Natural rubber parameter

One of our previous complaints was that we had more parameters than we knew what to do with Eq. (2.33) makes this problem even worse. It turns out, however, that using only two or three terms of Eq. (2.33) results in a usable equation with improved curve-fitting ability. Techniques have been developed for extracting acceptable parameters from experimental data in these cases (see Problem 4). Figure 2.9, for example, shows data collected from a sample of natural rubber, analyzed according to a two-term version of Eq. (2.33). The line in Fig. 2.9 is drawn according to the equation... 

Tables 5.4 and 5.5 predict that unvulcanised natural rubber (8 = 16.5) will be dissolved in toluene (8 = 18.2) and in carbon tetrachloride (8 = 17.5) but not in ethanol (8 = 26.0), all values being in units ofMPa. This is found to be true. Similarly it is found that there is a wide range of solvents for polystyrene in the solubility parameter range 17.2-19.7 MPa. ...

Like NR, SBR is an unsaturated hydrocarbon polymer. Hence unvulcanised compounds will dissolve in most hydrocarbon solvents and other liquids of similar solubility parameter, whilst vulcanised stocks will swell extensively. Both materials will also undergo many olefinic-type reactions such as oxidation, ozone attack, halogenation, hydrohalogenation and so on, although the activity and detailed reactions differ because of the presence of the adjacent methyl group to the double bond in the natural rubber molecule. Both rubbers may be reinforced by carbon black and neither can be classed as heat-resisting rubbers. 

ATBN - amine terminated nitrile rubber X - Flory Huggins interaction parameter CPE - carboxylated polyethylene d - width at half height of the copolymer profile given by Kuhn statistical segment length DMAE - dimethyl amino ethanol r - interfacial tension reduction d - particle size reduction DSC - differential scanning calorimetry EMA - ethylene methyl acrylate copolymer ENR - epoxidized natural rubber EOR - ethylene olefin rubber EPDM - ethylene propylene diene monomer EPM - ethylene propylene monomer rubber EPR - ethylene propylene rubber EPR-g-SA - succinic anhydride grafted ethylene propylene rubber... 

Gee ° has applied this method to the determination of the interaction parameters xi for natural rubber in various solvents. Several rubber vulcanizates were used. The effective value of VelV for each was determined by measuring its extension under a fixed load when swollen in petroleum ether. Samples were then swollen to equilibrium in other solvents, and xi was calculated from the swelling ratio in each. The mean values of xi for the several vulcanizates in each solvent are presented in Table XXXVI, where they are compared with the xi s calculated (Eq. XII-30) from vapor pressure measurements on solutions of unvulcanized rubber in some of the same solvents. The agreement is by no means spectacular, though perhaps no worse than the experimental error in the vapor pressure method. 

Calculations of the elastic properties, the main tensions and tensile strength of natural rubber carried out without using the empirical adjusting parameters are in good agreement with the experimental data. 

Finally, the solubility parameter of the adhesive and the substrate must be close. Without getting too teehnieal, the solubility parameter is a rough estimate of polarity. The old saying like dissolves like can be extended to like bonds like. More aeeurately, the solubility parameter is the ealeulated potential energy of 1 em of material for eommon solvents. Polymers are assigned solubility parameters of solvents in which they are soluble. Table 19.3 lists solubility parameters for various solvents and polymers. As an example of how to use this table, butadiene-acrylonitrile rubber with 6= 9.5 bonds natural rubber (6= V.9-8.3) to phenolic plastics (6= 11.5). Note that its solubility parameter is between that of the two substrates. 

Polymers with solubility parameters differing from those of the solvent by at least 2.0 H, will not dissolve in the solvent at room temperature. Thus although unvulcanized natural rubber (NR), unvulcanized styrene-butadiene elastomer (SBR), unvulcanized butyl rubber, and EPDM dissolve in gasoline or benzene, the vulcanized (cross-linked) polymers are swollen but will not dissolve due to the presence of the crosslinks. 

These authors have shown that this four-parameter equation for W fits the early data of Treloar29 on natural rubber. 

Nakajima and Hamel50 have derived expressions for calculating shear stresses from the Mooney torque values to give viscosities in agreement with those obtained from other instruments, and also an expression to correct for the edge effects.51 Bristow52 derived non-standard Mooney parameters for natural rubbers to improve the distinction between different grades. 

The system Cl-buty 1-natural rubber (or cw-polyisoprene) could not be resolved by differential solvent techniques because the polymeric solubility parameters were too similar. At one end of the spectrum—i.e., with styrene at — 25 °C—natural rubber could be highly swollen while restricting the chlorobutyl swell, but the reverse was not possible, as indicated by the swelling volumes in the trimethylpentane. As displayed in Table II, attempts to use a highly symmetrically branched hydrocarbon with a very low solubility parameter, served only to reduce both the swelling of natural rubber and chlorobutyl. (Neopentane is a gas above 10°C and a solid below — 20°C). Therefore, for this report the use of differential solvents in the study of interfacial bonding in blends was limited to systems of Cl-butyl and cw-polybutadiene or SBR. 

Three polymer pairs, polyethylene (PE)/polyisobutylene (PIB), PIB/ polystyrene (PS), and natural rubber (NR) /PS, are considered. The characteristic parameters, t>, p, T, for each of these polymers have been evaluated by Flory and co-workers and are used here as given. 

Blends of elastomers are routinely used to improve processability of unvulcanized rubbers and mechanical properties of vulcanizates like automobile tires. Thus, cis-1,4-polybutdiene improves the wear resistance of natural rubber or SBR tire treads. Such blends consist of micron-sized domains. Blending is facilitated if the elastomers have similar solubility parameters and viscosities. If the vulcanizing formulation cures all components at about the same rate the cross-linked networks will be interpenetrated. Many phenolic-based adhesives are blends with other polymers. The phenolic resins grow in molecular weight and cross-link, and may react with the other polymers if these have the appropriate functionalities. As a result, the cured adhesive is likely to contain interpenetrating networks. 

Because cyclohexane does not require an added stabilizer in the mobile phase, this means that ultraviolet (UV) detection at 220 nm can be used. This is important, as this type of detector is more sensitive than a refractometer. In fact, as natural rubber is a polymer with a very high molecular weight, it is recommended that low-concentration solutions at around 0.2 mg/mL are injected, so as to overcome viscosity effects and avoid excessive shearing of the macromolecules [7]. Of course, a light-scattering detector, or viscometer, can be added to the system to access the branching rate [8,9], which is an important parameter for natural rubber. 

Natural rubber of Mn = 2.23x10 was vulcanized with 2% sulfur. Calculate an estimate of the extent of swelling of the vulcanizate in benzene at equilibrium, given that the interaction parameter of rubber and benzene is 0.41. Assume that all sulfur is used in crosslinldng and that there is, on the average, one crosslink for every eight sulfur atoms. [Data Rubber density = 0.91 g/cm molar volume of benzene = 89.4 cm- /moL]... 

Schreiber and collaborators (44,45) reported such comparisons of interaction parameters obtained by GC and static methods for poly(dimethyl siloxane) (44) and natural rubber (45). A summary of their results for hydrocarbon solutes in poly(di-methyl siloxane) is given in Table 3 for both x (x ) and %i2 interaction parameters. 

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