Polymer Additives and

Reinforcements
 Polymer solubility-1
Schematic representation of the dissolution process for polymer molecules

a) Polymer molecules in solid state just

after being added to a solvent c) Second step: solvated polymer
molecules dispersed into solution

Solubility depends on;

Crystalinity
Molecular weight
Branching
Polarity

b) First step: a swollen gel in solvent Crosslinking degree

 Polymer solubility-2

G m  H m  TSm

Entropy change during mixing

Gibbs free energy

Enthalpy change during mixing

Solubility will occur if the free energy of mixing ∆Gm is negative.

The entropy of mixing is believed to be always negative.
Therefore, the sign and magnitude of ∆Hm determine the sign of ∆Gm.
 Polymer solubility-3

Two-dimensional lattice model of solubility for a Two-dimensional lattice model of solubility for a
low molecular weight solute polymer solute

http://www.pslc.ws/macrog/ps4.htm
 Water absorption of polymers
Polymer Water absorption(%)
polyester 0,2
polycarbonate 0,2
polystyrene 0,1
polyarcylonitrile 1,5
nylon 6,6 1,5
nylon 6 1,5
polytetrafluoroethylene 0
polypropylene 0
polyethylene 0
polyethyleneoxide 0,4
Polymer combustion

combustion products

flammable Region

gas layer
pyrolysis layer
Heated layer

Inner portion that is not affected from

combustion

Combustion rate
Polymer
(mm/min)
Sytrene-butadiene rubber 57
LDPE 39
HDPE 23
polypropylene 34
ABS 56
Conductive Polymers
 Electrical Properties-2

Dielectric constant Dielectric Force

Polymer
(1 kHz) (kV/mm)
Natural rubber 2,9 50
ABS 2,9 18
Polycarbonate 4,4 33
Nylon 6,6 4,1 16
Polyethylene terephthalate 3,0 15
Poly (vinyl chloride) 3,4 22
Polyethylene 2,5 18
 Density

Density Density
Material Material
(g/cm3) (g/cm3)
Al 2,70 PVAc 1,19
Fe 7,87 PP 0,90-0,92
Cu 8,96 Nylon 11 1,04
Au 19,32 Nylon 12 1,02
LDPE 0,91-0,94 Nylon 6 1,12-1,13
PS 1,05 Nylon 6,6 1,13-1,15
PVC 1,37-1,39 PC 1,2
Natural rubber 0,91 PAN 1,17
PET 1,34-1,39 PFTE 2,27
 Polymer Additives and Reinforcements
Additives are usually required;
To impart stability against the degradative effects of
various kinds of aging processes
Enhance product quality and performance.

Thermal and light stabilizers, antioxidants, and flame retardants.

(influence essentially the chemical interaction of polymers with the environment)

 Plasticizers, lubricants, impact modifiers, antistatic agents, pigments, and dyes.

(usually employed to reduce costs, improve aesthetic qualities, or modify the processing,
mechanical, and physical behavior of a polymer)

These additives are normally used in relatively small quantities

Nonreinforcing fillers are employed in large quantities to reduce overall formulation costs
provided this does not result in significant or undesirable reduction in product quality or
performance

 Alloying and blending

 Plasticizers-I
The principal function of a plasticizer is to reduce the Tg of a polymer so
as to enhance its flexibility over expected temperatures of application.

Plasticizers are usually high boiling organic liquids or low melting solids.
They are also sometimes moderate-molecular-weight polymers.
Like ordinary solvents, plasticizers act through a varying degree of solvating
action on the polymer.
Plasticization is difficult to achieve in nonpolar polymers like polyolefins and
highly crystalline polymers.

Polymer plasticization can be achieved either through internal or external incorporation of

the plasticizer into the polymer.

a) Internal plasticization involves copolymerization of the monomers of the desired polymer

and that of the plasticizer so that the plasticizer is an integral part of the polymer chain. Tg. The
most widely used internal plasticizer monomers are vinyl acetate and vinylidene chloride.

b) External plasticizers are those incorporated into the resin as an external additive. Typical
low-molecular-weight external plasticizers for PVC are esters formed from the reaction of acids
or acid anhydrides with alcohols.
Plasticizers-II
Monomeric plasticizers ( phthalate, terephthalate, adipate, phosphate esters)
Polymeric and permanent plasticizers
(Linear polyesters obtained from the reaction of dibasic acids such as adipic, sebacic, and
azelaic acids with a polyol )

Polymeric stabilizers have higher molecular weights than the monomeric

plasticizers, and less volatile when exposed to high temperatures either during processing or in
the end-use situations, less susceptible to migration and less extractible.

Epoxy Plasticizers (derived from vegetable oil, epoxidized soybean is an example)

confer heat stability and light stability on PVC products
have relatively low-temperature properties

The ideal plasticizer must satisfy three requirements;

Compatibility
Permanence requires low volatility, extractability, nonmigration, and heat
and light stability. Lack of permanence involves long-term diffusion into the
environment.

Efficiency
Also it should be odorless, tasteless, nontoxic, nonflammable and heat stable
Fillers and Reinforcements (Composites)-1
Different types of fillers are employed in resin formulations.

-Added to improve tensile strength & abrasion resistance,

toughness & decrease cost

The most common are;

calcium carbonate,talc, silica, wollastonite, clay, calcium sulfate,
mica, glass structures, and alumina trihydrate.
Fillers and Reinforcements (Composites)-2
Particulate-filled composites are generally isotropic
(they are invariant with direction provided there is a good dispersion of the fillers)

Fiber-filled composites are typically anisotropic. Fibers are usually

oriented either uniaxially or randomly in a plane. In this case, the
composite has maximum modulus and strength values in the
direction of fiber orientation.

For uniaxially oriented fibers, Young’s modulus, measured in the orientation direction
(longitudinal Modulus, EL)

Where Ef is the tensile modulus of the fiber, Em is the modulus of the matrix resin and
f is the volume fraction of the filler.
 Alloys and Blends-I
An alternative to the development of new polymers is the development
of alloys and blends that are a physical combination of two or more
polymers to form a new material.

To combine the best properties of each component in a single

functional material that consequently has properties beyond those
available with the individual resin components and that is tailored to
meet specific requirements.
To optimize cost/performance index and improve processability
of a high-temperature or heat-sensitive polymer.

The composition dependence of a given property, P, of a two-component polymer system may be

described by;

where P1 and P2 are the values of the property for the isolated components and C1, C2 are,
respectively, the concentrations of the components of the system. I is the interaction parameter that
measures the magnitude of synergism resulting from combining the two components
Alloys and Blends-II
 Alloys and Blends-III

Examples of the most significant commercial

engineering alloys are polystyrene (PS)-modified
poly(phenylene oxide) (PPO) and polystyrene (PS)-
modified poly(phenylene ether) (PPE).

We can combine amorphous polymer with a crystalline polymers to exploit the strengths of
each component while deemphasizing their weakness.
Example: Nylon, PET, PBT- crystalline polymers and offer excellent resistance, processing
ease and stiffness
PC and polysulfone (amorphous polymers) outstanding impact strength and dimensional
stability.
PC/PET blends (replacement for metal, including automotive, lawn and garden appliances
and electrical/electronic,consumer, industrial/mechanical, sporting and recreation, and
military equipment.)
Nylon/PPO blends (fenders and rocker panels of some automobiles, applications
demanding chemical resistant performance under high impact and high heat.
 Antioxidants and Thermal Stabilizers

Antioxidants
Free radical scavengers (Primary antioxidants, radical or chain terminators)-inhibit
oxidation through reaction with chain-propagating radicals
Ex: hindered phenols and aromatic amines
Peroxide decomposers (secondary antioxidants or synergists)- break down
peroxides into nonradical and stable products.
Ex:Organic phosphites and thioesters that serve to suppress homolytic breakdown.

Thermal Stabilizers;
Thermal stabilizers may be based on one or a combination of the following classes of
compounds;

Barium/cadmium (Ba-Cd), calcium/zinc (Ca-Zn), organotin, organo-antimony,

phosphite chelates, and epoxy plasticizers.

Ba/Cd stabilizer systems, which represent the largest share of the PVC stabilizer
market, are available as liquids or powders.
 UV stabilizers

 UV radiation in the range 290 to 400 nm has potentially degradative effects on

polymers since most polymers contain chemical groups that absorb this radiation and
undergo chain scission, forming free radicals that initiate the degradative reactions.

 UV stabilizers are employed to impede or eliminate the process of degradation and, as

such, ensure the long-term stability of polymers, particularly during outdoor exposure.

 Light stabilizers are typically UV absorbers or quenchers.

 The former preferentially absorbs UV radiation more readily than the polymer,
converting the energy into a harmless form.

 Quenchers exchange energy with the excited polymer molecules by means of an energy
transfer mechanism.

 Other UV stabilizers deactivate the harmful free radicals and hydroperoxides as soon as
they are formed
 Flame Retardants
The function of flame retardants in a resin formulation is ideally the
outright inhibition of ignition where possible. Where this is impossible,
a flame retardant should slow down ignition significantly and/or inhibit
flame propagation as well as reduce smoke evolution and its
effects.
The presence of flame retardants also tends to cause substantial
changes in the processing and ultimate behavior of commercial resins.
The burning characteristics of polymers are modified by
certain compounds;

aluminatrihydrates;

bromine compounds;
Flame retardants can be classified as; (based on
chlorinated paraffins and cycloaliphatics; the method of incorporation in the resin
formulation or mode of action)
 phosphorus compounds,notably phosphate esters;
Additives
and antimony oxides, which are used basically as Reactives
synergists with bromine and chlorine compounds
Intumescents
Nonflame retardant systems
 Colorants-I
The marketability of a polymer product quite frequently depends on
its color; therefore the purpose of adding a colorant to a resin is to
overcome or mask its undesirable color characteristics and enhance
its aesthetic value without seriously compromising its properties and
performance.

Colorants are available as; (they can be natural or synthetic)

Organic pigments -generally transparent, good brightness,
variable heat stability, light and migration fastness
Dyes-stronger, brighter and more transparent than pigments
- have poor migration fastness
Inorganic Pigments –largely mixed with metal oxides, generally
good to excellent light and migration fastness but variable
chemical resistance

Colorants are used in polymers either as raw pigments (and dyes), concentrates or precolored
compounds.
Colorants are avalaible in a variety or forms, including pellets, cubes, granules, powder, liquid, and
paste dispersions
 Colorants-II
Selecting a colorant for particular application;
The ability of the colorant to provide the desired color effect
Withstand not only process temperature (heat stability) encountered
during manufacture but also, for possible prolonged times, the
temperature in the end-use requirements

Migration fastness is related to the solubility of the colorant in the polymer.

Color migration is manifested by bleeding, blooming or plate-out
Inadequate light fastness of a colorant is manifested in the form of fading or
darkening

The colorant must be compatible with the base resin forming a homogeneous
mass and also it must not degrade or be degraded by the resin
Incompatibility of the colorant can affect mechanical properties, flame
retardancy, weatherability, chemical and UV resistance, heat stability of the resin
through interaction of the colorant with the resin and its additives.
 Antistatic agents
Antistatic agents are hydroscopic chemicals that can generate layer of water
for the removal of static charges generated on the polymer by pulling moisture
from the atmosphere.

There are essentially two types of antistats that are commonly used in
polymers to get rid of static electricity: those that are applied topically and
those that are incorporated internally into the polymer.
Both improve the conductance of polymer surfaces by absorbing and holding a
thin, invisible layer of moisture from the surrounding air onto the polymer
surface.

Major types of organic antistatic agents include quaternary ammonium

compounds, amines and their derivatives, phosphate esters, fatty acid
polyglycol esters, and polyhydric alcohol derivatives such as glycerine and
sorbitol.

Selection of the appropriate antistat depends on its compatibility with the

polymer, the end use of the part, and the desired level of antistatic activity.

Other factors that need to be considered include the effect of antistatic agent
on color, transparency, and finish of the polymer part; its possible toxicity;
stability during processing; and degree of interference with physical properties
and ultimately cost effectiveness.