不同极化态下有机铁电膜微观振动特性的AFM研究

借助原子力显微镜优异的空间分辨能力和锁相放大技术,实验研究了有机铁电薄膜在不同极化状态下的微观振动特性.负极化态时,薄膜表面振动与驱动电压呈线性且同相;而正极化态时,表面振动与驱动电压依然呈线性,但两者间存在180°相差.实验中清楚地观测到局域振动畴、非振动畴以及振动振幅相对较小的振动畴三者间的共存.本工作探讨了非活性铁电畴存在的可能性,并认为是陷阱电荷的箝制作用限制了铁电畴的活性.     

Molecular beam epitaxy of c-plane wurtzite GaN on nitridized a-plane β-Ga2O3

Epitaxial growth of GaN on β-Ga₂O₃ single crystal substrates by the molecular beam epitaxy technique is demonstrated for the first time. Standard and in-plane X-ray diffraction evidence the growth of c-plane wurtzite GaN on a-plane β-Ga₂O₃, the epitaxial relationship being 0 1 0_Ga2O3 1 1 2¯ 0_GaN and 0 0 1_Ga2O31¯ 1 0 0_GaN. Epitaxial growth without any buffer layer is achieved after an effective surface nitridation under NH₃ gas.     

Change in anisotropy of mechanical properties with β-phase stability in high Zr-containing Ti-based alloys

High Zr-containing β-type Ti-based alloys were designed using electronic parameters to investigate experimentally the effect of β-phase stability on their elastic and plastic properties. Texture structures formed by cold rolling or recrystallization were related closely to the β-phase stability and hence affected the mechanical properties. In tensile tests, as the β-phase stability decreased, non-linearity in the elastic zone was enhanced and the work hardening tended to be diminished. Also, it was found that the lower β-phase stability led to the weaker anisotropy of plastic properties, but to the stronger anisotropy of elastic properties.     

Molecular dynamics simulation of pressure effect on phase transition behaviour and dynamics in the isotropic and discotic nematic phases

Molecular dynamics simulation was performed at constant temperature and pressure to investigate the effect of pressure on molecular dynamics for disc-shaped molecules. The generic Gay-Berne model, GB(0.345, 5.0, 1, 3), was used to study the phase transition behaviour, and translational and rotational dynamics, under two different reduced pressures P^?, 10.0 and 20.0. Obvious shifts were detected in the transition temperatures. Both systems have the same phase sequence with different pressures: isotropic, discotic nematic and columnar phases. Translational motion is characterised by the parallel and perpendicular components of diffusion coefficients, with respect to the director in the orientational ordered phase. With regard to rotational dynamics, the correlation time of the first-rank orientational time autocorrelation function, which corresponds to end-over-end rotational motion of a molecule, has been investigated. A clear jump in the temperature dependence of the correlation time has been found at the isotropic-nematic phase transition point. The retardation factor g_|| as a function of the reduced temperature T^?/T_NI^? shows an apparent pressure effect on the rotational dynamics.     

Comparative determination of the α/β phase fraction in α+β-titanium alloys using X-ray diffraction and electron microscopy

A comparison is made between the measured α/β phase fractions in Ti-6246 using X-ray diffraction (XRD) and electron microscopy. Image analysis of SEM and TEM images was compared to the phase fraction estimate obtained using electron backscattered diffraction, lab and high-energy synchrotron XRD. There was a good agreement between the electron microscopic and diffraction techniques, provided that the microstructural parameters of grain size and texture are estimated correctly when using quantitative Rietveld refinement.     

Comparative study on Inclusion compounds of 4-Biphenylacetic acid with β-Cyclodextrin, Hydroxypropylated-β-Cyclodextrins, and methylated-β-Cyclodextrins

The inclusion behavior of Hydroxypropyl-β-Cyclodextrin (HP-β-Cyd) and of methylated-β-Cyclodextrins, heptakis-(2,6-di-O-methyl)-β-Cyclodextrin (DM-β-Cyd) and heptakis-(2,3,6-tri-O-methyl)-β-Cyclodextrin (TM-β-Cyd), in solution and solid state was compared with that of natural β-Cyclodextrin (β-Cyd) using an anti-inflammatory drug, 4-biphenylacetic acid (BPAA), as a guest molecule. The solubility of BPAA with β-Cyd and β-Cyd derivatives in aqueous solution were determined. Stability constants were calculated by phase solubility method at various pH values and temperatures. The formation of inclusion complexes with β-Cyd and β-Cyd derivatives in the solid slate were confirmed by infrared spectroscopy, differential scanning calorimetry and X-Ray diffractometry, and in the liquid phase by ultraviolet spectroscopy, circular dichroism and NMR studies. Dissolution rate and “in vitro” release of BPAA from complexes were examined. The results obtained suggest that DM-β-Cyd is more effective than other β-Cyclodextrins in improving the pharmaceutical properties of BPAA.     

Impact of β-Sheet Conformations on the Mechanical Response of Protein in Biocomposites

Proteins in biological nanocomposites play an important role in their mechanical response. Proteins in nacre, the inner layer of seashells, have been shown to have exceptional mechanical properties. One of the important nacre proteins, Lustrin-A, has abundance of polypeptides in zig-zag conformation called β-sheets. β-sheets of protein when present close to each other in multiple numbers could take the shape of a planar β-sheath like structure or a β-barrel to form a domain. In natural proteins both these types of structures are commonly found. However, the conformation of β-sheets in Lustrin-A is not known at this time. Effort has been made through this work to study the mechanical response of these β-planar sheath and β-barrel structures when subjected to external loads. Comparative study of the stress-deformation characteristics of these two types of structures has been made. Both these structures with almost similar number of amino acids have been extracted from one single spinach protein: Ferredoxin Reductase (1FNR). Steered molecular dynamics has been used to conduct these studies. The article deals with the separation of the two domains from the main protein, simulation details, and results comparing the responses.     

The effect of α1 plates on the martensitic transformation and shape memory effect in a β Cu–Zn alloy

The martensitic transformation and shape memory effect (SME) in a β Cu–Zn alloy containing various amounts of α₁ plates have been investigated. The results showed that the characteristic temperature of martensitic transformation decreased as the isothermal aging time increased. The crystal structure, twin relationships between martensite variants, and characteristics of martensitic transformation of the β Cu–Zn alloy were not affected by the existence of α₁ plates. However, the α₁ plates were distributed homogeneously in the parent phase and functioned as grain boundaries, hindering the progress of martensite variants, and reducing the effective grain size of the parent phase and the size of self-accommodating plate groups formed upon cooling. In addition, the strain recovery due to the SME decreased as the isothermal aging time increased (the quantity of α₁ plate increased) and/or imposed prestrain increased. Nevertheless, the SME mechanism in the β Cu–Zn alloy containing α₁ plates was not affected by the presence of the α₁ plates.     

Tight-binding molecular dynamics simulations of the vibration properties of α-titanium

Phonon thermal anomalies in α-titanium are studied by means of tight-binding microcanonical molecular dynamics simulations. The frequencies of the zone centre [0001]LO and TO phonons, and the [0001]TA phonon at are determined at different temperatures via the power spectrum of the autocorrelation function associated with the corresponding projections of atomic velocities. It is shown that even at very low temperatures the effects of anharmonicity in vibrational properties are strong and dependent on both wave propagation direction and frequency. In particular, the frequencies of the TO and TA phonons are shown to decrease while the frequency of the [0001]LO phonon increases with crystal temperature, in agreement with experiment.     

Synergetic effect of Re and Ru on γ/γ′ interface strengthening of Ni-base single crystal superalloys

The synergetic effect of Re and Ru on γ/γ′ interface strengthening of Ni-base SC superalloys has been investigated by performing DMol3 calculations. Results show that the synergetic effect of Re and Ru on the interface strengthening is better than that achieved by the individual Re or Ru due to Re-d/Ru-d, Re-d/Ni-d and Ru-d/Ni-d hybridizations. The electronic mechanism underlying the synergetic effect of Re and Ru on γ/γ′ interface strengthening is related to the charge transfer of electrons and the enhancement of d-bonding hybridization among Re---Ru, Re---Ni and Ru---Ni atoms.     

Semiempirical study of metallocenes adsorption on β-MgCl2

This work analyzes the adsorption of four metallocenes with different symmetry on two planes of β-MgCl₂: the (100) and the (110). The selected metallocenes are Cp₂ZrCl₂, Ind₂ZrCl₂, EtInd₂ZrCl₂ and Me₂SiInd₂ZrCl₂. The results of the calculations allow us to speculate that the chiral ansa metallocenes bridged with C₂H₄ could have chemical interaction with certain faces of the MgCl₂ surface during the stage of adsorption and subsequent precursors treatment, while the interaction of the others with the surface generates stable species depending on the surface geometry.     

Melting of thin γFe–C films having (100), (110) and (111) surfaces in terms of molecular dynamics simulation

Structural changes associated with melting of thin γFe–C films having (100), (110) and (111) surfaces have been investigated by molecular dynamics simulation. Structures of thin film and bulk models of γFe containing about 0–4 at.% C were calculated at constant temperatures between 1000 and 1800 K. The liquidus temperature for each thin film model decreased with increasing the C concentration. Comparison between the atomic number density distributions of Fe and C showed: (i) The atomic number density of C near the surface increases before the formation of liquid near the surface. (ii) This increase becomes more prominent as temperature rises. (iii) Melting of γFe–C alloy would be rate-controlled by diffusion of C from the solid phase to the solid–liquid interface. These findings suggest that the increase in the C concentration enhances atomic vibrations of Fe near the surface and promotes melting of Fe at lower temperatures. Furthermore, it has been concluded from Lindemann's law of melting that surface melting occurs in γFe–C alloy having (110) surface more easily.     

Amyloid Self‐Assembly of hIAPP8‐20 via the Accumulation of Helical Oligomers, α‐Helix to β‐Sheet Transition,and Formation of β‐Barrel Intermediates

The self‐assembly of human islet amyloid polypeptide (hIAPP) into β‐sheet‐rich nanofibrils is associated with the pathogeny of type 2 diabetes. Soluble hIAPP is intrinsically disordered with N‐terminal residues 8–17 as α‐helices. To understand the contribution of the N‐terminal helix to the aggregation of full‐length hIAPP, here the oligomerization dynamics of the hIAPP fragment 8–20 (hIAPP8‐20) are investigated with combined computational and experimental approaches. hIAPP8‐20 forms cross‐β nanofibrils in silico from isolated helical monomers via the helical oligomers and α‐helices to β‐sheets transition, as confirmed by transmission electron microscopy, atomic force microscopy, circular dichroism spectroscopy, Fourier transform infrared spectroscopy, and reversed‐phase high performance liquid chromatography. The computational results also suggest that the critical nucleus of aggregation corresponds to hexamers, consistent with a recent mass‐spectroscopy study of hIAPP8‐20 aggregation. hIAPP8‐20 oligomers smaller than hexamers are helical and unstable, while the α‐to‐β transition starts from the hexamers. Converted β‐sheet‐rich oligomers first form β‐barrel structures as intermediates before aggregating into cross‐β nanofibrils. This study uncovers a complete picture of hIAPP8‐20 peptide oligomerization, aggregation nucleation via conformational conversion, formation of β‐barrel intermediates, and assembly of cross‐β protofibrils, thereby shedding light on the aggregation of full‐length hIAPP, a hallmark of pancreatic beta‐cell degeneration.     

The influence of microstructure on the measurement of γ-γ′ lattice mismatch in single-crystal Ni-base superalloys

Lattice mismatch in multicomponent high refractory single-crystalline Ni-base superalloys has been measured in situ by hot-stage X-ray diffraction. Prior to X-ray examination, all samples were subjected to long-term aging treatments at 1120 °C to relieve coherency stresses. The resolution of the individual γ and γ′ peaks at high Bragg angles in the X-ray spectra and the magnitude of the misfit was found to be sensitive to the microstructure of the material. When the precipitation of coherent γ′ during cooling from the aging temperature could largely be suppressed, the corresponding matrix peaks were narrower and of higher intensity as compared with samples where cooling γ′ was present. Also, a slightly larger misfit, 0.04%, was measured in the microstructures where the cooling γ′ was not present. Procedures for deconvoluting X-ray data are outlined in detail, and the experimental results are discussed in terms of changes in phase compositions and misfit strains produced by the cooling γ′.     

Probabilistic prediction of minimum fatigue life behaviour in α + β titanium alloys

The objective of this work was to develop and demonstrate a probabilistic life prediction method for the prediction of minimum fatigue lives that are typically used in the design of fracture critical rotating turbine engine components. A Monte Carlo analysis was used to predict the variability in fatigue lives based on the distribution of microstructural features that lead to early crack initiation as well as the variability in small fatigue crack growth rates. Two titanium alloys, both with bimodal microstructures, were tested and analysed in this study. The distribution of critical microstructural features was calibrated based on test results and understanding of microstructure neighbourhood effects. Testing was conducted on both alloys and included both smooth and notched specimens. The predictions are presented and compared with the data for smooth and notch geometries for the various loading conditions. A parametric study was performed to identify the importance of several model inputs and to identify areas for future improvement.     

Molecular simulation on structure–property relationship of polyimides with methylene spacing groups in biphenyl side chain

In our early research, the experiment of three synthesized polyimides (PP0DA-PI, PP2DA-PI and PP6DA-PI) with different methylene spacing groups in biphenyl side chain but with the same backbone reveals that the PP6DA-PI with six methylene flexible spacing groups in biphenyl side chain has lower intrinsic viscosity, density and glass transition temperature than those of the PP0DA-PI without methylene spacing group and PP2DA-PI with two methylene spacing groups in biphenyl side chains but keeps the mechanical property to that of the PP0DA-PI and PP2DA-PI. The aim of this paper is to explain the addition of the methylene spacing groups leading to the diversity of polyimide’s properties; molecular mechanics and molecular dynamics techniques were adapted to generate reasonable molecular models to establish the structure–property relationship of polyimide. Lots of interesting results have been obtained as follows. The modeling of chain conformation shows that the biphenyl side groups in PP0DA-PI are almost vertical to the backbone, whereas the biphenyl side groups in PP6DA-PI are almost parallel to the backbone indicating that PP6DA-PI exhibits a strong intra-chain interaction leading to in situ reinforcement interaction between the main chain and the side chain validated by the charge density, dipole moment and force current property of the two phenyls in biphenyl side chains. For this reinforcement in PP6DA-PI, the original modulus has been enhanced to some extent. Meanwhile, though the PP6DA would be more reactive due to higher charge density on N atom of the diamine monomer, the bulk structure of the side chain hindering the polymerization approach of the monomers leads to lower intrinsic viscosity of PP6DA-PAA. The density of PP6DA-PI does not decrease excessively with respect to the increase in chain length because of the bended side chain in this system. Furthermore, using conformational grid scan, potential energy contour map illuminates that the addition of the methylene spacing group in biphenyl side chain decreases the energy barrier in synchronous rotational bonds of the backbone resulting in lower glass transition temperature of PP6DA-PI.     

Analysis of ISE in dynamic hardness measurements of β-Sn single crystals using a depth-sensing indentation technique

The dynamic indentation tests on (001) plane β-Sn single crystals having different growth directions under different peak indentation test load (10, 20, 30, 40, and 50 mN) has been investigated. The experimental results reveal that the measured hardness values exhibit a peak-load dependence, i.e., indentation size effect (ISE). Such peak-load dependence is then analyzed using the Meyer's law, the Hays–Kendall's approach, the Elastic/Plastic Deformation model, the Proportional Specimen Resistance (PSR) model, and the Modified PSR (MPSR) model. As a result, Modified PSR model is found to be the most effective for dynamic hardness determination of β-Sn single crystals.     

Influence of subgrain orientation on martensitic transformation in β1–Cu–Zn–Al-single crystals

In β₁–Cu–Zn–Al single crystals the course of cyclic martensititic transformation ‘β₁ parent phase↔γ′₁ martensite’ induced by tensile stress were studied with use of X-ray topography, light microscopy and etch pits. Two groups of single crystals were studied. The first one (OR) contained single crystals of subgrain boundaries parallel to the direction of elongation [001], the second one (RA) consisted of single crystals of random subgrain boundaries orientations. Single crystals from the RA group cracked after about 300 cycles of martensitic transformation; single crystals from the OR group did not crack even after 1200 cycles. In OR single crystals changes of dislocation density inside the subgrains caused by cycling occurred much more slowly than in the RA single crystals. This has been related to the dislocation movement from inside the subgrains to their boundaries.