Mooney-Rivlin measurements

In order to check this prediction, stress-strain measurements were made up to moderate strains at room temperature. The obtained data are plotted in the usual manner as a versus 1/X in Figure 8. Table V gives the Mooney-Rivlin constants 2C and 2C calculated from these plots and also the ratio C./Cj. 

Figure 8. Mooney-Rivlin plots for strain dependent measurements at 298 K. Key A, PDMS-BI , PDMS-B2 X, PDMS-B3 O, PDMS-B5 , PDMS-B6 , PDMS-B7 V, PDMS-B8 A, PDMS-B9 PDMS-B10.

Mooney-Rivlin constants obtained from strain dependent measurements at 298 K... 

The two network precursors and solvent (if present) were combined with 20 ppm catalyst and reacted under argon at 75°C to produce the desired networks. The sol fractions, ws, and equilibrium swelling ratio In benzene, V2m, of these networks were determined according to established procedures ( 1, 4. Equilibrium tensile stress-strain Isotherms were obtained at 25 C on dumbbell shaped specimens according to procedures described elsewhere (1, 4). The data were well correlated by linear regression to the empirical Mooney-Rivlin (6 ) relationship. The tensile behavior of the networks formed In solution was measured both on networks with the solvent present and on networks from which the oligomeric PEMS had been extracted. 

Number-average molecular weights are Mn = 660 and 18,500 g/ mol, respectively (15,). Measurements were carried out on the unswollen networks, in elongation at 25°C. Data plotted as suggested by Mooney-Rivlin representation of reduced stress or modulus (Eq. 2). Short extensions of the linear portions of the isotherms locate the values of a at which upturn in [/ ] first becomes discernible. Linear portions of the isotherms were located by least-squares analysis. Each curve is labelled with mol percent of short chains in network structure. Vertical dotted lines indicate rupture points. Key O, results obtained using a series of increasing values of elongation 0, results obtained out of sequence to test for reversibility. 

Networks were prepared in all cases using the amount of endlinking agent necessary to give a minimum Mc. Values of Mc were calculated from the Mooney-Rivlin elasticity coefficient Cj, determined from tensile stress-strain measurements (10),... 

In this contribution, we report equilibrium modulus and sol fraction measurements on diepoxidet-monoepoxide-diamine networks and polyoxypropylene triol-diisocyanate networks and a comparison with calculated values. A practically zero (epoxides) or low (polyurethanes) Mooney-Rivlin constant C and a low and accounted for wastage of bonds in elastically inactive cycles are the advantages of the systems. Plots of reduced modulus against the gel fraction have been used, because they have been found to minimize the effect of EIC, incompleteness of the reaction, or possible errors in analytical characteristics (16-20). A full account of the work on epoxy and polyurethane networks including the statistical derivation of various structural parameters will be published separately elsewhere. 

The results of stress-strain measurements can be summarized as follows (1) the reduced stress S (A- A ) (Ais the extension ratio) is practically independent of strain so that the Mooney-Rivlin constant C2 is practically zero for dry as well as swollen samples (C2/C1=0 0.05) (2) the values of G are practically the same whether obtained on dry or swollen samples (3) assuming that Gee=0, the data are compatible with the chemical contribution and A 1 (4) the difference between the phantom network dependence with the value of A given by Eq.(4) and the experimental moduli fits well the theoretical dependence of G e in Eq.(2) or (3). The proportionality constant in G for series of networks with s equal to 0, 0.2, 0.33, and 0. Ewas practically the same -(8.2, 6.3, 8.8, and 8.5)x10-4 mol/cm with the average value 7.95x10 mol/cm. Results (1) and (2) suggest that phantom network behavior has been reached, but the result(3) is contrary to that. Either the constraints do survive also in the swollen and stressed states, or we have to consider an extra contribution due to the incrossability of "phantom" chains. The latter explanation is somewhat supported by the constancy of in Eq.(2) for a series of samples of different composition. 

When using equilibrium stress-strain measurements, the cross-link density is determined from the Mooney-Rivlin equation ... 

Eq. (IV-26a) can be confronted with birefringence-strain data, which can also be written in a Mooney-Rivlin type equation. Remembering that the measured birefringence refers to the strained cross-section, the classical result for the Gaussian part is (171)... 

C0 and Ci can be determined with at least two independent measurements. The constant Q is obviously different from WLF or Mooney-Rivlin equations (Chapter 11). 

Overall cross-linking density data (Pt) of sulfur vulcanized (V)-EPTM and ENB-EPDM were obtained from stress-strain measurements performed under equilibrium conditions and u g the Mooney-Rivlin and Guth-Einstein uations. Chemical cross-linking density data (Pg) were obtained through the emiarical relationship found by... 

Figyre 3.16 Mooney-Rivlin plots [Eq. (3.38)] showing the effect of the temperature on stress-strain isotherms for model PDMS networks (15,16). The filled circles represent the reversibility of the elastic measurements, and the vertical lines locate the fracture points. (From Ref. 15.)... 

Fig. 12 Result of mechanical measurement performed on a magnetoelast filled with randomly distributed carbonyl iron. The concentrations of the filler particles are indicated on the figure. The cross-linker content was 3 wt % in each case. Neo-Hookean (left figure) and Mooney-Rivlin representations (rightfigure) are plotted...

Figure 6-6. Simulated Mooney-Rivlin plot, equation (6-82), for C2/C = 2. Solid line is the undistorted response of the material "data" are the results with a 1% (standard deviation) random error incorporated into both the force and length "measurements."...

That crystallization increases the elastic stress has already been demonstrated in Figure 6-8, in which the Mooney-Rivlin plot shows a rise at high extension ratios. However, it should be remembered that part of this increase is due to finite extensibility of network chains. In Figure 6-13 we show the stress-strain curves of natural rubber at two temperatures. At 0 °C there is considerable strain-induced crystallization, and we observe a dramatic rise in the elastic stress above X = 3.0. Wide-angle X-ray measurements show the appearance of crystallinity above this strain. At 60 °C there is little or no crystallization, and the stress-strain curve shows a much smaller upturn at high strains. The latter is presumably due only to the finite extensibility of the polymer chains in the network. 

Q and C2 in Pa. Mooney-Rivlin Equation constants. For the equation, see Ferry (1980). Weight swelling index measured in methyl ethyl ketone at 25° C. 

The measured results of a stretching experiment are normally treated with the empirical Mooney-Rivlin relation (Mooney 1940 Rivlin 1949), as given by... 

Dependence of Mooney-Rivlin ratio, 2C2/2C1, on the molecular weight between cross links. The factor 2C measures the departure from affineness as the elongation increases, and 2Cj approximates the high-deformation modulus. The ratio decreases with decrease in network chain molecular weight, and with increase in junction functionality, as predicted by theory. ... 

An alternative model which also describes stress-strain data for larger deformation is presented by the Mooney-Rivlin equation [40, 41], The equation describes the rubber elasticity of a polymer network on the basis that the elastomeric sample is incompressible and isotropic in its unstrained state and that the sample behaves as Hookean solid in simple shear. In a Mooney-Rivlin plot of a uniaxial deformation, the experimental measured stress cr, divided by a factor derived from classical models, is plotted as function of the reciprocal deformation 1/A ... 

For both the phantom and the affine networks, the reduced stress is calculated to be independent of deformation. However, stress-strain measurements carried out in uniaxial extension of dry and swollen networks have revealed departures from these predictions of simple models 5. These observations then gave rise to phenomenological equations like the Mooney-Rivlin expression, i.e. 

The strain measures for dry (unswollen) vulcanizates of a large number of natural rubbers, butadiene-styrene and butadiene-acrylonitrile copolymers, polydimethylsiloxanes, polymethylmethacrylates, polyethylacrylates and polybutadienes with different degrees of crosslinking and measured at various temperatures re confined within the shaded area in Fig. 1. These measures were determined from the stress as a function of extension at (or near) equilibrium, i.e. by applying Eq. (7). Therefore they only reproduce the equilibrium stress-strain relation for the crossllnked rubbers. In all cases the strain dependence of the tensile force (and hence of the tensile stress) was expressed in terms of the well-known Mooney-Rivlin equation, equating the equilibrium tensile stress to ... 

The copolymers listed in Table V were cured in the form of 0.01" thick films. The cured polymer was cut into strips one inch wide, and these strips were used for subsequent testing, direct measurement was made of the crosslink density of these polymers, but a relative value could be inferred from Mooney-Rivlin plots of the stress-strain data. 

Stress-strain measurements for PDMS samples filled with randomly distributed carbonyl iron particles, (a) On the basis of statistical theory of rubber elasticity and (b) Mooney-Rivlin representation of experimental data. Symbols represent different amounts of iron particles as indicated in the figure. 

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