Polymers:

Definition : A polymer is a large molecule, or macromolecule, composed of many repeated

subunits. Due to their broad range of properties,both synthetic and natural polymers play
essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic
plastics such as polystyrene to natural biopolymers such as DNA and proteins that are
fundamental to biological structure and function. Polymers, both natural and synthetic, are
created via polymerization of many small molecules, known as monomers. Their consequently
large molecular mass, relative to small molecule compounds, produces unique physical
properties including toughness, viscoelasticity, and a tendency to
form glasses and semicrystalline structures rather than crystals. The terms polymer and resin are
often synonymous with plastic.

Natural Rubber :
Natural rubber, also called by other names of India rubber, latex, Amazonian
rubber, caucho or caoutchouc, as initially produced, consists of polymers of the organic compound isoprene,
with minor impurities of other organic compounds, plus water. Thailand and Indonesia are two of the leading
rubber producers. Forms of polyisoprene that are used as natural rubbers are classified as elastomers.
Currently, rubber is harvested mainly in the form of the latex from the rubber tree or others. The latex is a
sticky, milky colloid drawn off by making incisions in the bark and collecting the fluid in vessels in a process
called "tapping". The latex then is refined into rubber that is ready for commercial processing. In major areas,
latex is allowed to coagulate in the collection cup. The coagulated lumps are collected and processed into dry
forms for marketing.
Natural rubber is used extensively in many applications and products, either alone or in combination with other
materials. In most of its useful forms, it has a large stretch ratio and high resilience, and is extremely
waterproof.

Hevea brasiliensis
The major commercial source of natural rubber latex is the Amazonian rubber tree (Hevea brasiliensis), a
member of the spurge family, Euphorbiaceae. This species is preferred because it grows well under
cultivation. A properly managed tree responds to wounding by producing more latex for several years.

Congo rubber
Congo rubber, formerly a major source of rubber, came from vines in the genus Landolphia (L. kirkii, L.
heudelotis, and L. owariensis).

Dandelion[
Dandelion milk contains latex. The latex exhibits the same quality as the natural rubber from rubber trees. In
the wild types of dandelion, latex content is low and varies greatly. In Nazi Germany, research projects tried to
use dandelions as a base for rubber production, but failed. In 2013, by inhibiting one key enzyme and using
modern cultivation methods and optimization techniques, scientists in the Fraunhofer Institute for Molecular
Biology and Applied Ecology (IME) in Germany developed a cultivar that is suitable for commercial
production of natural rubber. In collaboration with Continental Tires, IME began a pilot facility.
Properties :

Rubber latex:
Rubber exhibits unique physical and chemical properties. Rubber's stress–strain behavior exhibits the Mullins
effect and the Payne effect and is often modeled as hyperelastic. Rubber strain crystallizes.
Due to the presence of weakened allylic C-H bonds in each repeat unit, natural rubber is susceptible
to vulcanisation as well as being sensitive to ozone cracking.
The two main solvents for rubber are turpentine and naphtha (petroleum). Because rubber does not dissolve
easily, the material is finely divided by shredding prior to its immersion.
An ammonia solution can be used to prevent the coagulation of raw latex.
Rubber begins to melt at approximately 180 °C (356 °F).

Elasticity
On a microscopic scale, relaxed rubber is a disorganized cluster of erratically changing wrinkled chains. In
stretched rubber, the chains are almost linear. The restoring force is due to the preponderance of wrinkled
conformations over more linear ones. For the quantitative treatment see ideal chain, for more examples
see entropic force.
Cooling below the glass transition temperature permits local conformational changes but a reordering is
practically impossible because of the larger energy barrier for the concerted movement of longer chains.
"Frozen" rubber's elasticity is low and strain results from small changes of bond lengths and angles: this
caused the Challenger disaster, when the American Space Shuttle's flattened o-rings failed to relax to fill a
widening gap.[16] The glass transition is fast and reversible: the force resumes on heating.
The parallel chains of stretched rubber are susceptible to crystallization. This takes some time because turns of
twisted chains have to move out of the way of the growing crystallites. Crystallization has occurred, for
example, when, after days, an inflated toy balloon is found withered at a relatively large remaining volume.
Where it is touched, it shrinks because the temperature of the hand is enough to melt the crystals.
Vulcanization of rubber creates di- and polysulfide bonds between chains, which limits the degrees of
freedom and results in chains that tighten more quickly for a given strain, thereby increasing the elastic force
constant and making the rubber harder and less extensible.

Malodour[
Raw rubber storage depots and rubber processing can produce malodour that is serious enough to become a
source of complaints and protest to those living in the vicinity.[17]
Microbial impurities originate during the processing of block rubber. These impurities break down during
storage or thermal degradation and produce volatile organic compounds. Examination of these compounds
using gas chromatography/mass spectrometry (GC/MS) and gas chromatography (GC) indicates that they
contain sulphur, ammonia, alkenes, ketones, esters, hydrogen sulphite, nitrogen, and low molecular weight
fatty acids (C2-C5).
When latex concentrate is produced from rubber, sulphuric acid is used for coagulation. This produces
malodourous hydrogen sulphide.
The industry can mitigate these bad odours with scrubber systems.
Chemical makeup

Chemical structure of cis-polyisoprene, the main constituent of natural rubber. Synthetic cis-polyisoprene and natural cis-
polyisoprene are derived from different precursors, isopentenyl pyrophosphate and isoprene.

Latex is the polymer cis-1,4-polyisoprene – with a molecular weight of 100,000 to 1,000,000 daltons.

Typically, a small percentage (up to 5% of dry mass) of other materials, such as proteins, fatty acids, resins,
and inorganic materials (salts) are found in natural rubber. Polyisoprene can also be created synthetically,
producing what is sometimes referred to as "synthetic natural rubber", but the synthetic and natural routes are
different.[1] Some natural rubber sources, such as gutta-percha, are composed of trans-1,4-polyisoprene,
a structural isomer that has similar properties.
Natural rubber is an elastomer and a thermoplastic. Once the rubber is vulcanized, it is a thermoset. Most
rubber in everyday use is vulcanized to a point where it shares properties of both; i.e., if it is heated and cooled,
it is degraded but not destroyed.
The final properties of a rubber item depend not just on the polymer, but also on modifiers and fillers, such
as carbon black, factice, whiting and others.

Biosynthesis[]
Rubber particles are formed in the cytoplasm of specialized latex-producing cells called laticifers within rubber
plants.[20] Rubber particles are surrounded by a single phospholipid membrane with hydrophobic tails pointed
inward. The membrane allows biosynthetic proteins to be sequestered at the surface of the growing rubber
particle, which allows new monomeric units to be added from outside the biomembrane, but within the
lacticifer. The rubber particle is an enzymatically active entity that contains three layers of material, the rubber
particle, a biomembrane and free monomeric units. The biomembrane is held tightly to the rubber core due to
the high negative charge along the double bonds of the rubber polymer backbone.[21] Free monomeric units and
conjugated proteins make up the outer layer. The rubber precursor is isopentenyl
pyrophosphate (an allylic compound), which elongates by Mg2+-dependent condensation by the action of
rubber transferase. The monomer adds to the pyrophosphate end of the growing polymer. [22] The process
displaces the terminal high-energy pyrophosphate. The reaction produces a cis polymer. The initiation step is
catalyzed by prenyltransferase, which converts three monomers of isopentenyl pyrophosphate into farnesyl
pyrophosphate.[23] The farnesyl pyrophosphate can bind to rubber transferase to elongate a new rubber polymer.
The required isopentenyl pyrophosphate is obtained from the mevalonate pathway, which derives from acetyl-
CoA in the cytosol. In plants, isoprene pyrophosphate can also be obtained from the 1-deox-D-xyulose-5-
phosphate/2-C-methyl-D-erythritol-4-phosphate pathway within plasmids.[24] The relative ratio of the farnesyl
pyrophosphate initiator unit and isoprenyl pyrophosphate elongation monomer determines the rate of new
particle synthesis versus elongation of existing particles. Though rubber is known to be produced by only one
enzyme, extracts of latex host numerous small molecular weight proteins with unknown function. The proteins
possibly serve as cofactors, as the synthetic rate decreases with complete removal. [25]

Wool
Wool is the textile fiber obtained from sheep and other animals,
including cashmere and mohair from goats, qiviut from muskoxen, from hide and fur
clothing from bison, angora from rabbits, and other types of wool from camelids; additionally,
the Highland and the Mangalica breeds of cattle and swine, respectively, possess woolly coats.
Wool consists of protein together with a small percentage of lipids. In this regard it is chemically quite distinct
from the more dominant textile, cotton, which is mainly cellulose.

Properties of Wool Fiber:

For processing wool fiber, we should know about properties of wool fiber. Now I have discussed
the following properties of wool fiber.

1. Physical Properties of Wool Fiber:

 Specific Gravity: 1.31
 Length : 35 to 250 mm
 Color: The color of wool fiber could be white, near white, brown and black.
 Flame reaction : Odor of burnt horn
 Luster: Luster of course fiber is higher than fine fiber.
 Moisture Regain: 13-16% , very absorbent, decrease strength when wet, seem warmth,
will shrink in washing.
 Electrostatic reaction: Highly electrostatic at dry conditions
 Strength: Tenacity dry =1.35 g/d, Wet = dry 0.69 weak (Due to few H-bond)
 Elasticity: Breaking extension – 42.5 %, Recovery % – 69 at 5%
 Elongation at break: Standard elongation is 25 – 35% and 25 – 50% in wet condition.
 Feel or Hand: Soft.
 Resiliency: Excellent (due to crimp)
 Abrasion resistance: Good.
 Dimensional stability: Bad (For tendency of felting).
 Effect of Heat: Heat affects the wool fiber greatly.
 Effect of Sun Light: The fibers become discolored and develop a harsh feel.
2. Chemical Properties of Wool Fiber:
 Effect of Acids: Wool is attacked by hot concentrated sulphuric acid and decomposes
completely. It is in general resistant to mineral acids of all strength even at high temperature
though nitric acids tend to cause damage by oxidation. 
 Effects of Alkalis: The chemical nature of wool keratin is such that it is particularly
sensitive to alkaline substances. Wool will dissolve in caustic soda solutions that would
have little effects on cotton. Strong alkaline affect on wool fiber but weak alkaline does not
affect wool. 
 Effect of Resistance to Compression: Resistance to compression values are useful in
assessing the suitability of wool for specific end uses. Resistance to compression (R to C) is
the force per unit area required to compress a fixed mass of wool to a fixed volume.
Resistance to compression is related to fiber diameter and the form and frequency of crimp. 
 Effect of Resilience: Wool fibers can be stretched up to 50 percent of their original
length when wet and 30 percent when dry. 
 Effect of Organic Solvent: Wool does not affect in organic solvents. 
 Effects of Insects: Wool affected by insects. 
  Effect of bleach: Chlorine bleach is ordinary harmful to the wool. KMnO4, Na O  are 2 2

utilized for bleaching. 

 Effect of Micro Organism: It is affected by mildew if it remains wet for long time. 
 Dyeing ability: Wool absorbs many different dyes deeply, uniformly and directly
without the use of other chemicals. Because of this ability, wool is known for the beautiful,
rich colors that can be achieved. 
 Effect of Colorfastness: Like cotton wool is easy to dye. Acid dyes, chrome
and mordant dyes are utilized to dye this. The dye molecules are attracted into the
amorphous areas of wool. 

Silk
Silk is a natural protein fiber, some forms of which can be woven into textiles. The protein fiber of silk is
composed mainly of fibroin and is produced by certain insect larvae to form cocoons.[1] The best-known silk is
obtained from the cocoons of the larvae of the mulberry silkworm Bombyx mori reared in captivity
(sericulture). The shimmering appearance of silk is due to the triangular prism-like structure of the silk fibre,
which allows silk cloth to refract incoming light at different angles, thus producing different colors.

Physical Properties of Silk Fibre:

Tenacity - The silk filament is strong. This strength is due to its linear, beta configuration
polymers and very crystalline polymer system. These two factors permit many more hydrogen
bonds to be formed in a much more regular manner. Silk loses strength on wetting. This is due to
water molecules hydrolyzing a significant number of hydrogen bonds and in the process
weakening the silk fibre.

Specific gravity - Degummed silk is less dense than cotton, flax, rayon or wool. It has a
specific gravity of 1.25. Silk fibres are often weighted by allowing filaments to absorb heavy
metallic salts; this increases the density of the material and increases its draping property.

Elastic-plastic nature - Silk is considered to be more plastic than elastic because it’s

very crystalline polymer system does not permit the amount of polymer movement which could
occur in a more amorphous system. Hence, if the silk material is stretched excessively, the silk
polymers that are already in a stretched state (They have a betaconfiguration) will slide past each
other. The process of stretching ruptures a significant number of hydrogen bonds.
Silk Fibre Elongation - Silk fibre has an elongation at break of 20-25% under
normal condition. At 100% R.H. the extension at break is 33%.

Hygroscopic nature - Because silk has a very crystalline polymer system, it is less
absorbent than wool but it is more absorbent than cotton. The greater crystallinity of silk's
polymer system allows fewer water molecules to enter than do the amorphous polymer system of
wool. It absorbs water well (M.R.11%), but it dries fairly quickly.
Thermal properties - Silk is more sensitive to heat than wool. This is considered to
be partly due to the lack of any covalent cross links in the polymer system of silk, compared with
the disulphide bonds which occur in the polymer system of wool. The existing peptide bonds,
salt linkages and hydrogen bonds of the silk polymer system tend to break down once the
temperature exceeds 1000C.

Electrical properties - Silk is a poor conductor of electricity and tends to form static

charge when it is handled. This causes difficulties during processing, particularly in dry
atmosphere.

Hand feel - The handle of the silk is described as a medium and its very crystalline polymer
system imparts a certain amount of stiffness to the filaments. This is often misinterpreted, in that
the handle is regarded as a soft, because of the smooth, even
and regular surface of silk filaments.

Drapes Property - Silk fibre is flexible enough and if silk fibre is used to
make garments, then the fabric drapes well and this is why it can be tailored well too.

Abrasion resistance - Silk fabric possess good abrasion resistance as well

as resistance to pilling.

Effect of sunlight - Silk is more sensitive light than any other natural fibre. Prolonged
exposure to sunlight can cause partially spotted color change. Yellowing of silk fibre is generally
occurred due to photo degradation by the action of UV radiation of sunlight. The mechanism of
degradation is due to the breaking of hydrogen bonds followed by the oxidation and the eventual
hydrolytic fission of the polypeptide chains.

Chemical Properties of Silk Fiber:

Action of water - The absorption of water molecules takes place in the amorphous
regions of the fibre, where the water molecules compete with the free active side groups in the
polymer system to form cross links with the fibroin chains. As a result, loosening of the total
infrastructure takes place accompanied by a decrease in the force required to rupture the fibre
and increase extensibility. Treatment of silk in boiling water for a short period of time does not
cause any detrimental effect on the properties of silk fibre. But on prolonged boiling, silk fibre
tends to loss its strength to some degree, which thought to occur because of hydrolysis action of
water. Silk fibre withstands, however, the effect of boiling better than wool.

Effect of acids - Silk is degraded more readily by acids than wool. Concentrated sulfuric
and hydrochloric acids, especially when hot, cause hydrolysis of peptide linkages and readily
dissolve silk. Nitric acid turns the color of silk into yellow. Dilute organic acids show little effect
on silk fibre at room temperature, but when concentrated, the dissolution of fibroin may take
place. On treating of silk with formic acid of concentrated about 90% for a few minutes, a
swelling and contraction of silk fibre occur. Like wool, silk is also amphoteric substance, which
possesses the ability to appear as a function of the pH value either as an acid or as a base.

Effect of alkalis - Alkaline solutions cause the silk filament to swell. This is due to
partial separation of the silk polymers by the molecules of alkali. Salt linkages, hydrogen bonds
and Van der Waals' forces hold the polymer system of silk together. Since these inter-polymer
forces of attraction are all hydrolyzed by the alkali, dissolution of the silk filament occurs readily
in the alkaline solution. Initially this dissolution means only a separation of the silk polymers
from each other. However, prolonged exposure would result in peptide bond hydrolysis,
resulting in a polymer degradation and complete destruction of the silk polymer. Whatever, silk
can be treated with a 16-18% solution of sodium hydroxide at low temperature to produce crepe
effects in mixed fabric containing cotton. Caustic soda, when it is hot and strong, dissolves the
silk fibre.

Action of oxidizing agent - Silk fibre is highly sensitive to oxidizing agents.

The attack of oxidizing agents may take place in three possible points of the protein 1. At the
peptide bonds of adjacent amino groups,
1. At the N-terminal residues and
2. At the side chains
Though fibroin is not severely affected by hydrogen peroxide solution, nevertheless may suffer
from the reduction of nitrogen and tyrosine content of silk indicate that hydrogen peroxide may
cause breakage of peptide bonds at the tyrosine residues resulting in the weight loss of the fibre.
The action of chlorine solution on the silk fibroin is more harmful than does the solution of
hypochlorite. These solutions, even at their lower concentration, cause damage to fibroin.

Action of reducing agents - The action of reducing agents on silk fibre is still
a little bit obscure. It is, however, reported that the reducing agents that are commonly found in
use in textile processing such as hydrosulfite, sulfurous acids and their salts do not exercise any
destructive action on the silk fibre.

Cellulose :
Cellulose is an organic compound with the formula (C6H10O5)n, a polysaccharide consisting of a
linear chain of several hundred to many thousands of β(1→4) linked D-glucose units.[3]
[4]
 Cellulose is an important structural component of the primary cell wall of green plants, many
forms of algae and the oomycetes. Some species of bacteria secrete it to form biofilms. Cellulose
is the most abundant organic polymer on Earth. The cellulose content of cotton fiber is 90%, that
of wood is 40–50%, and that of dried hemp is approximately 57%.
Cellulose is mainly used to produce paperboard and paper. Smaller quantities are converted into
a wide variety of derivative products such as cellophane and rayon. Conversion of cellulose
from energy crops into biofuels such as cellulosic ethanol is under development as a renewable
fuel source. Cellulose for industrial use is mainly obtained from wood pulp and cotton.
Some animals, particularly ruminants and termites, can digest cellulose with the help
of symbiotic micro-organisms that live in their guts, such as Trichonympha. In human nutrition,
cellulose is a non-digestible constituent of insoluble dietary fiber, acting as a hydrophilic bulking
agent for feces and potentially aiding in defecation.

History
Cellulose was discovered in 1838 by the French chemist Anselme Payen, who isolated it from
plant matter and determined its chemical formula. Cellulose was used to produce the first
successful thermoplastic polymer, celluloid, by Hyatt Manufacturing Company in 1870.
Production of rayon ("artificial silk") from cellulose began in the 1890s and cellophane was
invented in 1912. Hermann Staudinger determined the polymer structure of cellulose in 1920.
The compound was first chemically synthesized (without the use of any biologically
derived enzymes) in 1992, by Kobayashi and Shoda.

The arrangement of cellulose and other polysaccharides in a plant cell wall.

Structure and properties

Cellulose has no taste, is odorless, is hydrophilic with the contact angle of 20–30 degrees,is
insoluble in water and most organic solvents, is chiral and is biodegradable. It was shown to melt
at 467 °C in pulse tests made by Dauenhauer et al. (2016). It can be broken down chemically into
its glucose units by treating it with concentrated mineral acids at high temperature.
Cellulose is derived from D-glucose units, which condense through β(1→4)-glycosidic bonds.
This linkage motif contrasts with that for α(1→4)-glycosidic bonds present
in starch and glycogen. Cellulose is a straight chain polymer. Unlike starch, no coiling or
branching occurs and the molecule adopts an extended and rather stiff rod-like conformation,
aided by the equatorial conformation of the glucose residues. The multiple hydroxyl groups on
the glucose from one chain form hydrogen bonds with oxygen atoms on the same or on a
neighbor chain, holding the chains firmly together side-by-side and forming microfibrils with
high tensile strength. This confers tensile strength in cell walls where cellulose microfibrils are
meshed into a polysaccharide matrix. The high tensile strength of plant stems and of the tree
wood also arises from the arrangement of cellulose fibers intimately distributed into
the lignin matrix. The mechanical role of cellulose fibers in the wood matrix responsible for its
strong structural resistance, can somewhat be compared to that of the reinforcement
bars in concrete, lignin playing here the role of the hardened cement paste acting as the "glue" in
between the cellulose fibers.

A triple strand of cellulose showing the hydrogen bonds (cyan lines) between glucose strands
Cotton fibres represent the purest natural form of cellulose, containing more than 90% of
this polysaccharide.
Compared to starch, cellulose is also much more crystalline. Whereas starch undergoes a
crystalline to amorphous transition when heated beyond 60–70 °C in water (as in cooking),
cellulose requires a temperature of 320 °C and pressure of 25 MPa to become amorphous in
water.[16]
Several different crystalline structures of cellulose are known, corresponding to the location of
hydrogen bonds between and within strands. Natural cellulose is cellulose I, with structures
Iα and Iβ. Cellulose produced by bacteria and algae is enriched in Iα while cellulose of higher
plants consists mainly of Iβ. Cellulose in regenerated cellulose fibers is cellulose II. The
conversion of cellulose I to cellulose II is irreversible, suggesting that cellulose I
is metastable and cellulose II is stable. With various chemical treatments it is possible to produce
the structures cellulose III and cellulose IV.
Many properties of cellulose depend on its chain length or degree of polymerization, the number
of glucose units that make up one polymer molecule. Cellulose from wood pulp has typical chain
lengths between 300 and 1700 units; cotton and other plant fibers as well as bacterial cellulose
have chain lengths ranging from 800 to 10,000 units.[6] Molecules with very small chain length
resulting from the breakdown of cellulose are known as cellodextrins; in contrast to long-chain
cellulose, cellodextrins are typically soluble in water and organic solvents.
Cellulose contains 44.44% carbon, 6.17% hydrogen, and 49.39% oxygen. The chemical formula
of cellulose is (C6H10O5)n where n is the degree of polymerization and represents the number of
glucose groups.[18]
Plant-derived cellulose is usually found in a mixture with hemicellulose, lignin, pectin and other
substances, while bacterial cellulose is quite pure, has a much higher water content and higher
tensile strength due to higher chain lengths.[6]:3384
Cellulose is soluble in Schweizer's
reagent, cupriethylenediamine (CED), cadmiumethylenediamine (Cadoxen), N-
methylmorpholine N-oxide, and lithium chloride / dimethylacetamide.[19] This is used in the
production of regenerated celluloses (such as viscose and cellophane) from dissolving pulp.
Cellulose is also soluble in many kinds of ionic liquids.[20]
Cellulose consists of crystalline and amorphous regions. By treating it with strong acid, the
amorphous regions can be broken up, thereby producing nanocrystalline cellulose, a novel
material with many desirable properties.[21] Recently, nanocrystalline cellulose was used as the
filler phase in bio-based polymer matrices to produce nanocomposites with superior thermal and
mechanical properties.[22]

Processing
Assay
Given a cellulose-containing material, the carbohydrate portion that does not dissolve in a 17.5%
solution of sodium hydroxide at 20 °C is α cellulose, which is true cellulose.[clarification
needed]
 Acidification of the extract precipitates β cellulose. The portion that dissolves in base but
does not precipitate with acid is γ cellulose.[citation needed]
Cellulose can be assayed using a method described by Updegraff (1969),[4] where the fiber is
dissolved in acetic and nitric acid to remove lignin, hemicellulose, and xylosans. The resulting
cellulose is allowed to react with anthrone in sulfuric acid. The resulting coloured compound is
assayed spectrophotometrically at a wavelength of approximately 635 nm.
In addition, cellulose can be represented by the difference between acid detergent fiber (ADF)
and acid detergent lignin (ADL).[23][24]
Luminescent conjugated oligothiophenes can also be used to detect cellulose using fluorescence
microscopy or spectrofluorometric methods.[25]
Biosynthesis
In plants cellulose is synthesized at the plasma membrane by rosette terminal complexes (RTCs).
The RTCs are hexameric protein structures, approximately 25 nm in diameter, that contain
the cellulose synthase enzymes that synthesise the individual cellulose chains.[26] Each RTC
floats in the cell's plasma membrane and "spins" a microfibril into the cell wall.
RTCs contain at least three different cellulose synthases, encoded by CesA (Ces is short for
"cellulose synthase") genes, in an unknown stoichiometry.[27] Separate sets of CesA genes are
involved in primary and secondary cell wall biosynthesis. There are known to be about seven
subfamilies in the plant CesA superfamily, some of which include the more cryptic, tentatively-
named Csl (cellulose synthase-like) enzymes. These cellulose syntheses use UDP-glucose to
form the β(1→4)-linked cellulose.[28]
Bacterial cellulose is produced using the same family of proteins, although the gene is
called BcsA for "bacterial cellulose synthase" or CelA for "cellulose" in many instances.[29] In
fact, plants acquired CesA from the endosymbiosis event that produced the chloroplast.[30] All
cellulose synthases known belongs to glucosyltransferase family 2 (GT2).[29]
Cellulose synthesis requires chain initiation and elongation, and the two processes are separate.
Cellulose synthase (CesA) initiates cellulose polymerization using a steroid primer, sitosterol-
beta-glucoside, and UDP-glucose. It then utilizes UDP-D-glucose precursors to elongate the
growing cellulose chain. A cellulase may function to cleave the primer from the mature chain.[31]
Cellulose is also synthesised by tunicate animals, particularly in the tests of ascidians (where the
cellulose was historically termed "tunicine" (tunicin)).[32]
Breakdown (cellulolysis)
Cellulolysis is the process of breaking down cellulose into smaller polysaccharides
called cellodextrins or completely into glucose units; this is a hydrolysis reaction. Because
cellulose molecules bind strongly to each other, cellulolysis is relatively difficult compared to the
breakdown of other polysaccharides.[33] However, this process can be significantly intensified in
a proper solvent, e.g. in an ionic liquid.
Most mammals have limited ability to digest dietary fiber such as cellulose. Some ruminants like
cows and sheep contain certain symbiotic anaerobic bacteria (such
as Cellulomonas and Ruminococcus spp.) in the flora of the rumen, and these bacteria
produce enzymes called cellulases that help the microorganism to digest cellulose; the
breakdown products are then used by the bacteria for proliferation.[35] The bacterial mass is later
digested by the ruminant in its digestive system (stomach and small intestine). Horses use
cellulose in their diet by fermentation in their hindgut via symbiotic bacteria which
produce cellulase to digest cellulose.[citation needed] Similarly, some termites contain in
their hindguts certain flagellate protozoa producing such enzymes, whereas others contain
bacteria or may produce cellulase
The enzymes used to cleave the glycosidic linkage in cellulose are glycoside
hydrolases including endo-acting cellulases and exo-acting glucosidases. Such enzymes are
usually secreted as part of multienzyme complexes that may include dockerins and carbohydrate-
binding modules.[37]
Breakdown (thermolysis)
At temperatures above 350 °C, cellulose undergoes thermolysis (also called ‘pyrolysis’),
decomposing into solid char, vapors, aerosols, and gases such as carbon dioxide.[38] Maximum
yield of vapors which condense to a liquid called bio-oil is obtained at 500 °C.[39]
Semi-crystalline cellulose polymers react at pyrolysis temperatures (350–600 °C) in a few
seconds; this transformation has been shown to occur via a solid-to-liquid-to-vapor transition,
with the liquid (called intermediate liquid cellulose or molten cellulose) existing for only a
fraction of a second.[40] Glycosidic bond cleavage produces short cellulose chains of two-to-
seven monomers comprising the melt. Vapor bubbling of intermediate liquid cellulose
produces aerosols, which consist of short chain anhydro-oligomers derived from the melt.[41]
Continuing decomposition of molten cellulose produces volatile compounds
including levoglucosan, furans, pyrans, light oxygenates and gases via primary reactions.
[42]
 Within thick cellulose samples, volatile compounds such as levoglucosan undergo ‘secondary
reactions’ to volatile products including pyrans and light oxygenates such as glycolaldehyde.[43]

Hemicellulose
Main article: Hemicellulose

Hemicelluloses are polysaccharides related to cellulose that comprise about 20% of the biomass

of land plants. In contrast to cellulose, hemicelluloses are derived from several sugars in addition
to glucose, especially xylose but also including mannose, galactose, rhamnose, and arabinose.
Hemicelluloses consist of shorter chains – between 500 and 3000 sugar units.[44] Furthermore,
hemicelluloses are branched, whereas cellulose is unbranched.

Derivatives
The hydroxyl groups (-OH) of cellulose can be partially or fully reacted with various reagents to
afford derivatives with useful properties like mainly cellulose esters and cellulose ethers (-OR). In
principle, though not always in current industrial practice, cellulosic polymers are renewable resources.
Ester derivatives include:

Cellulose Reagent Example Reagent Group R

 ester

Acetic acid and acetic
Cellulose acetate H or -(C=O)CH3
anhydride

Acetic acid and acetic

Cellulose triacetate -(C=O)CH3
anhydride

Organic Organic
Cellulose propionate Propionic acid H or -(C=O)CH2CH3
esters acids

Cellulose acetate Acetic acid and H or -(C=O)CH3 or -

propionate (CAP) propanoic acid (C=O)CH2CH3

Cellulose acetate butyrate Acetic acid and butyric H or -(C=O)CH3 or -

(CAB) acid (C=O)CH2CH2CH3

Nitrocellulose (cellulose Nitric acid or another

H or -NO2
nitrate) powerful nitrating agent
Inorganic Inorganic
esters acids
Sulfuric acid or another
Cellulose sulfate H or -SO3H
powerful sulfuring agent

The cellulose acetate and cellulose triacetate are film- and fiber-forming materials that find a variety of uses.
The nitrocellulose was initially used as an explosive and was an early film forming material. With camphor,
nitrocellulose gives celluloid.
Ether derivatives include:

Water E
Cellulose Group R = Applicatio
Reagent Example Reagent solubili numb
ethers H or n
ty er

Alkyl Halogenoalka Methylcellulos Chlorometh -CH3 Cold E461

nes e ane water-
soluble
 A
commercial
thermoplast
ic used in
Water-
Chloroethan coatings,
Ethylcellulose -CH2CH3 insolubl E462
e inks,
e
binders, and
controlled-
release drug
tablets

Chlorometh
Ethyl methyl ane and -CH3 or
E465
cellulose chloroethan -CH2CH3
e

Hydroxyal Epoxides Cold/ho Gelling and

Hydroxyethyl Ethylene
kyl -CH2CH2OH t water- thickening
cellulose oxide
soluble agent

Hydroxypropy
- Cold
l Propylene
CH2CH(OH) water- E463
cellulose (HP oxide
CH3 soluble
C)

Chlorometh
Hydroxyethyl Cold Production
ane and -CH3 or
methyl water- of cellulose
ethylene -CH2CH2OH
cellulose soluble films
oxide

Viscosity
Hydroxypropy Chlorometh modifier,
-CH3 or Cold
l methyl ane and gelling,
-CH2CH(OH) water- E464
cellulose (HP propylene foaming
CH3 soluble
MC) oxide and binding
agent

Ethyl Chloroethan -CH2CH3 or E467

hydroxyethyl e and —
 ethylene
cellulose CH2CH2OH
oxide

Often used
as
Carboxymethy Cold/H its sodium s
Halogenated
Carboxyal l Chloroaceti ot alt, sodium
carboxylic -CH2COOH E466
kyl cellulose (CM c acid water- carboxymet
acids
C) soluble hyl
cellulose
(NaCMC)

The sodium carboxymethyl cellulose can be cross-linked to give the croscarmellose sodium (E468) for use as
a disintegrant in pharmaceutical formulations.

Applications

Cellulose for industrial use is mainly obtained from wood pulp and cotton.[6] The kraft process is used to
separate cellulose from lignin, another major component of plant matter.

 Paper products: Cellulose is the major constituent of paper, paperboard, and card stock.

 Fibers: Cellulose is the main ingredient of textiles made from cotton, linen, and other plant fibers. It
can be turned into rayon, an important fiber that has been used for textiles since the beginning of the 20th
century. Both cellophane and rayon are known as "regenerated cellulose fibers"; they are identical to
cellulose in chemical structure and are usually made from dissolving pulp via viscose. A more recent and
environmentally friendly method to produce a form of rayon is the Lyocell process.
 Consumables: Microcrystalline cellulose (E460i) and powdered cellulose (E460ii) are used as
inactive fillers in drug tablets[45] and a wide range of soluble cellulose derivatives, E numbers E461 to
E469, are used as emulsifiers, thickeners and stabilizers in processed foods. Cellulose powder is, for
example, used in processed cheese to prevent caking inside the package. Cellulose occurs naturally in
some foods and is an additive in manufactured foods, contributing an indigestible component used for
texture and bulk, potentially aiding in defecation.[46]
 Science: Cellulose is used in the laboratory as a stationary phase for thin layer
chromatography. Cellulose fibers are also used in liquid filtration, sometimes in combination
with diatomaceous earth or other filtration media, to create a filter bed of inert material.
 Electrical insulation: Cellulose is used in different forms as insulation in transformers, cables and
other electrical equipment.[47]
 Energy crops:

The major combustible component of non-food energy crops is cellulose, with lignin second. Non-food

energy crops produce more usable energy than edible energy crops (which have a
large starch component), but still compete with food crops for agricultural land and water resources.
  Typical non-food energy crops include industrial hemp (though outlawed in some
[48]

countries), switchgrass, Miscanthus, Salix (willow), and Populus (poplar) species.

 Biofuel: TU-103, a strain of Clostridium bacteria found in zebra waste, can convert nearly any form of
cellulose into butanol fuel.[49][50]
 Building material: Hydroxyl bonding of cellulose in water produces a sprayable, moldable material as
an alternative to the use of plastics and resins. The recyclable material can be made water- and fire-
resistant. It provides sufficient strength for use as a building material.[51] Cellulose insulation made from
recycled paper is becoming popular as an environmentally preferable material for building insulation. It
can be treated with boric acid as a fire retardant.
 Miscellaneous: Cellulose can be converted into cellophane, a thin transparent film. It is the base
material for the celluloid that was used for photographic and movie films until the mid-1930s. Cellulose is
used to make water-soluble adhesives and binders such as methyl cellulose and carboxymethyl
cellulose which are used in wallpaper paste. Cellulose is further used to make hydrophilic and highly
absorbent sponges. Cellulose is the raw material in the manufacture of nitrocellulose (cellulose nitrate)
which is used in smokeless gunpowder.
 Pharmaceuticals: Cellulose derivatives, such as microcrystalline cellulose (MCC), have the
advantages of retaining water, being a stabilizer and thickening agent, and in reinforcement of drug
tablets.[52]

Hemp :
Hemp, or industrial hemp, is a strain of the Cannabis sativa plant species that is grown specifically for the
industrial uses of its derived products.[1] It is one of the fastest growing plants[2] and was one of the first plants
to be spun into usable fiber 10,000 years ago.[3] It can be refined into a variety of commercial items, including
paper, textiles, clothing, biodegradable plastics, paint, insulation, biofuel, food, and animal feed.[4][5]
Although cannabis as a drug and industrial hemp both derive from the species Cannabis sativa and contain
the psychoactive component tetrahydrocannabinol (THC), they are distinct strains with
unique phytochemical compositions and uses.[6] Hemp has lower concentrations of THC and higher
concentrations of cannabidiol (CBD), which decreases or eliminates its psychoactive effects.[6] The legality of
industrial hemp varies widely between countries. Some governments regulate the concentration of THC and
permit only hemp that is bred with an especially low THC content.

Uses
Hemp is used to make a variety of commercial and industrial products, including rope, textiles, clothing, shoes,
food, paper, bioplastics, insulation, and biofuel.[4] The bast fibers can be used to make textiles that are 100%
hemp, but they are commonly blended with other fibers, such as flax, cotton or silk, as well as virgin and
recycled polyester, to make woven fabrics for apparel and furnishings. The inner two fibers of the plant are
woodier and typically have industrial applications, such as mulch, animal bedding, and litter.
When oxidized (often erroneously referred to as "drying"), hemp oil from the seeds becomes solid and can be
used in the manufacture of oil-based paints, in creams as a moisturizing agent, for cooking, and in plastics.
Hemp seeds have been used in bird feed mix as well.[13] A survey in 2003 showed that more than 95% of hemp
seed sold in the European Union was used in animal and bird feed.[14]

Food:
Hemp seeds can be eaten raw, ground into hemp meal, sprouted or made into dried sprout powder. Hemp
seeds can also be made into a liquid and used for baking or for beverages such as hemp milk and tisanes.
[15]
 Hemp oil is cold-pressed from the seed and is high in unsaturated fatty acids.[16] The leaves of the hemp
plant, while not as nutritional as the seeds, are edible and can be consumed raw as leafy vegetables in salads,
and pressed to make juice.[17]
In 2011, the U.S. imported $11.5 million worth of hemp products, mostly driven by growth in the demand for
hemp seed and hemp oil for use as ingredients in foods such as granola.[18]
In the UK, the Department for Environment, Food and Rural Affairs treats hemp as a purely non-food crop,
but with proper licensing and proof of less than 0.2% THC concentration, hemp seeds can be imported
for sowing or for sale as a food or food ingredient.[19] In the U.S., imported hemp can be used legally in food
products and, as of 2000, was typically sold in health food stores or through mail order.[16]

Building material
Main article:  hempcrete

Concrete-like blocks made with hemp and lime have been used as an insulating material for construction. Such
blocks are not strong enough to be used for structural elements; they must be supported by a brick, wood, or
steel frame.[28] However, hemp fibres are extremely strong and durable, and have been shown to be usable as a
replacement for wood for many jobs, including creating very durable and breathable homes. The most common
use of hemp lime in building is by casting the hemp and lime mix while wet around a timber frame with
temporary shuttering, and tamping the mix to form a firm mass; after the removal of the temporary shuttering,
the solidified hemp mix is then ready to be plastered with a lime plaster.[29]
The first example of the use of hempcrete was in 1986 in France with the renovation of the Maison de la
Turquie in Nogent-sur-Seine by the innovator Charles Rasetti.[30] In the UK hemp lime was first used in 2000
for the construction of two test dwellings in Haverhill.[31] Designed by Modece Architects,[32] who pioneered
hemp's use in UK construction, the hemp houses were monitored in comparison with other standard dwellings
by BRE. Completed in 2009, the Renewable House is one of the most technologically advanced made from
hemp-based materials.[33] The first US home made of hemp-based materials was completed in August 2010 in
Asheville, North Carolina.[34]
A panellized system of hemp-lime panels for use in building construction is currently under test in a European
Union-funded research collaboration led by the University of Bath. The panels are being designed to assure
high-quality construction, rapid on-site erection, optimal hygrothermal performance from day one, and energy-
and resource-efficient buildings. The 36-month work program aims to refine product and manufacturing
protocols and produce data for certification and marketing, warranty, insurance cover, and availability of
finance. It also includes the development of markets in Britain, France, and Spain.[35]
Hemp is used as an internal plaster and is a mixture of hemp hurd (shive) mixed with larger proportions of a
lime-based binder. Hemp plaster has insulative qualities.[36]

Shellac :
Shellac is a resin secreted by the female lac bug, on trees in the forests of India and Thailand. It is processed
and sold as dry flakes (pictured) and dissolved in alcohol to make liquid shellac, which is used as a brush-on
colorant, food glaze and wood finish. Shellac functions as a tough natural primer, sanding sealant, tannin-
blocker, odour-blocker, stain, and high-gloss varnish. Shellac was once used in electrical applications as it
possesses good insulation qualities and it seals out moisture. Phonograph and 78 rpm gramophone
records were made of it until they were replaced by vinyl long-playing records from the 1950s onwards.
From the time it replaced oil and wax finishes in the 19th century, shellac was one of the dominant wood
finishes in the western world until it was largely replaced by nitrocellulose lacquer in the 1920s and 1930s.

Production

Lac tubes created by Kerria lacca

Drawing of the insect Kerria lacca and its shellac tubes, by Harold Maxwell-Lefroy, 1909

See also:  Lac

Shellac is scraped from the bark of the trees where the female lac bug, Kerria lacca (order Hemiptera,
family Kerriidae, also known as Laccifer lacca), secretes it to form a tunnel-like tube as it traverses the
branches of the tree. Though these tunnels are sometimes referred to as "cocoons", they are not cocoons in the
entomological sense.[2] This insect is in the same superfamily as the insect from which cochineal is obtained.
The insects suck the sap of the tree and excrete "sticklac" almost constantly. The least-coloured shellac is
produced when the insects feed on the kusum tree (Schleichera).

Colours and availability

Shellac comes in many warm colours, ranging from a very light blonde ("platina") to a very dark brown
("garnet"), with many varieties of brown, yellow, orange and red in between. The colour is influenced by the
sap of the tree the lac bug is living on and by the time of harvest. Historically, the most commonly sold shellac
is called "orange shellac", and was used extensively as a combination stain and protectant for wood panelling
and cabinetry in the 20th century.

Properties

Shellac is a natural bioadhesive polymer and is chemically similar to synthetic polymers, and thus can be

considered a natural form of plastic. It can be turned into a moulding compound when mixed with wood
flour and moulded under heat and pressure methods, so it can also be classified as thermoplastic.
Shellac scratches more easily than most lacquers and varnishes, and application is more labour-intensive,
which is why it has been replaced by plastic in most areas. But damaged shellac can easily be touched up with
another coat of shellac (unlike polyurethane) because the new coat merges with and bonds to the existing
coat(s). Shellac is much softer than Urushi lacquer, for instance, which is far superior with regard to both
chemical and mechanical resistance.
Shellac is soluble in alkaline solutions such as ammonia, sodium borate, sodium carbonate, and sodium
hydroxide, and also in various organic solvents. When dissolved in de-natured alcohol or ethanol, shellac
yields a coating of good durability and hardness.
Upon mild hydrolysis shellac gives a complex mix of aliphatic and alicyclic hydroxy acids and their polymers
that varies in exact composition depending upon the source of the shellac and the season of collection. The
major component of the aliphatic component is aleuritic acid, whereas the main alicyclic component
is shellolic acid.[11]
Shellac is UV-resistant, and does not darken as it ages (though the wood under it may do so, as in the case of
pine).[4]
History
The earliest written evidence of shellac goes back 3,000 years, but shellac is known to have been used earlier.
[4]
 According to the ancient Indian epic poem, the Mahabharata, an entire palace was built out of dried shellac.[4]
Shellac was in rare use as a dyestuff for as long as there was a trade with the East Indies. Merrifield[12] cites
1220 for the introduction of shellac as an artist's pigment in Spain. Lapis lazuli, an ultramarine pigment from
Afghanistan, was already being imported long before this.
The use of overall paint or varnish decoration on large pieces of furniture was first popularised in Venice (then
later throughout Italy). There are a number of 13th-century references to painted or varnished cassone,
often dowry cassone that were made deliberately impressive as part of dynastic marriages. The definition of
varnish is not always clear, but it seems to have been a spirit varnish based on gum benjamin or mastic, both
traded around the Merranean. At some time, shellac began to be used as well. An article from the Journal of
the American Institute of Conservation describes using infrared spectroscopy to identify shellac coating on a
16th-century cassone.[13] This is also the period in history where "varnisher" was identified as a distinct trade,
separate from both carpenter and artist.
Another use for shellac is sealing wax. Woods's The Nature and Treatment of Wax and Shellac
Seals[14] discusses the various formulations, and the period when shellac started to be added to the previous
beeswax recipes.
The "period of widespread introduction" would seem to be around 1550 to 1650, when the substance moved
from being a rarity on highly decorated pieces to being described in the standard texts of the day.

Uses
Historical
In the early- and mid-twentieth century, orange shellac was used as a one-product finish (combination stain
and varnish-like topcoat) on decorative wood panelling used on walls and ceilings in homes, particularly in the
US. In the American South, use of knotty pine plank panelling covered with orange shellac was once as
common in new construction as drywall is today. It was also often used on kitchen cabinets and hardwood
floors, prior to the advent of polyurethane.
Until the advent of vinyl, most gramophone records were pressed from shellac compounds.[15][16] From 1921 to
1928, 18,000 tons of shellac were used to create 260 million records for Europe.[7] In the 1930s, it was
estimated that half of all shellac was used for gramophone records.[17] Use of shellac for records was common
until the 1950s and continued into the 1970s in some non-Western countries.
Until recent advances in technology, shellac (French polish) was the only glue used in the making of ballet
dancers' pointe shoes, to stiffen the box (toe area) to support the dancer en pointe. Many manufacturers of
pointe shoes still use the traditional techniques, and many dancers use shellac to revive a softening pair of
shoes.[18]
Shellac was historically used as a protective coating on paintings.
Sheets of Braille were coated with shellac to help protect them from wear due to being read by hand.
Shellac was used from the mid-nineteenth century to produce small moulded goods such as picture
frames, boxes, toilet articles, jewelry, inkwells and even dentures. Advances in plastics have rendered shellac
obsolete as a moulding compound.
Shellac (both orange and white varieties) was used both in the field and laboratory to glue and stabilise
dinosaur bones until about the mid-1960s. While effective at the time, the long-term negative effects of shellac
(being organic in nature) on dinosaur bones and other fossils is debated, and shellac is very rarely used by
professional conservators and fossil preparators today.
Shellac was used for fixing inductor, motor, generator and transformer windings. It was applied directly to
single-layer windings in an alcohol solution. For multi-layer windings, the whole coil was submerged in
shellac solution, then drained and placed in a warm place to allow the alcohol to evaporate. The shellac locked
the wire turns in place, provided extra insulation, prevented movement and vibration and reduced buzz and
hum. In motors and generators it also helps transfer force generated by magnetic attraction and repulsion from
the windings to the rotor or armature. In more recent times, shellac has been replaced in these applications by
synthetic resins such as polyester resin. Some applications use shellac mixed with other natural or synthetic
resins, such as pine resin or phenol-formaldehyde resin, of which Bakelite is the best known, for electrical use.
Mixed with other resins, barium sulfate, calcium carbonate, zinc sulfide, aluminium oxide and/or cuprous
carbonate (malachite), shellac forms a component of heat-cured capping cement used to fasten the caps or
bases to the bulbs of electric lamps.

Current
It is the central element of the traditional "French polish" method of finishing furniture, fine string instruments,
and pianos.
Shellac, edible, is used as a glazing agent on pills (see excipient) and sweets, in the form of pharmaceutical
glaze (or, confectioner's glaze). Because of its acidic properties (resisting stomach acids), shellac-coated pills
may be used for a timed enteric or colonic release.[19] Shellac is used as a 'wax' coating on citrus fruit to prolong
its shelf/storage life. It is also used to replace the natural wax of the apple, which is removed during the
cleaning process.[20] When used for this purpose, it has the food additive E number E904.
Shellac coating applied with either a standard or modified Huon-Stuehrer nozzle, can be economically micro-
sprayed onto various smooth sweets, such as chocolate coated peanuts. Irregularities on the surface of the
product being sprayed typically result in the formation of unsightly aggregates ("lac-aggs") which precludes
the use of this technique on foods such as walnuts or raisins (however, chocolate-coated raisins being smooth
surfaced, are able to be sprayed successfully using a modified Huon-Stuehrer nozzle).
Shellac is an odour and stain blocker and so is often used as the base of "solves all problems" primers.
Although its durability against abrasives and many common solvents is not very good, shellac provides an
excellent barrier against water vapour penetration. Shellac-based primers are an effective sealant to control
odours associated with fire damage.
Shellac has traditionally been used as a dye for cotton and, especially, silk cloth in Thailand, particularly in the
north-eastern region. It yields a range of warm colours from pale yellow through to dark orange-reds and dark
ochre. Naturally dyed silk cloth, including that using shellac, is widely available in the rural northeast,
especially in Ban Khwao District, Chaiyaphum province. The Thai name for the insect and the substance is
"khrang" (Thai: ครั่ง).
Wood finish
Wood finishing is one of the most traditional and still popular uses of Shellac mixed with solvents or alcohol.
This dissolved Shellac liquid, applied to a piece of wood, is an evaporative finish: the alcohol of the shellac
mixture evaporates leaving behind a protective film.
Shellac as wood finish is natural and non-toxic in its pure form. A finish made of Shellac is UV-resistant. For
water-resistance and durability, it does not keep up with synthetic finishing products.
Because it is compatible with most other finishes, shellac is also used as a barrier or primer coat on wood to
prevent the bleeding of resin or pigments into the final finish, or to prevent wood stain from blotching.