Small angle X-ray scattering study of structural parameters of the aggregated state in polyamide 1010+BMI

The structural parameters of the aggregated state in the polyamide PA1010 and N,N'-bismaleimide-4,4'-diphenyl methane (BMI) system were computed by means of the desmearing intensity from SAXS and using the concept of the distance distribution function. The results revealed that the parameters Q, I(0), l(c) and L decreased with the increase BMI component, whereas O-s increased. The particle dimension Z for different BMI contents was less than 13.2 nm, and the maximum value of the distance distribution function P(Z) was found to be in the range Z = 6.5-7.0 nm.

THE EFFECT OF LOADING PARAMETERS ON FATIGUE BEHAVIOR OF INJECTION-MOLDED COMPOSITE

Flexural fatigue tests were performed on an injection-moulded glass-fiber reinforced blend of polyphenylene ether ketone and polyphenylene sulfide composite using four-point bending at a series of fixed mean stress levels with varying stress amplitude. Attention was given to identifying the effects of mean stress and stress amplitude on the fatigue life and failure mechanisms. It was found that the fatigue life of the studied material decreased sharply with increasing stress amplitude at a constant mean stress level and also decreased at a fixed stress amplitude with increasing mean stress. However, analyses of the fatigue data and failure behaviour reveal that, for the studied material, fatigue failure mechanisms depend on the relative importance of mean stress and stress amplitude. At a mean stress level of 80% ultimate flexural strength, the failure results from accumulation of creep strain, while at mean stress levels of 40%, 50% and 60% ultimate flexural strength, the magnitude of stress amplitude influences the type of failure mechanism. As stress amplitude is reduced, the fatigue failure mechanism changes from matrix yielding dominated to crack growth dominated fracture.

EFFECT OF THE CONCENTRATION OF THE ER3+ ION ON THE SPECTRAL INTENSITY PARAMETERS OF ER-YAG CRYSTALS

The absorption spectra of Er:YAG (YAG, yttrium-aluminium-garnet) crystals containing different concentrations of the trivalent erbium ion were measured and the spectral intensity parameters were calculated from these experimental spectra using the Judd-Ofelt model. The results indicate that the phenomenological intensity parameters, OMEGA(lambda) (lambda = 2, 4 and 6), vary as a function of the concentration of the Er3+ ion in the Er:YAG crystal, but no variation in the fluorescence-branching ratios as a function of the concentration of the Er3+ ion is found. An empirical formula is proposed to describe the relationship between the spectral intensity parameters and the Er3+ ion concentration in the Er:YAG crystal. The spectral intensity parameters exhibit a maximum in Er:YAG crystals containing about 1-1.5 at.% Er3+ ion. The effect of the Er3+ ion concentration on the spectral intensity parameters may be attributed to the inhomogeneous lattice distortion in the cell of the Er:YAG crystal caused by the dopant erbium ions.

RAPID-DETERMINATION OF KINETIC-PARAMETERS FOR THE ELECTROCATALYTIC REDUCTION OF DIOXYGEN BY VITAMIN-B12 ADSORBED ON GLASSY-CARBON ELECTRODE

In this paper, the electrochemical behavior of vitamin B-12, ie cyanocobalamin (abbr. VB12) in a weak acidic aqueous solution and adsorbed on glassy carbon (GC) surface (abbr. VB12(ad)/GC) in different pH buffer solutions have been described by using cyclic voltammetry (cv). It is found that VB12 and VB12(ad)/GC exhibit catalytic activity for the electroreduction of O2 according to two reduction peaks at -0.50 and -1.00 V vs. sce; but their electrocatalytic activity is very unstable. Based on the method of hydrodynamic amperometry [B. Miller and S. Bruckenstein, J. electrochem. Soc. 117, 1033 (1970)], some kinetic parameters for the electrocatalytic reduction of O2 by VB12(ad)/GC have been determined rapidly by using a linear rotation-scan method [Rongzhong Jiang and Shaojun Dong, Electrochim. Acta 35, 1451 (1990)]. These kinetic parameters indicate that the reduction of O2 on VB12(ad)/GC gives water predominantly in both potential ranges which correspond to those two reduction peaks. Possible reaction mechanisms have been suggested.

ANALYSIS OF ANGULAR OVERLAP PARAMETERS FOR THE LAOXEU3+ (X = CL, BR, I) SERIES

The Angular Overlap Model (AOM) is applied to the LaOX:Eu3+(X = Cl, Br, I) series involving sigma, pi, delta and phi effects based on the experimental energy levels. The calculations are made in two cases. (1) Consider oxygen and halogen having the same bond-length. (2) Consider the real structure. In both cases, the results show that for sigma-bonding parameters, the values of e(sigma) decrease with increasing charge number of halogen, i.e. Cl- > Br- > I-, this indicates that the bonding ability also decreases with this order. The absolute values of each parameter are much larger than zero-therefore they all must be included in a practical analysis. In the second case, the values of the e(pi) parameter are negative, which means a ''back-bonding'' is formed, and this is profitable for the formation of sigma-bonding, usually referred to as ''synergic effect''.

CRYSTAL-STRUCTURE AND THERMODYNAMIC PARAMETERS OF NYLON-1010

WAXD, SAXS, FTIR, DSC and density techniques have been used to investigate the crystal structure, crystal density rho(c), amorphous density rho(a), equilibrium heat of fusion DELTAH(m)degrees and equilibrium melting temperature T(m)degrees. By extrapolating the straight lines in the FTIR absorbance against density plot to zero intensity, rho(c) and rho(a) were estimated to be 1.098 and 1.003 g/cm3 respectively. The rho(c) obtained was too low in value. From X-ray diffraction patterns of uniaxially oriented fibres, the crystal structure of Nylon-1010 was determined. The Nylon-1010 crystallized in the triclinic system, with lattice dimensions: a = 4.9 angstrom, b = 5.4 angstrom, c = 27.8 angstrom, alpha = 49-degrees, beta = 77-degrees, gamma = 63.5-degrees. The unit cell contained one monomeric unit, the space group was P1BAR, and the correct value of rho(c) was 1.135 g/cm3. The degree of crystallinity of the polymer was determined as about 60% (at RT) using Ruland's method. SAXS has been used to investigate the crystalline lamellar thickness, long period, transition zone, the specific inner surface and the electron density difference between the crystalline and amorphous regions for Nylon-1010. The analysis of data was based upon a one-dimensional electron-density correlation function. DELTAH(m)degrees was estimated to be 244.0 J/g by extrapolation of DELTAH(m)degrees in the plot of heat of fusion against specific volume of semicrystalline specimens to the completely crystalline condition (V(sp)c = 1/rho(c)). Owing to the ease of recrystallization of melt-crystallized Nylon-1010 specimens, the well-known Hoffman's T(m)-T(c) method failed in determining T(m)degrees and a Kamide double extrapolation method was adopted. The T(m)degrees value so obtained was 487 K.

MOLECULAR-GEOMETRY AND CHAIN ENTANGLEMENT - PARAMETERS FOR THE TUBE MODEL

The tube diameter in the reptation model is the distance between a given chain segment and its nearest segment in adjacent chains. This dimension is thus related to the cross-sectional area of polymer chains and the nearest approach among chains, without effects of thermal fluctuation and steric repulsion. Prior calculated tube diameters are much larger, about 5 times, than the actual chain cross-sectional areas. This is ascribed to the local freedom required for mutual rearrangement among neighboring chain segments. This tube diameter concept seems to us to infer a relationship to the corresponding entanglement spacing. Indeed, we report here that the critical molecular weight, M(c), for the onset of entanglements is found to be M(c) = 28 A/([R2]0/M), where A is the chain cross-sectional area and [R2]0 the mean-square end-to-end distance of a freely jointed chain of molecular weight M. The new, computed relationship between the critical number of backbone atoms for entanglement and the chain cross-sectional area of polymers, N(c) = A0,44, is concordant with the cross-sectional area of polymer chains being the parameter controlling the critical entanglement number of backbone atoms of flexible polymers.

ANALYSIS OF ANGULAR OVERLAP PARAMETERS FOR EU3+ - LN2O2S (LN = LU, Y, GD, LA) CRYSTAL SERIES

The angular overlap model (AOM) is applied to 4f6 electron systems. The crystal field parameters are interpreted and covalency between 4f electrons and ligands is investigated based on the experimental energy levels. For Eu3+:Ln2O2S (Ln = Lu, Y, Gd, La) crystal series, we adopt two computational schemes. First of all, we assume that the distances to all ligands are equal, and then the distances to all ligands are divided into two groups, namely, oxygens as one group, sulfurs as the other. Of course, much information about covalency will be obtained from the latter case. Obviously, our results show that the covalency of Ln-O bonding is stronger than that of Ln-S bonding in line with much shorter bondlength for the former than that for the latter. The two schemes yield the same results, that is, for sigma and pi bonding, ligands are strong donors as well as sigma, pi effects are dominant over delta, phi effects.

GLASS-TRANSITION TEMPERATURE AND MOLECULAR-PARAMETERS OF POLYMER

A new relationship, which correlates the glass transition temperature (T(g)) with other molecular parameters, is developed by using Flory's lattice statistics of polymer chain and taking the dynamic segment as the basic statistical unit. The dependences of T(g) on the chain stiffness factor (sigma-2), dynamic stiffness factor (beta = -d ln-sigma-2/dT) and molecular weight of polymer are discussed in detail based on the theory. The theory is compared with experimental data for many linear polymers and good agreement is obtained. It is shown that T(g) is essentially governed by the chain stiffness factor at T(g). Moreover, a simple correlation between the parameter K(g) of the Fox-Flory equation (T(g) = T(g)infinity - K(g)/M(n)) and other molecular parameters is deduced. The agreement between theoretical predictions and experimental measurements of K(g) has been found to be satisfactory for many polymers.

DETERMINATION OF PARAMETERS OF FAST CHEMICAL REACTION OF ALIZARIN RED S BY SPECTROELECTROCHEMICAL METHOD WITH LOPTLC

The rate constant of very fast chemical reaction generally can be measured by electrochemical methods, but can not by the thin layer electrochemical methods because of the influence of diffusion effect. Long optical path length thin layer cell (LOPTLC) with large ratio of electrode area to solution volume can be used to monitor the fist chemical reaction in situ with high sensitivity and accuracy. It enable the adsorption spectra to be measured without the influence of diffusion effect. In the present paper, a fast chemical reaction of Alizarin Red S (ARS) with its oxidative state has been studied. The reaction equilibrium constant (K) under different potentials can be determined by single step potential-absorption spectra in LOPTLC. An equilibrium constant of 7.94 x 10(5) l.mol(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)'). Rate constant (k) under different potentials can be measured by single step potential-chronoabsorptiometry. A rate constant of 426.6 l.mol(-1).s(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)') with (E - E-1(0)') = 0.

Photosynthetic parameters of sexually different parts of Porphyra katadai var. hemiphylla (Bangiales, Rhodophyta) during dehydration and re-hydration

Physiological data from extreme habitat organisms during stresses are vital information for comprehending their survival. The intertidal seaweeds are exposed to a combination of environmental stresses, the most influential one being regular dehydration and re-hydration. Porphyra katadai var. hemiphylla is a unique intertidal macroalga species with two longitudinally separated, color distinct, sexually different parts. In this study, the photosynthetic performance of both PSI and PSII of the two sexually different parts of P. katadai thalli during dehydration and re-hydration was investigated. Under low-grade dehydration the variation of photosystems of male and female parts of P. katadai were similar. However, after the absolute water content reached 42%, the PSI of the female parts was nearly shut down while that of the male parts still coordinated well and worked properly with PSII. Furthermore, after re-hydration with a better conditioned PSI, the dehydrated male parts were able to restore photosynthesis within 1 h, while the female parts did not. It is concluded that in P. katadai the susceptibility of photosynthesis to dehydration depends on the accommodative ability of PSI. The relatively lower content of phycobiliprotein in male parts may be the cause for a stronger PSI after severe dehydration.

Estimates of genetic parameters for growth traits of the sea urchin, Strongylocentrotus intermedius

Heritabilities and genetic and phenotypic correlations were estimated for body weight, test diameter, and test height of the sea urchin from measurements on progeny resulting from 11 sires and 33 dams by artificial fertilization of 3 females by single males, and measurements at 8, 10, and 12 months after metamorphism. Point estimate for heritabilities based on the sire components of variance were moderate to high for body weight (0.21-0.49), test diameter (0.21-0.47), and test height (0.22-0.37). Genetic correlations were significant for body weight with test diameter (0.30similar to0.65) and test height (0.30similar to0.54) and test diameter with test height (0.31similar to0.65). Genetic correlation estimates, derived the nested design and half-sib correlation analysis used in this study, appear to provide reliable estimates. Significant phenotypic correlations were found for body weight with test diameter (0.82similar to0.86) and test height (0.49similar to0.83), and test diameter with test height (0.47similar to0.84). The phenotypic correlations for test height with body weight (0.491) and test diameter (0.467) at 12 months' of age were smaller than those earlier sampling periods.(C) 2004 Published by Elsevier B.V.