Modification of bismaleimide resin by poly(propylene phthalate), poly(butylene phthalate) and related (co)polyesters

Aromatic polyesters were prepared and used to decrease the brittleness of the bismaleimide resin composed of 4,4′-bismaleimidediphenyl methane (BMI) and o,o′-diallyl bisphenol A (DBA) (Matrimid 5292 resin). The aromatic polyesters included poly(propylene phthalate) (PPP), poly(2,2-dimethylpropylene phthalate) (PDPP), poly(butylene phthalate) (PBP) and poly(butylene phthalate-co-butylene terephthalate) (50mol% terephthalate unit) (PBPT). The polyesters were effective modifiers for decreasing the brittleness of the bismaleimide resin. For example, inclusion of 20wt% PPP (MW 18700) led to 50% increase in the fracture toughness (K_IC) with retention of flexural properties and a slight loss of the glass transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin. Micro-structures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The thermal stability of the modified resins was slightly lower than that of the unmodified resin as determined by thermogravimetric analysis. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified bismaleimide resin system. © 1998 SCI.     

Effect of surface properties of silica nanoparticles on their cytotoxicity and cellular distribution in murine macrophages

In this study, complexes composed of poly-l-tyrosine (pLT) and single-walled carbon nanotubes (SWCNTs) were produced and the dispersibility of the pLT/SWCNT complexes in water by measuring the ζ potential of the complexes and the turbidity of the solution were investigated. It is found that the absolute value of the ζ potential of the pLT/SWCNT complexes is as high as that of SWCNTs modified with double-stranded DNA (dsDNA) and that the complexes remain stably dispersed in the water at least for two weeks. Thermogravimetry analysis (TGA) and visualization of the surface structures of pLT/SWCNT complexes using an atomic force microscope (AFM) were also carried out.     

Stimulation of THP-1 Macrophages with LPS Increased the Production of Osteopontin-Encapsulating Exosome

Osteopontin (OPN) mediates bone remodeling and tissue debridement. The OPN protein is cleaved, but it is unclear how full-length (FL)-OPN or its cleaved form perform their biological activities in target cells. We, therefore, performed the molecular characterization of OPN in exosomes (Exo). The Exo were isolated from lipopolysaccharide (LPS)-stimulated phorbol 12-myristate 13-acetate (PMA)-differentiated THP-1 macrophages. The Exo were also isolated from PMA-differentiated THP-1 macrophages. The Exo were identified using the qNano multiple analyzer (diameter 59–315 nm) and western blotting with a CD9 antibody. LPS-stimulated cells produced more particles than non-stimulated cells. The presence of the FL or the cleaved form of OPN was confirmed using western blot analysis. A mixture of FL and cleaved OPN was also measured using an ELISA system (Ud-OPN) and their presence in the Exo was confirmed. Ud/FL ratios became low after LPS stimulation, indicating the enhanced encapsulation of FL-OPN in the Exo by LPS. These findings suggest that LPS stimulation of human macrophages facilitates the synthesis of FL-OPN, which is cleaved in cells or the Exo after release. These findings indicate that Exo is a suitable vehicle to transfer OPN to the target cells.     

Effect of wet-jet milling on the c-axis orientation of hydroxyapatite ceramics fabricated using a strong magnetic field

Controlling the crystal orientation of hydroxyapatite, an inorganic material that is a major component of human hard tissues is important to fabricate better artificial bones and artificial tooth roots. To obtain highly oriented hydroxyapatite ceramics under a strong magnetic field, a good dispersion of the raw materials in the slurry must be obtained. This study investigates the effect of wet-jet milling of a slurry on the orientation of hydroxyapatite ceramics fabricated using a strong magnetic field. Although the prolonged ball milling with ZrO₂ balls of the raw powder fractures the primary particles of hydroxyapatite, wet-jet milling is used to successfully pulverize agglomerated hydroxyapatite raw powder without changing the morphology of the primary particles. Evidently, ceramics with a highly oriented c-axis of hydroxyapatite are obtained by molding the wet-jet milled slurry in a strong rotating magnetic field. They exhibit anisotropy in fracture toughness, and the fracture toughness calculated from the crack length perpendicular to the rotating axis is higher than that calculated from the crack length parallel to it. Furthermore, these values are higher than those of randomly oriented hydroxyapatite ceramics, which may be owing to the crystal orientation dependence of the fracture toughness of the hydroxyapatite grains and grain boundaries.     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Crystal orientation of β-phase isotactic polypropylene induced by magnetic orientation of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide

Melt crystallization of isotactic polypropylene (iPP), containing crystallites of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide (DCNDCA) as a nucleating agent of the the β-phase iPP crystal, is carried out under a magnetic field (6 T) to obtain the alignment of the iPP crystal induced by magnetic alignment of DCNDCA. In a previous paper, DCNDCA was reported to undergo magnetic alignment in a liquid suspension. The obtained iPP sample exhibits alignment of the β-phase crystal with the c-axis aligned perpendicular to the magnetic field. The comparison of this alignment of iPP with the reported magnetic alignment of DCNDCA indicates that the β-phase crystal grows epitaxially on the DCNDCA crystal. The (330)_β plane of the iPP crystal lies on the bc-plane of the DCNDCA crystal in which the direction of the c-axis of the iPP coincides with the direction of the b-axis of the DCNDCA crystal.     

Particle velocity and solids circulation rate in a jet-spouted bed

Radial distribution of particle velocities, solids circulation rate and radial variation in bed voidage in a jet-spouted bed were investigated in a 0.2 m diameter conical-cylindrical column. The upward particle velocity is strongly dependent on gas velocity and its radial profile is the Gaussian. The solids circulation rates are of the same order of magnitude as those in a conventional spouted bed and are proportional to the gas velocity. Estimation of the variation in bed voidage in the radial direction revealed that the annulus voidage of about 0.90 was greater than the spout voidage of around 0.70. This tendency is contrary to that in a conventional spouted bed.     

Sintering of Confined Silica in Oxidized Silicon Particles

We observed electron-beam-induced sintering of amorphous silica in oxidized submicrometer silicon particles and analyzed the nature of mass transport in linear and triangular particle assemblies. The movement of silica around the rigid crystalline cores occurs rapidly and fills the necks, but the relative core positions in the sintered product depends on the initial geometry of the confined oxide. However, a thin layer of silica remains stable against the flow.     

Modification of cyanate ester resin by soluble polyimides

Soluble polyimides (PIs) were prepared as random or multiblock types with 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA) as acid dianhydride components and 4,4′‐bis(m‐aminophenoxy) diphenyl sulfone (m‐BAPS) as a diamine component by a one‐pot process and used to improve the brittleness of the cyanate ester resin. Random‐type PIs were more effective as modifiers than multiblock‐type PIs. The morphologies of the modified resins depended on PI structure, molecular weight, and concentration. The most effective modification of the cyanate ester resin was attained because of a heterogeneous phase structure composed of a flat matrix phase and phase‐inverted structures of the modified resin; a 15 wt % inclusion of a random PI (weight‐average molecular weight = 63,400) composed of 6FDA, s‐BPDA, and m‐BAPS (0.5/0.5/1.0 molar ratio) led to a 65% increase in the fracture toughness for the modified resin with a slight loss of flexural strength and a retention of flexural modulus and glass‐transition temperature, compared with the values for the unmodified resin. Water absorptivity of the modified resin was comparable to that of the unmodified resin up to 400 h, and then, water absorption of the modified resins increased considerably. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1–11, 2003