Crystal structures and elastic properties of superhard IrN2 and IrN3 from first principles

First principles calculations were performed to investigate the structural, elastic, and electronic properties of IrN2 for various space groups: cubic Fm-3m and Pa-3, hexagonal P3(2)21, tetragonal P4(2)/mnm, orthorhombic Pmmn, Pnnm, and Pnn2, and monoclinic P2(1)/c. Our calculation indicates that the P2(1)/c phase with arsenopyrite-type structure is energetically more stable than the other phases. It is semiconducting (the remaining phases are metallic) and contains diatomic N-N with the bond distance of 1.414 A. These characters are consistent with the experimental facts that IrN2 is in lower symmetry and nonmetallic. Our conclusion is also in agreement with the recent theoretical studies that the most stable phase of IrN2 is monoclinic P2(1)/c. The calculated bulk modulus of 373 GPa is also the highest among the considered space groups. It matches the recent theoretical values of 357 GPa within 4.3% and of 402 GPa within 7.8%, but smaller than the experimental value of 428 GPa by 14.7%. Chemical bonding and potential displacive phase transitions are discussed for IrN2. For IrN3, cubic skutterudite structure (Im-3) was assumed.

Synthesis and properties of novel soluble polyimides having a spirobisindane-linked dianhydride unit

A new synthetic procedure was elaborated allowing the preparation of semiaromatic dianhydride. N-Methyl protected 4-chlorophthalic anhydride was nitrated with HNO3 to produce N-methyl-4-chloro-5-nitrophthalimide (1). The aromatic nucleophilic substitution reaction between 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1-spirobisindane and 1 afforded spirobisindane-linked bis(N-methylphthalimide) (2), which was hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). The latter was polymerized with five different aromatic diamines to afford a series of aromatic polyimides. The properties of polyimides such as inherent viscosity, solubility, UV transparency and thermal stability were investigated to illustrate the contribution of the introduction of spirobisindane groups into the polyimide backbone. The resulting polyimides were readily soluble in polar solvents such as chloroform, THF and N-methyl-2-pyrrolidone. The glass-transition temperatures of these polyimides were in the range of 254-292 degrees C. The tensile strength, elongation at break, and Young's modulus of the polyimide film were 68.8-106.6 MPa, 5.9-9.8%, 1.7-2.0 GPa, respectively. The polymer films were colorless and transparent with the absorption cutoff wavelength at 286-308 nm.

A new class of high T-g and organosoluble polynaphthalimides

A new class of soluble six-membered ring polynaphthalimides (PNIs) was synthesized from asymmetrical fluorinated naphthalenesubstituted monomers. All the resulting PNIs were easily soluble in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO). and chloroform. They also showed good thermal stability with glass transition temperature of 340-386 degrees C, 10% weight loss temperature in excess of 529 degrees C. Polyimide 3c could be solution-cast into tough and flexible film. The film had a tensile strength, elongation at break, and Young's modulus of about 117.6 Wa, 23.6%, and 1.77 GPa, respectively. The gas permeation property of the film of 3c was investigated with oxygen permeability coefficient (PO2 = 3.99) and permeability selectivity coefficient of oxygen to nitrogen (P-O2/P-N2 = 5.27). Therefore, these materials are expected to be a good alternative to PIs based on five-membered rings with applications in gas separation membranes.

Studies on syntheses and properties of novel CeO2/Polyimide nanocomposite films from Ce(Phen)(3) complex

A series of cerium dioxide (CeO2,)/polyimide (PI) nanocomposites were successfully prepared from Ce(Phen)(3) and polyamic acid (PAA) via the solution direct-dispersing method, followed by a step thermal imidization process. TGA and XPS studies showed that the cerium complex decomposed to form CeO2, during the thermal imidization process at 300 degrees C. SEM observation showed that the formed CeO2, as nalloparticles was well dispersed in polyimide matrix with a size of about 50-100 nm for samples with different contents of CeO2. Thermal analysis indicated that the introduction of CeO2, decreased the thermal stability of nanocomposite films due to the decomposition of Ce(Phen)(3) in the imidization process, while the glass transition temperature (T-g) increased obviously. especially nanocomposite films with high loading of CeO2 exhibited a trend of disappearance off, DMTA and static tensile measurements showed that the storage modulus of nanocomposite films increased, while the elongation at break decreased with increasing CeO2 content.

The mechanical and thermal behaviors of glass bead filled polypropylene

Notch Izod impact strength of poly(propylene) (PP)/glass bead blends was studied as a function of temperature. The results indicated that the toughness for various blends could undergo a brittle-ductile transition (BDT) with increasing temperature. The BDT temperature (T-BD) decreased with increasing glass bead content. Introducing the interparticle distance (ID) concept into the study, it was found that the critical interparticle distance (IDc) reduced with increasing test temperature correspondingly. The static tensile tests showed that the Young's modulus of the blends decreased slightly first and thereafter increased with increasing glass bead content. However, the yield stress decreased considerably with the increase in glass bead content. Dynamic mechanical analysis (DMA) measurements revealed that the heat-deflection temperature of the PP could be much improved by the incorporation of glass beads. Moreover, the glass transition temperature (T-g) increased obviously with increasing glass beads content. Differential scanning calorimetry (DSC) results implied that the addition of glass beads could change the crystallinity as well as the melting temperature of the PP slightly.

Mechanical and thermal properties of glass bead-filled nylon-6

The mechanical and thermal properties of glass bead-filled nylon-6 were studied by dynamic mechanical analysis (DMA), tensile testing, Izod impact, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) tests. DMA results showed that the incorporation of glass beads could lead to a substantial increase of the glass-transition temperature (T-g) of the blend, indicating that there existed strong interaction between glass beads and the nylon-6 matrix. Results of further calculation revealed that the average interaction between glass beads and the nylon-6 matrix deceased with increasing glass bead content as a result of the coalescence of glass beads. This conclusion was supported by SEM observations. Impact testing revealed that the notch Izod impact strength of nylon-6/glass bead blends substantially decreased with increasing glass bead content. Moreover, static tensile measurements implied that the Young's modulus of the nylon-6/glass bead blends increased considerably, whereas the tensile strength clearly decreased with increasing glass bead content.

Low-compressibility and hard materials ReB2 and WB2: Prediction from first-principles study

First-principle calculations are performed to investigate the structural, elastic, and electronic properties of ReB2 and WB2. The calculated equilibrium structural parameters of ReB2 are consistent with the available experimental data. The calculations indicate that WB2 in the P6(3)/mmc space group is more energetically stable under the ambient condition than in the P6/mmm. Based on the calculated bulk modulus, shear modulus of polycrystalline aggregate, ReB2 and WB2 can be regarded as potential candidates of ultra-incompressible and hard materials. Furthermore, the elastic anisotropy is discussed by investigating the elastic stiffness constants. Density of states and electron density analysis unravel the covalent bonding between the transition metal atoms and the boron atoms as the driving force of the high bulk modulus and high shear modulus as well as small Poisson's ratio.

Mechanical and thermal properties of high-density polyethylene toughened with glass beads

Glass beads were used to improve the mechanical and thermal properties of high-density polyethylene (HDPE). HDPE/glass-bead blends were prepared in a Brabender-like apparatus, and this was followed by press molding. Static tensile measurements showed that the modulus of the HDPE/glass-bead blends increased considerably with increasing glass-bead content, whereas the yield stress remained roughly unchanged at first and then decreased slowly with increasing glass-bead content. Izod impact tests at room temperature revealed that the impact strength changed very slowly with increasing glass-bead content up to a critical value; thereafter, it increased sharply with increasing glass-bead content. That is, the lzod impact strength of the blends underwent a sharp transition with increasing glass-bead content. It was calculated that the critical interparticle distance for the HDPE/glass-bead blends at room temperature (25degreesC) was 2.5 mum. Scanning electron microscopy observations indicated that the high impact strength of the HDPE/glass-bead blends resulted from the deformation of the HDPE matrix. Dynamic mechanical analyses and thermogravimetric measurements implied that the heat resistance and heat stability of the blends tended to increase considerably with increasing glass-bead content.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.

Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Synthesis and characterization of polypropylene/montmorillonite nanocomposites via an in-situ polymerization approach

Polypropylene/montmorillonite (PP/MMT) nanocomposites were prepared by in-situ polymerization using a MMT/MgCl2/TiCl4-EB Ziegler-Natta catalyst activated by trietbylaluminum (TEA). The enlarged layer spacing of MMT was confirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components. X-ray photoelectron spectrometry (XPS) analysis proved that TiCl4 was mainly supported on MgCl2 instead of on the surface of MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXD patterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.

The deformation mechanism of polyphenylquinoxaline films

The plateau modulus of polyphenylquinoxaline (PPQ-E) films has been obtained by from their dynamic mechanical properties curves. Using these data, the entanglement density of PPQ-E films, 2.37 X 10(26) m(-3) Or 0.39mmol/cm(3),has been estimated. The deformation mechanism of polyphenylquinoxaline (crazing mechanism,or shear yielding mechanism, or both), can be predicted according to entanglement density values. The changes in morphology of PPQ-E films during tensile deformation have been observed by Polarized Light Microscope. The result shows that crazing first appears in the tensile process, then shear yielding appears. It needs to point out that the craze is terminated by micro-shear band and the direction of craze in shear band is also changed,which prevents the craze growth into crack and avoid the failure of material. This result is in accordance with the prediction on the basis of the entanglement density data. The morphology and structure of crazes in PPB-E thin film have been determined by TEM. The craze morphology of PPQ-E is mainly fibril craze consisting of micro-fibrils and micro-voids,the interface between bulk and craze is distinct. Multiply crazes, blunting of craze tip and shear deformation zone are also observed. This result reflects the accordance of entanglement density and the morphology and structure of crazes.

Investigating mechanical response of single chain polystyrene particles by scanning probe techniques

Single chain polystyrene particles were obtained by dilute solution casting method. The sample with both single chain polystyrene particles and multi-chain (more than 1000 molecular chains) polystyrene particles was obtained by a little more concentrate solution. Force modulation technique showed that single chain polystyrene particles were softer than multichain polystyrene particles. On the other hand, nanoindentation experiments on multi-chain particles and bulk polystyrene manifested that the elastic modulus of multi-chain polystyrene particles was very close to that of bulk polystyrene. Therefore, it was concluded that single chain polystyrene particles were softer than bulk polystyrene,which indicated that the density of intrachain entanglement points in the single chain polystyrene particles was not as large as that of the interchain entanglement points in the bulk state.

Nanostructure and mechanical measurement of highly oriented lamellae of melt-drawn HDPE by scanning probe microscopy

Scanning probe microscopy was used to simultaneously determine the molecular chain structure and intrinsic mechanical properties, including anisotropic elastic modulus and friction, for lamellae of highly oriented high-density polyethylene (HDPE) obtained by the melt-drawn method. The molecular-scale image of the highly oriented lamellae by friction force microscopy (FFM) clearly shows that the molecular chains are aligned parallel to the drawing direction, and the periodicities along and perpendicular to the drawing direction are 0.26 and 0.50 nm, respectively. The results indicate that the exposed planes of the lamellae resulting from the melt-drawn method are (200), which is consistent with results of transmission electron microscopy and electron diffraction. Because of the high degree of anisotropy in the sample, coming from alignment of the molecular chains along the drawing direction, the measured friction force, F, determined by FFM is strongly dependent on the angle, theta, between the scanning direction and the chain axis. The force increases as theta is increased from 0 degrees (i.e., parallel to the chain axis) to 90 degrees (i.e., perpendicular to the chain axis). The structural anisotropy was also found to strongly influence the measurements of the transverse chain modulus of the polymer by the nanoindentation technique. The measured value of 13.8 GPa with transverse modulus was larger than the value 4.3 GPa determined by wide-angle X-ray diffraction, which we attributed to anisotropic deformation of the lamellae during nanoindentation measurements that was not accounted for by the elastic treatment we adopted from Oliver and Pharr. The present approach using scanning probe microscopy has the advantage that direct correlations between the nanostructure, nanotribology, and nanomechanical properties of oriented samples can be determined simultaneously and simply.