Use of the helium medium for preparation of nano-sized powder materials by the example of industrial cement

Based on the phenomenon of the mechanodynamic diffusion of particles of the external medium in solids, a new in principle method has been proposed for the first time for producing nano-sized powder materials using industrial cement milled in a helium medium as an example. The temperature dependences of the extraction rate and the amount of helium in powders upon their heating in a temperature range of 20–1200°C have been obtained using mass spectrometry. It has been shown that milling of the cement powder of the M-400 brand using an MK-1 laboratory mill in helium leads to a considerable shift of its extraction curve towards lower temperatures compared with the air medium. The particle sizes of the powder milled in helium lie in a range of 5–10 nm, which is smaller than the powder size (～500 nm) after milling in the air medium by a factor of 100. The compression strength of cement samples obtained from the powders milled in helium increased by a factor of 2 compared with the strength of the samples from the initial material. The activation energies of helium extraction from the cement powders milled in helium and in air have been analyzed. The obtained results indicate a high efficiency of the method for producing nano-sized powder materials in the helium medium. The method can be used in the industrial scale based on the existing mill equipment with its minimal modernization.     

Dispersion of crystalline powder materials in gaseous media of different chemical compositions

The process of grinding of rutile and barite crystalline powders in a laboratory ball mill in different types of gaseous media (air, nitrogen, helium) has been investigated. Comparative evaluations of the intensity of the dispersion of these minerals have been performed and the particle sizes of powders obtained in different modes of their dispersion have been measured. A sharp increase in the intensity of this process in the helium medium as compared to the air and nitrogen media has been revealed and ultrafine-grained particles of barite powders have been obtained. The results of the performed investigations have demonstrated that the helium medium can be recommended for producing nanoparticles of powder materials in modern types of ball and bead mills with a drastic decrease in the time and energy consumptions required for their preparation.     

大气压低温氦等离子体射流的诊断研究

为了加快低温氦气等离子体射流的工程化进程,通过自主设计的同轴式介质阻挡放电等离子体射流发生器,在放电频率10 kHz,一个大气压条件下产生了稳定的氦气等离子体射流。通过分析不同工况下的电压电流波形可以发现单纯增加氦气体积流量只能小幅的增加电流脉冲幅值,而对放电时间、电流脉冲数的影响不大。增加放电峰值电压时电流脉冲幅值会得到较大幅度增加。通过发射光谱法对大气压氦气等离子射流的活性粒子种类、电子激发温度、电子密度进行了诊断。结果表明,大气压氦气等离子体射流中的主要活性粒子为He Ⅰ原子、N₂第二正带系、N+₂的第一负带系、羟基（OH）,H原子的巴尔末线系（H_α和H_β）与O原子,这表明虽然该试验中使用的氦气纯度已达99.99%,但其中仍残留有少量的空气,同时放电时大气中的空气会被卷吸到放电空间发生电离。还可以发现,主要活性粒子的相对光谱强度随氦气体积流量的增加及放电峰值电压的增大均呈现上涨的趋势。选用He Ⅰ原子的四条谱线对不同试验工况下的电子激发温度进行了计算,得到大气压氦气等离子体射流的电子激发温度在3 500~6 300 K之间,电子激发温度随放电峰值电压与氦气体积流量的增大总体上呈现上升的趋势。但由于反向电场的存在,某些峰值电压可能会出现电子激发温度下降的情况;根据Stark展宽原理对大气压氦气等离子体射流的电子密度进行了计算,发现电子密度的数量级可达1015 cm-3,同时增大峰值电压与氦气体积流量均可有效的提高射流中的电子密度。这些参数的研究对氦气等离子体射流在工程实际中的应用具有重要意义。     

Microhardness of armco iron samples with different initial structures after rolling in a helium or nitrogen medium

We have analyzed the dependences of microhardness H on load P for the surface layers of Armco iron samples with different initial structures, i.e., annealed and after equal-channel angular pressing (ECAP). The microhardness was measured in air after rolling of the sample in helium or nitrogen medium. It has been found that these mediums produce different effects on the H(P) dependences for preliminarily annealed samples compared to those subjected to ECAP. This is due to the differences in their initial defects structures and in the types of binding forces of helium atoms and nitrogen molecules with dislocations, which determine the intensity of their penetration into the surface layer of the samples under investigation. We have obtained curves that describe the release of helium from samples rolled in different mediums and have measured the amount of helium.

     

Effect of TiO2/Al2O3 film coated diamond abrasive particles by sol-gel technique

The diamond abrasive particles were coated with the TiO₂/Al₂O₃ film by the sol-gel technique. Compared with the uncoated diamonds, the TiO₂/Al₂O₃ film was excellent material for the protection of the diamonds. The results showed that the incipient oxidation temperature of the TiO₂/Al₂O₃ film coated diamonds in air atmosphere was 775 °C, which was higher 175 °C than that of the uncoated diamonds. And the coated diamonds also had better the diamond's single particle compressive strength and the impact toughness than that of uncoated diamonds after sintering at 750 °C. For the vitrified bond grinding wheels, replacing the uncoated diamonds with the TiO₂/Al₂O₃ film coated diamonds, the volume expansion of the grinding wheels decreased from 6.2% to 3.4%, the porosity decreased from 35.7% to 25.7%, the hardness increased from 61.2H_RC to 66.5H_RC and the grinding ratio of the vitrified bond grinding wheels to carbide alloy (YG8) increased from 11.5 to 19.1.     

Effect of gases on the temperature dependence of the electric conductivity of CVD multiwalled carbon nanotubes

The influence of various gaseous media on the temperature dependence of the electric conductivity σ of multiwalled carbon nanotubes (MWNTs) synthesized using the method of catalytical chemical vapor deposition (CVD) has been studied. The σ(T) curves were measured in a temperature range from 4.2 to 300 K in helium and its mixtures with air, methane, oxygen, and hydrogen. The introduction of various gaseous components into a helium atmosphere leads to a significant decrease in the conductivity of MWNTs in the interval between the temperatures of condensation and melting of the corresponding gas. Upon a heating-cooling cycle, the conductivity restores on the initial level. It is concluded that a decrease in σ is caused by the adsorption of gases on the surface of nanotubes.     

载气组份对空心玻璃微球炉内成球过程的影响

为实现惯性约束聚变靶用空心玻璃微球的干凝胶法高效制备,从数值模拟和工艺实验两个方面研究了载气组份对干凝胶粒子炉内成球过程及最终空心玻璃微球性能的影响。结果表明:载气组份显著影响粒子/微球与载气之间的热量和质量传递过程,但载气组份对粒子/微球在炉内的下落速度影响很小;提高载气中氦气的体积分数可以显著提高干凝胶粒子在吸热阶段的升温速率,更为迅速有效地完成封装过程,这不仅使得干凝胶粒子发泡成为空心球的比例增大,而且还有利于制备得到大纵横比的空心玻璃微球;但是,在载气中保持适当体积分数的氩气,有利于提高玻璃微球的表面质量和成品率。当载气中氦气的体积分数在50%~80%时,干凝胶粒子的成球率较高,空心玻璃微球的球形度、同心度和表面粗糙度能满足制靶要求。     

Fabrication of high performance Gd–Ba–Cu–O single grains in air using a practical melt processing technique

A practical processing route for the fabrication of LRE-Ba–Cu–O single grain superconductors has been developed at the University of Cambridge based on a generic, Mg-doped Nd-123 melt textured seed and suppression of the formation of the solid solution phase in air by enriching the precursors with higher Ba concentration. The processing of high performance Gd–Ba–Cu–O single grains using this processing route is described. The Mg-doped generic seed crystal has been used effectively to promote heterogeneous nucleation via a cold-seeding process. The Gd/Ba solid solution has been suppressed by enriching Gd–Ba–Cu–O precursor powders with two different Ba-rich compositions. This involved adding BaO₂ and GdBa₆Cu₃O_y (Gd-163) (a novel Ba-rich second phase) to the precursor powders, respectively. The Gd-163 phase has been observed not only to suppress formation of the solid solution phase, but also to promote increased heterogeneous grain size. A detailed further study has been carried out with an initial aim of optimizing the BaO₂ and Gd-163 phase content of the precursor composition to produce a single grain almost free of solid solution. Based on the optimized parameters, large single grain Gd–Ba–Cu–O superconductors have been fabricated in an air atmosphere and demonstrated to exhibit record trapped magnetic fields for this material melt processed in air in relatively small single grain samples. The trapped fields of samples produced in air atmosphere are at least comparable to those processed under reduced oxygen partial pressure.     

Emission of helium nuclei in heavy ion interactions at energies ≧ 100 MeV/nucleon

The energy and angular distributions of helium particles emitted in interactions between nuclei in the cosmic radiation and nuclei in photoemulsions at energies ≧ 100 MeV/nucleon have been studied. The data obtained is impossible to interpret on the basis of a statistical decay of excited nuclei. For example, it is found that more than 28% of the helium nuclei are emitted in processes different from simple evaporation. The differential energy distribution of the helium nuclei in the energy interval (40–200) MeV can be represented by the relationN(E)dE=constE ^?a dE, wherea≈1.2. The large spread in angles and energies of the fast helium particles emitted in heavy ion interactions can to a certain degree be understood, if it is assumed that interactions between nucleons and clusters of nucleons occur.     

A method for preparing samples for electron microscope studies of materials unstable in air

A simple sample preparation technique for materials unstable in air has been developed for electron microscope studies. The materials already exist in the form of particles, or they can be transformed by mechanical grinding. The technique consists of several stages: preparation of perforated or thin carbon films as substrates, mechanical grinding and ultrasonic treatment of the material under investigation in a liquid substance to form a suspension, and dripping the suspension onto a substrate placed in a microscope holder beforehand, followed by immediately placing the holder in the preliminary pumping chamber of the microscope.     

Influence of the gas density on the motion of a free plasma piston in the railgun channel

The influence of the gas density on the acceleration of a plasma armature inside the railgun channel filled with various gases (xenon, air, or helium) under atmospheric pressure is investigated experimentally and theoretically. It is shown that, after the discharge current has reached a steady value, the velocity of the glowing plasma front ceases to grow and remains constant as long as so does the current. The length over which the velocity saturates is equal to a few centimeters, i.e., is much shorter than the railgun channel length. The maximum velocity of the plasma piston meets a predicted limit, which is determined by the drag of the medium and a decrease in the acceleration of the plasma armature when a fraction of the material evaporated from the rails is involved into motion. The plasma composition depends on the electrode material. The velocities measured when the channel is filled with helium (V = 17.5 km/s) or air (V = 9.8 km/s) noticeably exceed the sound speed inside the plasma piston (5–7 km/s).     

A shadowed off-axis production of Ge nanoparticles in Ar gas atmosphere by pulsed laser deposition

In this work, we report on the production of Ge nanoparticles (NPs) in an inert Ar gas atmosphere by pulsed laser deposition (PLD) at room temperature (RT). The direct deposition of energetic particles/droplets resulting from the ablation process of the target material has been avoided by using an original and customized off-axis shadow mask (shadowed off-axis) deposition set-up where the NPs deposition on the substrate takes place by means of scattering between the NPs formed in the vapor phase and the background Ar atoms. It is found that the Ar gas pressure parameter has a relevant role in the crystallization process, with better crystallinity obtained as the background Ar pressure is raised for the given experimental conditions.     

Influence of environment and grinding on the crystallisation mechanism of ZrO2 gel

The influence of grinding and surrounding atmosphere on the thermal transformations of zirconia gel has been studied. The XRD analysis of the products obtained by thermal decomposition of zirconia gel has shown that pure tetragonal phase is obtained if the gel decomposition is carried out under high vacuum or dry inert atmosphere, while monoclinic zirconia results from the decomposition of the zirconia gel under air or inert gas saturated with water vapour. A mechanism for the thermal crystallisation of zirconia gel has been proposed from the study of the variation of the crystal size of the monoclinic and tetragonal zirconia phases formed as a function of the temperature and the surrounding atmosphere.The thermal decomposition of ground zirconia leads to the formation of ZrO₂ with a percentage of tetragonal phase closed to 90% irrespectively of the surrounding atmosphere. The stabilisation of the tetragonal phase by grinding seems to be connected with the formation of tetragonal zirconia nuclei that cannot be observed by XRD. The crystallisation enthalpy measurements carried out by DSC support this conclusion.     

Excitation and emission of hexavalent uranium in KMgF3

Single crystals of KMgF₃ containing uranium have been grown in an oxidizing atmosphere. Absorption, selective laser excitation and emission have been obtained at liquid helium temperature. There is a resonance line at 511.45 nm and this has been shown to be due to a magnetic dipole transition between singly degenerate levels. The polarized excitation results are consistent with a charge compensated UO₄ centre having D_4h symmetry.     

Effect of vanadium doping on structural, magnetic and optical properties of ZnO nanoparticles

V-doped ZnO nanoparticles were synthesized by heating metal acetates in organic solvent. All synthesized samples were annealed in air and reducing gas atmosphere at 600 °C for 8 h. The XRD patterns of both samples annealed in air and reducing atmosphere indicate that samples have polycrystalline wurtzite structure with increase in lattice constant with increase in V-doping. The particle sizes were calculated by using Scherrer's equation which lies in the range of 25-30 nm. The SEM images show that particles annealed in air and under reducing environment are spherical in nature. The EDX results reveal that samples contain V, Zn, and O contents only. The TPR results indicate that the system contains isolated VO_x, ZnO_x and bimetallic Zn: V (O_x) sites and indication of electronically excited bimetal sites. There is no signature of ferromagnetism in all samples annealed in air while room temperature ferromagnetism has been observed only under reducing atmosphere annealing. There is monotonically increase in saturation magnetization with V-doping concentration. UV-vis spectroscopy study shows that there is a linear increase in band gap energy with increase in V-doping, a direct evidence of change in magnetic properties due to V-doping and under reducing environment.     

Photoluminescence study of pure and Li-doped ZnO thin films grown by sol-gel technique

The effect of annealing atmosphere, temperature and aging on the photoluminescence of pure and Li-doped ZnO thin films has been investigated. Annealing the pure ZnO in N₂ and He above 800 °C results in green emission centered at ca. 500 nm; however annealing in air red-shifts the green emission to 527 nm. The visible emission of the Li-doped ZnO is found to be largely dependent on the annealing atmosphere. Warm-white photoluminescence with a broad emission band covering nearly the whole visible spectrum is obtained for the Li-doped ZnO films annealed in helium. The substitutional and interstitial extrinsic point defects created by lithium doping may mediate the relative concentration of the intrinsic defects and thereby tune the intrinsic-defect-related visible emission. The enhanced intensity ratio of near-band-edge ultraviolet emission to deep-level visible emission with aging time may be ascribed to both in-diffusion of oxygen from air and self-diffusion of oxygen interstitials to heal the oxygen vacancies during the aging process.     

Resolved line profiles of atomic oxygen resonance lamps used in the upper atmosphere

Line profiles of the 130-nm OI(³P-³S) resonance triplet emitted by r.f. excited helium/ oxygen lamps have been resolved using a photoelectric echelle spectrometer. These profiles have been reproduced using a self-absorbed double-Gaussian spectral distribution in which the relative amplitudes of the Gaussian components are functions of the oxygen and helium partial pressures in the lamps. Reasons for the form of the observed spectral distribution are suggested and the importance of the spectrometer measurements to studies of atomic oxygen in the upper atmosphere involving this type of lamp illustrated.     

Effect of the saturation conditions and structure on the retention of helium in structural materials

A comparison between the kinetics of helium desorption upon linear heating of samples saturated using various regimes is performed, and the effect of dislocations on the retention of helium in materials is estimated. In order to investigate the effect of the conditions of saturation of materials with helium on its retention, samples of austenitic stainless steel 0Kh16N15M3B saturated using various methods were studied, namely, helium irradiation in a cyclotron, in a magnetic mass-separation setup, inside IRT-2000 and BOR-60 reactors, and using the so-called “tritium trick” technique. The investigations show that when saturation of the samples with helium is accompanied by the introduction of radiation defects (in wide limits of helium concentrations and radiation damage), the kinetics of helium evolution from samples of this type is adequate to the kinetics of its evolution from samples irradiated in a reactor. The investigation of the kinetics of helium evolution from the samples of 0Kh16N15M3B steel both after a preliminary deformation and in the process of deformation showed that, in the process of heating, the helium atoms can migrate along dislocation pipes, resulting in a significant effect on the release of helium and its redistribution in the volume of the material. The activation energy for helium pipe diffusion in austenitic steel 0Kh16N15M3B is about 0.7 eV. Mobile dislocations favor the ejection of helium onto the surface of the material, to grain boundaries, interphase interfaces, etc.     

Preparation of activated carbons previously treated with sulfuric acid: A study of their adsorption capacity in solution

In the present work, cedar wood has been used as raw material for the preparation of activated carbons. The influence of a previous treatment with sulfuric acid on the textural properties of the carbonized and activated samples has been investigated. Finally, the adsorption capacity of para-nitrophenol in aqueous solution has been studied and the corresponding adsorption isotherms have been fitted to Langmuir's equation. The experimental results indicate that the previous dehydration of the raw material with sulfuric acid gives rise to an improvement in the porous texture and adsorption capacity of the activated carbons.     

Effect of small particle sizes on the measured density of nanocrystalline powders of nonstoichiometric tantalum carbide TaC<Subscript> <Emphasis Type="Italic">y</Emphasis> </Subscript>

Nanocrystalline powders of the nonstoichiometric tantalum carbide TaC_y (0.81 ≤ y ≤ 0.96) with an average particle size in the range from 45 to 20 nm have been prepared using high-energy ball milling of coarse-grained powders. The density of the initial coarse-grained and prepared nanocrystalline powders of TaC_y has been measured by helium pycnometry. The sizes of particles in tantalum carbide powders have been estimated using the X-ray diffraction analysis and the Brunauer–Emmett–Teller (BET) method. The density of TaC_y nanopowders measured by helium pycnometry is underestimated as compared to the true density due to the adsorption of helium by the highly developed surface of the nanocrystalline powders. It has been shown that the difference between the true and measured densities is proportional to the specific surface area or is inversely proportional to the average particle size of the nanopowders. The large difference between the true and measured pycnometric densities indicates a superhydrophobicity of the tantalum carbide nanopowders.