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stabilization Classification of additives Compounding of thermoplastics Rubber technology (vulcanization, reinforcement) Biodegradation and bioplastics Polymer recycling Life cycle assessment
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
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
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
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
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)
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!)
Interaction parameter , = interaction energy between chain segment and diluent (non ideal part, enthalpic contribution)
Hm = RTN12
Therefore we obtain:
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
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
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.
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
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)
1 Ficks law :
(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.
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)
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
Wettability The property is important for the following features: property modification: development of polimeric compounds with tailored surface properties
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
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
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
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
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).
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