Evolution of microstructure and texture in Ni49.4Ti38.6Hf12 shape memory alloy during hot rolling

This paper deals with the evolution of microstructure and texture during hot rolling of hafnium containing NiTi based shape memory alloy Ni49.4Ti38.6Hf12. The formation of the R-phase has been associated with the precipitation of (Ti,Hf)(2)Ni phase. The crystallographic texture of the parent phase B2 as well as the product phases R and B19' have been determined. It has been found that the variant selection during the B2 -> R phase transformation is quite strong compared to the case of the B2 -> B19' transformation. During deformation, the texture of the austenite phase evolves with strong Goss and Bs components. After transformation to martensitic structure, it gives rise to a 011]parallel to RD fiber. Microstructure and texture studies reveal the occurrence of partial dynamic recrystallization during hot rolling. Large strain heterogeneities that occur surrounding (Ti,Hf)(2)Ni precipitates are relieved through extended dynamic recovery instead of particle stimulated nucleation.

Optimization of HfO2 films for high transconductance back gated graphene transistors

Hafnium dioxide (HfO2) films, deposited using electron beam evaporation, are optimized for high performance back-gated graphene transistors. Bilayer graphene is identified on HfO2/Si substrate using optical microscope and subsequently confirmed with Raman spectroscopy. Back-gated graphene transistor, with 32 nm thick HfO2 gate dielectric, has been fabricated with very high transconductance value of 60 mu S. From the hysteresis of the current-voltage characteristics, we estimate the trap density in HfO2 to be in the mid 10(11)/cm(2) range, comparable to SiO2.

Instability in threshold voltage and subthreshold behavior in Hf-In-Zn-O thin film transistors induced by bias-and light-stress

Electrical bias and light stressing followed by natural recovery of amorphous hafnium-indium-zinc-oxide (HIZO) thin film transistors with a silicon oxide/nitride dielectric stack reveals defect density changes, charge trapping and persistent photoconductivity (PPC). In the absence of light, the polarity of bias stress controls the magnitude and direction of the threshold voltage shift (Δ VT), while under light stress, VT consistently shifts negatively. In all cases, there was no significant change in field-effect mobility. Light stress gives rise to a PPC with wavelength-dependent recovery on time scale of days. We observe that the PPC becomes more pronounced at shorter wavelengths. © 2010 American Institute of Physics.

Reactions of oxygen containing ligands in the coordination sphere of permethylhafnocene and permethyltantalocene

A series of terl-butylperoxide complexes of hafnium, Cp*₂Hf(R)(OOCMe₃) (Cp* = ((η⁵-C₅Me₅); R = Cl, H, CH₃, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, CH₂CHMe₂, CH=CHCMe₃, C₆H₅, meta-C₆H₃(CH₂)2) and Cp*(η⁵-C₅(CH₃)₄CH₂CH₂CH₂)Hf(OOCMe₃), has been synthesized. One example has been structurally characterized, Cp*₂Hf(OOCMe₃)CH₂CH₃ crystallizes in space group P2₁/c, with a = 19.890(7)Å, b = 8.746(4)Å, c = 17.532(6)Å, β = 124.987(24)°, V = 2498(2)ų, Z = 4 and R_F = 0.054 (2222 reflections, I > 0). Despite the coordinative unsaturation of the hafnium center, the terl-butylperoxide ligand is coordinated in a mono-dentate ligand. The mode of decomposition of these species is highly dependent on the substituent R. For R = H, CH₂CH₃, CH₂CH₂CH₃, CH₂CH₂CH₂CH₃, CH₂CHMe₂ a clean first order conversion to Cp*₂Hf(OCMe₃)(OR) is observed (for R CH₂CH₃, ΔHǂ = 19.6 kcal•mol^-1, ΔSǂ = -13 e.u.). These results are discussed in terms of a two step mechanism involving η²-coordination of the terl-butylperoxide ligand. Homolytic O-O bond cleavage is observed upon heating of Cp*₂Hf(OOCMe₃) R (R = C₆H₆, meta-C₆H₃(CH₃)₂). In the presence of excess 9,10-dihydroanthracene thermolysis of Cp*₂Hf(OOCMe₃)C₆H₆ cleanly affords Cp*₂Hf(C₆H₆)OH and HOCMe₃ (ΔHǂ = 22.6 kcal•mol^-1, ΔSǂ = -9 e.u.). The O-O bond strength in these complexes is thus estimated to be 22 kcal•mol^-1.

Cp*₂Ta(CH₂)H, Cp*₂Ta(CHC₆H₅)H, Cp*₂Ta(C₆H₄)H, Cp*₂Ta(CH₂=CH₂)H and Cp*₂Ta(CH₂=CHMe)H react, presumably through Cp*₂Ta-R intermediates, with H₂O to give Cp*₂Ta(O)H and alkane. Cp*₂Ta(O)H was structurally characterized: space group P2₁/n, a= 13.073(3)Å, b = 19.337(4)Å, c = 16.002(3)Å, β = 108.66(2)°, V = 3832(1)ų, Z = 8 and R_F = 0.0672 (6730 reflections). Reaction of terlbutylhydroperoxide with these same starting materials ultimately yields Cp*₂Ta(O)R and HOCMe₃. Cp*₂Ta(CH₂=CHR)OH species are proposed as intermediates in the olefin hydride reactions. Cp*₂Ta(O₂)R species can be generated from the reaction of the same starting materials and O₂. Lewis acids have been shown to promote oxygen insertion in these complexes.

Synthetic, kinetic and mechanistic studies in early transition metal systems. I. α- and β-hydrogen elimination reactions in derivatives of permethyltitanocene, -zirconocene, and -hafnocene. II. The reactions of aluminum alkyls with derivatives of permethylniobocene

The thermal decomposition of Cp*Ti(CH_3)_2 (Cp*≡ ƞ^5-C_5Me_5) toluene solution follows cleanly first-order kinetics and produces a single titanium product Cp*(C_5Me_4CH_2)Ti(CH_3) concurrent with the evolution of one equivalent of methane. Labeling studies using Cp*_2Ti- (CD_3)_2 and (Cp*-d_(15))_2Ti(CH_3)_2 show the decomposition to be intramolecular and the methane to be produced by the coupling of a methyl group with a hydrogen from the other TiCH_3 group. Activation parameters, ΔH^‡ and ΔS^‡, and kinetic deuterium isotope effects have been measured. The alternative decomposition pathways of α-hydrogen abstraction and a-hydrogen elimination, both leading to a titanium-methylidene intermediate, are discussed.

The insertion of unactivated acetylenes into the metal-hydride bonds of Cp*_2MH_2 (M = Zr, Hf) proceeds rapidly at low temperature to form monoand/ or bisinsertion products, dependent upon the steric bulk of the acetylene substituents. Cp*_2M(H)(C(Me)=CHMe), Cp*_2M(H)(CH=CHCMe_3), Cp*_2M(H)-(CH=CHPh), Cp*_2M(CH=CHPh)_2, Cp*_2M(CH=CHCH_3)_2 and Cp*_2Zr- (CH=CHCH_2CH_3)_2 have been isolated and characterized. To extend the study of unsaturated-carbon ligands, Cp*_2M(C≡CCH_3)_2 have been prepared by treating Cp*_2MCl_2 with LiC≡CCH_3. The reactivity of many of these complexes with carbon monoxide and dihydrogen is surveyed. The mono(2- butenyl) complexes Cp*_2M(H)(C(Me)=CHMe) rearrange at room temperature, forming the crotyl-hydride species Cp*_2M(H)(ƞ^3-C_4H_7). The bis(propenyl) and bis(l-butenyl) zirconium complexes Cp*_2Zr(CH=CHR)_2 (R = CH_3, CH_2CH_3) also rearrange, forming zirconacyclopentenes. Labeling studies, reaction chemistry, and kinetic measurements, including deuterium isotope effects, demonstrate that the unusual 6-hydrogen elimination from an sp^2-hybridized carbon is the first step in these latter rearrangements but is not observed in the former. Details of these mechanisms and the differences in reactivity of the zirconium and hafnium complexes are discussed.

The reactions of hydride- and alkyl-carbonyl derivatives of permethylniobocene with equimolar amounts of trialkylaluminum reagents occur rapidly producing the carbonyl adducts Cp*_2Nb(R)(COAlR'_3) (R = H, CH_3, CH_2CH_3, CH_2CH_2Ph, C(Me)=CHMe; R' = Me, Et). The hydride adduct Cp*_2NbH_3•AlEt_3 has also been formed. In solution, each of these compounds exists in equilibrium with the uncomplexed species. The formation constants for Cp*_2Nb(H)(COA1R'_R) have been measured. They indicate the steric bulk of the Cp* ligands plays a deciding factor in the isolation of the first example of an aluminum Lewis acid bound to a carbonyl-oxygen in preference to a metalhydride. Reactions of Cp*_2Nb(H)CO with other Lewis acids and of the one:one adducts with H_2, CO and C_2H_4 are also discussed.

Cp*_2Nb(H)(C_2H_4) also reacts with equimolar amounts of trialkylaluminum reagents, forming a one:one complex that ^1H NMR spectroscopy indicates contains a Nb-CH_2CH_2-Al bridge. This adduct also exists in equilibrium with the uncomplexed species in solution. The formation constant for Cp*_2N+/b(H)(CH_2CH_2ĀlEt_3) has been measured. Reactions of Cp*_2Nb(H)(C_2H_4) with other Lewis acids and the reactions of Cp*_2N+b(H)- (CH_2CH_2ĀlEt_3) with CO and C_2H_4 are described, as are the reactions of Cp_*2Nb(H)(CH_2=CHR) (R = Me, Ph), Cp*_2Nb(H)(CH_3C≡CCH_3) and Cp*_2Ti-(C_2H_4) with AlEt_3.

Síntese, caracterização e avaliação da capacidade bactericida de copolímeros à base de 2-vinilpiridina funcionalizados

Neste trabalho, dois copolímeros à base de 2-vinilpiridina (2Vpy), estireno (Sty) e divinilbenzeno (DVB) foram sintetizados empregando a técnica de polimerização em suspensão aquosa via radical livre. Os copolímeros com diferentes características morfológicas foram preparados variando a composição da mistura diluente, constituída por tolueno e n-heptano, solventes solvatantes e não solvatantes para as cadeias poliméricas. A caracterização estrutural desses materiais foi feita através de medidas de área específica, volume de poros, diâmetro médio de poros e densidade aparente. Além disso, esses materiais foram avaliados por microscopia ótica e eletrônica de varredura, por espectroscopia na região do infravermelho (FTIR), análise termogravimétrica (TGA) e análise elementar. Os copolímeros Sty-DVB-2Vpy foram modificados quimicamente através de reação de quaternização das unidades de 2Vpy usando dois reagentes: iodeto de metila e acrilonitrila. A quaternização dos copolímeros Sty-DVB-2Vpy foi confirmada através de espectroscopia de infravermelho, pelo aparecimento das bandas de absorção características do íon peridíneo e do grupo nitrila e também pela análise do comportamento térmico. Os produtos dessas reações foram submetidos à avaliação da capacidade bactericida através do método de contagem em placas contra suspensão de Escherichia coli. O copolímero do tipo gel quaternizado com iodeto de metila apresentou a maior ação bactericida registrada, com eficiência até a concentração de 104 células/mL. Contudo, a maioria dos materiais quaternizados não apresentou ação biocida significativa. Com o objetivo de maximizar a atividade bactericida dos materiais preparados, os copolímeros quaternizados e não quaternizados foram impregnados com iodo por meio de duas metodologias: em solução e em fase vapor. O teor de iodo incorporado foi quantificado por análise gravimétrica. Foi possível observar que os copolímeros quaternizados e impregnados com iodo se mostraram mais eficientes como agentes bactericidas que os copolímeros não funcionalizados impregnados com iodo. De uma forma geral, foi possível perceber que a ação bactericida dos polímeros é fruto da associação entre as suas características de porosidade, o grau de quaternização alcançado e o teor de iodo incorporado. Para efeito de comparação foram feitos também ensaios bactericidas com uma resina comercial à base de Sty-DVB com grupo amônio quaternário, VP OC 1950. Os testes mostraram que a resina comercial não possui atividade bactericida. A impregnação de iodo a essa resina comercial forneceu um material com ação biocida semelhante à do copolímero do tipo gel, quaternizado com iodeto de metila e impregnado com iodo

Methods for melting temperature calculation

Melting temperature calculation has important applications in the theoretical study of phase diagrams and computational materials screenings. In this thesis, we present two new methods, i.e., the improved Widom's particle insertion method and the small-cell coexistence method, which we developed in order to capture melting temperatures both accurately and quickly.

We propose a scheme that drastically improves the efficiency of Widom's particle insertion method by efficiently sampling cavities while calculating the integrals providing the chemical potentials of a physical system. This idea enables us to calculate chemical potentials of liquids directly from first-principles without the help of any reference system, which is necessary in the commonly used thermodynamic integration method. As an example, we apply our scheme, combined with the density functional formalism, to the calculation of the chemical potential of liquid copper. The calculated chemical potential is further used to locate the melting temperature. The calculated results closely agree with experiments.

We propose the small-cell coexistence method based on the statistical analysis of small-size coexistence MD simulations. It eliminates the risk of a metastable superheated solid in the fast-heating method, while also significantly reducing the computer cost relative to the traditional large-scale coexistence method. Using empirical potentials, we validate the method and systematically study the finite-size effect on the calculated melting points. The method converges to the exact result in the limit of a large system size. An accuracy within 100 K in melting temperature is usually achieved when the simulation contains more than 100 atoms. DFT examples of Tantalum, high-pressure Sodium, and ionic material NaCl are shown to demonstrate the accuracy and flexibility of the method in its practical applications. The method serves as a promising approach for large-scale automated material screening in which the melting temperature is a design criterion.

We present in detail two examples of refractory materials. First, we demonstrate how key material properties that provide guidance in the design of refractory materials can be accurately determined via ab initio thermodynamic calculations in conjunction with experimental techniques based on synchrotron X-ray diffraction and thermal analysis under laser-heated aerodynamic levitation. The properties considered include melting point, heat of fusion, heat capacity, thermal expansion coefficients, thermal stability, and sublattice disordering, as illustrated in a motivating example of lanthanum zirconate (La₂Zr₂O₇). The close agreement with experiment in the known but structurally complex compound La₂Zr₂O₇ provides good indication that the computation methods described can be used within a computational screening framework to identify novel refractory materials. Second, we report an extensive investigation into the melting temperatures of the Hf-C and Hf-Ta-C systems using ab initio calculations. With melting points above 4000 K, hafnium carbide (HfC) and tantalum carbide (TaC) are among the most refractory binary compounds known to date. Their mixture, with a general formula Ta_xHf_1-xC_y, is known to have a melting point of 4215 K at the composition Ta₄HfC₅, which has long been considered as the highest melting temperature for any solid. Very few measurements of melting point in tantalum and hafnium carbides have been documented, because of the obvious experimental difficulties at extreme temperatures. The investigation lets us identify three major chemical factors that contribute to the high melting temperatures. Based on these three factors, we propose and explore a new class of materials, which, according to our ab initio calculations, may possess even higher melting temperatures than Ta-Hf-C. This example also demonstrates the feasibility of materials screening and discovery via ab initio calculations for the optimization of "higher-level" properties whose determination requires extensive sampling of atomic configuration space.

Isotope shift studies in the rare earths and lead

Isotope shifts of K_α1 x-ray transitions were measured for the Neodymium isotopes Nd 142, 143, 144, 145, 146, 148 and 150, the Samarium isotopes Sm 147, 148, 149, 150, 152 and 154, the Gadolinium isotopes Gd 154, 155, 156, 157, 158 and 160, the Dysprosium isotopes Dy 162 and 164, the Erbium isotopes Er 166, 168 and 170, the Hafnium isotopes Hf 178 and 180 and the Lead isotopes Pb 204, 206, 207 and 208. A curved crystal Cauchois spectrometer was used. The analysis of the measurement furnished the variation of the mean square charge radius of the nucleus, δ˂r²˃, for 23 isotope pairs. The experimental results were compared with theoretical values from nuclear models. Combining the x-ray shifts and the optical shifts in Nd and Sm yielded the optical mass shifts. An anomaly was observed in the odd-even shifts when the optical and the x-ray shifts were plotted against each other.

Comparison of femtosecond and nanosecond laser-induced damage in HfO2 single-layer film and HfO2-SiO2 high reflector

HfO2 single layers, 800 run high-reflective (HR) coating, and 1064 ran HR coating were prepared by electron-beam evaporation. The laser-induced damage thresholds (LIDTs) and damage morphologies of these samples were investigated with single-pulse femtosecond and nanosecond lasers. It is found that the LIDT of the HfO2 single layer is higher than the HfO2-SiO2 HR coating in the femtosecond regime, while the situation is opposite in the nanosecond regime. Different damage mechanisms are applied to study this phenomenon. Damage morphologies of all samples due to different laser irradiations are displayed. (c) 2007 Optical Society of America.

离子束辅助反应制备的氧化铪薄膜特性

采用电子束直接蒸发氧化铪、无辅助电子束反应蒸发和离子束辅助反应蒸发金属铪3种沉积方式制备了单层HfO2薄膜,对样品的光学性能、结构特性以及激光损伤特性进行了研究。实验结果表明:通过反应沉积的方法可以有效减少缺陷产生并改善均匀性,施加离子辅助可以提高薄膜的折射率,在一定条件下还可以有效地降低吸收,但激光损伤阈值仍未达到直接采用氧化铪制备的水平;晶体结构方面,离子辅助条件下可以获得单斜相氧化铪薄膜,并且随着轰击能量的提高由(002)面的择优取向向(-111)面转变。

Electronic and mechanical properties of 5d transition metal mononitrides via first principles

The electronic and mechanical properties of 5d transition metal mononitrides from LaN to AuN are systematically investigated by use of the density-functional theory. For each nitride, Six Structures are considered, i.e., rocksalt, zinc blende, CsCl, wurtzite, NiAs and WC structures. Among the considered structures, rocksalt structure is the most stable for LaN, HfN and ALIN, WC structure for TaN, NiAs structure for WN, wurtzite structure for ReN, OsN, IrN and PtN. The most stable Structure for each nitride is mechanically stable. The formation enthalpy increases from LaN to AuN.

Perfectly Hydrophobic Silicone Nanofiber Coatings: Preparation from Methyltrialkoxysilanes and Use as Water-Collecting Substrate

Perfectly hydrophobic (PHO) coatings consisting of silicone nanofibers have been obtained via a solution process using methyltrialkoxysilanes as precursors. On the basis of thermal gravimetry and differential thermal analysis (TG-DTA) and Fourier transform infrared spectroscopy (FTIR) results, the formula of the nanofibers was tentatively given and a possible growth mechanism of the nanofibers was proposed. Because of the low affinity between the coatings and the small water droplet, when using these coatings as substrate for collecting water vapor, the harvesting efficiency could be enhanced as compared with those from bare glass substrate for more than 50% under 25 degrees C and 60-90% relative humidity. By removing the surface methyl group by heat treatment or ultraviolet (UV) irradiation, the as-prepared perfectly hydrophobic surface can be converted into a superhydrophilic surface.

Control led/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under Co-60 gamma-ray irradiation

A new vinyl acyl azide monomer, 4-(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 degrees C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under Co-60 gamma-ray irradiation in the presence of benzyl 1-H-imidazole-1-carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free-radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (< 1.20), and a linear relationship existing between In([M](0)/[M]) and the polymerization time. The data from H-1 NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR.

Mechanical properties of BPDA-ODA polyimide fibers

An aromatic polyimide was synthesized via a one-step polycondensation reaction between biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-oxydianiline (ODA) in p-chlorophenol. The polyimide (BPDA-ODA) solution dopes were spun into fibers by means of dry-jet wet spinning. The as-spun fibers were drawn and treated in heating tubes for improving the mechanical properties. The thermal treatment on the fibers resulted in a relatively high tensile strength and modulus. Thermal mechanical analysis (TMA) was employed to study the linear coefficient of thermal expansion (CTE). Thermal gravimetry analysis (TGA) spectra showed that the BPDA-ODA fibers possessed an excellent property of thermo-oxidative degradation resistance. The sonic modulus E-s of the polyimide fibers was measured.