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StructureProperty Relationships in Polymers

4.1 4.2 4.3 Structural Parameters .........................................................4-1
Molecular-Weight Averages Molecular Weight Between Cross-Links Particle Size and Particle Size Distribution

Properties of Wet Coatings.................................................4-2

Viscosity of Polymer Solutions Viscosity of Suspensions

Properties of Dried Films ...................................................4-4

The Glass Transition Temperature Tensile and Shear Moduli Other Properties

Subbu Venkatraman
Raychem Corporation

References .......................................................................................4-6

Most of the binders used in paints, varnishes, lacquer lms, and photolithographic coatings are made up of macromolecules. The nal dry coating consists predominately of a polymer, either cross-linked or un-cross-linked. The material may have been polymeric before application or cured to become a polymer after application. In either case, a knowledge of the properties of polymers as related to structural features helps in obtaining coatings with desired performance characteristics.

4.1 Structural Parameters

We begin by dening some important structural parameters of polymers.

4.1.1 Molecular-Weight Averages

As all polymers contain a distribution of molecules of differing masses, it is customary to dene averages of the distribution: M n (number average) = M w ( weight average) = Ni Mi Ni wi Mi wi

M v ( viscosity average) = [ w i M ia ]1// where Ni = number of molecules of molar mass Mi, and wi their weight, and is the MarkHouwink exponent dened by

4-1

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Coatings Technology: Fundamentals, Testing, and Processing Techniques

[] = KM v

(4.1)

where [] is the intrinsic viscosity. The number Mn is usually measured by nuclear magnetic resonance (NMR) spectrometry or osmometry; Mw can be obtained via light-scattering techniques, while intrinsic viscosity measurements yield estimates of Mv, Size-exclusion chromatography or gel permeation chromatography (GPA) can, in principle, be used to obtain all the averages mentioned above; care must be taken to ensure proper calibration of the column with standards that have the same molecular structure as the polymer of interest. Although different denitions exist for the breadth of a distribution, we will use the most common one involving the averages dened above: Mw Mn

MWD (molecular weight dispersity) =

A value of unity for this quantity denes a narrow distribution polymer; a value of 2 is obtained in condensation polymers, and higher values indicate considerable breadth of molecular weights. A measure of this quantity can be obtained via GPC, or a combination of NMR and light-scattering techniques.

4.1.2 Molecular Weight Between Cross-Links

This is dened as the average molar mass between successive cross-link sites in a network polymer and is denoted by the symbol Mc. It is a measure of the density of cross-linking and can be estimated from measurements of the equilibrium degree of swelling or of the modulus.

4.1.3 Particle Size and Particle Size Distribution

In the case of latexes, many properties of the wet and dry coatings are determined by the sizes of the latex particles. Estimations can be obtained directly through scanning electron micrography (SEM) if a lm can be made. For the suspension, however, it is more customary to use light-scattering techniques (Coulter model N4, Brookhaven model DCP-1000) or optical sedimentation techniques (Horiba CAPA700). In either case, it is possible to obtain a major portion of the particle size distribution.

4.2 Properties of Wet Coatings

Described below are some of the more important properties of coatings that are relevant to their ease of application, either in solution or as suspensions. Most wet coatings are brushed on (as with paints) or sprayed on (as with some epoxies used as insulation). The solution coatings are mostly polymer based, and thus a survey of the rheological properties of polymer solutions is given; in addition, some properties of suspensions are discussed.

4.2.1 Viscosity of Polymer Solutions

Although several theories of polymer solutions1 examine the dependence of viscoelastic properties on molecular parameters, we shall not discuss these here. Instead, we shall focus on some generally accepted empirical relationships. Most of these are covered extensively by Ferry.2 4.2.1.1 Dependence on Molecular Weight For pure polymers, the molecular weight dependence is usually expressed by the following type of relationship:

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StructureProperty Relationships in Polymers

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TABLE 4.1 Critical Molecular Weight of Source Polymers

Polymer Polyvinyl chloride Polyethylene Polyvinyl acetate Polymethyl acrylate Polystyrene Mc 6,200 3,500 25,000 24,000 35,000

Source: From D. W. Van Krevelen, Properties of Polymers, Elsevier, New York, 1976.3

0 = KM

(4.2)

where 0 is the zero-shear viscosity, and K is a solvent- and temperature-dependent constant. The value of the exponent is determined by the molecular weight range under consideration: for M < Mc, = 1 and for M > Mc, = 3.4 (4.3)

where Mc is a critical molecular weight that expresses the onset of entanglements between molecules. The magnitude of Mc is characteristic of the polymer structure; Table 4.1 gives some representative numbers. Although Mc signals the onset of topological effects on the viscosity, it is not identical to the molecular weight between entanglements, Me. (The latter quantity is estimated from the magnitude of the rubbery plateau modulus.) Approximately, we have Mc ~ 2Me (4.4)

Also, Mc is a function of polymer concentration. In the pure polymer (denoted by superscript zero), it attains its lowest value, M c0 ; in a solution of concentration C, its magnitude varies as discussed in Section 4.2.1.2. The exponent assumes the values quoted in Equation 4.3 only if the measured viscosity is in the socalled zero-shear-rate limit. At higher rates, assumes values lower than unity and 3.4, in the two regimes. 4.2.1.2 Concentration Dependence of the Viscosity As mentioned in Section 4.2.1.1, below a certain concentration, C*, entanglement effects are not significant. This concentration is estimated from the following: C* = M c0 M

(4.4a)

where M is the molecular weight of the polymer in the coating solution. The concentration C* cannot be estimated from a plot of 0 against concentration, however; the transition is not sharp, but gradual.4 No single expression for the concentration exists below C*; however, in the entangled regime, the expression 0 = C 5 M 3.4 (4.5)

works well for some polymers.5,6 This relation does not hold all the way to the pure polymer, where higher exponents are found.6 Equation 4.5 also does not hold in the case of polymer solutions in which there are other specic attractive forces, such as in poly(n-alkyl acrylates).7

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Coatings Technology: Fundamentals, Testing, and Processing Techniques

There are two reasons for a reduction in viscosity of a polymer upon dilution: (a) the dilution effect, which causes the solution viscosity to be between those of the two pure components, and (b) a decrease of viscosity due to a lowering of Tg upon dilution. The latter is solvent-specic and is the main reason for the apparent difculty in establishing a universal viscosityconcentration relationship for polymer solutions.

4.2.2 Viscosity of Suspensions

Many latex paints are suspensions in water or in an organic solvent. Their rheological properties differ from those of polymer solutions in several ways. The concentration dependence is of a different form, and in addition, there is a dependence on particle size. Also, at high concentrations, these suspensions tend to have structure, which usually refers to an aggregated network. The immediate consequences of the existence of a pseudonetwork are the phenomena of yield stress and thixotropy. We explore next the relationship of these quantities to the characteristics of the particles making up the suspension. 4.2.2.1 Concentration Dependence of the Viscosity In dilute suspensions, the concentration dependence is expressed by an extension of the Einstein equation: rel = = 1 + 2.5 + 14.12 s (4.6)

where s is the solvent viscosity, and is the volume fraction of the suspension. Equation 4.6 is valid for spherical particles without any interparticle interaction. Inclusion of long-range interaction (such as volume exclusion) merely changes the coefcient of the 2 term. Of greater interest are the rheological phenomena that occur in suspensions of particles that have short-range interactions, attractive or repulsive. In a comprehensive study, Matsumoto et al.8 have established the conditions for the existence of yield stresses in suspension. Their conclusions are as follows: 1. For particles with repulsive interactions, no yield stresses exist. 2. Suspensions of neutral particles, or particles with attractive forces, do exhibit yield stresses. 3. The magnitude of the yield stress increases with the concentration of the particles and with increasing ratio of surface area to volume. In this study, the existence of the yield stress was inferred from the presence of a plateau in the elastic modulus G, at very low frequencies; the magnitude of the yield stress was deduced from the height of the plateau modulus. A detailed and critical survey of the literature is given by Meitz.9 The other important rheological consequence of a pseudonetwork is thixotropy, dened elsewhere in this volume. The phenomenon is attributed to a time-dependent but reversible breakdown of the network.

4.3 Properties of Dried Films

4.3.1 The Glass Transition Temperature
The Tg is dened in various ways, but in a broad sense, it signals the onset of small-scale motion in a polymer. It is heavily inuenced by the chemical structure, in particular, by the bulkiness (steric hindrance) of pendant groups. (See Van Kreleven10 for an excellent discussion.) The molecular weight dependence of the glass transition is fairly straightforward and is given by the following: Tg = Tg M Mn (4.7)

where Tg is the limiting value of Tg at high molecular weights.

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StructureProperty Relationships in Polymers

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The effect of plasticizers on Tg is well documented.10 According to a theoretical treatment by Bueche,11 the Tg reduction by plasticizers can be calculated from Tg (solution) = Tg,p + ( KTg , s Tg , p ) s 1 + ( K 1) s

(4.8)

where Tg,p and Tg,s are the glass transition temperatures of the polymer and solvent, respectively, and s is the volume fraction of solvent. Then we write K= 1s gs 1 p gp ,1 < K< 3

where l = volume expansion coefcient above Tg, and g = volume expansion coefcient below Tg. To calculate the Tg of a solution, the Tg of the solvent should be known12 or estimated as 2Tm/3, and K is usually taken to be 2.5.

4.3.2 Tensile and Shear Moduli

Both tensile and shear moduli are functions of temperature, and of time in the case of viscoelastic polymers. We shall restrict our discussion to the temperature dependence of the isochronal moduli. (Because the tensile and shear moduli are related to each other through the use of an equation involving the Poissons ratio, the comments made here on the shear modulus G can be extended to the tensile modulus E, as well.) For semicrystalline polymers below Tg, the modulus can be estimated from13 G = Gg + X c2 (Gc Gg ) (4.9)

where Gg, Gc are the moduli for the fully amorphous and fully crystalline polymer, respectively, and Xc is the degree of crystallinity. Above Tg, the same equation can be used, but Gc far exceeds Gg, and Equation 4.9 reduces to G X c2 (Gc ) (4.10)

For amorphous polymers above Tg, the modulus is given by the rubber elasticity expression: Ge = RT Me

(4.11)

where M e0 is the entanglement molecular weight (see Section 4.2.1.2). This rubbery plateau for un-crosslinked polymers is observed only at molecular weights higher than M e0 . For cross-linked amorphous polymers above Tg (elastomers), the modulus is given in analogous fashion: RT Mc

(4.12)

where Mc is the molecular weight between permanent cross-linked junctions. When Mc exceeds Me, trapped entanglements also play a part in determining modulus:14

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Coatings Technology: Fundamentals, Testing, and Processing Techniques

RT + f e Ge Mc

(4.13)

where Ge is given by Equation 4.11 and fe is a probability factor for trapped entanglements. In the case of network imperfections, Equation 4.12 is modied.14,15 The quantity fe can be calculated if the reaction parameters for network formation are known.14,16,17

4.3.3 Other Properties

Several other properties of dried lms inuence performance characteristics. Examples are the coefcient of thermal expansion, ultimate mechanical properties, stress relaxation and creep, and dielectric properties. However, correlation of these properties with structure for polymeric lms is not well established; some of the more successful attempts are treated in Refs. 2 and 3.

References
1. R. B. Bird, R. C. Armstrong, and O. Hassager, Dynamics of Polymeric Fluids, Vol. 2. New York: Wiley-Interscience, 1987. 2. J. D. Ferry, Viscoelastic Properties of Polymers. New York: Wiley, 1980. 3. D. W. Van Krevelen, Properties of Polymers. New York: Elsevier, 1976. 4. Ref. 2, see discussion in Chapter 17. 5. J. W. Berge and J. D. Ferry, J. Colloid Sci., 12, 400 (1957). 6. G. Pezzin and N. Gligo, J. Appl. Polym. Sci., 10, 1 (1966). 7. Ref. 2, p. 510. 8. T. Matsumoto, O. Yamamoto, and S. Onogi, J. Rheol., 24, 279 (1980). 9. D. W. Meitz, Ph.D. thesis, Carnegie-Mellon University, December 1984. 10. Ref. 3, p. 383. 11. F. Bueche, Physical Properties of Polymers. New York: Wiley, 1962. 12. Ref. 3, p. 384. 13. Ref. 3, p. 266. 14. E. M. Valles and C. W. Macosko, Macromolecules, 12, 673 (1979). 15. P. J. Flory, Principles of Polymer Chemistry. Ithaca, NY: Cornell University Press, 1953, p. 458. 16. M. Gottlieb, C. W. Macosko, G. S. Benjamin, K. O. Meyers, and E. W. Merill, Macromolecules, 14, 1039 (1981). 17. D. S. Pearson and W. W. Graessley, Macromolecules, 13, 1001 (1980).

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