Textile Fibres II

Introduction

by
Dr. Supriyo Chakraborty
Evolution of human civilization.

Evolution of textile fibers

Synthetic fibers are spun from the polymers that are
synthesized using monomers joined together by
covalent bonds via process called polymerization.
Polymerization could proceed with several variations,
and thus they can be classified in various ways as
listed in following Figure.
If, for example, 9,000 metres of a yarn weigh 100 grams, the yarn is said
to be 100 denier; if 9,000 metres of another yarn weigh 45 grams, that
yarn is 45 denier; if 9,000 metres of a single filament weigh 3 grams,
that filament is of 3 denier. An instrument very suitable for rapid
determination of denier is the Torsion Denier Balance

1 meter =
39.37 inch
Sp gr = 1 gm/cm3

9000 meters = 900000 cm  1 gm

(CSA) Cross sectional area (cm2 ) × 900000 cm × 1 gm/cm3 = 1
CSA =
1 Pounds Per Square Inch to Megapascals = 0.0069, 1414 Mpa, 1GPa = 1000 MPa
10.28
 Cellulose.
Some work that was carried out at the Shirley Institute in 1955 was directed to determine
the degree of polymerisation and its distribution in cellulose rayons. Four rayons were used, ;
standard viscose, Tenasco, which is a medium high tenacity stretched viscose,
cuprammonium, and old-type Durafil, which is a very high tenacity highly stretched viscose
rayon. All four were nitrated with a mixture of

The chemical equation for the formation of the trinitrate is: 3 HNO3 + C6H7(OH)3O2 (H2SO4 )→ C6H7(ONO2)3O2 + 3 H2O

The process uses a mixture of nitric acid and sulfuric acid to convert cellulose into nitrocellulose. The quality of the cellulose is important.
Hemicellulose, lignin, pentosans, and mineral salts give inferior nitrocelluloses. In precise chemical terms, nitrocellulose is not a nitro compound, but
a nitrate ester. The glucose repeat unit (anhydroglucose) within the cellulose chain has three OH groups, each of which can form a nitrate ester. Thus,
nitrocellulose can denote mononitrocellulose, dinitrocellulose, and trinitrocellulose, or a mixture thereof. With fewer OH groups than the parent
cellulose, nitrocelluloses do not aggregate by hydrogen bonding. The overarching consequence is the nitrocellulose is soluble in organic solvents.

The cellulose nitrate so formed was dissolved in acetone and pre-cipitated in fractions—a bit at a time—by the
progressive addition of small lots of hexane to the acetone solution. The hexane is not a solvent for the cellulose
nitrate. The first fraction precipitated contains the longest molecules, those with the highest degree of
polymerisation; the second fraction contains the next longest and the last fraction contains the shortest. The
fractionation scheme
 MOLECULAR WEIGHTS OF FIRRFS
The molecules of which a monomeric material such as benzene or butyl alcohol is
composed are all of exactly the same weight and size (except in respect of very
small weight differences due to the presence of isotopes—a matter which we can
forget, as it has no bearing on our present considerations). But the molecules of a
polymer vary very considerably. Some will be very much longer than others. A
synthetic fibre that has perhaps half its molecules within the range of molecular
weight may well have a few as low as 1,000, and a few as high as 50,000. The
abundance of molecules of different molecular weights will vary as shown in Fig.
15(a); most will cluster round the mean. In cases where a polymer contains a
significant number of very short molecules (e.g., of the order of 2,000 molecular
weight) the average molecular weight will be considerably reduced by these, and
the most frequcnt molecular weight may be more significant—i.e., the molecular
weight that occurs most commonly in the group of molecules being considered.
15(a)

Formula for number average and weight average molecular weights

Cellulose molecule may contain about 9,000 glucose residues, with a molecular weight of about 1½ million. Undoubtedly, in
manufacture these long molecules are seriously reduced in length. Cuprammonium rayon has about 500 glucose residues in
its cellulose molecule, viscose rayon about 250, and cellulose acetate rayon about 300.

Synthetic Fibres. The molecular weights of synthetic fibres are high. So much is certain, although little reliability can be placed
on " exact " figures that are quoted, so long as different methods give different results. The molecular weight of nylon, for
example, is about 12,000—20,000. Vinyon is made from a co-polymer of vinyl chloride and vinyl acetate, and it has been
stated that polymers with satisfactory tensile properties are limited to a molecular weight range of 9500 - 28000

In order to obtain fibres with satisfactory tensile properties,

a minimum degree of polymerization, a minimum mean
molecular weight, must be reached.

One cannot, however, go on indefinitely, as beyond

perhaps 30,000 molecular weight, solubility and fusibility
fall off; and how is one to spin a fibre from a material that
can be neither dissolved nor melted?
• Measurement of viscosity of the solutions: As the length of molecule increases, so does the viscosity of its solution;
the long molecules of solute become entangled and inhibit the flow of solvent. Viscosity measurements of solutions of
nylon in m-cresol can be used as a control of the degree of polymerization reached during manufacture.

• Sedimentation using ultracentrifuge:

Ff
Fc

Fb
Viscosity Absolute viscosity. This is defined in c.g.s. units and is expressed in poises. It is not much used
in fibre work, but it may be noted that for liquids of similar densities, their times of flow through a
capillary. e.g., the viscometer shown in Fig. (prev. slide), are proportional to their absolute viscosities.
The following derived expressions are more commonly used; all are based on this relation between
absolute viscosity and time of flow.

Staudinger Equation
When polypropylene came along, R. Chiang of Hercules Powder
Co. made a somewhat similar investigation for it and found the
relation:

Vant Hoff equation

Valid only for ideal solutions

The rate of extrusion of the molten polypropylene, at 1900 C. under a standard pressure exerted by a
piston loading of 2 kg. applied over 0.71 cm2 of polymer, through an extrusion die of 0.082 in. diameter and
5/16 in. long is measured in grams over a 10 min. period.

Inherent viscosity of nylon. The methods described above could equally be applied to nylon. Carothers in. his basic
nylon patent (U.S. Patent 2,130,948 of 1938) defined the inherent viscosity of his nylon polymers by the relation:

where c is equal to 0.5%

If the polymer has an inherent viscosity below 0.4, it will not form satisfactory fibres; in the early days the
inherent viscosity of commercial nylon was about 0.6; nowadays it is usually within the range 1.0—2.0.
When non-round filaments are being spun, a high viscosity is essential; otherwise, if the melt is too fluid,
surface tension will pull the filaments to a circular section before solidification has taken place.
Fundamental Polymerisation reaction for Polyamide and Polyesters
(Condensation polymerisation)

If n = 50, which is about the lowest value at which useful fibres can be formed, the molecule would clearly be nearly
seventeen times as long as that just written at length. To extend it in part, it could be represented :

It is to note that the molecules of fibre-forming materials are themselves very long in comparison
with their other dimensions.
Ring Formation—A Danger in Fibre Syntheses
The polymerisation reaction already noted of ε-hydroxycaproic acid may be taken as typical of condensation
polymerization. The first stage is the condensation of two molecules, again, as already noted,

It is essential, therefore, in choosing monomeric materials

from which to synthesise fibre-forming materials, to select
those which cannot give rise to a stable ring system.
Provided that any ring system that could be formed would
contain more than six atoms, the reaction will go mainly to
form a linear polymer, although there will be a small
amount of ring formation. If the ring would contain eight
or more atoms the reaction will go practically exclusively to
the linear polymer.
 Example : Ionic Initiators, Fiedel Crafts -C=C-
Radical Initiators, Peroxides

Commercial Fibres Made by Addition Polymerisation There are many:

polyethylene and polypropylene which are poly- olefines; polyvinyl chloride;
polyvinylidene chloride such as Saran and others; all the polyacrylonitrile
fibres Orlon, Acrilan, Courtelle, and the modacrylics Dynel and Verel;
polyvinyl alcohol Vinylon fibres. These indicate the range; there are many
variants of those specifically mentioned. The most important single group is
the acrylics.
Chain-growth polymerization, as well as all other typical chain reactions are usually faster than those in
step-growth polymerizations and are typified by three normally distinguishable processes, viz.,
(i) initiation of the chain,
(ii) propagation or growth of the chain, and
(iii) termination of the chain. (A fourth process, chain transfer, may also be involved.)

Besides free radical mechanisms, discussed, there are several other mechanisms by which chain or
addition polymerization can take place. Prominent among these are ionic mechanisms in which the
growing chain end carbon bears a negative charge (carbanion) or a positive charge (carbonium ion). In
the former case, the polymerization is known as anionic polymerization and in the latter case as cationic
polymerization.
Differences between Condensation and Addition Polymerisations
Vinyl or addition polymerisations differ from condensation polymerisations in the following ways:

1. No small molecular substance is split off.

2. They are faster. The reaction, especially when ionic as opposed to free radical initiators are used,
may proceed very rapidly, and usually at a much lower temperature than is necessary for the
condensation type.

3. The molecular weight attained can be much greater; it is unusual in a linear condensation
polymerisation for molecular weights greater than 25,000 to be achieved, but in vinyl
polymerisations the molecular weight can run up to a few million.

4. They are more likely to include minor side reactions lead- ing to branching or to cross-linking.

5. If polymerisation is terminated at an early stage, the vinyl mixture will consist of some very long
completely polymerised molecules and a lot of unchanged monomers, with nothing intermediate;
the condensation mixture will contain practically no monomers and probably no very long
polymeric molecules but will consist of all sorts of low polymers: dimers, trimers, tetramers, etc.
2,3,4,6 1,2,3,6
Melt Spinning

Wet Spinning

Dry Spinning

Drawing
https://youtu.be/c9bOox0KCuM
The velocity gradient in (a) shear flow in a capillary, and (b) elongational flow in a spinline (the
corresponding velocity profiles are also shown).
https://youtu.be/c9bOox0KCuM
 Drawing

The drawing process can be done in a single process step to a fully oriented yarn (FOY) directly after spinning (as it
is shown in Fig. or in two process steps. In the latter case the fibres are only partly drawn to a partially oriented
yarn (POY) and the final drawing process to fully oriented yarn (FOY) is done at the next process step (e.g.
texturizing). Depending on the degree of orientation filament yarns have different names:
• LOY
• MOY
• POY
• HOY
• FOY
low oriented yarn medium oriented yarn pre (partially) oriented yarn high oriented yarn fully oriented yarn.
 Unit- I

Classification of man-made fibres, definition of regenerated and synthetic fibres,

Concepts of molecular weight, methods of determination of MW, Degree of
polymerization, Orientation and Crystallinity, Characteristics of fiber forming polymer.
Study of some Characterization methods such as birefringence and DSC methods for
property evaluation of produced fibres and polymeric materials. Introduction to
methods of fibre formation by melt spinning, dry spinning, & wet spinning, important
process parameters of spinning systems.
THE HYDROXYL GROUP: The cellulosic fibers are characterized by the possession of an immense number of hydroxyl
groups. Apart from the alginates, which chemically are related not very distantly to cellulose, no other fibres share this
constitutional feature.
1. The very high degree of polymerisation. High polymers are always increasingly
insoluble.
2. The mutual attraction between the hydroxyl groups
on one cellulose molecule and those on other cellulose
molecules aligned alongside it. These attractive forces
between the hydroxyl groups constitute an example of
hydrogen bonding and because of the very high
frequency of occurrence of hydroxyl groups in cellulose,
the sum of all the numerous attractive forces is
considerable.

These forces confer stability on the structure and make

it difficult for the water molecules to find their way into
it and disintegrate it by means of solution. The main
reason for the insolubility of cellulose in water is the size
of the molecule; it is unusual for substances made up of
such giant molecules to be soluble.
Melting Point of Nylon. It is noteworthy that if the chain length between the polar groups of nylon is increased, the
melting point falls. Nylon 6-10, made from hexamethylene diamine and sebacic acid, melts at 214o C., and this is what
might be expected. The -CONH- groups in nylon are polar, although not nearly so strongly polar as the hydroxyl groups
in cellulose, or as the free –NH2 and Melting Point of Nylon.

-COOH groups in the proteins. Nevertheless, some polarity exists, and some attractive forces obtain between the amide
linkages on adjacent molecules. This intermolecular bonding is not nearly so strong in nylon as in cellulose and the
proteins, but it does exist, and has to be reckoned with. Clearly, the shorter the chains between the amide-groupings,
the more frequently will these cross-attractions occur, and the more difficult it will be to separate the linear mole- cules.
Melting consists of separating the molecules, and it can naturally be accomplished more easily if there are fewer
intermolecular attractive forces.

N
The synthesis of fibres has been an achievement that has brought with it the possibility of making fibres with
specified properties. Naturally, it is not always possible to meet a specification; it is one thing to draw up a
specification of perfection, and usually quite another thing to match it.

Nevertheless, it is possible to some extent to modify the physical properties of synthetic fibres by suitably adjusting
their chemical composition.

It may be found that one substance, such as vinyl chloride, when polymerized gives fibres unsatisfactory in respect
of suppleness, and another substance, vinyl acetate, when polymerised has a very low softening temperature, and is
mechanically weak. Yet when the two substances are polymerised together, or co-polymerised, the properties of the
fibre are satisfactory in all these respects. In the case of vinyl chloride (88 per cent) and vinyl acetate (12 per cent),
the co-polymer Vinyon results. Other improved products—Verel and Dynel—are co-polymers of vinyl compounds
and acrylonitrile. So are most of the acrylic fibres.
Although the co-polymerisation of another component with the nylon 66 components ordinarily brings about a
reduction in melting point, there is an interesting exception to this generalisation. If the added component is of the
samc molecular length as the component it is partially replacing, then it can effect the substitution without disturbing
the molecular packing and without diminishing the forces between one molecule and another, and accordingly it does
not reduce the melting point. A specific example is of the partial sub- stitution of the adipic acid (length of molecular
unit A) by terephthalic acid (length of molecular unit A); the lengths of the two molecules are sufficiently close for
there to be little or no inter- ruption in the arrangement of the molecular chains. In fact, the substitution of
terephthalic for a portion of thc adipic acid in nylon does not reduce the melting point. It is safe to say, though, that
the substitution of terephthalic acid for a small portion of the sebacic acid in 610 nylon would reduce its melting point,
because the terephthalic acid molecule would be much shorter than the sebacic acid molecule.
In thc same way linear poly- as well as linear
polyesters. esters can be formed from pp'-
diphenylenc dicarboxylic acid, but not from its
isomers:

so they can be formed from 2 : 6-naphthalene

dicarboxylic acid, COOH in which the carboxyl
groups are sym- COOH symmetrically disposed.