Sizing Agents

&
Desizing
Requirement of a Good Size
Spun Yarns: require that size contribute to yarn strength and that
the protruding fiber ends be gIued down to make it Iess hairy. (The
sizing soIution must have a high viscosity to prevent penetration
into the yarn. most of the size remains on the yarn surface to coat
the yarn and gIue down the protruding hairs.)
Continuous FiIament Yarns: The main purpose of the size is to tie
aII of the fiIaments together making the yarn strong and abrasion
resistant. Viscosity needs to be Iow so that the soIution penetrates
into the yarn bundIe to give better adhesion between the size and
the fiber - better protection.
GeneraI requirements of a good size: tensiIe strength; abrasion
resistance; good adhesion; good extensibiIity; inexpensive; not
support miIdew growth; easy removaI; fIexibIe.
Sizing Agents
Materials that can be used as warp sizes
$tarches
Polyvinyl alcohol
Gums
Glue
Carboxymethyl Cellulose
Flours
Dextrine
Polyacrylic acid
Gelatins
$ynthetic polymers and copolymers
$tarch and polyvinyl alcohol are the polymers most often used
when sizing spun yarns.
$ynthetic polymers work best on filament yarns. These polymers
at times are blended with starch to improve starch's adhesion to
synthetic fibers.
$tarches
$tarches and flours have been the film former of choice for
textile sizing. The key difference between flours and starched
is the gummy substance :903. $tarches are flours which
have had the gluten been removed.
$ources of starches used textile sizing agents
Corn (maize)
Tapioca ( cassava)
Wheat
$weet potato
$ago
Rice
Yucca
Potato
Chemical constitution of starches
Amylose is a linear polymer, MW range
100,000 to 300,000 found in the interior
of the starch granule and account for 19
26% of the weight. t is soluble in hot
water, however , when the solution is
cooled, it will form strongly H - bond
between adjacent chains making it
difficult to re-solubilize.
Amylopectin is the major component
of starch and comprises the outer
sheath of the granule. A highly
branched high MW polymer (1.6M),
less water soluble than amylose.
aturaI starches cannot be used directIy in sizing. Cooking is necessary to
get the starch granuIes to form a homogenous soIution.
The starch granuIes are stirred in coId water and kept suspended by high
speed mixing.
As the temperature is raised, water penetrates through the amyIopectin
membrane soIubiIizing amyIose.
The granuIes sweII as more and more water diffuses in, expanding the granuIe
size to many time. The viscosity of the soIution increases and reaching a
maximum at the point where the swoIIen granuIes are crowding against each
other.
ProIonged heating and mechanicaI shearing cause the swoIIen granuIe
membrane to rupture aIIowing the soIubiIized amyIose to spiII into the buIk of
the soIution. At this point the viscosity begins to faII off, finds a stabiIized IeveI
and remains there.
The starch soIution can be considered as soIubiIized amyIose moIecuIes
intermingIed with ruptured swoIIen fragments of the amyIopectin membrane.
$tarch size preparation properties
Retrograding point
The starch soIution wiII remain fIuid as Iong as it is stirred and kept hot. However if
the soIution becomes concentrated by evaporation of water, and/or shouId the
soIution cooI down, an irreversibIe geI is formed which wiII not re-disperse, no
matter how Iong it is heated or stirred. MateriaIs that won't redissoIve once they
have been soIubiIized are said to retrograde.
ActuaIIy In the case of starch, the Iinear amyIose moIecuIes aIign themseIves, and
through hydrogen bonding, form 3-dimensionaI arrays that are difficuIt to break
apart. This pecuIiarity in starch is the reason specific processing conditions are
needed to economicaIIy remove it during desizing
$tarch size preparation properties
The working properties of starch soIutions (viscosity, retrograding point,
penetration into yarns etc.) are infIuenced by the origin of the starches. In addition
to naturaIIy occurring variations, there are chemicaI modifications where some of
the naturaI starch properties are aItered to make them more usefuI.
Modified Starches
1. Thin BoiIing Starch
Thin boiIing starches are made by adding a smaII amount of acid to a starch
suspension that is heId just beIow its geI point. The acid cIeaves the poIymer at the
gIucosidic Iinkage thereby Iowering the viscosity of a soIution made from it.
HydroIysis occurs within the granuIe without breaking the granuIe. MostIy corn
starch is used to make thin boiIing starches. Their soIutions stiII retrograde.
$tarch size preparation properties
2. Dextrin
Dextrin are made by heating dry starch with a mineraI acid. White dextrin is made
by heating at moderate temperatures and yeIIow dextrin is made by heating at
higher temperatures with Iess acid. The degree of hydroIysis is higher than for
thin boiIing starch so dextrin soIutions have Iower viscosity.
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Acid hydrolysis
D glucose unit
D glucose unit
aldehyde end group
Responsible for its reducing properties
3. British Gum
British gums are made by dry heating starch granuIes at 180
0
C without acid.
Some of the 1-4 acetaI Iinkages are broken and 1- 6 are formed. A more highIy
branched, Iower moIecuIar weight product is formed having more reducing end
groups. British gums are more water soIubIe and produce higher soIution
viscosity. They are mainIy used as print paste thickeners.
4. Oxidized Starch
Starch granuIes are oxidized with sodium hypochIorite which converts the 2-3
hydroxyI into -COOH groups breaking the ring at that point. Five to seven -
COOH groups per 100 anhydrogIucose are introduced. Sodium bisuIfite is
added to destroy excess hypochIorite. The granuIar structure is retained and
fiIms from oxidized starch are better than those formed from thin boiIing starch.
5. Starch Ethers
Starch ethers are made by reacting the hydroxyI groups in the anhydrogIucose
ring with appropriate reagents. These reactions add to the hydrophiIic nature of
the starch and decrease the abiIity to form hydrogen bonds between poIymers,
modifying soIution and dry fiIm properties.
Oxidation of Starch
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Starch ethers
Starch - OH +
CICH
2
COOH
Starch - O - CH
2
COOH (carboxyIated starch)
Starch - OH + R.CH - CH
2
O
Starch - O - CH - CH
2
OH
R
Where R = H - or CH
3
- (HydroxyethyI or hydroxypropyI starch
Desizing Starches
Once if a cooked starch soIution dried up and form a fiIm, it takes speciaI
chemicaI procedure to render it water soIubIe again
Enzymes
Acid hydroIysis
Oxidation
Each procedure has its own particuIar advantages and disadvantages
Enzymatic Desizing
Most appIied method in starch desizing.
Enzymes are high MW protein biocataIyst that are very specific in their
action.
AmyIase breaks down amyIose and amyIopectin into maItose a water
soIubIe disaccharide.
MaItase breaks down maItose into gIucose.
There are two types of amyIase: aIpha and beta.
AIpha amyIase attack the starch moIecuIar chain at random points. The
MW of the starch is rapidIy reduced Ieading to easy removaI.
Beta amyIase starts at chain end removing one maItose unit at a time, so
Ionger time is needed for compIete degrade of the starch.
There are 3 major sources of amyIase: maIt enzymes (aIpha and beta
amyIase mixture); Pancreatic enzymes (mainIy aIpha amyIase); and
BacteriaI enzymes (mainIy aIpha amyIase).
Optimum processing conditions for AmyIases
Desizing with Acids
MineraI acids wiII hydroIyze starch by attacking gIucosidic Iinkages. Acid
hydroIysis Iowers the moIecuIar weight and eventuaIIy reduce starch to gIucose.
HydrochIoric and suIfuric acids can be used.
One probIem with acid desizing is that ceIIuIose fibers are aIso degraded which is
why the method is not used much.
One advantage with using acids is that cotton fibers can be demineraIized.
InsoIubIe mineraI saIts are soIubiIized by acids making the removaI of such
troubIesome metaIs such as iron more compIeteIy.
Desizing with Oxidizing Agents
Sodium hypochIorite, sodium hypobromite and sodium or potassium persuIfate
wiII aIso degrade starch.
The reaction opens anhydrogIucose rings at the - 2,3 - hydroxyIs, converting
them into carboxyIic acid groups.
This method is not used much either because it degrades ceIIuIose fibers.
CarboxymethyI CeIIuIose (CMC)
CMC is made by the reaction of sodium chIoroacetate with ceIIuIose. The
degree of substitution can be controIIed up to a maximum of 3 Carboxy-
methyI groups per anhydrogIucose unit. For textiIe sizes, the DS is usuaIIy
1.5
More expensive than starch.
SoIubIe in coId water (no cooking step in appIication).
SoIution remain fIuid at room temperature and not retrograde.
Warm water onIy can remove the size.
Supports miIdew growth on storage of fabrics.
PoIyvinyI AIcohoI (PVA)
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Step I - synthesis of poIyvinyI acetate
Linear PVAc Branched
PVAc
Linear PVAc
AD
Branched PVAc
Step II - HydroIysis to PVA
SoIution properties of poIyvinyI aIcohoI
Water soIubiIity, viscosity of the soIution and fiIm properties are infIuenced by
the MW and degree of hydroIysis of the PVA.
As the number of acetate groups are converted to the corresponding - OH group,
the hydrophiIic nature of the poIymer increases up to a point where 88% of the
ester group are hydroIyzed.
When acetate ester groups remain the abiIity of the poIymer chains to form H-
bonds is interrupted by the ester group. This aIIows water moIecuIes easier
access to the -OH groups. (optimum water soIubiIity at 88% HydroIysis).
For textiIe sizing appIication, three grades are mainIy used.
% HydroIyzed SoIution temperature
FuIIy hydroIyzed 99 boiIing water
Intermediate hydroIyzed 95 70 C
PartiaIIy hydroIyzed 88 49 C
SoIution properties of poIyvinyI aIcohoI
Viscosity of the soIution is a function of moIecuIar weight. Low viscosity
soIutions are produced with Iow moIecuIar weight poIymers in the 25 to
35,000 range whereas poIymers in the 250 to 300,000 range give high
viscosity soIutions.
Properties of the dried fiIm are a function of both MW and the degree of
hydroIysis. Super tough fiIms are formed from high MW , fuIIy hydroIyzed
poIymers.
ffect of Heat-$etting on Removal of PVA
Greige heat-setting of fabrics with PVA size may insoIubiIize the size. When PVA
fiIms are heated above 120
0
C, water is eIiminated from the poIymer backbone to
form either unsaturation, or to form ether crossIinks between poIymer chains.
Either reaction wiII aIter the water soIubiIity of the poIymer. Once unsaturation
starts, the doubIe bond activates the spIitting out of a second moIe of water to
form a conjugated system. Conjugation is responsibIe for the darkening coIor of
the poIymer fiIm.
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AcryIic
Sizes
PoIyacryIic acid is a water soIubIe poIyeIectroIyte that has exceIIent adhesion
to nyIon therefore it is used to size fiIament nyIon yarns. The affinity is through
hydrogen bonding of the -COOH with amide and amine end groups in the nyIon
poIymer.
Synthesis of PoIyacryIic Acid
Desizing of poIyacryIic acid : By converting the -COOH to -COOa, water
soIubiIity of the poIymer is increased and hydrogen bonding with the fiber is
overcome. PoIyacryIic can readiIy be desized by saturating the fabric with aIkaIi
and washing out the soIubiIized size.
AcryIic acid can be co-poIymerized with many vinyI and acryIic monomers.
UsuaIIy acryIate esters (ethyI, butyI) are co-poIymerized with acryIic and
methacryIic acid. These co-monomers reduce water soIubiIity and increase
poIymer fIexibiIity and adhesion. As the free acid, the number of carboxyI
groups in the copoIymer are not sufficient to render the copoIymer water
soIubIe; however, when they are converted to the corresponding aIkaIi saIt,
the copoIymer becomes water soIubIe. These properties are put to good use
in water jet weaving. The size is appIied on the acid side, rendering the dried
fiIm insensitive to water. Water insensitivity is needed in water jet weaving
because buiId-up of water sensitive sizes on heaI-shafts and other Ioom parts
wiII cause Ioss of weaving productivity.
Effect of Heat- Setting on RemovaI
acryIic sizes are sensitive to greige heat setting. The carboxyI groups can
spIit out one moIe of water between two groups on adjacent poIymer chains
and form an anhydride. These anhydrides densify the poIymer structure,
sIowing down the penetration of water and aIkaIi. With time and temperature.
these anhydrides can be broken and the poIymer wiII re-dissoIve. The
carboxyIs are aIso capabIe of reacting with the amine end groups on the
nyIon surface to form amides. Once this happens, it is virtuaIIy impossibIe to
break these bonds and the size wiII be permanentIy fixed to the fiber.
Anhydride formation