ADDITIVES IN PLASTICS

M.Amutharasan
Officer - PADC.

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Agenda
Additives Introduction
Why Additives in polymer?
Classification of Additives
(Mechanism, Function, Application )
Surface Property Modifiers
Processing Modifiers
Mechanical Property Modifiers
Chemical Property Modifiers
Aesthetic Property Modifiers

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Additives

What is mean by additives?

A compound or substance added to a polymer to improve
or alter some characteristic of the polymer

Dhal

End Product

Masala

Polymer

Additives

End Product

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Why additives in plastics?

Additives Make Plastics Easier To Process
Additives Make Plastics Look good
Additives Save Money
Additives Make Plastics Safe
Additives Make Plastics Clean And Healthy
Additives Make Plastics Work Longer
Additives Respect The Environment

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Additives
Classificat
ion
Mechanical Property
Modifiers

Plasticizers

Impact modifiers

Fillers
Nucleating agents

Chemical Property Modifiers

Processing Modifiers

Surface Property
Modifiers

Slip Agents

Antiblocking agents

Lubricants

Antistatic agents

Antifogging agents

Processing Aid

Slip agents and

lubricants

Thickening agents

Heat stabilizers

Blowing agents

Aesthetic Property Modifiers

Antioxidants

Colorants (Dyes and pigments)

Flame retardants

Odorants

Ultraviolet stabilizers

Nucleating agents

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Surface
Property
Slip Agents
Modifiers
Antiblocking agents

Lubricants
Antistatic agents
Antifogging agents

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Slip Additives
Why Slip

Slip additives are used to reduce a films sliding

resistance over itself or parts of converting equipment

Useful in high speed packaging processes

Slip Measurement

Measured by: Coefficient of Friction

Example:

Important's of slip :

Example: Pouching machine output (meter/min)

Without Slip = 25 Nos Pouches

With slip = 40 Nos Pouches

Steramides,

Erucamides

Oleamides

Can run optimum machine speed

Function of Slip Additive is to reduce COF

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Slip
Migration
Mechanism

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AntiBlocking:
Blocking
Adhesion between the film layer

The blocking results in increased friction

(resistance to motion)
Blocking can be controlled by the use of antiblocking additive.
Examples:

Synthetic Silica Gel

Limestone

Natural Silica

Talc

Organic Anti-block additives

Importantsof
ofAntiblock:
Antiblock:
Importants
Example:Slitting/Lamination
Slitting/Laminationmachine
machinespeed
speed
Example:

WithoutAntiblock
Antiblock==80
80meter/min
meter/min(Poor
(PoorQuality)
Quality)
Without
WithAntiblock
Antiblock=120
=120meter/min
meter/min(Good
(GoodQuality)
Quality)
With

Easyopening
openingpouch
pouchfor
formaterial
materialfilling
filling
Easy

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Mechanism

Antibloc
k

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Static Electricity:

Antistatic
Agent

Atoms can hold a positive or negative charge. If the material is an insulator ,this
charge can be held and not move.

Antistitic Agent:

Reduces the static electric charge on the surface of the part.

Antistatic agents are used where charge build up on surfaces may cause
problems

Due to the hygroscopic nature of antistats a conductive layer is formed on the

polymer

Example:

Ethoxylated amine (EA),

Glycerol monostearate (GMS)

Lauric diethanolamide (LDN)

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Applicati
Antistatic bag, used to contain devices, such as
ons of
graphics cards or hard disk drives.
Antistati
Antistatic garments, used in electronics,
c Agents
telecommunications and defense applications.

Antistatic mat, ranging from small mats for keyboards,

mice and larger for people to stand on.

Antistatic strap, consisting of a metal component

which presses against the skin when worn on the wrist
or heel, in turn relayed to an electrical ground

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Polymer

Antist
atic
Commonly Used Antistats
Agent

Polyethylene
Ethoxylated alkylamines,
(HDPE,LDPE,LLDPE)/PP
Glycerol monostearate
Lauric diethanolamide
Alkyl quatemary
Rigid PVC
Ammonium Chloride
Sodium alkyl Sulfonates
Sodium alkyl Sulfonates
Plasticized PVC
Glycerol monostearate
PET
Sodium alkyl Sulfonates
Polycarbonate
Sodium alkyl Sulfonates
Ethoxylated alkylamines,
Styrenics(ABS,PS,HIPS)
Sodium alkyl Sulfonates

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Antistati
c time):
i. Static decay time (or charge decay
Time required to dissipate
a certain fraction of an
Measure
applied 5 kV static charge & measured in seconds.
ments
ii. Surface resistivity

It is simply the resistance of a product at its surface

and is measured in Ohms .

Surface resistivity (109 to 1013 Ohms) antistatic

Surface resistivity > 1014 Ohms insulative

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Lubric
Lubricants reduce the frictional heating & shear between two
ants
surfaces.

Creates a cushioning effect between the molecules.

Lubricants are used to facilitate processing of polymers and may

serve as lubricants in the application.

Lubricants decrease the frictional forces between:

Polymer : Polymer

Polymer : Metal

Polymer : Filler

Filler : Filler

Filler : Metal

Classification:

External Lubricant

Internal Lubricant

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Classification of Lubricants
External Lubricants
Typically provide lubrication between the
polymer and the metal surface of the
processing equipment.
Insoluble in polymer
Example:

Polyethylene waxes, Paraffins,

Metal Stearates, Esters, Amides,

Fatty Acids etc..

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Lubricant
Internal Lubricants
s
Semi-Soluble in polymer

Typically reduce bulk viscosity

through partial compatibility with
the polymer, thus opening the
polymer chain with the lubricants
soluble component while
providing intermolecular
lubrication with the less soluble
portion of the molecule.
Example:

Fatty alcohols, EVA Wax etc..

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Internal Lubricants

General
EffectsExternal
of Lubricants
Lubricants
Provide metal release

Promote flow

Exhibit good clarity

Help reduce process temperature

Promote weld line strength

Slow fusion/ recrystallization

Improve die filling

Can cause delamination

Reduce die swell

Can lower weld line strength

Reduce back Pressure

Can cause surging

Lower HDT

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Lubricants
Advantages of Lubricant:

Helps improve the appearance of dull parts by providing a

smooth, high gloss finish.

Promotes efficient colorations of the plastic at low use rates

Reduce the wear on processing machinery.

Application:

Lubricant additives are principally used in injection molding and

blow molding operations where high shear has the potential to
destroy the desired properties of the final part.

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Fogging:

Antifogging
Agent

Fogging is the term used to describe the formation of small

discrete droplets of water on the surface of transparent plastic
films.

How fog occurs in film:

when there is a temperature differential between the inside and

the outside of an enclosed atmosphere causing localized cooling
at the interface

Causes:

Reducing the aesthetic quality in food Packing.

In agriculture film it reduce light transmission, reduction in

growth and crop yield.

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Antifogging
Function of Antifogging Agent:
Agent
Antifogging agent that migrate to the surface both raising the surface
energy of the polymer and lowering the surface energy of any water
droplets.

This changes the interfacial tension between water and polymer

surface allowing the condensed water droplets to spread into a
continuous and uniform transparent layer on the fabricated film.

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Chemical
Property
Antioxidants
Modifiers

Flame retardants

Ultraviolet stabilizers

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Antioxidant
Need of Antioxidants

Polymer oxidation occurs during

Types of Antioxidant:

manufacturing &end use time due to

Primary Antioxidant (Ex.phenolic)

heat, sunlight, mechanical stress etc.

Results

Loss of strength, stiffness

Discoloration

Loss of gloss

Secondary Antioxidant (Ex.

Phosphites or phosphonites)

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Classification of Antioxidant
Primary

Used to protect the finished product.

Effective way to protect the polymer during processing, especially when the polymer
undergoes multiple heat.

Phenolic-based additives

Secondary

It is used as a process stabilizer.

This type of stabilization ensures performance over the life of the finished good.

Phosphites or thioesters based additives.

Primary/Secondary Combination

Both primary and secondary antioxidants are often used in a combination. In this way, the
polymer is protected both during the processing step and throughout its service life.

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Application
of
Antioxidant

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Flame Retardants

Polyolefin materials are flammable material.

Additives needed to prevent polymer materials from burning.

To increase ignition resistance and reduce rate of flame spread.

Flame Retardants limit the spread of fire and save lives by

allowing time to escape.

FRs are used in HIPS, ABS, epoxy, nylon, thermoplastic,

polyester, foams, polyolefin's, other textiles.

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Flame-retardant
FRs Types:

Brominated flame retardants,

Chlorinated flame retardants,

Phosphorous-containing flame
retardants,

Nitrogen containing flame

retardants,

Inorganic flame retardants.

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Applica
Furniture
tion Of
Electrical &Electronics TV, Switch boards,computer,
copier, handhelds, toys FR

Appliances hair dryer, microwave, wire and cable

Transportation car and airplane cushion and interior

plastics

Interior home and office finishes curtains, shades,

carpets, lighting.

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UV
Ultraviolet (UV) stabilizers, that protect polymeric and other lightStabilizer
sensitive materials from degradation by sunlight and artificial
sources of UV light.

UV radiation causes chemical and physical changes in plastics.

These stabilizers function by absorbing high energy UV radiation and

then releasing it at lower energy level that is less harmful to the
polymer.

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UV Stabilizer

UV Radiation
IR Radiation

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Effect of UV Radiation

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Class

Classificati
on of UV
Stabilizer

Product

Benzophenones

Absorbers

Benzotriazoles
Aryl esters (salicylates, hydroxybenzoate)

Quenchers

Nickel organics

Screeners
carbon black,

Free-radical terminators

Hindered amine light stabilizers (HALS)

(monomeric, oligomeric)

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Application
of UV
Stabilizer

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Processing
Modifiers
Blowing agents

Processing Aid
Slip agents
Lubricants

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Blowi
ng
Agent

Foaming agents, also referred to as blowing agents, are chemicals

that cause the formation of cells and voids as a result of gas
release.

Foaming can be described in a four steps.

Foaming agent must be homogeneously dispersed in the

polymer during the liquid or melt state (it may also be
incorporated into the chemical makeup of the polymer)

The formation of many individual small cells results as the

foaming agent releases the gas.

The individual cells are allowed to grow into larger cell Third,
cell

Finally, the polymer is stabilized by cooling, cross linking or

otherwise increasing the viscosity to impair cell growths

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Classification of Blowing Agent

Physical blowing agent.

Gas : air, nitrogen, carbon dioxide.
Low-boiling liquid : pentane, CFC (not to be used now, because of

ozone

depletion)

Chemical blowing agent.

Byproduct CO2 for polyurethane synthesis.
Decompose on heating and give off nitrogen.

Function:

The vaporization of the blowing agents generates the expansion of the polymeric

matrix, allowing the foam to rise.

The quantity of blowing agent is responsible for the final density of the foam.

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Blowing Agent

Examples :

Azocarbonamide

Sodium bicarbonate

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Applicatio
Blowing agent is a key-component to obtain good insulation
n of
properties (low thermal conductivity).
Blowing
Agent

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Polymer Processing Aids

Polymer processing aids are a group of materials used to

improve the processability of (high molecular weight) polymers.

Function of PPA:

Eliminate melt fracture and improve surface finish.

Reduce die-buildup.

Improve throughput & minimize energy consumption.

Reduce the incidence of gel formation.

Improve processability of recycled or reground polymer.

Application

Blown film to fiber,

Injection molding,

Profile extrusion,

Pipe/tubing and cabling processes

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Role of Polymer Processing Aid

Die Build Up

Types:

An amide of a saturated or
unsaturated carboxylic acid.

A saturated or unsaturated alkylene

bis-amide of a saturated or
unsaturated dicarboxylic acid.

An aliphatic hydrocarbon polymer.

Boron Nitride

With PPA no
die buildup

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Role of Polymer Processing Aid

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Without
PPA- Melt
Narrow dies / high extrusion outputs brings high shear rates
fracture
Change of velocity at the die exit brings melt fracture (also
referred as sharkskin)

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With PPAMakes a coating on barrel & die extruder inner surface

Melt
Reduces shear rate / viscous drag in the die :
fracture
Occurrence of melt fracture is delayed / extruder output
is increased
Surface aspect is improved !

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Mechanical
Property
Plasticizers
Modifiers
Nucleating agents

Fillers

Impact modifiers

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Plasticizers

A plasticizer is a liquid that is added to polymer, making

that polymer softer, more flexible and easier to process.
Plasticizer mostly used in PVC
UPVC-Application

PPVC-Application

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Plasticizer
Mechanism:
Plasticizer molecules reduce s
polymer-polymer interactive
forces and prevent the formation of a rigid network.

Reduce Melt Viscosity

Result is increased flexibility, softness &

elongation

Examples

Phthalates

Trimellitates

Phosphates etc.
Extrusion of plasticized PVC are used to make garden hose,
medical tubing , auto floor mats, gaskets and wire insulation

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Why Nucleators?

Nucleati
ng
agent/
Clarifiers

PP is a semi-crystalline polymer. Nucleating agents increase the crystallization

rate and the overall percent crystallinity of the polymer.

Faster crystallization rate allows for higher productivity in molding and extrusion
processes.

Overall percent crystallinity of the polymer improves the stiffness & heat
deflection temperature

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Nucl
eatin
g
agent

Clarifiers are Organic material, Can gives more clarity.

Example: Dibenzylidene sorbitol (DBS)

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Advanges:

Nucleating agent

Reduced cycle times

Example:

Homogeneous crystallization in thick parts and

Sodium,lithium salts.

films

Sorbitol Derivatives (DBS,MDBS)

Upgrading stiffness, impact strength, abrasion

resistance, enhanced surface, optical properties.

Reduced Spherulites Structure

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Fillers
Fillers are added to polymers mainly to reduces cost and
improve the properties of the material.

Polymers use less expensive fillers to replace some of the

volume of more expensive materials.

Fillers can improve processing, abrasion resistance, density

control, dimensional and thermal stability, and optical
effects.

Example: Carbon black,Talc,Silica,Minaral,glass Fillers etc.

Selection Criteria:

Particle Size Distribution

Particle Shape

Surface area of particle

Chemical composition

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Fillers Dispersion

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Why Fillers?
Properties

Effects

Advantages
Thermal Stability

Reduce the cost.

Reduce the shrinkage

Reduce the warpage in thin wall

molded articles

Stiffness
Tear Resistance

Reduces Flammability

Printability

Improve dimensional Stability

Improves adhesion and

Disadvantages
Processability
Strength
Moisture Barrier

Printability

Improves Opacity

Improves HDT and thermal

conductivity.

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Fillers
Applicati
on

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Impact
Modifier

Impact Modifier is a type of additive used to improve impact strength by

controlling Craze propagation and withstand at high loads.

In order to fulfill the industry requirements, polymers, such as polyamide,

polyester, PVC or bioplastics, need improved impact resistance.

Mechanism

Craze propagation
The principle is to disperse impact modifiers into the brittle matrix, a
dampening phase capable to absorb energy and stop craze propagation.

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Applicati
on of
Impact
Modifier

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Coloran
ts

Colors playing important role in Politics as well as Plastics too.

May eliminate the need for external color treatment (painting).

Colorants is a substrate added polymer to get attractive look.

Classification:
Pigments
Dyes

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Pigments

Colorant
s-

Pigments are insoluble in polymer.

Ease of wetting or dispersion.

Resistance to light, heat and chemical

It gives dull & opaque color

Pigments

Master Batches
Classification:

Organic Pigments(Pthalocyanines,Azo pigments)

Inorganic Pigments (titanium dioxide, iron oxide)

Application:

Used in Polyolefin's (LLDPE,LDPE,HDPE,PP)

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Colorants
Dyes

Soluble within Polymers & disperse easily

Stronger than pigments and give brighter colors and are

more transparent

Allows light to pass

It will bleed out when exceeds the limit

Dyes Insoluble in Polyolefin's.

Dyes Example:

Anthraquinones

Perinones

Application:

Used in Nylon,ABS, PC,PMMA,GPPS

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Colorant
Most common white pigments:
s
Titatiumtitatiumdioxide(TiOdioxide(TiO2) and Barium Sulphate,
Lithopone)

Most common black pigment: carbon black

Colored pigments are often chosen based on the processing

temperature:
Pthalocyanines mostly used at present.
Cadmiums, Iron Oxide, Cobalt aluminates are not used now
a days because of high toxic

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Pigments
Applications

The pigments can be used to colour

Thermoplastics,

Lacquers,

Inks (including printing inks),

Cosmetic articles,

Baking varnish,

Glass,

Synthetic resins.