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Coating Technology
Coating Technology
4
StructureProperty
Relationships in
Polymers
4.1
4.2
4.3
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.
Ni Mi
Ni
M w ( weight average) =
wi Mi
wi
4-1
2006 by Taylor & Francis Group, LLC
4-2
[] = KM v
(4.1)
Mw
Mn
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.
4-3
Mc
Polyvinyl chloride
Polyethylene
Polyvinyl acetate
Polymethyl acrylate
Polystyrene
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
4-4
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.
= 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.
M
Mn
(4.7)
4-5
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.
(4.9)
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:
G
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
4-6
G
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
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).