Toughening of syndiotactic polypropylene with chalk

We hypothesized that polymer crystal anisotropy is advantageous for toughening of polymer composites involving easy slip network of oriented crystalline layers around filler particles. To this end, composites of syndiotactic polypropylene (sPP) with high concentration of submicrometer calcium carbonate particles were prepared and examined because usual sPP crystals exhibit high packing anisotropy. The specific orientation of sPP lamellae around chalk grains was found, which is supposed to facilitate the plastic deformation of polymer matrices. The compression molded bars of the composite exhibited markedly higher Izod impact strength than those of neat sPP. Toughening was even enhanced in the injection molded composite, for which 4.5‐fold increase in the impact strength was achieved. Injection‐induced orientation of the disordered form I sPP crystals was enhanced in the composite. The injection molded tensile specimens exhibited also a good drawability. Debonding at chalk–sPP interface occurred both during the impact and tensile tests facilitating the plastic deformation of sPP matrix. Chalk did not have any significant influence on the thermal properties of the composites but it affected the rheological behavior, increasing the loss and storage moduli, and the viscosity. Highly filled sPP composite exhibited solid‐like behavior in a molten state with the storage modulus exceeding the loss modulus in the entire frequency range. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43651.     

Heavy Metals in Stream Sediments from the Coquimbo region (Chile): Effects of Sustained Mining and Natural Processes in a Semi-arid Andean Basin

Abstract.   Active sediments from the Elqui River in Chile were sampled 4 times at 10 sites during 2000. Concentrations of Ag, Ba, Cd, Co, Cr, Hg, Mn, Mo, Ni, Pb, Sr, Ti, V, Al, Ca, Fe, K, Mg, Na, P, and S were normal. Zinc levels were clearly high, and those of Cu (hundred to thousands ppm) and As (tens to hundreds ppm) were highly anomalous. Dissolved Cu (0.1-12.7 ppm) and Zn (0.2-2.2 ppm) levels were also very high. The anomalies of the upper tributaries are due to the El Indio–Tambo Au-Cu-As district and large hydrothermal alteration zones at altitudes between 3500–4500 m. Lower on the river, old and active tailing waste deposits and on-going mining operations in the Talcuna Cu (Pb) district are responsible. Partially eroded tailing deposits in the alluvial plain of the Elqui River and its tributaries, and especially in the El Indio-Tambo district, after mine closure in 2000, warrant special attention.     

Effect of polymer structure on the molecular dynamics and thermal behavior of poly(allyl acetoacetate) and copolymers

In this paper, dielectric and calorimetric studies of the small-molecule glass former allyl acetoacetate monomers as well as its newly synthetized homopolymer and copolymers with different styrene composition were performed in both the liquid and glassy states. The molecular dynamics studies by the broadband dielectric spectroscopy and the stochastic temperature modulated differential scanning calorimetry enabled us to explore relaxation processes of examined materials in the wide frequency range. We found that the copolymers reveal two co-existing glass transitions characterized by the glass transition temperatures, which are very close to those of the corresponding homopolymers. These results suggest that the copolymers exhibited some sequences of acetoacetate units with a microphase-separated morphology in agreement with the value of reactivity ratio previously determined. We investigated effects of copolymerization compositions on the glass transition temperature, the isobaric fragility index, the dielectric and calorimetric intensity, and the dynamic heterogeneity on the glass transitions of the materials.     

Cavitation during deformation of semicrystalline polymers

Cavitation phenomenon is observed during deformation in many semicrystalline polymers above their glass transition temperature. Numerous voids (cavities) both nanometer and micrometer size are formed inside amorphous phase between lamellae during deformation of a polymer. The cavitation is observed only in tension, never during compression or shearing. Most often used methods of voids detection are: microscopies (SEM, TEM, AFM and light microscopy), small angle X-ray scattering and measurements of density. Usually the voids are detected close to yielding or at yielding, strongly suggesting that yielding is often caused by cavitation. However, there is a competition between two processes: breaking of amorphous phase leading to cavitation and plastic deformation of lamellar crystals. Which process occurs first depends on the relation between compliances of those two phases. If the crystals are weak and defected their deformation occurs (mostly by chain slips mechanism) without cavitation. If the crystals in a polymer are thick and more perfect then the barrier for their deformation, represented by shear yielding stress, is increased and the cavitation sets in first and yielding is determined by the stress needed for cavitation. Further deformation involves deformation of crystals due to rapid local change of stress around voids. The influence of different morphological factors: crystal thickness, crystallinity degree, arrangement of crystalline elements (e.g. in spherulites), morphology of amorphous phase (free volume, entanglements, tie molecules) were analyzed. Experimental factors, such as temperature of deformation and rate of deformation influence remarkably the formation of cavities. Cavitation is generated at points where a high local triaxial state of stress is developed. Triaxiality of stress can be amplified by a notch, even very mild notch with large radius of curvature stimulates generation of cavities. Evolution of nano-cavities into micro-cavities and change of their shapes with increasing deformation were evidenced by SAXS. Initially voids are oriented perpendicularly to deformation direction, however, with increasing elongation they become oriented along deformation direction. Stress whitening is visual sign of cavitation and is caused be light scattering either by microvoids or by assemblies of nanovoids.     

On the dynamic self-diffraction in methylene blue-sensitised gelatine

Dynamic self-diffraction processes have been observed and analysed for methylene blue-sensitised water-swollen gelatine (MBSG). A degenerate two-wave mixing experiment performed on thick samples of MBSG with 10 mW, 632.8 nm wavelength He Ne laser light allowed for the formation of phase- and amplitude-transient holographic gratings. Single-beam propagation characteristics through MBSG were measured with a Mach-Zehnder interferometer. The observed energy transfer between the writing beams in the two-beam coupling experiment and the considerable temporal oscillations of diffraction efficiency are explained by simple formulae. Two processes are considered: the time-dependent phase shift between the writing beams and the transverse self-phase modulation effects (self-focusing and interference ring formation).     

Residual stresses in epoxy systems by 3-D photoelastic method

The new 3-D photoelastic method was applied to the studies of residual stresses around spherical inclusion in polymeric matrices. Full stress tensor for several model samples was measured. The extent of significant stresses is not greater than three radii of an inclusion. It was found that the stress follows the 1/R³ rule at distances far from the inclusion, while in the narrow zone at the interface a plateau is observed. The level of stress ranges from few MPa up to the plastic yield of the polymeric matrix. The radial stress component is usually twice as large as the tangential stress component. Radial negative stress and tangential positive stresses are found in configuration with a hard inclusion, while radial positive stress and tangential negative stresses are in the systems with soft inclusion. The pressure in the matrix at points around inclusions calculated from the stress tensor is always near zero MPa, which indicates the action of purely deviatoric stresses in the matrix.     

Influence of Nb5+ ions on phase transitions and polar disorder above TC in PbZrO3 studied by Raman spectroscopy

Micro-Raman light scattering experiments on PbZrO₃ (PZO) single crystal doped with Nb⁵⁺ have been investigated. Special attention was paid to the paraelectric (PE) phase in which nominally forbidden first-order Raman spectra were detected at temperatures far above the phase transition T_C. Complex Raman spectra were observed in the vicinity of three structural phase transitions. These results mainly from the coexistence of phases with different symmetries in a wide temperature range below T_C. The Raman measurements have been compared with dielectric and optical observations and proved that polar nanoregions in a centrosymmetric lattice appear well above T_C. It was shown that doping ABO₃ perovskites with heterovalent ions like Nb⁵⁺ unbalances charge neutrality of the lattice and strongly extends the temperature range of polar regions. The investigations performed point out that in the PE matrix the interaction between electrons and lattice vibrations, as recently suggested for pure PZO, plays an important role.     

Hydrostatic pressure influence on electric relaxation response of bismuth manganite ceramics

Electrical impedance of bismuth manganite ceramics was studied under ambient and high hydrostatic pressure. Local disorder of crystal lattice was confirmed using XRD and DSC. Two relaxation processes were discerned. One was attributed to small polarons, which showed a changeover from variable range hopping features related to Fermi glass and structural disorder to the nearest neighbor hopping behavior in higher temperature range related to uniform distribution of energy levels. Hydrostatic pressure shortened relaxation times that would be interesting for applications. The second process, which was assigned to the nearest neighbor hopping of polarons, also exhibited a changeover to glassy features in a high-temperature range.