Development of a new advanced process for manufacturing polyacetal resins. Part III. End-capping during polymerization for manufacturing acetal homopolymer and copolymer

Conventionally, acetal homopolymer or copolymer is obtained by the polymerization of formaldehyde or trioxane, following the end-capping using acetic anhydride or unzipping of the unstable polymer end fraction. First, Asahi Chemical developed a new process to obtain an end-capped polymer during polymerization of highly purified formaldehyde using acetic anhydride as the chain-transfer agent. Use of highly purified formaldehyde and endcapping during polymerization using acetic anhydride as a chain-transfer agent or an endcapping agent will provide a simple process for manufacturing acetal homopolymer. The polymerization mechanism was confirmed by infrared spectroscopy analysis and proton NMR analysis of the polymer obtained. Second, for the acetal copolymer, purified trioxane was copolymerized with ethylene oxide in the presence of methylal, which gave an endcapped polymer with high thermal stability. Two new intermediates from the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN) and 1,3,5,7,10-pentaoxacyclododecane (POCD), were isolated and a new initiation mechanism was proposed. © 1993 John Wiley & Sons, Inc.     

Effect of Composition on the Oxygen Tracer Diffusion in Transparent Yttrium Aluminium Garnet (YAG) Ceramics

The grain boundary structure and oxygen tracer diffusion in transparent yttrium aluminum garnet (YAG) ceramics varying from 2% excess of Y₂O₃ to 0.5% excess of Al₂O₃ were studied. The characterization of the specimens is as follows: (i) For the Y₂O₃-excess specimen, a second phase (yttrium aluminum perovskite: YAP) containing silicon in the grain boundary was found, (ii) For the Al₂O₃-excess specimen, both aluminum-rich particles (alumina) and a silicon-rich segregant layer were observed in the grain boundary. The volume diffusion of the oxygen tracer is little influenced by the excess composition. In contrast, the grain boundary diffusion of the oxygen tracer is suppressed in the Y₂O₃-excess specimens, compared to Al₂O₃-excess specimens. These differences are thought to result from the chemical reaction between the second phase and the intergranular liquid phase during the sintering.     

Study on ozone treatment of water-soluble polymers. I. Ozone degradation of polyethylene glycol in water

Polyethylene glycol (molecular weight 8000) was degraded by ozone in 1% aqueous solution of pH 12. Chemical oxygen demand of the solution decreased with increasing ozone consumed. Intrinsic viscosity of the solution lowered exponentially as a result of the ozonization. The number of breaks calculated from the viscosity indicated that two molecules of ozone were consumed for one cleavage of the polymer chain. The molecular weight distribution obtained by gel permeation chromatography was very broadened and molecular weight was lower as well, and the polymer chain was found to be cleaved randomly by ozone. The production of formic ester, ethylene glycol, diethylene glycol, triethylene glycol, and hydrogen peroxide was confirmed by IR, NMR, gas chromatography, and chemical analysis. These observations could be accounted for by electrophilic attack of ozone on the ether bond.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Self-assembly phenomenon of hydroxyapatite nanocrystals on chondroitin sulfate

Self-assembly phenomenon of hydroxyapatite (HAp) nanocrystals on chondroitin sulfate (ChS) templates was investigated. A HAp/ChS hybrid was synthesized through a precipitation method with a calcium hydroxide suspension and phosphoric acid solution containing the ChS. The preferential alignment of the crystallographic c-axis of the HAp crystals parallel to the long axis direction of the ChS templates was observed to occur with the chemical interactions between the HAp crystals and the functional groups of the ChS. This phenomenon was interpreted by the crystallochemical specific nucleation and growth of the HAp crystals regulated by the pre-organized functional groups of the ChS template. Practical implication may involve a biomimetic artificial bone or cartilage can be made through a precipitation method with suitable bio-organics.     

Crystal growth and structure analysis of twin-free monoclinic hydroxyapatite

Single crystals of hydroxyapatite were grown by a flux method using Ca₃(PO₄)₂ and Ca(OH)₂ under 100 MPa of Ar gas. The crystals obtained had stoichiometric composition of Ca₁₀(PO₄)₆(OH)₂ and some of them were twin-free single crystals. From X-ray diffraction analyses, the space group was confirmed to be monoclinic P2₁/b with cell parameters a=0.9419(3) nm, b=1.8848(6) nm, c=0.6884(2) nm, and =119.98(2)°. The detailed crystal structure was determined with a reliability factor R_w=0.033; the O atoms of OH were located just on the 2₁ axis while the H atoms of OH occupied the positions a little deviated from the 2₁ axis. The origin of this structure was ascribed to the formation of hydrogen bonds between the H atoms of the OH ions and the specific O atoms of the PO₄ ions.     

Toward ideal (trans)esterification by use of fluorous distannoxane catalysts

1,3-Disubstituted tetrakis(fluoroalkyl)distannoxanes, (XR(2)SnOSnR(2)Y)(2) (R = C(6)F(13)C(2)H(4) and C(4)F(9)C(2)H(4)), are highly fluorophilic and exhibit large partition coefficients in favor of fluorocarbon solvents over common organic solvents due to a double-layered structure where the stannoxane core is covered by fluoroalkyl groups. Under catalysis of these Lewis acids, fluorous technology allows novel transesterification and esterification in which a 100% yield of the desired esters is achievable with reactants in a strict 1:1 ratio. The catalysts are recovered from the fluorous phase quantitatively. More practically, the catalyst in fluorocarbon solution can be recycled for use in the next reaction repeatedly.     

Intermetallic compound formation between lead-free solders (Sn) and Cu or Ni electrodes

A kinetic model based on the principle of maximum degradation rate of the total system free energy, MDR law using thermodynamic data, is proposed and successfully applied to the selection of the first intermetallic compound (IMC) phase in Cu/Sn and Ni/Sn diffusion couples. The first phases predicted with this model for Cu/Sn and Ni/Sn are Cu₆Sn₅ and Ni₃Sn₄, respectively, resulting in good agreement with experimental observations.     

Oxygen Diffusion in Single- and Poly-Crystalline Zinc Oxides

¹⁸O diffusion coefficients were measured in zinc oxide ceramics using a secondary ion mass spectrometer. The results are interpreted as indicating extrinsic behavior. The values of the lattice diffusion coefficients with higher valence dopants compared with zinc ions are greater than lower valence dopant such as lithium ions. Using the data at deeper depth, the grain boundary diffusivity of oxide ions was also evaluated. Although the lattice diffusion coefficients varied by two orders of magnitude, the products of grain boundary width and grain boundary diffusion coefficient were less sensitive to the type of dopants.