Polymer matrices, mechanical studies

In a natural fiber polymer composite, natural fiber is incorporated in a definite volume in the polymer matrix. Mechanical properties can be enhanced by increasing the fiber volume in a composite, but after a certain level, it may start decreasing due to the poor bonding between fiber and matrix. Oksman et al. [9] studied the effect of fiber loading with epoxy polymer. As shown in the Table 22.5, sisal fiber... 

It can be noted that other approaches, based on irreversible continuum mechanics, have also been used to study diffusion in polymers [61,224]. This work involves development of the species momentum and continuity equations for the polymer matrix as well as for the solvent and solute of interest. The major difficulty with this approach lies in the determination of the proper constitutive equations for the mixture. Electric-field-induced transport has not been considered within this context. 

In their study of branched PSA, Maniar et al. (1990) found that the molecular architecture of branched polymers affects the release kinetics in a variety of ways. They found that the branched polymers degraded faster than linear PSA of comparable molecular weight (Maniar et al., 1990). They also noted that drug (morphine) release profiles were more characteristic of bulk erosion than surface erosion An initial lag time during which very little drug was released was associated with the time required for water to swell the polymer. This was followed by a period of relatively fast release, which tapered off as the device disintegrated. The polymer matrix lost its mechanical integrity before the release experiment was complete (Maniar et al., 1990). Despite the increase... 

Roudaut et al. (1999a) used low-frequency pulsed-proton NMR and dielectric dynamic mechanical spectroscopies to study molecular mobility in glassy bread (<9%) as a function of temperature. Based on NMR results, they reported that some (if not all) of the water molecules were much more mobile than the polymer matrix whose relaxation time could not be measured within the 20-p,s dead time of the RF probe. 

Two commercial disazo disperse dyes of relatively simple structure were selected for a recent study of photolytic mechanisms [180]. Both dyes were found to undergo photoisomerism in dimethyl phthalate solution and in films cast from a mixture of dye and cellulose acetate. Light-induced isomerisation did not occur in polyester film dyed with the two products, however. The prolonged irradiation of Cl Disperse Yellow 23 (3.161 X = Y = H) either in solution or in the polymer matrix yielded azobenzene and various monosubstituted azobenzenes. Under similar conditions the important derivative Orange 29 (3.161 X = N02, Y = OCH3) was degraded to a mixture of p-nitroaniline and partially reduced disubstituted azobenzenes. 

The results of the delayed stress on radiation studies presented above (Figure 7) are also consistent with the mechanism of gas buildup within the polymer specimens as the cause of the accelerated creep. An additional interesting conclusion is that applied stress should increase the rate at which gases diffuse out of a polymer specimen. This is not unreasonable in view of the fact that this conclusion is reached for stress application during irradiation, when expansion of the polymer matrix by the internally generated gas would be expected to facilitate gas diffusion. (Actually, one would expect increased gas diffusion in stressed glassy polymers, even in the absence of radiation, owing to the low Poisson ratio in such materials.)... 

A few studies have reported the embedding of an MIP film between two membranes as a strategy for the construction of composite membranes. For example, a metal ion-selective membrane composed of a Zn(II)-imprinted film between two layers of a porous support material was reported [253]. The imprinted membrane was prepared by surface water-in-oil emulsion polymerisation of divinylbenzene as polymer matrix with 1,12-dodecanediol-0,0 -diphenylphosphonic acid as functional host molecule for Zn(II) binding in the presence of acrylonitrile-butadiene rubber as reinforcing material and L-glutamic acid dioleylester ribitol as emulsion stabiliser. By using the acrylonitrile-butadiene rubber in the polymer matrix and the porous support PTFE, an improvement of the flexibility and the mechanical strength has been obtained for this membrane. 

Further developments of the work include a more accurate study of the mechanisms of desulfurization processes using instrumental improvements. This will enable an easy quantitation of gas yield and a thermochemical approach of elemental processes. We also have been using model polymers to better study the interactions of pyrite and sulfur with the organic matrix during coal pyrolysis, oxidation and combustion (34 and to examine more accurately the specific role of organic sulfur in thermal degradation processes. 

Thermo-mechanical analysis (TMA)26 and DMTA292 have been used to study the viscoelastic properties of bread, a composite two-phase system. The moisture dependence of Tg was similar to that of pure amorphous starch and gluten.242,282 293-295 At the moisture content of bread, water exerts its full plasticization effect on the composite polymer matrix, reducing the effective Tg to about -10° to - 12°C,26,292 well below normal shelf life storage temperatures of this product. 

Provided in this chapter is an overview on the fundamentals of polymer nanocomposites, including structure, properties, and surface treatment of the nanoadditives, design of the modifiers, modification of the nanoadditives and structure of modified nanoadditives, synthesis and struc-ture/morphology of the polymer nanocomposites, and the effect of nanoadditives on thermal and fire performance of the matrix polymers and mechanism. Trends for the study of polymer nanocomposites are also provided. This covers all kinds of inorganic nanoadditives, but the primary focus is on clays (particularly on the silicate clays and the layered double hydroxides) and carbon nanotubes. The reader who needs to have more detailed information and/or a better picture about nanoadditives and their influence on the matrix polymers, particularly on the thermal and fire performance, may peruse some key reviews, books, and papers in this area, which are listed at the end of the chapter. 

Pulse radiolysis experiments on solid polymers have provided new insight into the mechanism of radiation damage of polymers. Recent studies on some practically important polymers clarified the pathways of transfer of radiation-induced excitation energy from polymer matrix to additives thus the roles of additives in the radiation resistance or sensitivities of polymers are understood in terms of elementary energy transfer processes. The usefulness of this method is verified not only in the basic science but also in the field of application. 

The Ni and Pt complexes can also be incorporated into polymer films of quaternized poly(vinylpyridine) (PVP) and deposited onto the transparent electrode (84). Photocurrents are enhanced to microamps (pA), an increase that may be attributed to either the effect of immobilization of the complexes near the electrode surface or an increase of the excited-state lifetimes in the polymer matrix. However, the effective concentrations of the complexes in this study were much greater than for the acetonitrile solutions in their earlier work. The polymer films are not stable to continuous photolysis, and voltammograms of the films are quite sensitive to anions used in the supporting electrolyte. The system can be stabilized by using a polymer blend of PVP and a copolymer containing quaternary ammonium ion and including [Fe(CN)6]4- in the electrolyte solution (85). Upon irradiation of the visible MLCT bands of [M(mnt)2]2 (M = Ni, Pt), photocurrents are produced. The mechanism (Scheme 4) is believed to involve photooxidation of the metal bis(dithiolene) triplet state by the Sn02 electrode, followed by [Fe(CN)6]4 reduction of the monoanion, with completion of the ET cycle as ferricyanide, Fe(CN)6 3, diffuses to the other electrode and is reduced. 

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