Solid-state 109Ag CP/MAS NMR spectroscopy of some diammine silver(I) complexes

Solid-state cross-polarization magic-angle spinning (CP/MAS) NMR spectra were recorded for the compounds [Ag(NH3)2]2SO4, [Ag(NH3)2]2SeO4 and [Ag(NH3))]NO3, all of which contain the linear or nearly linear two-coordinate [Ag(NH3)2]+ ion. The 109Ag CP/MAS NMR spectra show centrebands and associated spinning sideband manifolds typical for systems with moderately large shielding anisotropy, and splittings due to indirect 1J(109Ag,14N) spin-spin coupling. Spinning sideband analysis was used to determine the 109Ag shielding anisotropy and asymmetry parameters Deltasigma and eta from these spectra, yielding anisotropies in the range 1500-1600 ppm and asymmetry parameters in the range 0-0.3. Spectra were also recorded for 15N and (for the selenate) 77Se. In all cases the number of resonances observed is as expected for the crystallographic asymmetric units. The crystal structure of the selenate is reported for the first time. One-bond (107, 109Ag,15N) coupling constants are found to have magnitudes in the range 60-65 Hz. Density functional calculations of the Ag shielding tensor for model systems yield results that are in good agreement with the experimentally determined shielding parameters, and suggest that in the solid compounds Deltasigma and eta are reduced and increased, respectively, from the values calculated for the free [Ag(NH3)2]+ ion (1920 ppm and 0, respectively), primarily as a result of cation-cation interactions, for which there is evidence from the presence of metal-over-metal stacks of [Ag(NH3)2]+ ions in the solid-state structures of these compounds.     

CHEMICAL MORPHOLOGY IN GRAFTING ACRYLAMIDE TO POLYETHYLENE

The scanning force microscopy (SFM)/chemical force microscopy (CFM) were used to study the growth of grafted polyacrylamide (PAM) chains onto polyethylene (PE)-film with varying grafting time.Results from the CFM reveal reduced interaction between the probe and areas with grafted-PAM on the surface.The topography and the friction trace- minus-retrace (TMR) images are complementary to one another resulting from the reduced interaction of the probe that has specificity to chemical domains.     

Influence of liquid crystalline polymer and recycled PET as minor blending components on rheological behavior,morphology, and thermal properties of thermoplastic blends

In this study, the potential of recycled poly(ethylene terepthalate) (rPET) as a well‐defined reinforcing material for the in situ microfibrillar‐reinforced composite (iMFC) was investigated in comparison with that of liquid crystalline polymer (LCP). Each dispersed phase (LCP or rPET) was melt blended with high density polyethylene (PE) by using extrusion process. The rheological behavior, morphology, and the thermal stability of LCP/PE and rPET/PE blends containing various dispersed phase contents were investigated. All blends and LCP exhibited shear thinning behavior, whereas Newtonian fluid behavior was observed for rPET. The incorporation of LCP or rPET into PE significantly improved the processability. A potential of rPET as a processing lubricant by bringing down the melt viscosity of the blend system was as good as LCP. The elongated LCP domains were clearly observed in as‐extruded strand. Although the viscosity ratio of the rPET/PE system was lower than that of the LCP/PE blend system, most rPET domains appeared as small droplets. An addition of LCP and rPET into the PE matrix improved the thermal resistance significantly in air but not in nitrogen. The obtained results suggested the high potential of rPET as a processing aid and good thermally resistant material similar to LCP. Copyright © 2009 John Wiley & Sons, Ltd.     

Solid-state NMR studies of some tin(II) compounds

High-resolution NMR spectra of [Formula: see text] nuclei, particularly (119)Sn and (31)P, in solid tin(II) phosphite, SnHPO(3), and tin(II) phosphate, SnHPO(4), are presented. The results are discussed in relation to the crystal structures. Spinning sideband analysis has been carried out for both nuclei, giving information on the shielding tensors. Satellite peaks allow the indirect Sn,Sn coupling constants to be determined. Surprisingly large values of 2600+/-200Hz and 4150+/-200Hz are reported for SnHPO(3) and SnHPO(4) respectively. The satellite peaks were investigated by using a single Hahn echo for each refocusing time, which showed that the observed splittings result from (119)Sn, (117)Sn coupling. For SnHPO(3), the calculated relative intensities of the satellites for six intra-layer coupling interactions are in agreement with the experiment values, but for SnHPO(4) the coupling appears to be inter-layer in nature. Tin-119 (and in one case phosphorus-31) shielding tensor data derived from MAS NMR are also reported for four other crystalline tin(II) compounds, namely tin diphosphate, tin oxalate, tin sulphate and calcium tin ethylenediamine tetraacetate.     

Rheology,morphology and tensile properties of thermotropic liquid crystalline polymer/polypropylene in‐situ composites

Blends of various grades of polypropylene (PP) with a thermotropic liquid crystalline polymer (TLCP), namely a copolymer of p‐benzoic acid and ethylene terephthalate (60/40 mole ratio) were prepared as extruded films. A thermoplastic elastomer styrene (ethylene‐butylene) styrene (SEBS) was used as a compatibilizer. Melt viscosities of all specimens were measured using a plate‐and‐plate rheometer with oscillating mode in the shear rate region of 1 ‐ 200 rad/s. Addition of SEBS compatibilizer resulted in an increase of the blend viscosity. Observation of the blend morphology revealed an improvement of TLCP dispersion. The TLCP fiber aspect ratio (length to diameter) in the extruded film also increased after addition of SEBS. As a result, the film modulus in extrusion direction was enhanced. The tensile strength of the film specimen was also increased due to an improvement of interfacial adhesion.     

Chlorination and characterization of natural rubber and its adhesion to nitrile rubber

Chlorinated natural rubber (CNR) vulcanized sheets were prepared by immersing the NR sheets in sodium hypochlorite solution for various chlorination times ranging from 0 to 30 min. The degree of chlorination as indicated by X-ray Absorption Near-Edge Spectroscopy (XANES) implied that the chlorine content increases with the chlorination time from 0 to 10 min then levels off. Atomic Force Microscopy (AFM) showed an evolution of the surface roughness and stiffness. These two properties increased gradually with chlorination time. The bond strength between CNR and nitrile rubber (NBR) also increased gradually. The data showed cohesive failure beginning at 1 min and extending throughout the 30 min of the study. The maximum peel strength was found at 1 min of chlorination time and decreased afterwards. The decrease in peel strength was caused by the increase in surface stiffness of NR that acted as weak boundary layer. The surface stiffness governed the peel strength between NR and NBR.