Fracture toughening of epoxy matrices with blends of resins of different molecular weights and other modifiers

The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004     

Structure and properties of the mesophase of syndiotactic polystyrene. VIII. Solvent sorption behavior of syndiotactic polystyrene/p‐chlorotoluene mesophase membranes

A crystalline δ form of a syndiotactic polystyrene (sPS) membrane was prepared from a solution of sPS (1 wt %) and p‐chlorotoluene (p‐CT) by a solution‐casting method. The mesophase (δ empty form) of sPS was obtained by the extraction of the guest solvent from the δ form of sPS by a stepwise solvent‐extraction method. The sPS/p‐CT mesophase membrane [p‐CT (A‐M)] was used for the sorption of 1 mol % p‐CT for different times and for the sorption of different concentrations of p‐CT, chlorobenzene (CB), p‐xylene (p‐X), toluene, and chloroform for 48 h. The presence of solvents in the sPS membrane was confirmed by IR analysis. A thermal study revealed that the sorption amount of 1 mol % p‐CT increased with increasing immersion time, and the sorption amounts of different solvents increased with increasing solvent concentration. Differential scanning calorimetry results showed that the desorption peak temperature increased as the amount of the solvent increased in the clathrated sPS membrane. Wide‐angle X‐ray diffraction results showed that 2θ at 8.25° was slightly shifted toward 8°, and there was no change in the peak position at 10° for p‐CT (A‐M), which was immersed in different solvents (1 mol %); however, the intensity of 2θ at 10° was not similar for all the samples. Among the solvents used for the sorption studies at 1 mol %, p‐CT (A‐M) could sorb more p‐CT and CB than p‐X, toluene, and chloroform. The solvent sorption isotherm was the Langmuir sorption mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3439–3446, 2004     

Geometrical Molecular Structure Design Concept in Approach to Homo- and Heterometallic Precursors of Advanced Materials in Sol–Gel Technology

The article describes the principles of the Single Source Precursor approach to inorganic materials and introduces the Geometrical Molecular Structure Design Concept (MSDC) based on the choice of a proper molecular structure type for the desired precursor and completing it with ligands providing both the necessary number of donor atoms and the sterical protection of the chosen core. Application of MSDC is illustrated with examples taken from development of new approaches in the synthesis of oxide and sulfide catalysts and ferroelectric oxide materials.     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 2004     

Addition–fragmentation chain transfer: Molecular weight distributions and retardation in the system methyl methacrylate/methyl α‐(bromomethyl)acrylate

A detailed investigation of addition–fragmentation chain transfer (AFCT) in the free‐radical polymerization of methyl methacrylate (MMA) in the presence of methyl α‐(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (k_add) over 60–120 °C resulted in E_add = 21.7 kJ mol^?1 and A_add = 2.18 × 10⁶ M^?1 s^?1 and a very weak temperature dependence of the chain‐transfer constant (E_add ≈ E_p). The rate coefficient for fragmentation of adduct radicals at 60 °C was estimated as k_f ≈ 39 s^?1 on the basis of experimental data of the MMA conversion and the concentration of 2‐carbomethoxy‐2‐propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2640–2650, 2004     

Synthesis under Micromave Irradition and Crystal Structure of 4''-Acetylbenzo-15 -crown-5thiosemicarbazone

The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds.     

On the recognition problem of quasi-homogeneous locally nilpotent derivations in dimension three

We give a criterion to decide if a given w-homogeneous derivation on A?k[X₁,X₂,X₃] is locally nilpotent. We deduce an algorithm which decides if a k-subalgebra of A, which is finitely generated by w-homogeneous elements, is the kernel of some locally nilpotent derivation.     

Contact hypersurfaces of Kaehler manifolds

Contact hypersurfaces of a Kaehler manifold have been characterized and classified, assuming the second fundamental form to be Codazzi (in particular, parallel). We have also discussed the special cases when the ambient space is a (i) Calabi-Yau manifold and (ii) a complex space-form.     

A real algorithm for the Hermitian eigenvalue decomposition

Modifying complex plane rotations, we derive a new Jacobi-type algorithm for the Hermitian eigendecomposition, which uses only real arithmetic. When the fast-scaled rotations are incorporated, the new algorithm brings a substantial reduction in computational costs. The new method has the same convergence properties and parallelism as the symmetric Jacobi algorithm. Computational test results show that it produces accurate eigenvalues and eigenvectors and achieves great reduction in computational time.The work of this author was supported in part by the National Science Foundation grant CCR-8813493 and by the University of Minnesota Army High Performance Computing Research Center contract DAAL 03-89-C-0038.The work of this author was supported in part by the University of Minnesota Army High Performance Computing Research Center contract DAAL 03-89-C-0038.