Viscoelastic elastomers

Plrvlcs, J., Castelli, V., "Elastomer Viscoelasticity Effectb in Compliant Surface Bearings," Columbia University Lub. Res. Lab., Report No. 20, 1972. 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

International Rubber Hardness. The International mbber hardness test (ASTM D1415) (2) for elastomers is similar to the Rockwell test ia that the measured property is the difference ia penetration of a standard steel ball between minor and major loads. The viscoelastic properties of elastomers require that a load appHcation time, usually 30 seconds, be a part of the test procedure. The hardness number is read directly on a scale of 0 to 100 upon return to the minor load. International mbber hardness numbers are often considered equivalent to Durometer hardness numbers but differences ia iadenters, loads, and test time preclude such a relationship. 

As mentioned earlier, the contact-mechanics-based experimental studies of interfacial adhesion primarily include (1) direct measurements of surface and interfacial energies of polymers and self-assembled monolayers (2) quantitative studies on the role of interfacial coupling agents in the adhesion of elastomers (3) adhesion of microparticles on surfaces and (4) adhesion of viscoelastic polymer particles. In these studies, a variety of experimental tools have been employed by different researchers. Each one of these tools offers certain advantages over the others. These experimental studies are reviewed in Section 4. 

Tackifying resins enhance the adhesion of non-polar elastomers by improving wettability, increasing polarity and altering the viscoelastic properties. Dahlquist [31 ] established the first evidence of the modification of the viscoelastic properties of an elastomer by adding resins, and demonstrated that the performance of pressure-sensitive adhesives was related to the creep compliance. Later, Aubrey and Sherriff [32] demonstrated that a relationship between peel strength and viscoelasticity in natural rubber-low molecular resins blends existed. Class and Chu [33] used the dynamic mechanical measurements to demonstrate that compatible resins with an elastomer produced a decrease in the elastic modulus at room temperature and an increase in the tan <5 peak (which indicated the glass transition temperature of the resin-elastomer blend). Resins which are incompatible with an elastomer caused an increase in the elastic modulus at room temperature and showed two distinct maxima in the tan <5 curve. 

The energy release rate (G) represents adherence and is attributed to a multiplicative combination of interfacial and bulk effects. The interface contributions to the overall adherence are captured by the adhesion energy (Go), which is assumed to be rate-independent and equal to the thermodynamic work of adhesion (IVa)-Additional dissipation occurring within the elastomer is contained in the bulk viscoelastic loss function 0, which is dependent on the crack growth velocity (v) and on temperature (T). The function 0 is therefore substrate surface independent, but test geometry dependent. 

An investigation of the mechanism of adhesive failure of polydimethylsiloxane elastomers was conducted [75]. The study showed that the total adhesive failure energy could be decomposed into energies for breaking chemical bonds, breaking physical bonds and deforming the bulk viscoelastic elastomer. 

PMMA-b-PBA shows improved izod impact strength compared to PMMA homopolymer (41). Polyisobutylene (PIB) or its hydrogenated one (PIB-H) also acts as an impact modifier [31]. PSt-b-PIB, PSt-b-PIB-H, and PMMA-b-PIB-H derived from MAI have high- and wide-range molecuiar weight and show high flexibiiity and flow property [42]. The improved flexibiiity of PMMA-b-PEG synthesized as an elastomer, was confirmed by dynamic viscoelastic measurement [43]. 

Dynamic mechanical measurements for elastomers that cover wide ranges of frequency and temperature are rather scarce. Payne and Scott [12] carried out extensive measurements of /a and /x" for unvulcanized natural mbber as a function of test frequency (Figure 1.8). He showed that the experimental relations at different temperatures could be superposed to yield master curves, as shown in Figure 1.9, using the WLF frequency-temperature equivalence, Equation 1.11. The same shift factors, log Ox. were used for both experimental quantities, /x and /x". Successful superposition in both cases confirms that the dependence of the viscoelastic properties of rubber on frequency and temperature arises from changes in the rate of Brownian motion of molecular segments with temperature. 

The process of viscoelastic braking just described has certain parallels with the dynamic adhesion of elastomers. When, for example, a rubber strip is peeled from a rigid substrate, the effective, or apparent, work of adhesion, W, is usually much greater than the intrinsic, or reversible, energy of adhesion, Wq, given by the Dupre equation [15] ... 

Viscoelastics Certain silicone elastomers undergo changes in shear modulus under the influence of electric fields, which might be useful in active mechanical damping applications. 

Some viscoelasticity results have been reported for bimodal PDMS [120], using a Rheovibron (an instrument for measuring the dynamic tensile moduli of polymers). Also, measurements have been made on permanent set for PDMS networks in compressive cyclic deformations [121]. There appeared to be less permanent set or "creep" in the case of the bimodal elastomers. This is consistent in a general way with some early results for polyurethane elastomers [122], Specifically, cyclic elongation measurements on unimodal and bimodal networks indicated that the bimodal ones survived many more cycles before the occurrence of fatigue failure. The number of cycles to failure was found to be approximately an order of magnitude higher for the bimodal networks, at the same modulus at 10% deformation [5] ... 

The strength and extensibility of a noncrystallizable elastomer depend on its viscoelastic properties (28,29), even when the stress remains in equilibrium with the strain until macroscopic fracture occurs. In theory, such elastomers have a time- or rate-independent strength and ultimate elongation, but such threshold quantities apparently have not been measured, though rough estimates have been made (28,30). 

Figure 4 shows stress-strain curves measured at an extension rate of 94% per minute on the TIPA elastomer at 30°, —30°, and —40°C. With a decrease in temperature from 30° to -40°C, the ultimate elongation increases from 170% to 600%. The modulus Ecr(l), evaluated from a one-minute stress-strain isochrone, obtained from plots like shown in Figure 1, increases from 1.29 MPa at 30°C to only 1.95 MPa at —40°C. This small increase in the modulus and the large increase in the engineering stress and elongation at fracture results from viscoelastic processes. 

Resistance to flow or resistance to relative motion within a substance. Although viscosity is usually applied to liquid it is replacing the less precise term plasticity in relation to unvulcanised elastomers. See Viscoelasticity. 

Polymers are viscoelastic materials meaning they can act as liquids, the visco portion, and as solids, the elastic portion. Descriptions of the viscoelastic properties of materials generally falls within the area called rheology. Determination of the viscoelastic behavior of materials generally occurs through stress-strain and related measurements. Whether a material behaves as a viscous or elastic material depends on temperature, the particular polymer and its prior treatment, polymer structure, and the particular measurement or conditions applied to the material. The particular property demonstrated by a material under given conditions allows polymers to act as solid or viscous liquids, as plastics, elastomers, or fibers, etc. This chapter deals with the viscoelastic properties of polymers. 

When there is no volume change, as when an elastomer is stretched, Poisson s ratio is 0.5. This value decreases as the Tg of the polymer increases and approaches 0.3 for rigid solids such as PVC and ebonite. For simplicity, the polymers dealt with here will be considered to be isotropic viscoelastic solids with a Poisson s ratio of 0.5, and only deformations in tension and shear will be considered. Thus, a shear modulus (G) will usually be used in place of Young s modulus of elasticity E Equation 14.2) where E is about 2.6G at temperatures below Tg. 

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