Polymer Additive

“Any substance that is added generally in

small concentration to resins in order to
alter the properties either to facilitate
processing or to change the physical,
chemical or electrical properties of end
products”
 Additives=Performance+
property-preservation/retention
All these examples clearly show:

* Performance
* Property retention/preservation/protection
in severe service environment/condition

Polymer additives essential to provide

Performance
Property protection
Property preservation
 Additives Can

o Change the properties of plastic materials

o Enlarge the field of application drastically
o Protect your plastic against alteration and
degradation
o Help to meet the recycling requirements
o Extend the lifetime of product
o Differentiate with others
 Features of Additives
Should be efficient in their function.
Should be stable under processing and service
conditions.
Should not bleed or bloom.
Should be non-toxic and should not impart taste or
odour.
Should not adversely affect the properties of the
polymers.
Should be cheap.
Requirements
 Polymer additive can spoil
quality if care not taken properly
Quality of additive quite difficult to convert into
plastic properties
Chemical quality alone can not justify its use in
polymer
Numerous suppliers
Slow process of approval
Select standard additive product from leading
suppliers and not go for cost saving
Loss will be significantly high
Plastic Additives
 Functions of polymer additive
PERFORMANCE

POLYMER
ADDITIVES

PROPERTY
PROCESSABILITY
RETENTION
PRESERVATION
 Additives classification
Property modifier
Plasticizer
Impact modifier
Blowing agent
Coupling agent
Nucleating agent
Organic peroxide
Reinforcing agent
Additive classification
Property extender

Flame retardant
Heat stabilizer
Antioxidant
Light stabilizer
Antistatic agent
Additives classification
Processing aid

Lubricant
Mould release agent
Anti block additive
Slip additive
Classifications of Additives
Plastic Additives

Additives to modify plastics Additives achieve their effect

Properties by physical means by chemical reactions

Plasticizers Heat stabilizers

Lubricants Antioxidants
Impact modifiers UV absorbers
Fillers Flammable Retardants, etc
Pigments, etc.
 Additives which assist processing
Additives are classified according to their specific function rather than on a
chemical basis:

Processing Stabilizers : The resistance of polymer to

thermal degradation

Lubricant (External and : Frictional behavior of melt on

Internal) the metal surface

Processing Aid and Flow : Melting viscosity of the

Promotors polymer.

Thixotropic Agents : Processing variables

 Additives which modify bulk properties

a) Plasticizer
b) Reinforcing Fillers
c) Toughening Agents

Additives used to reduce formulation cost

a) Fillers
b) Diluents and extenders
 Additives for surface modification

a) Anti-static agents
b) Slip additives
c) Adhesion promoters
d) Anti wear additives

Additives used for optical modifier

a) Nucleating agents
b) Colorants
 Additives for anti aging properties

a) UV Absorber
b) Fungicides

Additives used for others

a) Blowing agents
b) Flame retardant
c) Bio or photo degradable
d) Foaming agents
Advantages of chain extender additives
 PLASTICIZER

A plasticizer may be defined as a substance which when

incorporated into a polymeric material improves:

o Flexibility and Processability

o Alters temperature depends properties such as

softening point low temperature flexibility

o Significantly effects tensile strength, elongation at

break and impact properties.

 Plasticizer Requirement

The plasticizer achieve these effects by reducing the

physical intermolecular forces between polymer
chains, thereby increasing chain mobility which results
in softening.

Chemically, plasticizers are generally high boiling,

non-volatile solvents, usually ester type organic
compounds, polar and with a relatively high molecular
weight.

The degree of polarity in a plasticizer depends to

some extent on the attractive forces between the
polymer chains.
 Types of Plasticizer
 Primary Plasticizer

 Secondary Plasticizer

Primary Plasticizer:
It should have a sufficient level of compatibility with
the polymer for use as sole plasticizer at all addition
levels giving a useful modifying effect and should not
exude from plasticized material.
For example DOP (Di octyl phthalate), Di iso octyl
phthalate Phosphates- Tricresyl Phosphate (TCP)
,Sebacetes ,Adipates etc
 Secondary Plasticizer

 Secondary plasticizer have lower gelation capacity and limited

compatibility with the polymer and are normally only used in mixture
with a primary plasticizer.
 They enhance the plasticizing performance of primary plasticizers.
When these are used as a cheap partial replacement for a primary
plasticizer to reduce cost that are called extenders e.g. chlorinated
paraffin, hydrocarbons,Di-octyl Sebacates (DOS), Adipic Acid
Polyesters ,Epoxidised oil

 Note: The plastizer may be primary or secondary depending on the

substrates such as mineral oils are primary for Poly (diene)s but
secondary for PVC.
 Mechanism of Plasticizer Action

 Lubricity Theory

 Gel Theory

 Mechanistic Theory

 Free Volume Theory

 Solvation Theory

 Thermodynamic Theory

 Polarity Theory
 Gel Theory
 The theory assumes the formation of an internal three
dimensional honeycomb structure or gel.
 Plasticizer molecules becomes attached to a given active
group only to be replaced by another.
 Considers the rigidity in an unplasticized resinous mass
to be caused by an internal three dimensional honey
comb structure or gel formed by loose attachments
between the resin macromolecules which occurs at
intervals along the molecular chains.
 Gel Theory
 The action of plasticizer on a resin with many points of
attachment along the polymer chains is breakage of the
attachment and masking of the centers of force which
holds the polymer chains together by selectively solvating
the polymer at these points.
 This results in a dynamic equilibrium, when a certain
fraction of the force centre of the polymer chain are
marked by the plasticizer under a given condition i.e.
concentration, temperature and pressure.
 Lubricity Theory
 This theory views the resistance to deformation as arising
from intermolecular friction. According to this theory the
plasticizer acts as a lubricant to facilitate movement of
the resin macromolecules over each other, thus reducing
the internal resistance to deformation.
 Plasticizer act as lubricant in exhibiting non-bonding
forces with the polymer.
 Lubricants lower intermolecular forces thereby causing
partial plastcizing.
 It decreases melt viscosity and facilitate processing.
 Lubricity Theory
 The resistance of a resin to deform is due to inter

molecular friction.

 The plasticizer acts as a lubricant to facilitate the

movement of macromolecules over each other and

provides internal lubricity.

 Thus, these lubricants both internal and external do not

allow the resin to melt.

 Technological Functions of Plasticizer

 Plasticize polymer.
 Decrease modulus of elasticity and tensile strength at
break.
 Increase extensibility and elongation at break.
 Improves flexibility.
 Improves reversed bending strength.
 Improves toughness and impact strength.
 Lower glass transition temperature.
 Extend applicability of polymer to lower temperature.
 Improves adhesion to various substrates.
 Technological Functions of Plasticizer

 Improve lubricity properties and reduce friction.

 Improve gloss and appearance of surface.
 Reduce electro statically chargeability.
 Act as internal lubricant.
 Reduce adhesion to melt surfaces.
 Lower processing temperature.
 Reduce melt viscosity
 Lower film forming temperature (in adhesion and lattices)
 Improve wetting and dispersion and pigment and filler.
 Choice of Plasticizer
Selection of plasticizer is done on basis of following:
 Volume cost analysis
 Compatibility
 Processing characteristics
 Thermal, electrical and mechanical properties
 Resistance to water, chemicals, weathering, dirt and
microorganism.
 Toxicity.
 Effect on rheological properties.
 ANTIOXIDENT

• Antioxidant retards oxidation and thus retard

the resulting ageing of the polymer
• Antioxidant used for stabilizing oxidative
degradation.
• Antioxidant as added as early possible in the
life cycle of the polymer (before drying stage of
the polymers)
• The numerous and diverse applications of
plastics today possible for development of
suitable antioxidants.
 Effect of Oxidation on Polymer Properties

• Oxidation occurs in the polymer during

# Manufacturing
# Storage
# Processing
# End use

• Plastics are sensitive to oxidation

• Stability against oxidation arise from

# Chemical structure of polymers
# Difference in the manufacturing process
# Morphology (crystalline, orientation)
# Commercial; polymer contains catalyst residue and
functional groups which sensitize oxidation
 Effect of Oxidation on Polymer Properties
• Virtually all polymeric materials undergoes oxidation due to
reaction with oxygen.
• Due to oxidation polymer turns to discoloration, loss of gloss or
transparency chalking and surface crack.
• Due to oxidation of polymers loss of mechanical properties
such as impact strength, elongation, tensile strength.
• Loss of physical properties such as water absorption, density
and visual
• Loss of chemical properties such as resistance to acid and
alkali, volume and mass etc.
 Oxidation of Polymers
• The reaction of organic compounds with molecular oxygen is
called auto-oxidation (oxidative degradation) because these
reactions are proceeds automatically
• During auto-oxidation of polymers there are mainly four types of
reaction:
# Initiation reaction generating the free radicals
# The propagation reaction
# Chain branching reaction yielding oxidation products
# Termination reactions elimination the free radicals
from system
 Initiation and Propagation
Generation of free radicals through heat, radiations, mechanical
stress, catalyst residue.
REACTION
Initiation

Propagation
Reaction of an oxygen molecules with free radicals corresponding
peroxy radicals
e.g. Alkyl radicals (P∙) transform rapidly to peroxy radicals (POO ∙)
in presence of oxygen
 Propagation and Chain Branching

Peroxy radicals (POO∙) abstract hydrogen from the neighboring

polymeric segment and forms hydro peroxide (POOH) and a new
free radical site.

Chain branching reaction involves decomposition of hydro

peroxides through
 Monomolecular decomposition (a)
 Psudeo-monomolecular reaction (b)
 Bimolecular reaction (c)
 Propagation and Chain Branching

REACTION
 Auto-oxidation of Polypropylene

 Presence of oxygen formed yield hydroperoxides and leads to further chain propagation,
chain branching and chain termination.
 Formation of free radicals by interaction with oxygen or catalyst residues.
 Thermal oxidation of PP consist mainly in the formation of aldehyde, ketones, carboxylic
acid, esters and -lactones.
 Presence of primary, secondary and tertiary hydrogen atoms in PP makes it susptable to
oxidation.
 The formation of hydro peroxide group through intermolecular hydrogen abstraction by six
member transition state.
 Block of hydroperoxide group leads the bimolecular decomposition of hrdroperoxides
 Monomolecular breakdown of a alkoxy radicals yields to methylketones and primary alkyl
radicals.
 Auto-oxidation of Polypropylene

The radical formed in the initiation, propagation and chain branching steps are not only
able to fix oxygen and abstract hydrogen but subject to molecular decomposition
reactions.
e.g. Decomposition of alkoxy radicals (PO*)
REACTION

Such reaction leads to chain scission thus decreases molecular weight of polymer
Auto-oxidation of Polypropylene
 Auto-oxidation of Polyethylene

Thermal oxidation of polyethylene leads to form ketenes,

carboxylic acid, aldehydes and volatile.
Oxidation leads to chain scissions by long chain branching
and cross linking.
Cross linking occurs through free radicals combinations
involving alkyl, alkoxy and peroxy radicals.
Reaction
 Auto-oxidation of Polyethylene

Thermal oxidation of polyamides leads to detoriation of the

mechanical properties.
Degradation occurs by free radicals attack on the hydrogen
atoms of the methylene groups to the nitrogen atoms.

Reaction
 Auto-oxidation of Styrene Polymers

The oxidation of PS forms volatile products like phenol,

benzaldehyde and acetophenone.
Thermal oxidation of PS leads to physical change through
intermolecular hydrogen abstraction.
Chain scissions of PS attribution by decomposition of
tertiary alkoxy radicals.
Presence of oxygen in PS decrease molecular weight during
processing.
Reaction
 Methods of oxidation stabilization

Structural modification of the polymer (e.g. co-polymerization

with vinyl group containing antioxidant)
Capping of the end groups.
Physical stabilization by orientation of the polymer (stretching)
Addition of stabilizing additives:

ANTIOXIDANT
 Classification of Antioxidant

Antioxidants are chemical entities, which retard oxidation and thus retard
the resulting aging of the polymer. Usually, they are effective at
concentration of a fraction of one percent. It is desirable to add the
antioxidant as early as possible in the life cycle of a polymer.
It is possible to use more than one antioxidant and this may give synergistic
effect more than 200%.

Antioxidant are of two types based on the function and mechanism:

1. Primary antioxidant (chain termination) – Radical Scavengers
2. Secondary antioxidant (hydroperoxide decomposing)
 Primary Antioxidant

They act rapidly and termed as ‘Radical scavengers’

E.g. Sterically hindered phenolics and secondary aromatic amines
Hindered Phenolics:
 They are high molecular weight and sensitive to thermal and
oxidative degardtion due to formation of free radicals and
peroxides.
 They protect againest degradtion at high processing
tempertaure and highly efficient, low in volatality and non-
staining with wide toxicological clecareance and are effective at
a very low dosage (0.01-0.1%).
 Secondary Antioxidant

They reacts with hydroperoxide to produce non-radical

products and are therefore, ofetn termed as ‘hydroperoxide
decomposers’
They differ from phenols and amines and on decomposed by
reaction with hydroperoxide, rather than containing it.
They are particularly useful in synergistic combination with
primary antioxidant.
There are two mechanism of antioxidant

1.Stabilization of chain breaking antioxidant

a. Chain Breaking Donor Mechanism (CB-D)
b. Chain Breaking Accepter Mechanism (CB-A)

2. Stabilization by preventive antioxidant.

 Chain Breaking Acceptor Mechanism (CB-A)

o The chain carrying radicals add to the inhibitor.

o The radiclas involved in this recation are alkyl radicals.
o CB-A mechanism forms product of phenols like dienones,
quinones, methides, stibene quinones and benzoquinones.
Flame retardant

“A flame retardants is a chemical compound which

adapts polymers to applications where fire safety is a
consideration.”
WHY IT IS USED ?
Thermoplastics are hydrocarbons sometimes contains
O(PC), N(Nylon), Halogen(PVC) etc.
These are easily combustible in the presence of oxygen
& fire.
Fire retardants prevent the thermoplastic material from
fire.
 Basic Requirements of Flame Retardants

 The flame retardants should provide durable flame retarding

effect by adding small quantity of additive.
 It should be cheap.
 It should be no means cause corrosion of the processing
equipment.
 It should not be affect the mechanical & physical property of
the base resin.
 It should be non-toxic.
 It should not be decompose at processing temperature.
 It should not volatilize.
 Classification of Flame Retardants

(1) BASED ON MECHANISM OF ACTION

(a) Causing char formation in pyrolysis zone:
E.g. Cellulose + phosporus compound(F.R.).
Dehydration (flame)
Unsaturated compound
Crosslinking char.
BASED ON (CONTD)………..
(b) F.R. that decompose to give –
# Product which cools the pyrolysis zone

Alumina decomposes
e.g. Polymer + Alumina flame to give water vapour
which cool the
pyrolysis zone

# Non flammable gases CO2 that

e.g. Polymer +sodium bicarbonate flame cutt the
supply of O2
BASED ON (CONTD………)
(c) Retarding combustion process in vapour phase-
It is possible by tracking free radicals.
(2) BASED ON COMPOSITION
(1) CHLORINE CONTAINING
e.g. Tetrachlorobisphenol-A --- Used for PC.
e.g. Chlorinated styrene --- Used as a comonomer for styrene &
ABS
e.g. Hexachloroendomethylenetetrahydrophalic acid --- Used for
unsaturated polyester
e.g. Hexachlorocyclopentadiene --- Used for polyolephine
ADVANTAGE– Favourable price
DISADVANTAGE-(1) Low thermal stability
(2) Applicable for thermoplastic below 200*C
 BASED ON COMPOSITION (CONTD…..)

(2) BROMINE CONTAINING

e.g. Dibromopentaerythrital --- Used for Linear Polyester &
Polyurethanes
e.g. Hexabromocyclododecane --- Used for Polyolefins
e.g. Octabromodiphenyl --- Used for Linear Polyester & ABS.
e.g. Hexabromobenzene --- Used for Polyamides
e.g. Tetrabromobisphenol-A --- Used for PC. & Epoxy resin.
ADVANTAGE –(1) On weight basis it is twice effective as
Chlorine containing.
(2) Because of smaller quantities it hardly
influence the mechanical properties.
DISADVANTAGES – (1) Reduces the U.V. stability
(2) Higher price than organic chlorine
compound.
 BASED ON COMPOSITION (CONTD…….)
(3) PHOSPHOROPUS CONTAINING
e.g. Quaternary phosphonium compound --- Used for ABS
&Polyolefins.
e.g. Read Phosphorus & Alkali salts of Phosphoric acids ---
Used for Polyamides
(4) BORON CONTAINING
e.g. Borax & Boric acid --- These forms a glassy layer
which protects the flammable plastic from flame &
oxygen
 APPLICATIONS FOR FLAME RETARDED THERMOPLASTIC

 ELECTRICAL , TRANSPORTATION , BUILDING &

FURNITURE INDUSTRIES
(1) ELECTRICAL - Flame retarded strenic polymers --- used
for cabinet of T.V. & phonodevices.
(2) TRANSPORTATION – Flame retarded polyamides --- used
for Aircraft & Ship construction.
(3) BUILDING – Flame retarded Polyolefins.
(4) FURNITURE – Flame retarded Polyolefins HIPS & ABS.
 Physiological Effects of Combustion Gases

COMBUSTION GASES HAZARD RESPONSE

(1) Carbon monoxide produced
in all fires.
(2) Carbon dioxide.
(3) Nitrogen dioxide –produced
from cellulose nitrate.
(4) Hydrogen cyanide –
produced from combustion of
polyacrylonitrile,nylon,polyur
ethane etc.
(1) 1% fatal when inhaled for 1
min.
(2) Toxic by it self only in high
concentration.
(3) Strong pulmonary irritant
capable of causing
immediate death as well as
delayed injury.
(4) Rapidly fatal.
COUPLING AGENTS
 Introduction
Definition: A coupling agent is a chemical which
improves the adhesion between two phases in a
composite material.
The two examples of composite materials
i) Resins containing glass fiber reinforcement;
ii) Thermosetting and thermoplastics containing
particulate fillers.
Example : Coupling agent for glass fiber is
Organosilanes.
Ex: Methacrylato-chromo chloride used for glass fibres
& Polyester resin
Organosilanes are used for PVC , ABS and PA
 COUPLING AGENTS FOR GF REINFORCED PLASTICS

It promote adhesion and thereby facilitate the

load transfer.
Promote sizing which means to bind together a
large number of delicate filaments into more
robust strands which convert continuous
filaments into woven fabrics or so that they can
survive as short fibre bundles in thermoplastics
processing machinery.
Coupling agent used for sizing for the glass
fibre is Polyvinyle aceatate.
 Mechanical Properties of the GF reinforced plastics

Many mechanical properties are improved by

appropriate coupling agents applied to the glass fibres:
(a) transverse tensile strength;
(b) short beam shear strength;
(c)10 degrees off-axis tensile strength.
(d) shows a crack propagation normal to the fibre
reinforcement, facilitated by excessively good adhesion
between fibres and matrix.
 ORGANOSILANES
A silane is a chemical compound containing a
hydrogen-silicon bond and referred to as silicon
hydrides, e.g. SiH4, or SiC13H.
Organosilanes are the organic compounds in
which the hydrogen atom is replaced by the
organic compound.
The main limitation is that at least one of the
groups must be reactive towards the functional
groups of the polymer, and at least one of the
others must be reactive towards the fibre or
mineral surface, so as to produce a chemical
'bridge'.
Action of silane coupling agents.
In addition to silanes, a variety of
organometallics (primarily titanates, but also
zirconates, aluminates, and zircoaluminates)
are used as coupling agents.
A specialty class of coupling agent are the
maleated polyolefins.
Maleic anhydride unit reacts with surface
hydroxyl groups (or siloxy group in the case
of pretreated fillers) while the polymeric
portion cocrystallizes with the polymer
matrix.
Their main applications are in glass-filled
PP composites.
The addition of 1–2% maleated PP can
improve the tensile strength of a 30% glass-
filled PP by up to 40%.
 Heat stabilizers

Mode of Action of Stabilisers

PVC heat stabilisers usually act either

by removing hydrogen chloride from the mix as soon as it forms

(because as stated above, HCl is a catalyst for further degradation)
or
by reacting with the allylic chloride units formed during PVC
degradation.
The mechanism of action of mixed metal stabilisers can be
explained by considering the Ba-Zn carboxylate combination. It is
believed to involve three main reactions:

oThe exchange of carboxylate groups for the labile allylic chlorine

atoms in PVC, forming zinc chloride which, instead of acting as a
strong Lewis acid catalyst for degradation; then:

oReacts with barium carboxylates to produce barium chloride; the

latter then:

oReacts with and removes the hydrogen chloride.

Stabilizers a) Heat
1. Heat speeds up the oxidation (aging) process
a. Aging – loss of both visual and mechanical properties
a.Visual – discoloration (yellowing), loss of gloss or transparency,
chalking, surface cracks
b.Mechanical – loss of impact strength, elongation, tensile, etc.

b. Highly unsaturated (ready to share electrons) polymers are much more

sensitive to oxidation
c. Stability depends on:
a.Chemical structure

b.Manufacturing process

c.Morphology (crystallinity, orientation)

2. Many of today’s plastics applications and processes would not be possible

without the use of anti-oxidants.
Heat Stabilizers (continued)
3. Various means of retarding thermal oxidation.
a. Structural modification of the polymer – e.g.
copolymerization with vinyl group containing antioxidants
b. Capping of end groups - mainly polyacetal
c. Physical stabilization by orientation
d. Addition of antioxidants – most common
method
Heat Stabilizers (continued)
4. Most polymers are thermally stable when not in the presence of
Oxygen. Autoxidation – the reaction of organic compounds
with molecular Oxygen.
a. Three main reactions need to be taken into account
1.Initiationreactions – generation of free radicals
a) Initiation reactions are caused by heat, mechanical stress, or a
combination of the two.
b) Peroxy free radicals are formed
2.Propagation – chain branching reactions, leads to reduction in molecular
weight
3.Termination reactions – elimination of free radicals from the system

a) Free radicals consumed

b) Causes some degree of cross-linking
Heat Stabilizers (continued)
5. Types
A. Most important types of Anti-oxidants interfere in chain
breaking or chain propagation steps
1)Tin– commonly used in pipes
2)Lead – used in many

outdoor applications
3)Mixed metals – Ba+Ca

used in PVC
B. Secondary types
– destroy hydroperoxide
groups
Heat Stabilizers (continued)
6. Polymers can be oxidized at any point in their life cycle;
manufacturing, storage, drying, processing, and end use.
A. Stabilizers are consumed – must put enough into polymer to
see it through its life cycle
 Light stabilizers(UV stabilizers)

Mechanism of action of light stablizers

Light-Absorbing Fillers

The addition of screening fillers reduces the penetration of the light into the
polymer. The ability of carbon black to absorb UV radiation is well known. It has
the advantage over conventional organic additives,

Organic UV Absorbers

These substances are added in much smaller doses. They compete with
chromophores, absorbing the light in a way that does not lead to destructive
reactions, turning it into heat, or undergoing fluorescence or phosphorescence.

Organic UV absorbers are much less effective than the inorganic ones but,
when used in conjunction with other antioxidants, such as hindered phenols or
hydroperoxide decomposers, there is a strong synergistic effect.
Heat Stabilizers (continued)

7. Concerns
A.Toxicity

B.Color stability

C.Thermal stability
D.Hydrolitic stability

E.Volatility

F.Compatibility
 Stabilizers b) Light

Light Stabilizers - chemical compounds capable of interfering with

the physical and chemical processes of light-induced
degradation (mainly UV)
1. Carbon Black and other colorants may also protect plastics from
the effects of light, they are considered pigments.
A. Only compounds which confer slight or no discoloration
are considered light stabilizers.
The UV absorber must be capable of absorbing light at or near to the
point in the spectrum at which the polymer in question absorbs harmful
radiation most easily, i.e., in the range 260-400 nm (a tendency to undergo
absorption in the visible region will colour the polymer).

The most important UVAs are derivatives of 2-hydroxybenzophenone

and 2-
hydroxybenzotriazole. Hydroxyphenyltriazines are also used. Less
common UVAs include the oxanilides and cyanoacrylates.

Excited State Quenchers

Quenchers protect polymers by dissipating energy that has already been
absorbed by a chromophore, without causing degradation. They do this
either by generating heat or by emitting fluorescent or phosphorescent
radiation.

The best-known quenchers are nickel chelates, such as nickel

dibutyldithiocarbamate.
Incorporation of Photoantioxidants Such As Hindered Amine Light
Stabilisers (Derivatives of 2,2,6,6-Tetramethylpiperidine)

HALS operate by a combination of different mechanisms,

including the trapping of free radicals,

 the deactivation of hydroperoxides,

and the formation of charge transfer complexes with oxygen.

 Light Stabilizers (continued)

2. Most important light stabilizers

A. 2-hydroxybenzophones
B. 2-hydroxyphenyl benzotriazoles
C. Hindered amines (HALS – hindered amine light
stabilizers)
D. Organic Nickel compounds
 Light Stabilizers (continued)

3. Concentrations used are generally 0.05%-2% - 2% rarely used

4. Mechanism
A. Light hits polymer – either reflected, absorbed, or scattered.
Only absorbed light has a degenerative effect.
? Which type of polymer is more sensitive to photo oxidation?
B. Light that is absorbed excites the chromophoric group, and
when oxygen is present photo oxidation occurs – free radicals
form
C. Effects are magnified by heat, oxygen,
and humidity
 Light Stabilizers (continued)
5. Methods of Stabilization – tested w/ accelerated weathering
A. Prevent UV absorption or limit it
1)UV absorbers convert the UV radiation into heat
a. Must be very stable or will be consumed quickly
b. Disadvantage – must have a certain absorption depth
(thickness) for good protection – not good for films or
coatings
B. Deactivate the excited state of the chromophoric group –
quenchers, able to take over the energy of the chromophoric
group.
C. Transform hydroperoxides into more stable compounds
without
generating free radicals – free radical scavengers (HALS)
 Light Stabilizers (continued)

7. Influence of pigments on light stabilizer performance – most

articles are colored
A. Pigments can act as sensitizers
and reduce the stability of the
polymer – most common in
organic reds and yellow pigments
B. Some pigments increase stability,
especially in thick samples
C. Some pigments take over the role
of stabilizer and prevent UV
radiation from reaching the
deeper layers of the polymer
D. Color can strongly influence the
surface temperature of the part
 FILLERS

Solid additives incorporated into the polymer to modify its physical properties &
mechanical properties.
Type of filler.
Inert fillers.
Function
o They very often modify polymer properties
o Reduce die swell on extrusion.
o Increase modulus.
o Increase Hardness
o Improve electrical insulation properties.
o Reduce tackiness,
o Reduce tensile strength
o Impact energy.
Example:-
- Caco3 (china clay)

-BaSO4
Classification of Inert filler

 Average particle size and size distribution

.
 Particle shape and porosity.

 Chemical nature of the surface.

 Impurities such as frit and metal ions.

Reinforcing fillers
The term reinforcing filler has been coined to describe discontinuous additives, the
form, shape, and/or surface chemistry of which have been suitably modified with
the objective of improving the mechanical properties of the polymer, particularly
strength.

Mechanism Inorganic reinforcing fillers are stiffer than the matrix and deform less,
causing an overall reduction in the matrix strain, especially in the vicinity of the
particle as a result of the particle/matrix interface.

Function
There are effective mainly in elastomer
 They also increase tensile strength in plasticized PVC.
Classification of Reinforcing fillers
 An extensity factor the total amount of surface area of filler per unit
volume in contact with the elastomer.
 An intensity factor the specific activity of the filler polymer interface
causing chemical and physical bonding.
 Geometrical factors such as structure and porosity of the particles.
Example:-
Carbon Black, Fine Particle Silica, Al(OH)2,Zinc Oxide and Calcium
Silicates
Classification of fillers according to five primary functions, as follows:

 mechanical property modifiers (and further subdivision according to aspect

ratio);

 fire retardants;

 electrical and magnetic property modifiers;

 surface property modifiers;

 processing aids.

Additional functions may include degradability enhancement, barrier

characteristics, anti-ageing characteristics, bioactivity, radiation absorption,
warpage minimization, etc.
Chemical families of fillers for
plastics
Particle morphology of fillers
Fillers and their functions
 Antistatic Agents
Unless they are protected, Plastics have tendency to accumulate
electrostatic charges at every step their lives ,in processing,during
transit ,Storage & at the consumer’s Dust attracted to the surface create
electrical hazards even electrical shocks.
Type of Antistatic agents.

-Internal Antistatic Agents

-External Antistatic Agents.

Function -
-Internal &External Antistatic Agents dissipate the static charges by
increasing the surface conductivity of products.
-External agents are subject to wear and exposure. Therefore Internal agents
provide longer-term protection than do external agents.
-Because of their shorter –term durability, external require greater concentration
than Internal.
-They must be compatible with the polymer but there must be certain amount of
incompatibility in order to migrate to the surface.
-
On the surface, they attract moisture form the atmosphere to provide the surface
conductivity,
- The external agents are usually applied by dipping or spraying. whereas
Internal
agents are compounded with the polymer .
Example :- Amines, anionics, and quaternary ammonium compounds.
Definition of Anti-Static Materials
 Blowing Agents

Many polymers are used in a cellular form in which the polymer matrix is filled
with gas-filled cells. Over the years many methods have been devised for producing
cellular polymers of which the most important are the following:
1.Incorporation of a chemical compound which decomposes at some stage of the
processing operation to yield volatile reaction products. These are known as chemical
blowing agents.
2.Incorporation of low boiling liquids which volatilise during processing. Such volatile
blowing agents are important with polystyrene and polyurethanes.
3.Diffusion of gases into the polymer under pressure with subsequent expansion of the
composition at elevated temperatures after decompression. Such a process can be
employed with a wide variety of polymers.
4. Incorporation of powdered solid carbon dioxide which volatilises at elevated
temperatures. This process has been used in conjunction with PVC pastes.
5. Chemical reactions of polymer intermediate during polymerisation and/or
cross-linking. This is important with polyurethanes.
6. Mechanical whipping of polymers in a liquid form and subsequent ‘setting’ in
the whipped state. The manufacture of latex rubber foam is the best-known
example of this approach.
7. Incorporation of hollow or expandable spheres of resin or of glass
(microballoons).
8. Leaching out of soluble additives.
Function
 Blowing agents are used to create a cellular structure in structural foam
moldings.
 They used in making flexible sheeting and coated fabrics or PVC.
 Cellular plastics are produced by injecting air or nitrogen into the melt
stream mechanically.
 Adding a solid or chemical blowing agents are added by compounding.
 Direct metering into the machine hopper with a proportioning feed device
is used fore the liquid type blowing agents.
Amount varies with the application and the concentration is usually 2% or
smaller.
Blowing agents ate selected according to their gas yield, the melt viscosity ,
processing temperature of the resin & Temperature at which the agent
decomposes.
 Correlate the temperatures of the agent and resin so that the agent will
decompose when the melt so at the proper viscosity.

Example- Azodicarbonamides, azobisformamide, and hydrazides and

compounds that liberate N2 & CO2 when heated form the basis of Chemical
blowing agents.
Chemical Blowing agents used commercially
 STRUCTURE OF FOAMS

As a result of this the texture and properties of cellular plastics

can be widely controlled through such variables as average
cell size, cell size distributions (including the possibility of
some very large cells being present in a structure largely
composed of small cells), degree of intercommunication
between cells and the use of non-cellular skins. Such
variables are in turn controlled by processing conditions and
by the use of cell nucleating agents and cell stabilisers in
addition to the blowing agent.
LIST OF CHEMICAL BLOWING AGENT LISTED IN TABLE
 CHEMICAL BLOWING AGENTS

A number of general comments may be made about chemical blowing agents. In

addition to the requirements common to all additives there are some special
requirements. These include:
1.The need for gases to be evolved within a narrow but clearly defined temperature
range and in a controlled and reproducible manner.
2.The decomposition temperature should be suitable for the polymer. For example, a
decomposition temperature for a blowing agent system for PVC should not be above
the maximum possible processing temperature that can be used if significant
degradation is not to occur.
3.Gases evolved should not corrode processing equipment. Whilst many hundreds
of materials have been investigated as blowing agents the number in actual use is
very small.
 Polyurethane Foam: Carbon dioxide formed as a result of th
chemical reaction between di-isocyanates and water.
 Physical blowing agents
They are additives which are non-reactive in the chemical sense
and consist either of volatile liquids (organic, or inorganic, e.g.
water) or compressed gases, such as carbon dioxide or nitrogen,
which are dissolved under pressure in the polymer so as to form a
foam when the pressure is released.
Processing of foamed plastics requires special equipments as the
physical blowing agents are in the liquid state and the polymer is
also in the molten state.
Examples: Aliphatic hydrocarbon and their chlorofluoro analogue.
These are soluble in the molten pressurized plastic and upon
reduction of the processing pressure these solvents volatilize and
forms the cells.
The efficiency of the BA depends upon the solubility in the polymer
at a specific temperature, pressure
 Physical blowing agents

 Factors affecting the growth of the cell.

pressure of the gas as its solubility in the polymer decreases.
Efficiency of the dispersion
Melt temperature
Presence of the nucleating agent
 Colorants

The majority of plastic parts produced are colored. In its

natural state, most thermoplastics have a yellowish or
straw-colored tint to them.

Color is important because it imparts quality or perceived

value to the parts in question.
There are many variables that can affect color in plastic parts
 Base material type
 Part thickness
 Processing conditions
 Colorant mean particle size
 Colorant particle shape
 Colorant type

Think about the automotive sector of the plastics industry- they are trying to
color match automotive body panels made in different areas of the
country in different machines and at different cycle times.

Color is extremely important to them and they have invested a lot of time
and effort to establish consistent test methods.
Function of colorants
 Colorants ate added to resins to impart a variety of end
product aesthetic properties.

 These provide include hue, opacity, transparency, fluorescence,

iridescence, and pearlescence.
Types of colorants
-DYES
-PIGMENTS
 DYES

Function
Dyes are usually soluble, although not always when reducing with
some resins.
 They are small size particles.
 It is used primarily to give brilliant transparent color to clear
plastics.
 They are added to pigments to change their tonal value.
The fine particle size of dyes enables them to be used in
extrusions.
 They reduce plugging of screen packs.
 They have the advantages of migrating easily.
 They readily bonding to plasticizers,
Their disadvantages include poor resistance to chemicals ,Processing
temperatures ,Limited stability to light & also have tendency to bleed.
 PIGMENTS

Types
-ORGANIC PIGMENTS.
-INORGANIC PIGMENTS
 ORGANIC PIGMENTS.
Function
 Pigments are large particles that scatter light by diffraction and refraction.
 Organic pigments are made from dyes that have been made insoluble.
 They remain solid particles suspensions in polymer matrices.
 They differ widely in performance, and an evaluation of requirements
should be made by the processor before making a choice.
Example- Azo pigments( disazos are superior to monoazo in heat stability, light
fastness, and bleed resistance)
 INORGANIC PIGMENTS
Function
 Inorganic pigments consist of salts & oxides of metal.
 The colors of Inorganic pigments are not so brilliant as with dyes and
organic pigments.
 They have fair tinting strength and good hiding powers.
 Inorganic pigments tend to resist high processing temperatures.
 They are readily dispersible.
Example –
Oxides of Titanium(white) ,Iron(red), Cd(Yellow) Chromates, Molybdates ,
suplfates , sulfides &salts of Metal Like Lead Zinc, mercury barium etc.
 Forms of Colorant used

Pigments are applied as dry, as compounds, as colors concentrates, in

paste form.
-Dry colors are particulate blends that contain no resin.

-Compounds are pellets nlended or pigment and resin by

custom compounds is used where the ultimate in color uniformity is
required.
-Color concentrates contain higher loadings than the compounds and are let
down or mixed with uncolored resin, the pellets are easy to weigh, and
they have good dispersion capabilities because of the mixing that they have
already undergone. Color concentrates are widely used by thermoplastic
processors.
The amount of concentrates used can run as high as 5 % of
the total product, but is usually 1 or 2 %.
-Processors of vinyl or liquid thermo sets are wide users of paste
concentrates. There are dispersed in vinyl plasticizers or directly into the resins
in the case of thermo sets. Such as polyesters, epoxies, and urethanes.
 Problems with consistency with
colorants
1. Lot-to-lot differences – like paint – slight differences
between batches
2. Slight differences within lot
3. Process can influence final color
a.Heat history
b.Shear heating

c.% crystallinity

4. Thickness of part will change

apparent color
5. Particle size can be significant
6. Colorant can affect process
Colorants can affect process and properties
1. Lubricants can affect flow properties

2. Base material for masterbatch changes

3. Definite affect on crystallinity – distortion, brittleness

Color Variation
Parts too dark Parts too light or streaked
Lower temperatures Raise temps
Lower speeds Raise back pressure
Lower back pressure Ensure good mixing – Additive Ensure good
mixing feeder
Reduce LDR Increase LDR
Use a filter or dispersion disk
Common problems with colorants
1. Metamerism
2. Dichroism
3. Thermal Stability
Very important when using organic colorants
Important even when using inorganic colorants - high
heat history can change the color by changing the color
of the base resin
Common problems with colorants
4. Migration – mobility of colorants or other additives as a
result of partial solubility.
1.Organic only

2.3 types

5. Plate Out - deposition of pigment containing plastics or

plastic constituents on mold or die surfaces (Acetal)
Types of Migration
1. Solvent Bleeding – the release of coloring constituents into
an organic liquid – primarily Dyes and Organic Pigments

2. Contact Bleeding – color

transfer in a solid/solid system

1. Blooming – migration of pigment particles to the surface of

the part. Produces a bronze-like haze. (Organic Pigments)
Plate Out
1. Causes surface (finish) defects of parts

2. Can cause problems with flow in hot runner systems

3. Caused by inadequate compatibility of one of the

ingredients

4. Can cause stress concentrations - pits

 Mold Release Agents
Mould release agents are substances which help to separate
the molding, i.e. the product, from its mould when it has
been made.

The choice of release agent depends on the size &

complexity of the molding operation, and on the quality of
the surface finish required.

Two types :
 Internal release agent
 External release agent
 INTERNAL RELEASE AGENTS
Internal release agents are used in molding compounds,
including injection molded plastics.

Examples are zinc stearate, calcium stearate, Aluminium

stearate, and stearic acid for lower temperature moulding.

These are added to the polymer during compounding at

about the 1 to 3% level.
 EXTERNAL RELEASE AGENTS
External mould release agents use with thermosets resins,
mainly in open mould and low throughput operations.

Examples:
 Hydrocarbon waxes

 Poly(viny1 alcohol) solutions, can be sprayed or brushed.

 Cellulose acetate, dissolved in acetone used in GF reinforced plastics.

 PTFE and related fluorinated polymers are prayed.

 Silicone release agents :

 External Mold Release
Prevents adhesive bonding of rubber to the mold.

Ensures high quality part surface.

Two different types of mold release agents currently used:

Conventional and Semi-permanent Release Agent.
 Conventional Mold Release Agents

Silicone is the most common release agent, and it is

available in solvent-based and water-based forms.

Works by transferring significant portion of release film to

the molded part.

There is little or no bonding to mold; no cross-linking.

Molded parts bonded later will require extensive cleaning.

 Conventional Mold Release Agents
Soap is the most commonly used release agent for this
material.

Works by transferring significant portion of release film to

the molded part.

Little or no bonding to mold; no cross-linking.

High surface tension of soap solution yields a difficult ease

of release.
 Semi-Permanent Mold Release
Cross-linkable polymers that are available in solvent-based
and water-based forms.

Require a short cure time allowing carrier to evaporate &

release polymers to bond a mold.

Bonding is responsible for durability and abrasion

resistance (hence multiple releases).

Use of EZ-KOTE SPRA result in continuously cross-linked

release film with low transfer to part, low build-up on
mold, and low defect rate.
 Semi-Permanent Mold Release Agents

PTFE is the most common SPRA. It is available in solvent

and water-based forms.

EZ-KOTE 100% Fluoropolymer cross-linkable Non PTFE

polymers are the latest SPRA technology.

Bonding is responsible for durability and abrasion

resistance (hence multiple releases).

Low surface tension is responsible for ease of release.

 Antiblocking Agents
All polymer films tend to stick to themselves. This adhesion is
termed as BLOCKING.
Film blocking is experienced most frequently on polyolefin films
such as PE and PP.
 In order to prevent film surfaces from blocking, small amounts
of powdered materials is incorporated in polymer, called anti-
blocking agents.
Examples
For high grade packaging films: synthetic silicas such as
fumed silica, silica gel or zeolites.
Lower-quality and pigmented film grades : Naturally
occurring silicas and minerals such as clay, diatomaceous earth
(DE), quartz or talc.
These anti-blocking agents create imperfections on the film’s
surface and prevent the total contact of the two film layers,
reducing blocking.
 Continued …..
The primary causes of blocking are pressures or temperatures
that the film may encounter during extrusion, use, or storage.
Film hardness and the presence of additives such as plasticizers
have a substantial influence on blocking.

A relatively soft PVC will block to a greater degree than a

relatively hard film such as PET or HDPE.

For any type of film, increasing temperature, pressure, or

processing time under varying temperatures and pressures
will increase the degree of blocking.
 Blocking can be reduced by:

Introducing a thin coating of a non-sticking compound of micron-

sized solid particles.

Creating microscopic roughness on the surface of the film to

separate layers.

Silica gel in micronized form has the greatest potential in anti-

blocking.

The loading in the film depends on the film characteristics, the end
use, and the efficiency of the anti-block.

Synthetic silica gel may vary from 1000 ppm in an LLDPE film and
talc up to 5000 ppm in LLDPE.
 FACTORS AFFECTING ANTI-BLOCK PERFORMANCE

Average particle size, particle size distribution, particle

shape and particle strength.

Average particle size is generally in the range of 6-20% of

the film thickness in LDPE & PP films.

The narrow distributions ensure that the largest number of

particles are of the most efficient size.

The strength of the anti-blocking agent particles is

important in order to retain size and shape during the high
shear conditions encountered when the anti-blocking agent
is incorporated in the polymer resin.
 INCORPORATION OF ANTI-BLOCKING AGENTS

Direct addition at the final concentration, or via a

concentrate or master batch that is added to resin to achieve
the final concentration.

The concentration of anti-block may range from 5 to 10%

for synthetic silica to 30-50% for talc.

To achieve the most thorough mixing, the blended

materials are then fed into a mixer/compounder which may
be batch equipment, such as a Banbury or Henschel; or into
a twin-screw compounding extruder and melt compounded.
Nucleating Agents
 INTRODUCTION

All known nucleating additives are “heterogeneous”

nucleators; that is, they present a heterogeneous surface to
the Polymer melt during cooling that promotes polymer
crystallization through epitaxial effects.

During the cooling phase, a well-dispersed nucleating agent

in molten Polymer, through this epitaxial or template-like
effect, causes the formation of many more polymer crystals
at a higher temperature as compared to the same resin
without a nucleating agent. This process is shown pictorially
in Figure 1.
 Classes of Nucleating Agents

Commercial nucleating agents can be divided into three classes.

These will be identified as follows:

• Conventional Nucleating Agents – examples include minerals such

as talc and calcium carbonate and aromatic carboxylic acid salts such as
sodium and lithium benzoate.

• Advanced Nucleating Agents – examples include phosphate ester

salts. Advanced nucleating agents generally give higher crystallization
temperatures and improved stiffness vs. conventional nucleating agents.

• Hyper Nucleating Agents – examples include organic carboxylic

acid salts. Hyper nucleating agents give higher crystallization
temperatures and more isotropic shrinkage vs conventional and advanced
nucleating agents.
Nucleating agents increase the temperature at which polymers begins to
crystallize upon cooling and increase the overall rate of crystallization.

These effects result in shorter part cooling times in injection molding

processes, which translate into shorter molding times and increased
productivity.

The polymer crystallization temperature (polymer Tc) can be measured by

differential scanning calorimetry (DSC) following ASTM D-794-85.