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POLYMER TECHNOLOGY AND SUSTAINABILITY AA2010-2011 Review of physical principles (solubility, diffusivity, wettability) Principles of mixing Degradation and

stabilization Classification of additives Compounding of thermoplastics Rubber technology (vulcanization, reinforcement) Biodegradation and bioplastics Polymer recycling Life cycle assessment

Polymer technology and sustainability


Frontal lessons Exercitations (numerical exercises, experimental techniques with lab, case hystories) Seminars led by industrial experts Visit to an industrial plant (production of recycled PET nonwovens for roofing)

Final oral exam (in italian or english)

Bibliography: Copy of all the slides/presentations + (consultation only)


H. Zweifel, Plastics Additives Handbook, Hanser, Munich 2001 C. Rauwendaal, Polymer Mixing, Hanser, Munich 1998 I. Manas-Zloczower, Z. Tadmor, Polymer Mixing and Compounding, Hanser, Munich 1994 L. Mascia, The Role of Additives in Plastics, Arnold, London 1974 H.H. Jellinek, Aspects of Degradation and Stabilization of Polymers, Elsevier, Amsterdam 1978 F. La Mantia, Handbook of Plastics Recycling, RAPRA, Shawbury 2002

Introduction to the concept of polymer formulation A polymer molecule becomes polymeric materials only when formulated (mixed) with suitable additives Compounding is the term indicating the industrial process of mixing the raw polymers with additives Additives are used for the following purposes:
To modify (improve) the material properties (durability, mechanical, optical etc) To improve processing Cost reduction

Additives can be miscible (homogeneous, like stabilizers) as well as heterogeneous (like fillers and pigments)

Classification of additives Polymer modifiers and processing aids see for ex. L. Mascia, The Role of Additives in Plastics, Hanser (1985)
1. 2. 3. 4. 5. 6.

Additives which assist processing Additives which modify mechanical properties Surface property modifiers Optical properties modifiers Anti-ageing additives Others

Examples of property modifiers (mechanical, electric conductivity, fire retardancy)


Function
Fillers / reinforcing agents

Structure
Oxides (glass, MgO, SiO2, Al2O3) Hydroxides (Al(OH)3) Salts (CaCO3, BaSO4, CaSO4, fosfati) Silicates (talc, mica, kaolin, clay) Metals Carbon-graphite, polymeric fibres Esters, chlorinated paraffins, oxidized vegetal oils Rubbers (EPR, EPDM, NBR, NR, EVA) Peroxides, sulphur, silanes. Sb2O3, chlorinated paraffins, Al(OH)3, Mg(OH)2, phosphates, brominted organics c. black, graphite, metals

Organics Plasticizers Tougheners Crosslinkers Fire retardants and smoke suppressants Conductive

Examples of processing aids and antiageing


Function
Heat stabilizers

Examples
Primary antioxidants (sterically hindered phenols), hydroperoxide decomposers (organophosphites, thioesters) Fatty acids and their derivatives, paraffin waxes, metallic soaps, ester and amide waxes, silicones, fluoropolymers Phenols, arylamines, phosphites Chelants Pigments (c. black, TiO2), UV adsorbers, radical scavengers (HALS) Thiocompounds, organometallic compounds

Lubricants

Antiaging Antioxidants Metal deactivators Photostabilizers Biocides

Function
Surface modifiers
Antistatics Antifog Antiwear Adhesion promoters

Examples
Ethoxylated amines, ammonium salts, non-ionic surfactants Non-ionic surfactants Graphite, PTFE, MoS2 Silanes, block and grafted copolymers Inorganics: oxides (Ti, Fe, Cr), sulfides, chromates Organics: c. black, phtalocyanines, azo compounds etc. Antraquinones, azo and bis-azo compounds

Optical properties modifiers


Pigments

Soluble dyes SiO2, talc, benzoates Nucleants

Blowing agents
Physical action Chemical action Hydrocarbons, halocarbons, N2, CO2 NaHCO3, azocarbonamide etc.

Physical principles
Solubility and compatibility Solubility has a thermodynamic meaning and it involves molecular mixing and formation of single-phase systems. Compatibility is a technological term which may involve formation of both single-phase and stable multi-phase systems (like most polymer compounds). Solubility is influenced by m.w., chemical nature, additive amount, matrix morphology etc. For binary systems at constant pressure we have: Gm = Hm T Sm Solubility occurs when Gm < 0. Sm is always positive (mixing increases disorder)

From classical thermodynamics we know:


Hm / Vtot = [(E1/V1)0.5 (E2/V2)0.5]2 1 2 =(1 2)2 1 2 Ei vaporization energies, Vi molar volumes, i volume fractions

Ei/Vi = cohesive energy density CED


(Ei/Vi)0.5 = i solubility parameter

Hm is always positive or eventually = 0 (athermal mixing),


therefore unfavourable for solubility

Flory-Huggins theory (recall): 2D lattice model

1 = diluent and 2 = polymer The lattice is made by N1 + xN2 dots 1 = N1 V / (N1 V + x N2 V) = N1/(N1+xN2) 2 = xN2 V / (N1 V + xN2 V) = xN2/(N1+xN2)

The overall change in free energy upon mixing is Gm = -TSmid + non ideal contribution According to Boltzman we have

Smid = R ln
with = number of configurations accessibile to the system = No!/(N1!N2!)

We obtain -TSmid = RT (N1 ln1 + N2 ln2)

Interaction parameter , = interaction energy between chain segment and diluent (non ideal part, enthalpic contribution)

Hm = RTN12
Therefore we obtain:

Gm/N = RT(1 ln1 + (2/x) ln2 + 1 2 )

Gm / RT = N1 ln1 + N2 ln2 + N1 2

Extension to the case of polymer blends (V/Vr is the number of lattice sites)
Gm / RT = (Gm / RT) (Vr/V) = A/XA ln1 + B/XB ln2 + A B

Mixing entropy tends to zero with increasing m.w.

varies from 0 (good miscibility) e 0.5 (theta temperature).

By comparing Flory-Huggins equation and solubility paramater we obtain

= V/(NRT) (1-2)2 = Vr/(RT) (1-2)2

V/N = molar volume of the solution

Solubility parameter The cohesive energy density is CED = (Hvap RT)/V (E = H RT). The solubility parameter is: = CED0.5 in cal0.5/cm3/2 = 0.4888 MPa0.5

As a general rule materials with similar are mutually miscible (solubility).

In case of polymers an experimental determination of is unfeasible (distillation). Indirect methods: Solubility tests Swelling tests after crosslinking (better)

Numerical methods (group contribution method, see B. Van Krevelen, Properties of Polymers, Elsevier,1990): = Fi/(Mi/) = Fi/Vi F = molar attraction constant for the solubility parameter = density.

Chemical group CH3-CH2CH (tertiary) C (quaternary) -CH=CH-phenyl -NHCO-NHCOO-CO-COO-

F, in (J.cm3)0.5.mol-1 420 280 140 0 444 1517 1228 1483 685 512

Hansen solubility parameters: there are various contributions (dispersive, polar, hydrogen bonding) of VdW forces to the overall CED, they must be treated separately. 2 tot= 2d + 2p + 2h Hansen solubility parameters can be represented graphically in a 3D space

R is the interaction radius of a given polymer; for each additive to be added we can calculate a R point R = (2d,p 2d,s)2 + (p,p p,s)2 + (h,p h,s)2
if R/R < 1 solubility is predicted, this occurs when each i is < 25%.

Polymer regular solutions theory applied to binary polymer/additive systems Regular solutions = H whatsoever, S ideal. Gm = Hm TSm If the additive are solid crystalline (i.e. stabilizers) with T < Tf, an additional term must be considered: Gf = Hf T Sf = Hf (1-T/Tf) since at equilibrium Tf = Hf/Sf and Sf = Hf/Tf

The solubility equation is given by the sum of three positive terms -lna = Hf/RT (1 T/Tf) + (1-Vp/Va) + with a volume fraction of additive 1 term: dipends only on the solid character of the additive 2 term: volume ratio (entropic non combinatorial) 3 term: polymer-additive interaction parameter (enthalpic) Solubility a will increase on decresing those 3 contributions.

Temperature dependence of solubility (Vant Hoff plot, assuming V indepedent over T) -dlna/d(1/T) Hf/R + dH/d(1/T) = Hf/R + Hm/R = Hsol/R Normally solubility increases with T The experimental determination of additive solubility in a polymer matrix can be carried out putting in contact the two materials in form of thin films and measuring the timedependent diffusion process

Examples, Vant Hoff plot for 3 stabilizers in PP (the slope is proportional to Hsol) and solubility tables

Physical state of additives in polymers:


Various cases are feasible as shown by phase diagrams

Horizontal line: temperature quenching after compounding Curve A : the additive is always insoluble (es. fillers and pigments) Curve B: additive is always soluble (es. plasticizer) Curve C: solubility at high temperature with following phase separation when the polymer is still molten (microparticle formation, they act as reservoirs) Curve D: solubility at high temperature with following phase separation only when the polymer is already solid (metastabile states, blooming)

Diffusion Diffusion is a mass transfer driven by a concentration gradient. It is important for the following features: mechanisms of loss of additives (leaching, blooming, food contamination etc) mechanism of action of some additives which need to move for being effective (i.e. stabilizers) formulation of barrier polymers (packaging)

Hp: one molecule, monodirectional flow through a isotropic surface A

1 Ficks law :

Flux = J = 1/A dm/dt = - D (dC/dx)

(J in kg/m2 s)

This is the law concerning steady diffusion (J constant with time) D = diffusion coefficient (in m2/s) The concentration gradient is given by dC/dx = (CA-CB)/(xA-xB)

2 Ficks law :

dC/dt = D (d2C/dx2)

It can be applied for cases when both J and dC/dX can change over time. Only approximated solutions with known boundary conditions are feasible

We can determine D by measuring the amount of additive permeated into the polymer film Mt vs. time (sorption curves) Mt / M = K tn
1. 2. 3. case I, or fickian diffusion, with n = 0.5. The rate of diffusion is << polymer relaxation times. case II, with n=1. The rate of diffusion is >> relaxation times (solvent stress crazing) anomalous diffusion, with n comprised between 0.5 and 1.

In case of fickian diffusion (frequent) we draw the Mt-t1/2 curve

Various anomalies are feasible

Determination of D (simplified 2 Ficks law solution): from the slope k of the initial part of the sorption curve (for M / M < 0.4)

b = film thickness
M / M = 4/b (D t/)0.5 k = 4M/b (D/)0.5 Determination of S (solubility coefficient): from the limiting, asymptotic value of the sorption curve The permeability coefficient P will be given by P = D S S is thermodynamic and will depend mainly on D is kinetic and will depend on free volume /Tg

Morphology effect on D: diffusion involves only amorphous phases Temperature effect: D = Do exp(-ED/RT)

Effect of polymer type:

D = Do exp(-ED/RT) exp(-Bd/f)

f = fractional free volume of the polymer (related to T-Tg) Bd = volumetric parameter proper of the additive

Effect of molecular weight: D = KM-a a = 1.5 2.5


Increasing the m.w. of the additive means lower solubility but also less migration

Wettability The property is important for the following features: property modification: development of polimeric compounds with tailored surface properties

release etc.) (higher wettability means better inkability, adhesivity etc)

(lower wettability means hyprophobic treatmants, antistick-

processing aid: better wetting of solid additives (pigments) during mixing, work of adhesion etc.

Wetting of a solid involves the displacement of air by the action of a liquid (like a molten polymer) Surface = interphase between solid and gas Interface = interphase between solids and/or liquids An interphase can be represented thermodynamically as the reversibile work dW spent to create it, as in the case of formation of a soap film

Surface energy
dW = .l .dX = Es/A (in J/m2) Es = energy spent to increase the interfacial area of A. Surface tensioni s the tangential stress opposed by the liquid to the creation of a new surface (in N/m) For liquid systems surface energy and surface tension are equivalent and the term are used interchangeably in polymer technology.

tend to return in the bulk putting the material in a state of tension. The surface tension depend on the intensity of cohesive forces (polarity of material)

Surface tension = the surface atoms are in an energetically anisotropic state and

High surface tension solid = easy wettability Low surface tension solid = difficult wettability Typical for polymers Typical for ionic solids (fillers, pigments) 20-50 mN/m >200 mN/m

Surface tension of a solid can be estimated through measurements of contact angle .

Contact angle the angle at which a liquid/vapor interface meets a solid surface

Young equation (thermodynamic equilibrium, ideal case for rigid, homogenous and flat surfaces): lv cos = sv sl lv = surface tension of the liquid in equilibrium with vapour (known) = surface tension of the solid in eq. with vapour (unknown) sv = interfacial tension sl Vectorial form of Young equation:
vapour

lv
liquid

sv sl
solid

Better surface wetting for cos 1, favored by high sv and low lv Complete wetting when sv > sl + lv

Critical surface tension of wetting c (Zisman)

Estrapolation of to zero angle (cos =1) from measurements with homologous series of liquids

Note = the extrapolated value will depend on the choice of the solvent series

Its better to separate dispersive and polar contributions of surface tension.

Fowkes: = d + p + h + Owens-Wendt method: calculation of the interfacial tension sl according to a geometric mean approximation, to be used in the Young equation: sl = sv + lv -2(svd. lvd)0.5 2(svp. lvp)0.5 Measurements with at least two liquids with known surface tension components are needed to solve the equation system, generally water and diiodomethane are used. The final result will be sv = svd + svp , generally higher than c

Polymer wettability depend on their polarity. Fluoropolymers show the least wettability values, while polymers with polar bonds (like polyamides) are those with highest surface tension

Contact angle hysteresis


Real surfaces show difference in advancing and receding contact angle during dynamic experiments

Hysteresis is due to roughness and/or chemical heterogeneity. Time-dependent hysteresis is due to sorption or surface enrichment of specific functional groups (see antifog additives).

Work of adhesion
A good wetting is needed but not enough to achieve a efficient pigment/filler dispersion in a polymer compound. We need also a very high interfacial adhesion Dupr equation (work of adhesion Wa) Wa = 1 + 2 - 12 = sv - sl + lv Young-Dupr equation: Wa = lv (1 + cos ) Best adhesion is achieved for high surface tension liquids capable to give low contact angle with the surface

How to estimate interfacial tension? 12 = 1 + 2 -2(1 2)0.5 (10.5 20.5)2 with Wa = 2(1 2)0.5 = interaction parameter of Good-Girifalco 1 per materials with comparable polarity 0 for materials with different polarity polarity = p / (p + d).

Example: dispersing agents/compatibilizers for polymer compounding

Several compatibilizers are also used to lower interfacial tension ion polymer blends.
method Functionalized polymers giving strong interactions/chemical bonds Copolymer with miscible segment Copolymer with reactive groups Low molecular weight chemicals example PVC/NBR, PVC/MBS PA6/EPR-g-MA EPDM/PMMA + EPDM-g-MA PS/EPDM + S-EB-S PVC/PS + PCL-b-PS PA6,6/EPM + EPM-g-MA PA6/PP + PP-g-AA PA6,6/PET + p-TSOH NR/PA6 + peroxides

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