POLYMER NETWORK-POLY(ETHYLENE GLYCOL)COMPLEXES WITH SHAPE MEMORY EFFECT

The complexes of poly(methacrylic acid-co-methyl methacrylate) network with poly(ethylene glycol) stabilized byhydrogen bonds were prepared. By introducing the poly(ethylene glycol), a large difference in storage modulus below andabove the glass transition temperature occurred and the complexes exhibited shape memory behaviors. The morphology ofcomplexes was studied by using DSC, WAXD, and DMA. The results indicate that the fixed phase of this kind of novelshape memory materials is the network, and the reversible phase is the amorphous state of PEG:PMAA complex phase. Theshape recoverability almost reaches 100%. This type of complexes can be regarded as a novel shape memory network.     

Structural Efficiency and Microstructural Modeling of Wet Gels and Aerogels

We present a microstructural model of aerogels that includes the effect of particle necks, tortuosity and dangling ends on the scaling of elastic moduli with density. Relative neck radii can be determined for sintering series of silica aerogels and for Resorcinol Formaldehyde (RF) aerogels produced with different catalyst concentrations. The density of elastically ineffective dangling ends and the tortuosity can be estimated using information from thermal conductivity and elastic modulus measurements in silica aerogels. Typical values for the load bearing mass range from >50% for high density and heat treated aerogels to <10% of the total mass for low density wet-gels.     

Interplay of Electronic Structure and Bulk Properties in 2D and 3D Ternary Carbonitrides from First Principles

The changes in electronic structure and hardness as inferred from the bulk modulus are investigated for model structures of ternary compounds XC₃N₃ (X = B, Al, P, As, Ga) within the framework of density functional theory (DFT). The optimisations of the proposed two‐ (2D) and three‐dimensional (3D) structures and the calculations of the bulk moduli are performed by a pseudo potential method. The electronic structures are calculated with the augmented sphere wave method (ASW). The obtained hardness for 2D BC₃N₃ system (B₀ ～ 220 GPa) points to a magnitude close to that of graphitic C₃N₄. For heavier X atoms it decreases rapidly. This is equally observed for the 3D systems examined in the β‐C₃N₄ structure for which B₀(β‐BC₃N₃) amounts to ～330 GPa. Within the magnitude of the well known hard material cubic BN, the BC₃N₃ phases can be predicted as candidates for ultra hard materials. The electronic effect induced by the chemical nature of the X substitutional was examined according to its position in the periodic table i.e. X_III or X_V. Both, band structures and the electron localisation function (ELF) were used for this analysis. The ELF plots show a decreasing covalency with heavier X‐atoms. Potential applications of the devised systems are proposed such as dopings with atoms (Li, rare gas) and molecules (N₂).     

Aging effect on the mechanical properties of hybrid gels

Sol-gel derived unsupported films and thin rods have been obtained from co-hydrolysis of triethoxysilane and methyldiethoxysilane. The materials are flexible, dense and transparent. Films and rods have been aged for different periods of time in air at room temperature. The elastic modulus has been measured by means of tensile or flexural tests. Measurements showed an increase of elastic modulus with aging time and showed different values for films and rods. The observed evolution of mechanical properties has been related to a corresponding structural modification as highlighted mainly by MAS-NMR studies. Analyses pointed out the crucial role of condensation processes and showed that the stiffness increase arises from the formation of relatively few bonds which link and constrain pre-existing mobile network regions.     

Quantitative evaluation of stress distribution in bulk polymer samples through the comparison of mechanical behaviors between giant single‐crystal and semicrystalline samples of poly(trans‐1,4‐diethyl muconate)

The Raman shift and crystallite modulus were measured under the application of tensile force for a giant single crystal and a series of uniaxially oriented semicrystalline samples of poly(trans‐1,4‐diethyl muconate) (polyEMU). The apparent Raman shift factor α^app or a vibrational frequency shift per 1 GPa tensile stress was higher for the semicrystalline samples with lower crystallinity or lower bulk modulus. The apparent crystallite modulus E or Young's modulus along the chain axis in the crystalline region was not constant but varied remarkably between the giant single crystal and semicrystalline samples. A systematic change in α^app and E among the polyEMU samples with different preparation history could be interpreted quantitatively on the basis of a mechanical series parallel model consisting of crystalline and amorphous phases. The origin of different E and α^app was speculated to be a stress concentration on the taut‐tie chain contained as a parallel crystalline component in the mechanical model. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 444–453, 2003     

General analysis of the measurements of the lateral crystal lattice moduli of semicrystalline polymers by x-ray diffraction and the application to nylon 6

A mathematical representation based on a linear elastic theory is proposed by which one may investigate the dependences of molecular orientation and crystallinity on the crystal lattice moduli and linear thermal expansion coefficients in the direction perpendicular to the chain axis as commonly measured by x-ray diffraction. In the theoretical calculation, a previously introduced model was employed in which oriented crystalline phase is surrounded by oriented amorphous phase and the strains of the two phases at the boundary are identical. The mathematical analysis indicated that the lateral crystal lattice moduli and linear thermal coefficients as measured by x-ray diffraction may be different from the intrinsic crystal moduli and linear thermal coefficients of a crystal unit cell, depending on the structure of the polymer solid. The numerical calculation was applied to nylon 6. As a result, it may be confirmed that the lateral crystal lattice moduli measured by x-ray diffraction are sensitive to the morphology of the bulk speciments and close to the intrinsic crystal moduli if the morphology of the test specimen can be represented by a parallel model with respect to the original stretching longitudinal direction.     

Swelling behavior and mechanical properties of endlinked poly (dimethylsiloxane) networks and randomly crosslinked polyisoprene networks

Measurements of the equilibrium degree of swelling and of the equilibrium modulus were performed on poly(dimethylsiloxane) networks (PDMS) and on polyisoprene vulcanizates. The results support the concept that topological interactions between network chains, e.g. entanglements or the like, have a large influence on the rubber elastic behavior, at least within a certain range of network densities.PDMS networks having network chains of different lengths and varying functionlities of the crosslinks were prepared in bulk by endlinking fractionated ,-divinyl PDMS via multifunctional hydrogen-siloxanes (f=3 to 22). Natural rubber (NR) and synthetic liquid polyisoprene (IR) were cured in bulk with various amounts of dicumyl peroxide to give randomly crosslinked samples.The experimentally determined moduli and degrees of swelling were compared with theoretical predictions based on the phantom network theory and affine network theory, taking into account only chemical crosslinks. The observed discrepancies can be traced back to a contribution of topological interactions (trapped entanglements) to the total effective network density. The modulus and swelling data are consistent, thus ruling out non-equilibrium effects.     

Influence of high pressure treatment on rheological and other properties of egg white

Abstract

The paper deals with the influence of high pressure treatment of fresh egg white on its properties and protein composition (individual amino-acids predicted as a function of pressure and time levels). The rheological properties are changed by high pressure from Newtonian to non-Newtonian behaviour, with increasing apparent viscosity as the pressure and time increased. The pH, whipping ability, foam stability, gel strength of heat induced gels after treatment and the whole protein content, were also predicted.

The results showed that the foam stability is increased with increasing pressure and time of processing. The foam volume is also increased with pressure. The pH did not change with pressure or time of processing. Composition of proteins as indicated by individual amino-acids did not exhibit statistically important changes. Gel strength of heat induced gels prepared from previously pressured liquid whites showed no important change of values with pressure or time of treatment. The modulus of elasticity showed a decrease for samples pressured to 400 MPa for 5 up to 15 minutes.     

Study of Temperature and UV Wavelength Range Effects on Degradation of Photo-Irradiated Polyethylene Films Using DMA

Plastic bags mostly made of polyethylene (PE) cause pollution as solid waste due to their non-degradability nature. Initiation of a degradative process by enhanced photo-oxidation is a possible method for an accelerated degradation. This paper presents temperature treatment effects on PE films where photodegradation was initiated using ultraviolet (UV) irradiation in the ranges of 200–300 nm and 300–400 nm for 2 hr. Effects of temperature of 40°C and 55°C on non-UV-irradiated and UV-irradiated PE films processed by conventional methods were investigated and evaluated after 50 hr, 150 hr, and 350 hr of temperature exposure. The effects of UV wavelength range irradiation on the degradation were deduced. Measuring the dynamic moduli using a dynamic mechanical analyzer monitored the degradation. The decrease in average storage modulus was 62% with treatment at 55°C, higher than the 16% drop at 40°C for unirradiated samples after 350-hr exposure. Cross-linking in UV-exposed samples, characterized by an increase in dynamic modulus (stiffening), was observed followed by a reduction of storage modulus. Temperature treatment at 55°C together with 300–400-nm UV range irradiation resulted in the largest increase, i.e., 22% after 150 hr, followed by the largest reduction of storage modulus, i.e., 74.6% for a cumulative 350-hr exposure.     

Wrinkle morphologies with two distinct wavelengths

Wrinkles with two distinct wavelengths formed sequentially on the same surface are investigated. A series of aligned wrinkles are formed through local strain application on a partially crosslinked elastomer. After the formation of these primary wrinkles, the elastomer is fully crosslinked, and a mechanical compressive strain is applied to the sample orthogonal to the primary wrinkles. This mechanical strain results in smaller secondary wrinkles superimposed on the larger primary aligned wrinkles. Resulting biaxial morphologies suggest that the primary pattern directs the formation of the smaller wrinkles. The modulus mismatch of the substrate on primary and secondary wrinkle formation dictates the ratio between the two resulting wavelengths, as well as the specific biaxial morphologies, ranging from zigzag ridges to ellipsoidal bumps or corn‐on‐the‐cob structures to the classic herringbone. The sequential strain wrinkling process has the potential to be used on an industrial scale for the facile formation of surface topography with two discrete, tunable lateral dimensions over large surface areas. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012