SURFACE PROPERTY MODIFIERS

Polymer Surface influences:

•Friction & Wear
•Adhesion to other substrates
•Surface Conductivity
Which in turn is influenced by
•Surface Roughness
•Polarity of Chemical groups
•Boundary layers of foreign matter
 SURFACE PROPERTY MODIFIERS

Additives which increase as Surface Roughness

Anti Blocking & Anti Slip Additives
Block: Ability of a layer of film to adhere to another layer of film
Slip: Ability of a layer of film to slide past another layer of film
Surface roughness reduces the intimacy of contact
By incorporation of incompatible microscopic particles causing micro
fractures
By incorporation of rubber particles Differential shrinkage
Excessive use of anti blocking additive adversely affects optical properties
Excessive use of anti slip additive causes wet blocking
Diatomaceous earth, Silica flour, Zeolites, Fatty Acid Amides, Waxes,
Boron Nitride
 SURFACE PROPERTY MODIFIERS
Additives which form Boundary layer
By exudation of the additive
Solid Lubricants: Reduces friction & wear
Molybdenumdisulfide, Graphite, PTFE Powder
Antistatic Agents:
Static charge develops on the surface when two surfaces are separated
Static charge build up depends on rate of generation & rate of decay
Static Charge build up poses lot of problems
Dissipated by:
Grounding
Increasing moisture content
External Antistatic agents By solution application Susceptible to removal
Internal Antistatic agents Exude Forms conductive layer
Ionic materials Quaternary Ammonium Compounds
Hydrophilic Materials Polyglycols, Polyhydric Alcohols, Sulfonic,Phosphoric
acid derivatives
 SURFACE PROPERTY MODIFIERS
Additives which alter Surface Polarity
Adhesion Promoters:
Adhesion depends on the type of chemical bonds at interface of
polymer & substrate
Surface tension between Polymer & Substrate should be low for good
wetting characteristics
Substrate Polar Polymer Non Polar Additive Compatible polar low m.w.
Monomolecular layer Dosage & Compatibility
• Phosphorous Compounds By Chelation with metal ions
• Acids Stearic, Salicylic, p-chlorophenylsubstituted fatty acids
• Amines Piperidines
• Coupling Agents ( R’-O-)a-M-(R-X )4-a
(Tetravalent M = Silicon,Titanium,Zirconium)
 OPTICAL PROPERTIES MODIFIER

Polymer response to visible light (400-700 nm)

Ability to transmit, absorb, reflect incident light
% Transmission = [1 – (R.I. – 1)2/ ( R.I.2 + 1)] X 100
Transmission also depends on Light Scatter
Light Scatter depends on surface irregularities & scattering centers
(particles & voids)
Particle size ~ λ/2 Scatter maximum
Particle size << λ Scatter drops significantly
Ii = Isc + Iabs + Itr
Transmission T= Itr/Ii = 1-Fabs –Fsc
Backward Scatter (Milkiness) & Forward Scatter (Haze)
Gloss = Ir (45)deg /Ii
 OPTICAL PROPERTIES MODIFIER

Colorants
Surface coating or dyeing, Introducing Chromophores, Mass Coloration
Dyes: Soluble Bleeding, Migration, Reactive, Poor light fastness, Lack of
heat stability
Pigments: Insoluble, Heat Stability, Light Fastness, Dispersability,
Chemically inert
Pigment Dispersion Lack of dust, handling ease
Optimum particle size for color value, tinting strength, transparency,
opacity characteristics
Inorganic : Unreactive Stable TiO2, Metal Oxides, Metallic Salts
Elemental : Carbon Black
Organic: Based on chemical structure Bright
Phthalocyanines :Stability to light, heat, Chemical agents
 OPTICAL PROPERTIES MODIFIER
Fluorescent Pigments: Fluorescent dyes incorporated into thermoset resin
matrix, cured, ground
Absorb in U.V. or Visible light & reemit at other visual wavelengths.
U.V. absorption of additives inhibit the efficiency
Brighter color reflected than incident light
Luminescent & Phosphorescent Pigments: ZnS, CdS & ZnO Crystals
Store U.V. or Visible light & reemit visible light of weak intensity for short
duration when all light sources removed. Fragile, liable to fracture
Optical Brighteners:
Absorb in near U.V. ~ 350-380nm & reemit in the blue end of visible spectrum
~ 430-450nm
High degree of purity & Excellent dispersion essential prerequisites
Light reflected by an object
Diffuse Reflectance at λ (DR) λ = -----------------------------------------------------
Light reflected by an ideal white surface
MgO reflects light radiation almost completely
DR of PS WITH 0.5% TiO2 decreases from longer to shorter wavelengths
DR of Optical Brighteners in shorter wavelength region exceeds DR of MgO
Additives capable of U.V. absorption has an adverse effect
 OPTICAL PROPERTIES MODIFIER

• Benzosulphonic & Sulphonamides derivatives of 4-

naptholtriazolyl stilbene
• Vinylene bisbenzoxazoles
• 4-alkyl-7-dialkyl amino coumarins
 OPTICAL PROPERTIES MODIFIER

Additives altering light transmission characteristics

Amorphous Polymers Good light transmission
Crystalline Polymers Internal haze Differences in R.I. between
crystalline & Amorphous phase
Spherulites > λ Internal Scatter
Reduce crystallinity
Polymorphic Maximise crystals of lowest density
Reduce the size of spherulites to < λ by nucleation
Nucleating AgentsK,Na,Li Benzoates
 FLAME RETARDANTS
Combustion Mechanism
Source of external energy → Rise in Polymer Temperature
Rate of increase depends on rate of supply,thermal,geometrical characteristics
Thermal decomposition ( Pyrolysis) Formation of free radicals Oxygen attack
Ignition & rate of flame propagation – Ease & rate of formation of OH∙
CO2 & H2O Exothermic reaction Auto catalytic Auto ignition
Gas phase consists of gases, liquids, charred solids, smoke
Solid particles leads to formation of less reactive ∙OOH
Combustible gases & oxygen ( LOI ) above ignition temperature cause ignition
Combustion follows ignition Ease of combustion function of bond cohesive
energy
Combustion followed by flame propagation
Flammability of polymers depend on 1)Chemical Structure 2)Intrinsic
flammability of volatiles 3)Ratio of combustible matter in gas phase
FLAME RETARDANTS
 FLAME RETARDANTS

Reactives: Special intermediates (Highly Halogenated or Phosphorous

Compounds) incorporated into polymer structure during crosslinking
Epoxy, Polyesters, Polyurethanes
Free from leaching, migration, volatilization Expensive
Additives: Flexible, Less expensive
Fire Retardants function by one or more of four mechanisms
1)Chemically interfere with free radical oxidation process reducing rate of
formation of highly reactive OH∙
Halogen Compounds with Sb2O3
I>Br>Cl>F Aliphatic > Alicyclic . Aromatic
R-X → R∙ + X∙ + R’H → HX + R’ + ∙OH → H2O + X∙
RCl + Sb2O3 → SbOCl(s) (245-280)→ Sb4O5Cl2 (s)+ SbCl3(g) 410-475→
Sb3O4Cl2(s) + SbCl3(g) 475 – 565 → Sb2O3(s) + SbCl3(g) 658 → Sb2O3(l)
Halogen transports highly active Sb trap to gas phase
 FLAME RETARDANTS

Phosphorous Compounds
Synergy with Halogen compounds
O O
║ ║
(RO)2P-OR + HX → (RO)2P-OH +RX
Halides function in gas phase
Acidic derivatives of Phosphorous in the condensed phase
Metal cations have an antagonistic effect stable metal phosphates
Sb2O3 converted to non volatile SbPO4

Phosphoric Acid promotes char formation

 FLAME RETARDANTS

2) Produce large volumes of incombustible gases diluting oxygen supply

Lower rate of combustion Drop in temperature < Ignition temperature
Water, Ammonia, Nitrogen, Sulfur dioxide, Hydrogen halides
(NH4)2SO4 Al(OH)3
3)React, Decompose, Change state endothermically
Absorb heat Drop in temperature , Ignition Selfextinction
4)Forming an impervious fire resistant coating cut of oxygen supply
Intumescent Thermal Insulation Reduction of volatiles
Zinc, Calcium Borate Hygroscopic
High molecular weight Organoborates
Poly alcohol + Blowing Agent + Dehydrating Agent
FLAME RETARDANTS
FLAME RETARDANTS
 SMOKE SUPRESSANT

Not much success Promotes oxidation

Al(OH)3, Mg(OH)2,Zinc Borate, Zn3(PO4)2Mo &Sn compounds
Function as catalysts Modify pyrolysis mechanism

Benzene → Smoke
↑
PVC → cis,trans polyene → crosslinked polymer
↓ ↓
all trans polyene char