf(on)ated or oxidized. The
reaction is extended to both the neutral oil and the surfactant, to make them less
volatile and more flame resistant. Fish oil is the usual substrate for this treatment,
but it has been extended to fatliquor from mineral oil and paraffin wax (e.g., 15).
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lubricants and antistatic agents, known in the trade as spin finishes. Mechanisms of
their action in the fiber and yarn-forming processes are discussed. Oils and fats in
the form of their surface-active derivatives are also used in scouring, dyeing, and
softening. It is important to note that synthetic oils have replaced most of the natural oils in the processing of textiles. Natural oils are used mainly as their fatty acid
derivatives.
8. PROCESSING OF FIBERS
8.1. Spinning
In the textile trade, spinning refers to the production of yearns by twisting staple
fibers, as well as the production of yarns from synthetic polymers by the extrusion
of continuous filaments through spinnerettes. In the spinning of staple fibers, yarns
are produced at relatively high speeds by the alignment, drawing, and twisting of
fibers in automatic machines. Stout (30) has studied the role of lubrication in spinning of staple fibers. Open-end spinning (31), used mainly for short staple fibers, is
a more recent spinning method that eliminates the intermediate step of fiber alignment. In open-end spinning, fibers are brought to a twisting location in a chamber
by air turbulence. The stability and the efficiency of this process depends on good
fiber cohesion, which prevents yarn breakage. Treating the staple fiber with an oil
promotes fiber cohesion, in addition to lubrication against hard surfaces of the
processing machines to prevent abrasive damage.
Melt or solution spinning of synthetic fibers is a marvel of modern technology.
Fiber lubrication, which is of the utmost importance in this high-speed process, is
achieved by the application of spin finisha combination of oils and surfactants. A
typical spin line for the production of polyester staple fiber is shown schematically
in Figure 2. The number of filaments, which can vary from tens to thousands, come
into contact with various parts of the machinery, some of which are heated for proper fiber modification. To replenish the lost finish and to ensure adequate lubrication,
PROCESSING OF FIBERS
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Figure 2. Schematic of a typical spin line for the production of staple fibers.
the finish is applied more than once at strategic locations along the spin line. Spin
finishes are also applied to solution spun fibers, after the regeneration step. As these
finishes protect the fibers in subsequent processing, an even distribution at low addon is an important requirement. Methods of determining the distribution of finishes
on fibers and yarns have been developed (32).
8.2. Texturing
As a result of crimp, natural fibers form relatively bulky yarns. These produce soft
fabrics that are preferred by the consumer. Texturing is a process that imparts bulk
to melt-spun continuous filament yarns, by introducing crimp in the individual filaments. False-twist friction texturing is one such process (33). The heated yarn is
passed between ceramic friction discs rotating in opposite directions, which introduces a temporary twist in the yarn. The twist is undone as the yarn leaves the discs,
leaving a permanent crimp in the individual filaments. The mechanism of texturing
has been presented (34). Application of a proper finish is critical for the success of
this process in which the interfiber friction should be low and the fiberdisc friction
should be high. Formulating a finish that achieves these two opposing requirements
at a high temperature without degradation is a challenge (35). The effect of
volatilization of a lubricant on yarn friction has been investigated (36). The nature
of the finish plays an important role in the uniformity of the textured yarn and consequently in the quality of the fabric.
8.3. Weaving and Knitting
Solid fats, like tallow, are sometimes used as lubricants on sized warp yarns in shuttle looms. Without such lubricants, warp yarns can unravel and break as a result of
the abrasion of the size by the shuttle and the heddle. This would introduce defects
in the fabric and will also affect the efficiency of the weaving process. In knitting,
the lubrication of the yarns is also important. Lack of lubrication results in nonuniform yarn movements that affect the quality of the fabric.
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where A is the area of real contact (much smaller than the geometrical area) at the
asperities and s is the shear strength of the junctions. This is shown schematically in
Figure 3. When a liquid film of a low-shear strength material is introduced at the
interface, some of the solidsolid junctions are replaced by the liquid film. The new
friction force is given by (38)
F 0 Aas 1 asl ;
where a is the fraction of the surface with solidsolid junctions and sl is the shear
strength of the liquid. It should be noted that F 0
F because a
1 and sl
s.
Adhesion of the lubricant film to the solid surface is an important requirement.
Lack of adhesion will lead to the squeezing of the lubricant film out of the interface
and the re-establishment of the solidsolid junctions (39, 40). This will render the
lubricant less effective. The work of adhesion W between a liquid lubricant and
the solid surface is given by (41)
W s1 cos y;
where s is the surface tension of the liquid and y is the contact angle, which is a
measure of the interaction between the liquid and the solid. As, for a given solid
Figure 3. Schematic of the effect of a lubricant film on the formation of adhesive junctions at a
solidsolid interface.
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Figure 4. Schematic of the effect of viscosity and sliding speed on hydrodynamic friction. W is
the normal load (44).
surface, cos y is inversely related to the surface tension of the liquid (42), proper
formulation of a lubricant to maximize W by adjusting s and cos y is important.
The solidliquid interaction parameter, cos y, also plays an important role in the
spreading and penetration of the liquid lubricant into the yarn (43). This type of
friction at low sliding speed is known as boundary friction, and lubrication in
this regime is known as boundary lubrication (38).
A different frictional behavior is observed in the lubrication of fibers and yarns at
high speeds (44). Friction appears to increase with the sliding speed. Hydrodynamic
origin of this behavior was first explained by Reynolds (45) based on the lubrication
of bearings rotating at high speeds. According to this theory, at high rates of shear,
hydrodynamic pressure is generated in the lubricant film, which supports the
normal load at the interface. The friction coefficient is found to be a function of
the product of viscosity (Z) and the sliding speed V. This relationship between
the friction coefficient (m) and ZV is seen in the hydrodynamic region of
Figure 4, at high values of ZV=W (44). In the boundary friction regime, at low
values of ZV=W, high friction results from the solidsolid junctions. Under these
conditions, abrasive wear is the result. As the formation of adhesive junctions is a
time-dependent phenomenon, at high sliding speeds, fewer adhesive junctions are
formed, and therefore, friction decreases with an increase in sliding speed.
Stick-slip phenomenon, which is characteristic of boundary friction, disappears
(46). In the hydrodynamic region, on the other hand, high coefficients of friction
need not be indicative of abrasive wear. In this friction regime, under the conditions
of good adhesion, a lubricating finish film is always present at the solidsolid
interface.
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F 2s sinj y
where R is the fiber radius, 2d is the distance between the fibers, j is the half-angle
subtended by the liquid bridge at the center of the fibers, y is the contact angle, and
s is the liquid surface tension. The first term on the right-hand side is the attraction
due to the component of surface tension parallel to the line joining the fiber centers.
The second term is the Laplace pressure of the liquid bridge, whose magnitude
depends on y. It is at a maximum when y 0, and is negative when y > p=2.
Therefore, repulsion between the fibers is possible if the second term in Equation 4
becomes negative and is numerically larger than the first. Physically, this means
liquidair interface of the bridge is convex rather than concave. It is important to
note that the presence of liquid bridges in the yarn makes a small but significant
contribution to the strength of the yarn (47).
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66.0%
8.5
8.5
2.8
10.0
4.2
UCON is a random copolymer of ethylene oxide (EO) and propylene oxide (PO)
and can be considered as a synthetic oil. POE is poly(oxyethylene), which is a
homopolymer of EO. Random EO-PO copolymers are typical of synthetic oils
used as lubricants in textile processing (53, 54). PLURONICS (BASF) are block
copolymers of EO and PO. Both of these copolymers can be produced with viscosities ranging from that of a thin oil to that of a thick paste. Oils of appropriate
viscosity give hydrodynamic lubrication in the high-speed spinning of synthetic
fibers. The hydrophilelipophile balance (HLB) in these polymers can be varied,
by changing the EOPO composition, to suit the aqueous solubility requirements.
The other major synthetic oils used in textile processing are the silicone oils, based on
the polymers of dimethyl siloxane, (CH3)3Si
O
(
Si(CH3)2
O
)nSi (CH3)3 (55).
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Similar to the copolymers of EO/PO, these polymers can also be produced with a
range of molecular weights and varying viscosities. In contrast to the EOPO copolymers, these have much lower surface energies and spread easily on a surface to
give very thin films. Therefore, they make rather poor boundary lubricants. However, because of the low surface tension and high wettability with other surfaces,
they make good hydrodynamic lubricants (42). For the same reasons, these oils
are often used in soil and water-repellent treatments of fabrics (56, 57). More
recently silicone oils have been combined with POEs and EOPO copolymers to
produce surfactants with varying HLB numbers and are used as lubricants and
emulsifying and spreading agents (58). In general, silicones are known to be better
lubricants than the EOPO-based copolymers. The brief nature of this review
precludes detailed discussion of the rather voluminous literature available in this
area.
Mineral oils of different viscosity are used in the spinning of natural and synthetic fibers (59). These are paraffins of varying molecular weights, byproducts
of the petroleum industry.
Apart from lubricants, spin finishes contain antistatic and spreading and emulsifying agents. These are generally alkyl sulfates, alkylbenzene sulfonates, sulfonated
fats and oils and poly(ethylene glycol)-modified fatty acids, fatty acid amides, fatty
alcohols, and fatty amines. Potassium alkyl phosphates are extensively used in the
production of polyester staple fibers.
10.3. Scouring
Here oils and fats are used principally as detergents and wetting agents in the cleaning of natural fibers, to remove, for example, fats and waxes from cotton and wool
(60) and in removing finishes used as processing aids in the manufacture of synthetics. Generally, anionic surfactants are used in this process. As most natural
and synthetic fibers have negative charges on the surfaces, anionics will not adsorb
strongly and therefore can be rinsed out easily. Among the nonionic surfactants,
alkyl, alkylphenol, fatty acid, and fatty-acid-amide-modified POEs are more common. The pH of the bath is an important consideration in the selection of the proper
surfactants.
10.4. Dyeing
In dyeing, surfactants are used as wetting agents. They are also used in the formulation of disperse dyes. A stable suspension of the dye is prepared with the help of
an anionic surfactant, such as alkyl or aryl alkyl sulfonate. It has been shown that
dyeing takes place through the aqueous phase by the slow dissolution of the solid
dye particles (61, 62). The presence of the surfactant helps the dissolution of
the dye.
In special cases, cationic surfactants are used as dye-leveling agents (63, 64).
Cationic dyes with temperature-sensitive diffusion coefficients often yield non-uniform shades, because of the difficulty of maintaining constant temperatures in large
REFERENCES
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industrial dye baths. Cationic surfactants used in these dye baths diffuse into the
fiber ahead of the dye molecules and occupy some of the sites. This, in general,
reduces the rate of dyeing, but improves uniformity. Overall dye uptake is not affected
because at the end of the process the surfactant molecules are displayed by the dye molecules. Quaternized long-chain surfactants are generally used for this purpose.
10.5. Softening
Fabrics often feel rough after scouring and washing. Ionic as well as nonionic surfactants are used to soften such fabrics (65). Several mechanisms have been suggested for the softening effect. In the case of low-molecular-weight ionic and
nonionic surfactants, softening has been attributed to the moisturizing and lubrication of the fibers in the fabric. When the interfiber friction is low, the fabric deforms
easily by the slippage of fibers over one another. This results in a softer hand. As
a result of low molecular weight and lack of substantivity, these effects tend to be
temporary, and the fabric needs to be treated after every wash. A more permanent
softening is achieved by the surface deposition of an elastomeric polymer, which
forms interfiber bonds. Surface-deposited silicones (66) are known to be superior
in this respect. A principal drawback of these polymeric softeners is that they interfere with the water absorbency of the fabric because of their hydrophobic nature. A
rather unusual application of silicones is in the shrink proofing of wool garments
(67). In this instance, the interfiber bridges prevent unidirectional fiber migrations
that otherwise would lead to the felting of the fabric.
11. CONCLUDING REMARKS
The foregoing discussion shows the importance of oils and fats in the processing of
textiles. As a result of oxidative stability, synthetic oils have superseded their natural counterparts. However, fatty acids from natural oils still play an important role
in the processing of textiles. There is considerable pressure on the textile industry to
reduce the amounts of these additives, or to eliminate them completely, because of
the environmental implications of the effluents (68). In response to this, considerable effort is being made in the industry to develop additive-free processes.
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