Strength of magnesium oxide under high pressure: evidence for the grain-size dependence

X-ray diffraction patterns from magnesium oxide compressed in a diamond anvil cell up to 55 GPa have been recorded and the differential stress (a measure of compressive strength) and grain-size (crystallite size) determined as a function of pressure from the line-width analysis. The strength agrees well with the uniaxial stress component (another measure of compressive strength) derived earlier from the line-shift data. The strength increases while the crystallite size decreases steeply as the pressure is raised from ambient to ∼10 GPa. The increase in strength is much smaller at higher pressures. The strength-pressure data are explained by combining the grain-size dependence of strength and the shear-modulus scaling law. The dependence of strength on grain-size has not been considered in the past in the discussion of high-pressure strength data.     

Compression of silver in a diamond anvil cell: Pressure dependences of strength and grain size from X-ray diffraction data

Two silver samples, coarse grained (c-Ag, grain size 300±30 nm) and nanocrystalline (n-Ag, grain size 55±6 nm), are compressed in a diamond anvil cell in separate experiments. The pressure is increased in steps of ∼3 GPa and the diffraction pattern recorded at each pressure. The grain size and compressive strength are determined from the analysis of the diffraction line-widths. The grain size of c-Ag decreases rapidly from 300±30 nm at ambient pressure to 40±8 nm at 15 GPa, and then gradually to 20±3 nm at 40 GPa. After pressure release to ambient condition, the grain size is 25±4 nm. The strength at ambient pressure is 0.18±0.05 GPa and increases to 1.0±0.3 GPa at 40 GPa. The grain size of n-Ag decreases from 55±6 nm at ambient pressure to 17±4 nm at 15 GPa and to 14±3 nm at 55 GPa. After release of pressure to ambient condition, the grain size is 50±7 nm. The strength increases from 0.51±0.07 GPa at ambient pressure to 3.5±0.4 GPa at 55 GPa. The strength is found to vary as the inverse of the square-root of the grain size. The results of the present measurements agree well with the grain-size dependence of strength derived from the hardness versus grain size data at ambient pressure available in the literature.     

Electrodeposition of nanocrystalline Zn-Ni alloy from alkaline glycinate bath containing saccharin as additive

Nanocrystalline Zn-Ni (crystallite sizes 13-68 nm) alloy coatings were produced from an alkaline glycinate bath containing saccharin as additive. X-ray diffraction (XRD) was used to determine the phase composition and average crystallite size of nanocrystalline Zn-Ni alloy coatings. The average grain size of a deposit was also studied by transmission electron microscopy (TEM). The effects of saccharin concentration and current density on the crystallite size and surface roughness of the coatings were studied. Crystallite size and average surface roughness were diminished as a result of increasing saccharin concentration. Scanning electron microscopy (SEM) examination showed that coatings had a colony-like morphology and the colony size was increased with increasing current density. Microhardness testing was carried out in order to determine the degree of dependence of this mechanical property on the crystallite size. It was found that microhardness did not depend on crystallite size (Hall-Petch).     

Unexpected high stiffness of Ag and Au nanoparticles

We studied the compressibility of silver (10 nm) and gold (30 nm) nanoparticles, n-Ag and n-Au, suspended in a methanol-ethanol mixture by x-ray diffraction (XRD) with synchrotron radiation at pressures up to 30 GPa. Unexpectedly for that size, the nanoparticles show a significantly higher stiffness than the corresponding bulk materials. The bulk modulus of n-Au, K(0)=290(8) GPa, shows an increase of ca. 60% and is in the order of W or Ir. The structural characterization of both kinds of nanoparticles by XRD and high-resolution electron microscopy identified polysynthetic domain twinning and lamellar defects as the main origin for the strong decrease in compressibility.     

Effect of complex inter-site couplings on the excitation energy transfer in the FMO complex

The laser irradiation effects on surface, structural and mechanical properties of zirconium (Zr) have been investigated. For this purpose, Zr samples were irradiated with Excimer (KrF) laser (λ ≈ 248 nm, τ ≈ 18 ns, repetition rate ≈ 30 Hz). The irradiation was performed under the ambient environment of oxygen gas at filling pressure of 20 torr by varying laser fluences ranging from 3.8 to 5.1 cm^-2. The surface and structural modification of irradiated targets was investigated by scanning electron microscope (SEM) and X-ray diffractometer (XRD). In order to explore the mechanical properties of irradiated Zr, the tensile testing and Vickers micro hardness testing techniques were employed. SEM analysis reveals the grain growth on the irradiated Zr surfaces for all fluences. However, the largest sized grains are grown for the lowest fluence of 3.8 J cm^?2. With increasing fluence from 4.3 to 5.1 J cm^?2, the compactness and density of grains increase whereas their size decreases. XRD analysis reveals the appearance of new phases of ZrO₂ and Zr₃O. The variation in the peak intensity is observed to be anomalous whereas decreasing trend in the crystallite size and residual stresses has been observed with increasing fluence. Micro hardness analysis reveals the increasing trend in surface hardness with increasing fluence. The tensile testing exhibits the increasing trend of yield stress (YS), decreasing trend of percentage elongation and anomalous behaviour of ultimate tensile strength with increasing fluence.     

Effects of passage of 200 MeV Ag9+ ions in indium phosphide at different depths

Indium phosphide sample was irradiated with 200?MeV Ag⁹⁺ ions for the fluence of 2?×?10¹³?ions?cm^?2. The sample was chemically etched down up to 240?nm depth to investigate the distribution of defects at different regions. Raman scattering and glancing incidence X-ray diffraction spectra were recorded at different depths. The stress estimated from Raman shift was found to increase with depth up to 160?nm and thereafter it decreased and at a depth of 224?nm sample did not show any stress. Phonon coherence length estimated from the Phonon Confinement Model was found to vary between 43 and 18?nm with respect to depth. Glancing incidence X-ray diffraction results revealed the decrease in crystallite size from 16.12 to 1.00?nm in different depth regions.     

Plasma-based sputtering of indium tin oxide for the application of photovoltaic cells

Transparent and conducting indium tin oxide (ITO) thin films were deposited on soda lime glass substrates by RF plasma magnetron sputtering at room temperature. The effect of thickness (100, 200 and 300?nm) on the physical (structural, optical, electrical) properties of ITO thin films was investigated systematically. It is observed that with an increase in thickness, the X-ray diffraction data indicate polycrystalline films with grain orientations predominantly along (222) and (400) directions; the average grain size increases from 10 to 30?nm; the optical band gap increases from 3.68 to 3.73?eV and the transmission decrease from 80% to 70% . Four-point probes show a low resistivity (2.4×10^?5?Ω?cm) values for film with a thickness 300?nm. Present work shows that the ITO is a promising transparent conductive oxide material for the solar cell application.     

Crystal microstructure of annealed nanocrystalline Chromium studied by synchrotron radiation diffraction

The microstructure of electrodeposited nanocrystalline chromium (n-Cr) was studied by using synchrotron radiation (SR) diffraction, SEM, TEM, and EDX techniques. The as-prepared n-Cr samples show the standard bcc crystal structure of Cr with volume-averaged column lengths varying from 25 to 30 nm. The grain growth kinetics and the oxidation kinetics were studied by time resolved SR diffraction measurements with n-Cr samples annealed at 400, 600, and 800 °C. The grain growth process is relatively fast and it occurs within the first 10 min of annealing. The final crystallite size depends only on the annealing temperature and not on the initial grain size or on the oxygen content. The final volume-averaged column lengths observed after 50 min annealing are 40(4), 80(1), and 120(2) nm for temperatures 400, 600, and 800 °C, respectively. It is shown that annealing ex situ of n-Cr at 800 °C both under vacuum and in air gives a grain growth process with the same final crystallite sizes. The formation of the Cr₂O₃ and CrH phases is observed during annealing.     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

Grain size reduction of copper subjected to repetitive uniaxial compression combined with accumulative fold

This paper reports a novel method of repetitive uniaxial compression combined with accumulative fold for preparing bulk submicron- to nanocrystalline copper starting with a coarse grained counterpart. Grain size reduction and microstrain variations of the high purity copper samples after different passes of compression and fold are investigated by scanning electron microscope and x-ray diffraction (XRD), respectively. Our results show that the average grain size of samples decreases from about 830nm to 127nm as the number of compression passes increases to 30. Microstrain in the compressed sample is found to increase for the first 20 passes, but to decrease at the last 10 passes. The variations of compressive yield strength and the shift of XRD peaks to larger diffraction angles are observed in the squeezed sample. Our experimental results demonstrate that the repetitive uniaxial compression combined with accumulative fold is an effective method to prepare bulk nanocrystalline metallic materials, in particular for soft metals such as Cu, Al and Pb.     

Effects of ultrasonic agitation on adhesion strength of micro electroforming Ni layer on Cu substrate

Micro electroforming is an important technology, which is widely used for fabricating micro metal devices in MEMS. The micro metal devices have the problem of poor adhesion strength, which has dramatically influenced the dimensional accuracy of the devices and seriously limited the development of the micro electroforming technology. In order to improve the adhesion strength, ultrasonic agitation method is applied during the micro electroforming process in this paper. To explore the effect of the ultrasonic agitation, micro electroforming experiments were carried out under ultrasonic and ultrasonic-free conditions. The effects of the ultrasonic agitation on the micro electroforming process were investigated by polarization and alternating current (a.c.) impedance methods. The real surface area of the electroforming layer was measured by cyclic voltammetry method. The compressive stress and the crystallite size of the electroforming layer were measured by X-ray Diffraction (XRD) method. The adhesion strength of the electroforming layer was measured by scratch test. The experimental results show that the imposition of the ultrasonic agitation decreases the polarization overpotential and increases the charge transfer process at the electrode–electrolyte interface during the electroforming process. The ultrasonic agitation increases the crystallite size and the real surface area, and reduces the compressive stress. Then the adhesion strength is improved about 47% by the ultrasonic agitation in average. In addition, mechanisms of the ultrasonic agitation improving the adhesion strength are originally explored in this paper. The mechanisms are that the ultrasonic agitation increases the crystallite size, which reduces the compressive stress. The lower the compressive stress is, the larger the adhesion strength is. Furthermore, the ultrasonic agitation increases the real surface area, enhances the mechanical interlocking strength and consequently increases the adhesion strength. This work contributes to fabricating the electroforming layer with large adhesion strength.     

全谱拟合法研究聚丙烯腈基碳纤维形成过程中晶态结构演变

通过全谱拟合法对碳纤维制备过程中不同阶段纤维的XRD谱图进行处理,得到不同阶段纤维的微观结构参数,研究了聚丙烯腈(PAN)基碳纤维制备过程中晶态结构的演变.全谱拟合法基于晶体衍射的严格物理理论,拟合目标为整个衍射谱,并不是个别衍射峰,所得结果具有更高的可信度.研究结果表明:PAN原丝中的高分子链沿纤维轴高度取向,表观晶粒尺寸为6.5 nm左右;经过预氧化处理,纤维中的有序结构遭到破坏,表观晶粒尺寸锐减.纤维中逐渐形成梯形结构并沿纤维轴取向,从而形成新的有序结构;经过碳化处理后,环状梯形结构转变为碳的层状结 关键词： 碳纤维 晶体结构 XRD 全谱拟合法     

Structural and optical analysis of 60Co gamma-irradiated thin films of polycrystalline Ga10Se85Sn5

The present study focuses on the effects of gamma irradiation on structural and optical properties of polycrystalline Ga₁₀Se₈₅Sn₅ thin films with a thickness of ～300?nm deposited by the thermal evaporation technique on cleaned glass substrates. X-ray diffraction patterns of the investigated thin films show that crystallite growth occurs in the orthorhombic phase structure. The surface study carried out by using the scanning electron microscope (SEM) confirms that the grain size increases with gamma irradiation. The optical parameters were estimated from optical transmission spectra data measured from a UV–vis-spectrophotometer in the wavelength range of 200–1100?nm. The refractive index dispersion data of the investigated thin films follow the single oscillator model. The estimated values of static refractive index n₀, oscillator strength E_d, zero frequency dielectric constant ε₀, optical conductivity σ_optical and the dissipation factor increases after irradiation, while the single oscillator energy E_o decreases after irradiation. It was found that the value of the optical band gap of the investigated thin films decreases and the corresponding absorption coefficient increases continuously with an increase in the dose of gamma irradiation. This post irradiation changes in the values of optical band gap and absorption coefficient were interpreted in terms of the bond distribution model.     

Influences of Co doping on the structural and optical properties of ZnO nanostructured

Pure and Co-doped ZnO nanostructured samples have been synthesized by a chemical route. We have studied the structural and optical properties of the samples by using X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), field-emission transmission electron microscope (FETEM), energy-dispersive X-ray (EDX) analysis and UV–VIS spectroscopy. The XRD patterns show that all the samples are hexagonal wurtzite structures. Changes in crystallite size due to mechanical activation were also determined from X-ray measurements. These results were correlated with changes in particle size followed by SEM and TEM. The average crystallite sizes obtained from XRD were between 20 to 25 nm. The TEM images showed the average particle size of undoped ZnO nanostructure was about 20 nm whereas the smallest average grain size at 3% Co was about 15 nm. Optical parameters such as absorption coefficient (α), energy band gap (E _g ), the refractive index (n), and dielectric constants (σ) have been determined using different methods.     

Synthesis and tailoring of GaN nanocrystals at room temperature by RF magnetron sputtering

We report here the synthesis of hexagonal GaN nanocrystals on p-silicon substrates by Radio-Frequency (RF) magnetron sputtering without substrate heating or by post-deposition annealing treatment. GaN nanocrystals are synthesized and tailored as a function of RF power at constant Ar and N₂ flow rates (working pressure). The observed reduction in grain sizes as a function of RF power has been correlated with an increase in compressive strain. The effect of RF power on crystallite orientation has been determined by diffraction intensities using the degree of c-axis orientation. Atomic force microscopy shows uniform lateral nanocrystal sizes with spherical in shape by insignificant difference in Root-Mean-Square (RMS) roughness values for all the deposited thin films. Transmission electron microscope and field emission-scanning electron microscope studies have been performed to understand the surface morphologies and grain sizes. Thus, tailoring the size of the nanocrystals has been discussed by correlating RF powers, working pressures and cathode voltages on lattice vibrations.     

Conductivity drop and crystallites redistribution in gold film

Electrical conductivity of Au film deposited on Si(100), Si(111) and BK7 glass substrates, ranging from 20 nm to 1000 nm, was measured. Conductivity drop and a decrease of averaged crystallite size are observed around film thickness of 200 nm. Investigation of the conductivity drop led to the discovery that a redistribution of crystallites of {111} and {220} occurs in the conductivity drop region. By analyzing the relationship of distribution of crystallites, averaged crystallite size and conductivity ratios and together with the atomic force microscope pictures, leads to the conclusion that the thermal conductivity drop region is caused by the presence of many small crystallites. These small crystallites are responsible for yielding a lower averaged crystallite size and causing a higher grain boundary scattering. PACS 73.50; 68.47.De; 68.55.Jk     

Measuring grain rotation at the nanoscale

In this paper, we introduced a method to measure grain rotation of nanomaterials under external stress using a high pressure diamond anvil cell and the Laue microdiffraction technique at a synchrotron facility. We used tungsten carbide marker crystals to investigate grain rotation activities of 3 and 500?nm nickel media. Our results show that the grain rotation of 3 and 500?nm nickel nanocrystals increase with pressure and finally rotation of 500?nm nickel tends to stop at a lower pressure/stress level than 3?nm nickel. 3?nm nickel nanocrystals show a higher rotation magnitude than 500?nm nickel nanocrystals. Our measurements show an effective method to study the grain rotation of nanomaterials especially in ultrafine nanocrystals.     

Effect of ambient gas on structural and optical properties of titanium oxynitride films

Titanium oxynitride films have been deposited on glass substrates by reactive RF magnetron sputtering of titanium target. The influence of oxygen partial pressure in N₂ + Ar and N₂ + He mixtures was examined on structural and optical properties of titanium oxynitride films. The prepared samples were characterized by X-ray diffraction, EDS, surface profilometer, AFM and contact angle measurement system. With increase in oxygen partial pressure, the grain size decreases from ∼70 nm to ∼50 nm in N₂ + Ar mixture, while from ∼60 nm to ∼37 nm in N₂ + He mixture. The thickness calculated from optical transmission data and surface profilometer is in good agreement with each other. The deposited samples are hydrophobic by nature and the contact angle was found to decrease with increase in oxygen partial pressure. Samples prepared in oxygen partial pressure ≥5.5% show transmittance of about 97% in the visible region of the spectrum in both N₂ + Ar and N₂ + He mixtures. The atomic mass of the sputtering gas (Ar and He) significantly affects the primary crystallite size, orientation as well as band gap. We were able to relate the better crystallisation of titanium atoms with low partial pressure of oxygen when films are deposited in helium instead of argon due to Penning ionization.     

High-pressure torsion-induced grain growth and detwinning in cryomilled Cu powders

Two mechanisms for deformation-induced grain growth in nanostructured metals have been proposed, including grain rotation-induced grain coalescence and stress-coupled grain boundary (GB) migration. A study is reported in which significant grain growth occurred from an average grain size of 46?nm to 90?nm during high pressure torsion (HPT) of cryomilled nanocrystalline Cu powders. Careful microstructural examination ascertained that grain rotation-induced grain coalescence is mainly responsible for the grain growth during HPT. Furthermore, a grain size dependence of the grain growth mechanisms was uncovered: grain rotation and grain coalescence dominate at nanocrystalline grain sizes, whereas stress-coupled GB migration prevails at ultrafine grain sizes. In addition, detwinning of the preexisting deformation twins was observed during HPT of the cryomilled Cu powders. The mechanism of detwinning for deformation twins was proposed to be similar to that for growth twins.     

Structural and mechanical properties of nano-crystal TiN coatings

The structural and mechanical properties of TiN coatings prepared by ion beam assisted deposition (IBAD) were studied. The coatings have a polycrystal structure with grain size of ≈10nm or less. The hardness of the coatings increases with increasing grain size of TiN crystallites. The coating with grain size of 10.3 nm even has a superhardness of 44.7 GPa. The relationship between the hardness and the grain size in the nano-crystalline coatings was discussed on the basis of grain-boundary triple junctions.