Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. III. Adhesive Joint Strengths of Grafted Power Feed Copolymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. Power feed copolymer had a very broad glass transition temperature compared with random copolymer, even if grafting and/or crosslinking were introduced to the system. This tendency was almost the same as the non-grafted power feed copolymer where only low molecular weight surfactant was used.

Adhesive joint strengths of power feed copolymers were evaluated compared with random copolymers. In the case of usual linear power feed copolymer, the adhesive joint strengths were not higher than those of random copolymer, which was considered to be due to the lower film strengths of the power feed copolymer. Power feed copolymer having grafting showed slightly higher adhesive joint strengths over a wide range of temperatures than random copolymer. When crosslinking was introduced to the system, power feed copolymer showed much higher adhesive joint strengths over a wide temperature range.     

Polymerization of macromers

Summary The possibility of group transfer polymerization of methyl methacrylate-terminated polystyrene macromer (MA-PSt) was explored by using 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene and tris(dimethylamino)sulfonium difluorotrimethylsilicate as initiator and catalyst, respectively. The results obtained at the polymerization temperature of 0°C were undesirable. However, the oligomerization at -78°C gave almost quantitatively oligo(MA-PSt) of which the degree of polymerization was in good agreement with the mole ratio of macromer to initiator. The GPC curve of oligo(MA-PSt) was sharp and symmetrical. In addition, it was shown by the copolymerization with methyl methacrylate that the polymerizability of the macromer was markedly enhanced in the presence of methyl methacrylate comonomer.     

Dispersion of SiC in Aqueous Media with Al2O3 and Y2O3 as Sintering Additives

It has been well accepted that polyethylene imine (PEI) is an effective dispersant for silicon carbide (SiC) in aqueous media. However, after the addition of sintering additives (Al₂O₃ and Y₂O₃), this dispersing effect is reduced significantly. In this work, a second dispersant, citric acid, was used to resolve this problem. It was found that citric acid could decrease the slurry viscosity (without sintering additives) and enhance the PEI adsorption on SiC particle surface. The optimal amount of citric acid required to achieve a minimum viscosity for 55 vol% SiC suspensions was equal to ∼0.87 wt% (at pH ∼6.8). With the aid of citric acid, well-stabilized SiC suspensions (containing sintering additives) were realized, which exhibited slight shear thinning rheologies. After tape casting and SPS sintering, dense SiC samples were obtained with a homogeneous fine-crystalline microstructure. Results showed that citric acid was an effective dispersant for improving the dispersion of SiC particles containing sintering additives.     

Effect of pressure on phase transition and morphology of bulk poly(trans-1,4-butadiene)

The effect of pressure on the melting, solid-solid transition, and crystallization of poly(trans-1,4-butadiene) (PTBD) was investigated using the pressure range of 1–3000 kg/cm². D.t.a. measurements showed that, the melting and transition temperatures increase with increasing pressure, whose pressure coefficients are 38°C per 1000 kg/cm² and 22°C per 1000 kg/cm², respectively. These values were in fairly close agreement with those calculated from the Clausius-Clapeyron equation. Morphological studies using electron microscope and small-angle X-ray scattering method revealed that, the samples crystallized with relatively small supercoolings under normal or high pressure, are formed of distinct lamellae 400–800 Å thick. The lamellar thickness was inappreciably dependent on crystallization pressure. The significant effect of pressure on crystallization was recognized in a tendency of the crystallinity to increase, with increasing crystallization pressure. This pressure effect was explained by the mechanism that, the increased pressure might make the packing of molecular chains in liquid, more dense and that the secondary crystallization might be accelerated, to increase the lateral dimensions of lamellae.     

Preparation of soluble TiCl3 catalysts by reduction of TiCl4 with Grignard reagents and their use for copolymerization of ethylene with propylene

Summary Preparations of soluble TiCl₃ catalysts by reduction of TiCl₄ with some types of Grignard reagents were carried out in halogenated hydrocarbon solvents by using appropriate ethers as donor. The soluble TiCl₃·MgX₂·ether complex catalysts and triisobutylaluminum as co-catalyst showed high activities for the copolymerization of ethylene with propylene. It was first found that the soluble TiCl₃·MgX₂·ether complex catalysts enhance the activities for the copolymerizations in the same manner as solid titanium catalysts supported on MgCl₂ which show high activities for homopolymerizations of olefin monomers. The copolymers obtained possessed low crystallinities. Also, the copolymers seem to contain microblock sequences and have outstandingly high tensile strength and elongation at break compared to copolymers by the conventional VOCl₃/Al(Et)_1.5Cl_1.5 catalyst system.     

Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles

The synthesis of magnetite nanoparticles coated with a well-defined graft polymer is reported. The magnetite nanoparticles with an initiator group for copper-mediated atom transfer radical polymerization (ATRP), 2-(4-chlorosulfonylphenyl) ethyltrichlorosilane (CTCS) chemically bound on their surfaces were prepared by the self-assembled monolayer-deposition method. The surface-initiated ATRP of methyl methacrylate (MMA) was carried out with the CTCS-coated magnetite nanoparticles in the presence of free (sacrificing) initiator, p-toluenesulfonyl chloride. Polymerization proceeded in a living fashion, exhibiting first-order kinetics of monomer consumption and a proportional relationship between molecular weight of the graft polymer and monomer conversion, thus providing well-defined, low-polydispersity graft polymers with an approximate graft density of 0.7 chains/nm². The molecular weight and polydispersity of the graft polymer were nearly equal to those of the free polymer produced in the solution, meaning that the free polymer is a good measure of the characteristics of the graft polymer. The graft polymer possessed exceptionally high stability and remarkably improved dispersibility of the magnetite nanoparticles in organic solvent.     

The yttrium effect on the corrosion resistance of CO2-laser processed MCrAlY coatings

To improve the corrosion resistance and to study the effect of yttrium in the behavior of coatings produced by thermal spraying MCrAlY (M=Ni, Co) powders, CO₂ laser processing was conducted. Three methods were used: (1) a combination of gas flame and plasma spraying in air followed by laser glazing in argon, (2) low-pressure plasma spraying (LPPS) and laser glazing in argon, and (3) LPPS and laser-gas (O₂) alloying. Laser glazing in argon of the MCrAlY coatings sprayed in air promoted formation of weakly adherent agglomerates of Al–Y oxides and an alumina-chromia solid solution. Glazing in argon atmosphere of LPPS CoNiCrAlY and NiCrAlY coatings caused the formation of nickel aluminides besides the formation of Y–Al compounds. Gas (O₂)-alloying of these coatings produces continuous and adherent (yttrium-containing) alumina and chromia layers. The effects of yttrium on the characteristics of the oxides formed in the coatings during laser glazing, laser-gas alloying, and high-temperature oxidation is discussed. This work also investigated the oxidation resistance of the laser-processed MCrAlY coatings in air and in the presence of 85 mol/o V₂O₅–Na₂SO₄ fused salt at 900°C.     

Integration of 3-D shape construction and assembly to realize micro systems

In order to make micro 3-D structures, we are designing a table-sized factory, namely Nano Manufacturing World (NMW). In NMW, we challenged to use a new process fused by semiconductor process for preciseness and machine process for 3-dimensionality. In order to realize the new process, we designed three new mechanisms in this paper: multi-face shape making beam, co-focus rotational robot and micro mechanical tools. Through an evaluation to actually make a micro Gojunoto with the mechanisms, we confirmed their validities for functions of integration of 3-D shape construction and assembly.     

High-intensity multi-bunch beam generation by a photo-cathode RF gun

A multi-bunch photo-cathode RF gun system has been developed as an electron source for the production of intense quasi-monochromatic X-rays based on inverse Compton scattering. The desired multi-bunch beam is 100 bunches/pulse with a total charge of 500 nC and a bunch spacing of 2.8 ns. We modified the gun cavity of a ‘BNL-type IV’ RF gun to allow a CsTe cathode plug in the end plate. The system uses a four-dipole chicane beam line to allow the injection of laser light normal to the cathode surface. We compensate the gun cavity beam loading caused by the high-intensity multi-bunch electron beam by injecting the laser pulse before RF power has filled the cavity. We have achieved a total intensity of 220 nC in 100 bunches with a bunch-to-bunch energy spread under 1.3% (peak-to-peak). This paper concentrates on experiments to generate the high-intensity multi-bunch beam with compensation of the bunch-to-bunch energy spread due to heavy beam loading.     

Degradation behavior of moduli in extruded pure magnesium during low- to giga-scale cyclic tension fatigue

The mechanical properties of extruded pure magnesium during cyclic tension fatigue in the low- to giga-scale regime at room temperature have been investigated using ultrasonic reflection methods with longitudinal and shear waves. The acoustic velocities and calculated Young’s and shear moduli decreased by a large percentage with an increase in the number of cycles in all cycle modes due to growth of grain boundary voids. The eventual degradation of the properties was largest during giga-cycle fatigue, in which the moduli decreased by ～9%. The elastic behavior depended on the drive stress and the number of cycles rather than on fatigue time. Longitudinal and shear wave propagation characteristics and investigations of a grain boundary before and after fatigue using electron backscatter diffraction based on field-emission scanning electron microscopy and focused ion beam transmission electron microscopy revealed that the largest boundary void gap width was less than several nanometers (almost closed). The Poisson’s ratio and bulk modulus were affected notably by the void gap, in which the threshold corresponds to the longitudinal wave amplitude. Other damage phase data were determined using scanning electron microscopy, Vickers hardness, and surface roughness tests under progressive fatigue; these results also indicated slight grain boundary degradation.