Influence of nanosized magnesia on the hydration of borehole-sealing cements prepared using different methods

Gas drainage is an efective technology for gas control in coal mines.A high borehole-sealing quality is the fundamental precondition for efcient gas drainage.The expansibilities of cement pastes used in borehole-sealing processes are critical for the borehole-sealing efect.Nanosized magnesia expansive agents are used to improve the expansibilities of cement pastes and improve the borehole-sealing efect.Nuclear magnetic resonance spectrometry and scanning electron microscopy were adopted to study the efects of nanosized magnesia on the hydration of borehole-sealing cements used with diferent preparation methods.The results showed that an increase in the mass fraction of the nanosized magnesia promoted cement hydration,and the mass fraction was positively correlated with the promotion efect.The use of diferent preparation methods did not change the water-phase distribution in the cement.When using the wet-mixing preparation method,nanosized magnesia promoted the induction,acceleration,and deceleration periods of hydration;when using the dry-mixing preparation method,the nanosized magnesia promoted the induction period of cement hydration,and the promotion efect was less obvious than that seen when using the wet-mixing method.When using the wet-mixing preparation method,the nanosized magnesia was uniformly dispersed,thus enlarging the surface area of the reaction,which provided more nucleation sites for the hydration products of the cement and therefore accelerated the hydration reaction.When using the dry-mixing preparation method,the nanosized magnesia powders were dispersed nonuniformly and aggregated.Under these conditions,only a few nanosized magnesia particles on the surfaces of the aggregated clusters took part in hydration,so only a small number of nucleation sites were provided for the hydration products of cement.This led to inconsistent hydration of cement pastes prepared using the dry-mixing method.The surface porosity of the cement prepared with the wet-mixing preparation method frst decreased and then increased with increases in the mass fraction of the nanosized magnesia.The cement surface exhibited compact hydration products and few pores,and the surface was relatively smooth.In comparison,the surface porosity of the cement prepared using the dry-mixing method fuctuated with increasing mass fraction of the nanosized magnesia,resulting in a rough cement surface and microfractures on some surfaces.The two preparation methods both reduced the surface porosity of the cement.The wet-mixing preparation was more efective and consistent in improving the compactness of the cement than the dry-mixing preparation.These results provide important guidance on the addition of nanosized magnesia in borehole-sealing engineering and the selection of cement preparation methods,and they also lay a solid foundation for realizing safe and efcient gas drainage.

γ-Fe中氢扩散行为的第一性原理研究

不锈钢中氢脆问题一直是研究者们关注热点,然而至今为止,对于钢中合金元素及空位与H原子之间的作用机理依然不清晰.采用第一性原理方法研究了H原子在不同体系下γ-Fe(Fe8H、Fe7Cr/MoH、Fe7H)的扩散激活能、扩散系数以及扩散过渡态,对比了H原子在不同体系γ-Fe中的扩散难易程度,并从电子结构层次解释其相互作用.研究结果表明,空位的存在会改变H原子在γ-Fe中的扩散路径.在含空位的晶胞中H原子稳定存在于空位附近的近四面体间隙中,并沿空位附近的四面体间隙或八面体到四面体间隙路径扩散.γ-Fe中空位对H原子的影响是局域性的,一方面是捕获H原子的陷阱;另一方面降低了H原子的扩散激活能,促进H原子的扩散.而Cr/Mo的掺杂会降低空位对H原子的束缚,也会抑制H原子的扩散.

The Preparation of Nanosized Pd/ZSM-23 Bifunctional Catalysts for n-Hexadecane Hydroisomerization by Employing PHMB as the Growth Modifi er

The development of highly effective metal-zeolite bifunctional catalysts for the hydroisomerization of n-alkanes is a paramount strategy to produce second-generation biofuels with high quality.In this study,polyhexamethylene biguanide hydrochloride(PHMB)is precisely added to the initial gel to synthesize nanosized ZSM-23 zeolites(Z23-x PH).Due to orientation adsorption and steric hindrance effects of PHMB,each sample of Z23-x PH demonstrates enhanced mesoporosity in comparison with the conventional Z23-C zeolite.Furthermore,the Bronsted acid density of the Z23-x PH samples is also signifi cantly reduced due to a reduction in the distribution of framework Al at T2-T5 sites.The corresponding Pd/23-C and Pd/Z23-x PH bifunctional catalysts with 0.5 wt%Pd loading for n-hexadecane hydroisomerization are prepared by incorporating ZSM-23 zeolites as acid supports.According to the catalytic test results,the suitable addition of PHMB can effectively promote the iso-hexadecane yield.The Pd/Z23-2PH catalyst with an n_(PHMB)/n(_Si)molar ratio of 0.002 demonstrates the highest maximum iso-hexadecane yield of 74.1%at an n-hexadecane conversion of 88.3%.Therefore,the employment of PHMB has provided a simple route for the development of highly effective Pd/ZSM-23 catalysts for n-alkane hydroisomerization.

Room-temperature degradation of o-xylene in simulated air using an online-regenerable plasma-catalysis reactor with low amounts of nanosized noble metals on Co_(3)O_(4)

The plasma catalytic degradation of o-xylene in simulated air was improved by loading low amounts of Pt,Pd,or Au onto Co_(3)O_(4).At room temperature,o-xylene conversion and CO_(x)selectivity using a0.1 wt%Pt/Co_(3)O_(4)catalyst reached 98.9%and 80%,and the energy efficiency was at the top level in comparison with values in the literature.A stable o-xylene degradation performance could be obtained by online regenerating the heat-insulated reactor with a high energy density.After characterization,it was found that the loading of nanosized Pt not only increased the Co^(3+)/Co^(2+)ratio,where the Co^(3+)benefitted the formation of reactive oxygen species,but also conduced Pt^(0)to oxygen activation,resulting in effective promotion of complete o-xylene oxidation.Operando plasma diffuse reflectance infrared Fourier transform spectroscopy demonstrated the complete o-xylene oxidation and proved that Pt played a key role in the complete oxidation of o-xylene.

Prolonged lifetime and enhanced separation of photo- generated charges of nanosized α-Fe2O3 by coupling SnO2 for efficient visible-light photocatalysis to convert C02 and degrade acetaldehyde

To develop efficient visible-light photocatalysis on α-Fe2O3, it is highly desirable to promote visible-light-excited high-energy-level electron transfer to a proper energy platform thermodynamically. Herein, based on the transient-state surface photovoltage responses and the atmosphere-controlled steady-state surface photovoltage spectra, it is demonstrated that the lifetime and separation of photogenerated charges of nanosized α-Fe2O3 are increased after coupling a proper amount of nanocrystalline SnO2. This naturally leads to greatly improved photocatalytic activities for CO2 reduction and acetaldehyde degradation. It is suggested that the enhanced charge separation results from the electron transfer from α-Fe2O3 to SnO2, which acts as a proper energy platform. Based on the photocurrent action spectra, it is confirmed that the coupled SnO2 exhibits longer visible-light threshold wavelength （-590 nm） compared with the coupled TiO2 （-550 nm）, indicating that the energy platform introduced by SnO2 would accept more photogenerated electrons from α-Fe2O3. Moreover, electrochemical reduction experiments proved that the coupled SnO2 possesses better catalytic ability for reducing CO2 and O2. These are well responsible for the much efficient photocatalysis on SnO2-coupled α-Fe2O3.

Ce对10Cr5MoV钢α-Fe晶粒尺寸及奥氏体长大行为的影响

采用背散射电子衍射技术对不含稀土和含稀土Ce的两种试验钢的α-Fe晶粒尺寸进行测量分析。结果表明,稀土Ce的加入使得α-Fe晶粒细化,形成的弥散细小的稀土夹杂成为异质形核核心,提高了回火过程再结晶形核率;固溶稀土的拖曳与钉扎作用延迟了再结晶的开始和结束时间,增加了再结晶转变的驱动力,降低了再结晶发生温度。采用不同的奥氏体化工艺对两种试验钢进行奥氏体化处理,研究Ce对奥氏体长大行为的影响。发现在880~1180℃加热、保温30~90 min奥氏体化条件下,试验钢的奥氏体长大指数n及晶粒长大速率常数K减小,奥氏体长大激活能Q与晶粒长大扩散频率因子M0增大,Ce的加入对奥氏体长大行为有抑制作用。

基于六偏磷酸钠-Fe^(2+)的铁盐脱氮反应器运行性能及微生物学特征研究

以实验室高效反硝化反应器中的反硝化污泥作为接种污泥,启动自养型六偏磷酸钠-Fe^(2+)脱氮反应器,试验采用模拟废水通过88 d的不间断运行,研究了铁盐脱氮工艺的脱氮效能及其微生物学特性。结果表明,当反应器硝态氮容积负荷为0.42 kg/(m^(3)·d)时,最高稳定氮去除负荷为0.41 kg/(m^(3)·d);当Fe^(2+)容积负荷为4.92 kg/(m^(3)·d)时,最大铁去除负荷为2.77 kg/(m^(3)·d)。反应器稳定运行时硝态氮、Fe^(2+)的去除率分别达94.6%、52.6%,最佳效能可维持28 d。反应器运行到第82天时,颗粒污泥由黄色变为灰褐色,颗粒解体,污泥比活性逐渐升高,比反硝化活性由0.71 mg[N]/(g[VSS]·h)升高到2.3 mg[N]/(g[VSS]·h),同比上升224%;比铁氧化活性由7.3 mg[Fe]/(g[VSS]·h)升高到15 mg[Fe]/(g[VSS]·h),同比上升105%。六偏磷酸钠-Fe^(2+)脱氮作为一种新型自养反硝化技术,不仅增强了活细菌的生物活性和反硝化活性,还延长了铁盐脱氮污泥反硝化的高效期。

腐蚀介质在γ-Fe(111)表面吸附的第一性原理研究

氯化物熔盐作为传热储热工质,在太阳能热发电系统中应用时会造成金属管道的腐蚀和失效,严重威胁系统的运行安全.本文采用第一性原理方法,构建了不同腐蚀介质(Cl原子、H原子、O原子、OH基团以及H_(2)O分子)在γ-Fe(111)表面的吸附微观物理模型,并阐明了其吸附性能.结果发现:Cl原子和H原子在γ-Fe(111)表面最稳定的吸附点位为Fcc位,O原子和OH基团最稳定的吸附位点为Hcp位,H_(2)O分子最稳定的吸附位点位Top位.另外,O原子在γ-Fe(111)表面的吸附能和得到的电荷数最大,分别为-8.073 eV和0.53.这为管道的腐蚀研究提供了理论支撑.

α-Fe材料辐照促进应力腐蚀开裂计算模拟研究

对于压水反应堆结构,辐照促进应力腐蚀开裂(IASCC)是其最主要的失效机制。理解辐照条件下辐照缺陷与微裂纹之间的相互作用,是理解辐照促进应力腐蚀开裂微观机制的重要一步。在本研究中,利用反应力场分子动力学(ReaxFF-MD)方法,模拟了体心立方结构(α相)的纯铁在辐照-应力-腐蚀三因素耦合作用下的演化过程,并对其进行腐蚀模拟与拉伸应变模拟,研究辐照促进应力腐蚀开裂底层物理机制及影响因素。

Synthesis of Nanosized NaY Zeolite by Confined Space Method

Nanosized NaY crystals have been prepared from metakaolin and sodium silicate by confined space synthesis with starch additive. It is found that the product has a narrow crystal size distribution (50-100 nm), high Si/Al ratio (Si/Al=4.6-6.1), high surface area (1090 m2/g) and the average diameter of nanosized NaY (75 nm) synthesized is 30 nm, it is smaller than that of without starch additive.

Photocatalytic Activity of Nanosized ZnWO_4 Prepared by the Sol-gel Method

Nanosized ZnWO4 photocatalysts were successfully synthesized via the sol-gel process in a temperature range of 450-800℃. The grain size, crystal size, and crystallinity of ZnWO4 particles increased with the increase of calcina- tion temperature and prolonging calcination time. The photocatalytic activity was measured for the degradation of an aqueous Rhodamine-B（RhB） solution and gaseous formaldehyde（FAD）. With the increase of calcination temperature and time, the activities increased to a maximum and then decreased. ZnWO4 photocatalyst prepared at 550℃ for I0 h showed the highest activity, which is similar to the photocatalytic activity of P25TiO2 for the degradation of gase-ous FAD. High crystallinity, large surface area, and good dispersion are responsible for the high photocatalytic per- formance of the prepared ZnWO4.

Study on Desulfurization Efficiency and Products of Ce-Doped Nanosized ZnO Desulfurizer at Ambient Temperature

Ce-doped nanosized ZnO desulfurizer was prepared by homogeneous precipitation,and its desulfurization efficiency at ambient temperature was investigated through dynamic experiments.The results showed that the desulfurization activity of nanosized Ce-ZnO had improved greatly,compared to nanosized ZnO desulfurizer.Nanosized Ce-ZnO desulfurizer was characterized by XRD,TPD-MS,XPS,and TEM.The research results indicated that doping Ce decreased the particle size of the nanosized ZnO desulfurizer and ZnS was the principal desulfurization product.There were adsorption complexes of HS and S on the surface of desulfurizer as well.Only a small amount of vapor appeared in the tail gas on the condition of meeting the precision of desulfurization.

PREPARATION OF NANOSIZED METAL-OXIDE ULTRAFINE POWDERS BY ATOMIZING-COMBUSTION TECHNIQUE

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Aromatization over nanosized Ga-containing ZSM-5 zeolites prepared by different methods:Effect of acidity of active Ga species on the catalytic performance

Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO;species（[GaO;]a） that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO;]aspecies with stronger Lewis acid sites produced a better synergism with moderate Br?nsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga;O;phase and small amounts of GaO;species that are mainly located on the external surface（[GaO;];）, which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples（Gax-NZ5） exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield（i.e.,65.4 wt%） was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.

Preparation of nanosized W/Cu composite powder by sol-gel technique

Cu(NO3)(2) and (NH4)(6)H(2)W(12)O(40)center dot 4H(2)O were used to prepare W/Cu nanosized composite powder by sol-gel technique. The influences of heat treatment process, pH value of the solution and the amount of an addition agent on particle size were investigated by DSC, XRD and TEM. The results show that, at a certain heat treatment temperature, the W/Cu nanoparticle size increases with the pH value or the amount of the addition agent increasing.

Hydrothermal preparation and persistence characteristics of nanosized phosphor SrS:Eu^(2+),Dy^(3+)

Nanosized long-persistent phosphors SrS：Eu^2＋, Dy^3＋ were prepared by the hydrothermal method.The samples were characterized by X-ray powder diffraction, transmission electron microscopy, and charge-coupled device spectrometry.The persistence characteristic was studied using the decay curves.The results showed that the emission intensity decreased sharply with temperature increasing, although the particle size increased.The S2-vacancies caused by oxidization served as shallow traps, and Dy3＋ served as deep traps in SrS：Eu^2＋, Dy^3＋.The afterglow intensity of SrS：Eu^2＋, Dy^3＋ was higher than that of SrS：Eu2＋ prepared at the same temperature.However, the minimization span of initial afterglow with temperature for the former sample was larger than that for the latter.Binary-doped phosphor decayed more slowly than the singly doped one.The afterglow of SrS：Eu^2＋, Dy^3＋ decayed more quickly with the increase of sintering temperature.

Synthesis of nanosized tungsten carbide from phenol formaldehyde resin coated precursors

Nanosized tungsten carbide was synthesized from phenol formaldehyde resin （PF） coated tungsten precursors. The process has three steps in which nanosized tungsten particles were first coated with PF, then the precursors were carburized at 950℃, and finally the carburized powders were treated in flowing wet hydrogen atmosphere at 940℃ to remove the uncombined carbon. The obtained powders were characterized using X-ray diffraction analysis （XRD）, field-emission scanning electron microscopy （FESEM）, small angle X-ray scattering （SAXS）, and combustion-gas-volume method. The results indicated that single-phase WC could be synthesized using excessive PF as carburizer at a much lower temperature compared with using mixed carbon black. After wet hydrogen treating, the mean size of the obtained WC particles was 94.5 nm and the total carbon content was 6.18 wt.%.

Synthesis of Nanosized SSZ-13 Zeolite and Performance of Its Mixed Matrix Membrane for CO2/CH4 Separation

Nanosized SSZ-13 zeolite was synthesized by traditional hydrothermal method using N,N,N-trimethyl-1-adamantanaminium hydroxide as the structure-directing agent (SDA). The influence of different preparative conditions of nanosized SSZ-13 was investigated systematically. The synthetic zeolites were characterized by X-ray powder diffraction (XRD), nitrogen physisorption, and scanning electron microscopy (SEM). By means of the self-assembled method, the thin SSZ-13/polyvinyl alcohol nanocomposite membranes were obtained by incorporating the nanosized SSZ-13 zeolite into the polymeric precursor (polyvinyl alcohol (PVA)). The permeation properties of pure CO2 and CH4 through the mixed matrix membranes (MMMs) were measured. The results showed that the highly crystalline SSZ-13 zeolite in a dispersed nanocrystal form with a controllable particle size of 100 nm could be hydrothermally synthesized by optimizing the synthetic parameters and the selectivity of CO2/CH4 of the MMMs could reach a value of 40 by changing the amount of nanosized SSZ-13 zeolite.

Indium tin oxide nanosized composite powder prepared using waste ITO target

Indium tin oxide （ITO） nano-particles were prepared directly using waste ITO target, which had been coated by magnetron controlled sputtering. The waste ITO target was cleaned with de-ionized water, and then dissolved in acid, filtrated, neutralized, manipulated through azeotropic distillation and finally dried, and in this way the precursor of indium tin hydroxide was obtained. The nanosized rio composite powder was prepared after the precursor heat-treated at 500℃ for 2 h. TEM images show a narrow distribution of particle size is 5-20 nm and the particle size can be controlled. Its granule has a spherical shape and the dispersion of the particle is well. X-ray diffraction （XRD） patterns indicate the only cubic In2O3 phase in the ITO powder hot-treated at 500℃. The purity of ITO composite powder is 99.9907%. The content of radium within filtrate was detected by using the EDTA titration of determination of indium in the ITO powder and ITO target. Appropriate amount of SnCl4.5H2O was dissolved in the filtrate, and then ITO powder containing 10 wt.% SnO2 was successfully prepared by heat-treating.

Synthesis and Photoconductivity of Nanosized Phthalocyanine

Functional phthalocyanine （Pc） compounds of H2Pc, TiOPc, FePc and CIAIPc were synthesized with a yield of 46.7%, 91.2%, 37.4% and 34.0%, respectively. Nanosized TiOPc was synthesized via a one-step sol-gel method and effects of surfactant doses, nucleation temperature on TiOPc particle size and photoconductivity were investigated. When re（PEG）： m（TiOPc） was 0.1 and nucleation temperature was 0℃, the as-obtained TiOPc had the smallest particle size and largest specific surface area, which were 60 nm and 83m^2/g, respectively. TiOPc synthesized under these conditions also exhibits excellent photoconductivity with charging potential V0, dark decay speed Rd and energy for half-discharging of potential E1/2 being 1160 V, 30 V/s and 0.6 1x.s, respectively.