Conversion kinetics of container glass batch melting

Understanding the batch-to-glass conversion process is fundamental to optimizing the performance of glass-melting furnaces and ensuring that furnace modeling can correctly predict the observed outcome when batch materials or furnace conditions change. To investigate the kinetics of silica dissolution, gas evolution, and primary foam formation and collapse, we performed X-ray diffraction, thermal gravimetry, feed expansion tests, and evolved gas analysis of batch samples heated at several constant heating rates. We found that gas evolving reactions, foaming, and silica dissolution depend on the thermal history of the batch in a similar manner: the kinetic parameters of each process were linear functions of the square root of the heating rate. This kinetic similarity reflects the stronger-than-expected interdependence of these processes. On the basis of our results, we suggest that changes in furnace operating conditions, such as firing or boosting, influence the melting rate less than what one would expect without consideration of batch conversion kinetics.     

A novel multiscale approach to brittle fracture of nano/micro‐sized components

Principles and advantages of a new concept based on the ab initio aided strain gradient elasticity theory are shown in comparison with the classical Barenblatt cohesive model. The method is applied to the theoretical prediction of the critical energy release rate and the crack tip opening displacement at the crack instability in nanopanels made of germanium and molybdenum crystals. The necessary length scale parameter l₁ is determined for germanium and molybdenum by the best gradient elasticity fits of ab initio computed screw dislocation displacements and phonon dispersions. Values of ab initio computed critical energy release rates and crack opening profiles revealed that the length l₁ is related to inflexion points of profiles. A novel ab initio method in combination with continuum mechanics was successfully tested to replace molecular statics dependent of availability of interatomic potentials. The asymptotic strain gradient elasticity solution for displacement components near the crack tip in materials with cubic lattice was also derived.     

The putative Saginaw impact structure,Michigan, Lake Huron,in the light of gravity aspects derived from recent EIGEN 6C4 gravity field model

The hypothetical impact structure in the Saginaw Bay (Michigan, USA, Lake Huron) has been tested by the gravity data derived from the recent gravity field model EIGEN 6C4 (expanded to degree and order 2190, with ground resolution of ~9?km). The following gravity field aspects were used: the gravity disturbances/anomalies, second derivatives of the disturbing potential (Marussi tensor), two of three gravity invariants, their specific ratio (known as 2D factor), the strike angles, and the virtual deformations. These gravity aspects are sensitive in various ways to the underground density contrasts. For the Saginaw Bay area, we confirm that we do not see any typical impact crater in terms of gravity disturbance or the radial second order derivative, possibly because of the thick layer of the ice located at the place and time of the impact. But the “combed” strike angles (one type of the gravity aspects we use) disclose a trace of high pressure to the SE/S/SW of the Bay and may be due to an impacting body. Thus, we provide circumstantial evidence of the Younger Dryas impact hypothesis.     

Phase transition in swollen gels

Summary The photoelastic behaviour of two networks — polyacrylamide (PAAm) and of a network prepared by the copolymerization of acrylamide with 5 mol.% sodium methacrylate — was investigated in water-acetone mixtures. For the PAAm network the dependence of all photoelastic characteristics on the composition of the mixture is continuous. At 54 vol.% acetone in the mixture, the ionized network undergoes a transition which gives rise to jumpwise changes in the shear modulus, deformational-optical coefficient, C, and in the refractive index of the gel, n_g. While in the collapsed state the optical anisotropy of the statistical segment is negative, –3×10^–24 cm³ (indicating an interaction between the side chains), in the expanded state it is positive, 0.5 × 10^–24 cm³. The dependence of all optical characteristics on the composition of the mixtures suggests that: (a) in both networks we have a transition between two conformational states of the chain; while for the ionized network the transition is a discrete one, for the nonionized network it takes place in the range between 30 and 45 vol.% acetone in the mixture; (b) in both networks the gels are optically homogeneous throughout the whole range of compositions of the mixtures (and thus also in the close vicinity of the collapse of the ionized network).     

The participation of crown ethers in the initiation of group-transfer polymerisation

Summary The use of crown ethers in conjunction with alkali metal salts, as catalysts in group-transfer polymerization, is discussed.     

Anionic polymerization of acrylates. XIV. Synthesis of MMA/acrylate block copolymers initiated with ester-enolate/tert-alkoxide complex

Diblock copolymers of methyl methacrylate (MMA) with 2-ethylhexyl, butyl, ethyl or tert-butyl acrylate (EtHA, BuA, EtA, t-BuA) have been prepared by the ligated anionic polymerization initiated with methyl 2-lithioisobutyrate (MIB-Li) in the presence of an excess of Li tert-butoxide (t-BuOLi) in toluene/THF mixture at −60 or −78 °C. The copolymers, prepared at −60 °C, show MWD with a hint of bimodality, indicating partial deactivation of the living PMMA upon addition of acrylic monomer. At −78 °C, the extent of this deactivation is distinctly lower, the formed block copolymers, in particular, poly(MMA-b-EtHA), have unimodal MWD and exhibit tails only in the lower-molecular-weight region. Poly(MMA-b-EtHA)s were extracted with acetonitrile dissolving PMMA; very small parts of the crude products dissolved, whereas prevailing parts remained as solids documenting thus formation of block copolymer in a high yield. Surprisingly, the highest amount of self terminated PMMA was found in block copolymerization of MMA with t-BuA at both the temperatures, the products of which had clearly bimodal MWDs. This finding is shortly discussed on the basis of relatively slow propagation of t-BuA in comparison with EtHA, BuA and EtA.     

Antagonistic effects on mechanical properties of microfibrillar composites with dual reinforcement: Explanation by FEA model of soft interface

Nanofillers (NF) in microfibrillar composites support melt‐drawing and may lead to improved performance. However, antagonistic effects have also been found. The deterioration of mechanical properties by drawing in the presence of NF, as found by other authors in analogous undrawn systems, has not yet been explained. Experiments indicating the importance of NF migration between the HDPE matrix and the PA6 fibrils in the course of drawing have led to a tentative conclusion of changed crystallinity in the interfacial area resulting in a layer with reduced modulus. This was confirmed by the finite element analysis considering the formation of a “soft” interface as a result of reduced content of HDPE spherulites at the fiber surfaces. The results show a marked impact of this phenomenon on modulus. This original concept presents a basis for explaining some antagonistic effects in multicomponent polymer systems and a tool for the more rational design of composite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44712.     

Impact of particle morphology on structure,crystallization kinetics,and properties of PCL composites with TiO<Subscript>2</Subscript>-based particles

Crystallization kinetics of polycaprolactone (PCL) filled with TiO₂-based particles (TiX) was shown to depend on the TiX particle type and concentration, which were associated with a slight polymer matrix degradation. The partially degraded, shorter, and more mobile polymer chains increased the overall crystallization rate at the initial stage of crystallization, while at the later stages, the non-nucleating TiX particles acted as a sterical hindrance, slowing down the crystallization process. The PCL/TiX composites were prepared by melt-mixing and contained 2.5 and 5 wt% of the filler. The investigated TiX particles included isometric anatase microparticles (mTiO₂) and titanate nanotubes with high-aspect ratio (TiNT). Light and electron microscopy showed very homogeneous dispersion of the mTiO₂ particles in the PCL matrix, while the TiNT formed large agglomerates. In situ polarized light microscopy displayed faster isothermal crystallization of all PCL/TiX composites, but the micrographs indicated that the TiX particles did not act as nucleation centres. Isothermal DSC experiments, evaluated in terms of Avrami theory, confirmed the PLM results and showed that the overall rate of isothermal crystallization increased in the following order: PCL <PCL/TiNT <PCL/mTiO₂. Non-isothermal DSC and rheological measurements revealed the correlation between the crystallization rate and the polymer matrix degradation—the well-dispersed mTiO₂ particles with high specific surface caused the highest PCL degradation and, consequently, the earliest start of non-isothermal crystallization as well as the fastest isothermal crystallization. Microindentation hardness measurements confirmed that the partial degradation of the polymer matrix did not have a significant impact on the mechanical performance of PCL/mTiO₂ composites.     

Long-term studies (1871-2000) on acidification and recovery of lakes in the Bohemian Forest (central Europe)

This paper evaluates long-term changes in the atmospheric depositions of S and N compounds, lake water quality, and biodiversity at eight glacial lakes in the Bohemian Forest over the past 130 years. This time interval covers (i) the 'background' pre-acidification status of the lakes, (ii) a period of changes in the communities that can be partly explained by introduction of fish, (iii) a period of strong lake acidification with its adverse impacts on the communities, (iv) the lake reversal from acidity, which includes the recent status of the lakes. The lake water chemistry has followed-with a characteristic hysteresis-both the sharp increase and decline in the deposition trends of strong anions. Remarkable changes in biota have mirrored the changing water quality. Fish became extinct and most species of zooplankton (Crustacea) and benthos (Ephemeroptera and Plecoptera) retreated due to the lake water acidification. Independent of ongoing chemical reversal, microorganisms remain dominant in the recent plankton biomass as well as in controlling the pelagic food webs. The first signs of the forthcoming biological recovery have already been evidenced in some lakes, such as the population of Ceriodaphnia quadrangula (Cladocera) returning into the pelagial of one lake or the increase in both phytoplankton biomass and rotifer numbers in another lake.