Sintered silicon nitride/nano-silicon carbide materials based on preceramic polymers and ceramic powder

A flexible method is presented, which enables the fabrication of porous as well as dense Si₃N₄/nano-SiC components by using Si₃N₄ powder and a preceramic polymer (polycarbosilazane) as alternative ceramic forming binder. The SiCN polymer benefits consolidation as well as shaping of the green body and partially fills the interstices between the Si₃N₄ particles. Cross-linking of the precursor at 300 °C increases the mechanical stability of the green bodies and facilitates near net shape machining. At first, pyrolysis leads to porous ceramic bodies. Finally, subsequent gas pressure sintering results in dense Si₃N₄/nano-SiC ceramics. Due to the high ceramic yield of the polycarbosilazane binder, the shrinkage during sintering is significantly reduced from 20 to 15 lin.%. Investigations of the sintered ceramics reveal, that the microstructure of the Si₃N₄ ceramic contains approx. 6 vol.% nano-scaled SiC segregations, which are located both at the grain boundaries and as inclusions in the Si₃N₄ grains.     

Effects of nematic coupling on the phase behaviour of nematogen mixtures

The phase behaviour of binary nematogen mixtures of side‐chain liquid crystal crosslinked polymers and low molecular weight liquid crystals is investigated with particular emphasis on the effects of nematic coupling. The cross nematic quadrupole parameter ν₁₂ is assumed to be proportional to the geometric average of ν₁₁ and ν₂₂ characteristic of single nematogens. In the weak coupling limit, the proportionality constant is lower than 1, and the phase diagram exhibits a reduced miscibility of the nematogens. In the case of strong coupling, the proportionality constant exceeds 1 resulting in higher miscibility. This is characterized by a nematic order that extends to temperatures above the upper nematic–isotropic transition temperature. A wide region of miscibility emerges showing a single nematic phase. Nematogens having similar nematic–isotropic transition temperatures exhibit different phase properties from systems with widely separated transition temperatures. Effects of the polymer volume fraction at crosslinking, rubber elasticity parameters of the network, and the Flory–Huggins interaction parameter on the equilibrium phase diagram of these systems are discussed. © 2001 Society of Chemical Industry     

Wachstumsmessungen von Kristallen in sauberen und verunreinigten Lösungen: Einzelkristall vs. Kollektiv

Information about crystal growth rates and the influence of impurities are essential for the design of industrial crystallization processes. Here, the influence of trivalent metal ions Fe³⁺ in solution and adsorbed in the crystal on the growth and dissolution rate is investigated. The results clearly show kinetic and thermodynamic effects caused by impurities which have to be taken into account in the equipment design. Furthermore, effects of growth rate dispersion must be excluded by investigation of crystal collectives. Additionally, the crystal growth data should be obtained from real starting solutions.     

Polymer chain mobility in polyelectrolyte multilayers

Free-standing polyelectrolyte multilayer membranes have been formed by the layer-by-layer technique using a dip-coating apparatus. The polymer-chain mobility has been studied by ¹H relaxation in the rotating frame T _1rho NMR with ¹³C chemical shift resolution. For each of the individual polymers a single relaxation component has been observed for all resolved signals. In the multilayer a significantly different relaxation time T _1rho has been observed with a minor second component. The interaction between the oppositely charged polyelectrolytes influences the molecular mobility.     

Phase Behavior of Poly(butyl acrylate) Networks in Nematic Liquid Crystal Solvents

Summary: This paper reports the phase behavior of photochemically crosslinked poly(butyl acrylate) networks in nematic liquid crystal (LC) solvents. The swelling properties are studied as a function of temperature for two low molecular weight nematic LCs, 4‐cyano‐4′‐pentylbiphenyl (5CB) and the eutectic mixture of cyanoparaphenylenes (E7). Chemically crosslinked polymer networks were formed by the UV radiation of initial solutions of the reactive monomer, butyl acrylate, a crosslinker (hexanediol diacrylate), and a photoinitiator. To obtain different network densities, the ratio of butyl acrylate to hexanediol diacrylate was varied prior to polymerization/crosslinking reactions. Immersion in an excess of the LC solvent allowed for the measurement of size increase by polarized optical microscopy in terms of temperature. Length, width, and diagonal ratios were calculated considering swollen to dry network states of the samples. In general, swelling leads to an increase in the network size by increasing the temperature with a significant dependence on the degree of crosslinking. A large shift in the swelling ratio was found in the vicinity of the nematic to isotropic transition temperatures of the LCs.

     

Effects of skim milk concentrate dry matter and spray drying air temperature on formation of capsules with varying particle size and the survival microbial cultures in a microcapsule matrix

The impact of total solid (TS) content in combination with the feed rate and air inlet temperature on the survival of Lactobacillus paracasei ssp. paracasei F19 after spray drying in a skim milk matrix has been investigated and correlated with the capsule size. Depending on the experimental conditions, the survival rates ranged from 64 to 0.2%. The higher the air inlet temperature, the lower was the survival rate and an inversely correlation between the TS content and particle size has been determined. These results clearly indicate that process stress analyses and product-related characteristics must not be regarded separately.     

Remendable polymers via reversible Diels–Alder cycloaddition of anthracene‐containing copolymers with fullerenes

Poly(lauryl methacrylate)s with anthracene moieties in the side chain were converted with C₆₀‐fullerene and phenyl‐C₆₁‐butyric acid methyl ester (PCBM), resulting in new remendable (self‐healing) polymeric materials. The utilization of differently substituted anthracene monomers enabled the tuning of the reactivity and the resulting mechanical properties. Copolymers with different contents of the anthracene moieties were synthesized and characterized using size exclusion chromatography, ¹H nuclear magnetic resonance (NMR) spectroscopy as well as differential scanning calorimetry (DSC). ¹H NMR spectroscopic studies were utilized in order to investigate the reversibility of the Diels–Alder reaction between copolymers with C₆₀‐fullerene and PCBM, respectively, in solution. In order to investigate the conversion of the polymers with C₆₀‐fullerene and PCBM in bulk, additionally, DSC, nanoindentation, rheology, atomic force microscopy (AFM), 3D microscopy, simultaneous thermal analysis (STA) and FT‐Raman investigations were performed. The fullerene‐containing copolymers could be healed in a temperature range of 40–80 °C. Consequently, a new generation of low temperature remendable polymers could be established. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45916.     

Development of novel 1,2,3,4-tetrahydroisoquinoline derivatives and closely related compounds as potent and selective dopamine D3 receptor ligands

Based on N-alkylated 1,2,3,4-tetrahydroisoquinoline derivatives, which are structurally related to the partial agonist BP 897, a series of novel, selective dopamine D3 receptor antagonists has been synthesised. Derivatisation included changes in the arylamide moiety and the tetrahydroisoquinoline substructure leading to compounds with markedly improved selectivities and affinities in the low nanomolar concentration range. From the 55 structures presented here, (E)-3-(4-iodophenyl)-N-(4-(1,2,3,4-tetrahydroisoquinolin-2-yl)butyl)acrylamide (51) has high affinity (Ki(hD3)=12 nM) and a 123-fold preference for the D3 receptor relative to the D2 receptor subtype. Its pharmacological profile offers the prospect of a novel radioligand as a tool for various dopamine D3-receptor-related in vitro and in vivo investigations.     

Static and Dynamic Mechanical Behavior of Electron Beam‐Cured Monomer and Monomer/Liquid Crystal Systems

Summary: This paper discusses static and dynamic mechanical properties of electron beam‐cured mixtures made of the nematic liquid crystal (LC) E7 and either tripropyleneglycol diacrylate (TPGDA) or propoxylated glycerol triacrylate (GPTA) as monomers differing essentially by their functionality. Dilution of the initial mixture with LC leads to a significant weakening of the film mechanical strength. Strong effects were found on Young modulus and rubbery state modulus. As the concentration of LC increases, these mechanical parameters drop significantly together with the glass transition temperature of the polymer showing a plasticizing effect. The results for the glass transition temperatures for the polymer and the LC were confirmed by thermograms obtained by differential scanning calorimetry.

Storage tensile modulus versus temperature of EB‐cured TPGDA/E7 films for different LC concentrations.