扩散火焰中Cr2O3气溶胶尺寸研究

采用激光动态光散射测量技术,通过（氢气＋铬）／空气扩散火焰研究了含铬废物燃烧过程中Cr2O3的气溶胶颗粒尺寸。通过求解轴对称形式的Navier-Stokes方程,计算出流场、温度场和组分（包括颗粒）浓度,采用离散分区模型对Cr2O3气溶胶颗粒进行了数值模拟。     

开放体系下碳热还原氮化法制备(Cr,Ta)_2CN固溶体粉末的研究

以Cr2O3、Ta2O5和纳米碳黑为原料,在开放体系的流动N2气氛条件下,采用碳热还原氮化法制备出了(Cr,Ta)2CN固溶体粉末,利用XRD、SEM、EDS等分析测试手段对制备过程中的物相演变规律和微观形貌变化进行了研究。研究结果表明,碳热还原氮化法制备(Cr,Ta)2CN固溶体粉末过程中物相演变顺序为Cr2O3、Ta2O5、C→Cr2O3、Cr3C2、Cr7C3、Cr Ta O4、C→Cr2O3、Cr7C3、Cr Ta O4→(Cr,Ta)2CN。在N2流量为500 m L/min、烧结温度为1 500℃保温2 h的条件下,可制备出粒度约5μm、游离碳和氧含量分别为0.16%,0.085%的单相(Cr,Ta)2CN固溶体粉末。     

粉煤灰提铝残渣特性及处理Cr3+酸性溶液的研究

为了实现对粉煤灰提取氧化铝残渣的利用,对粉煤灰提铝残渣的颗粒特性及处理含Cr3+酸性溶液的效果与机理进行研究,通过对该粉煤灰提铝残渣进行化学成分、物相、比表面积、形貌等分析,对残渣的颗粒特性进行分析研究。结果表明:该残渣化学成分主要为Ca(OH)2、Ca2Si O4,结构疏松多孔,具有较大的比表面积,并且具有强碱性;基于残渣的特点,将其用于处理含重金属Cr3+的酸性溶液,用0.12 g的残渣可使100 m L Cr2(SO4)3质量分数为1.598×10-3的酸性溶液中Cr3+去除率达到99%,溶液p H由2.54增大为6.01;处理后的Cr3+几乎完全以Cr2O3形式沉淀。     

基于铝锆鞣制废弃物制备Al_2O_3-ZrO_2/MMT纳米复合材料及其应用研究

基于制革过程中铝锆鞣制废弃物制备铝锆双氧化物(Al2O3-ZrO2),采用Al2O3-ZrO2负载MMT片层制备铝锆双氧化物/蒙脱土(Al2O3-ZrO2/MMT)纳米复合材料。采用X射线衍射(XRD)、透射电镜(TEM)和扫描电镜(SEM)对Al2O3-ZrO2/MMT纳米复合材料进行表征,并对吸附Cr3+影响因素进行分析。结果表明,Al2O3-ZrO2进入MMT的片层间,所制备的Al2O3-ZrO2/MMT纳米复合材料属于插层型,吸附后的Al2O3-ZrO2/MMT表面有Cr3+存在,吸附Cr3+主要以表面吸附、离子交换和静电吸附为主;pH值4时,Cr3+的去除以吸附为主,pH值4时,Cr3+的去除以碱沉淀和吸附共同作用完成;含Cr3+废水中Na+和Ca2+离子的存在会抑制Al2O3-TiO2/MMT对Cr3+的吸附。     

电弧离子镀AlCrN沉积层初期氧化形貌、组构及反应机制

为了弄清AlCrN涂层在高温环境中的抗氧化机制,采用电弧离子镀技术制备了AlcrN涂层,对真空退火和短时氧化处理后的沉积层采用扫描电镜(SEM)、X射线衍射(XRD)分析和元素成分(EDS)进行了观察和分析.结果表明:真空退火处理的沉积层中CrN相逐渐转变为Cr2N,并释放出N2;在900,1000℃下氧化1～5 h,沉积层中部分Cr2N与O2反应生成Cr2O3,此时涂层的物相以Cr2N和Cr2O3为主,并含少量CrAlN相;氧化至10 h,沉积层表面生成以Cr2O3和Al2O3为主的氧化膜,此氧化膜的生成有利于涂层抗氧化性能的提高.     

粉末冶金Ag-Cr合金在纯氧气中的氧化

研究了粉末冶金Ag-35Cr(PM Ag 35Cr)和Ag-69Cr(PM Ag-69Cr)合金在700～800℃及0.1 MPa纯氧气中的氧化.PM Ag 35Cr合金在700～800℃纯氧气中氧化形成了复杂的氧化膜,包括Cr2O3、复合氧化物AgCrO2及其下面铬的内氧化区.PM Ag-69Cr合金形成了双层氧化膜,外层为复合氧化物AgCrO2,内层为Cr2O3,铬的内氧化被完全抑制.PM Ag-Cr合金在氧化过程中,铬向外的扩散受到合金中的两相及铬粒子颗粒较粗大等因素的限制,致使铬含量高达69%(质量分数,下同)时,合金氧化后也没有形成单一的Cr2O3外氧化膜.合金内氧化引起的体积膨胀导致在内氧化区出现压应力,使得PM Ag-35Cr合金氧化膜最外层出现了纯银.     

铬、铝、硅对铁基高温合金抗氧化性能的影响

采用正交设计的实验方法探讨了铬、铝、硅元素含量对铁基高温合金抗氧化性的影响规律。为获得稳定的抗氧化能力,上述各元素的含量应分别高于17%Cr,4%Al,1.5%Si。结果表明:当三元素同原子比时对铁基高温合金抗氧化性的影响次序为Si最大,Al次之,Cr最小。结构平坦、组织致密、颗粒细小均匀的氧化膜抗氧化性较好,反之较差。当氧化膜由Cr2O3,Al2O3,SiO2,Fe(Ni)Cr2O4多种氧化物组成复合氧化膜时于1250℃表现为强抗氧化性,当缺少Al2O3或SiO2时表现为弱抗氧化性。     

ZnO及填料对磷酸铬铝基复合材料性能的影响

以磷酸铬铝(ACP)为基体,高硅氧纤维布为增强材料,Cr2O3和Al2O3为填料,通过热压成型制得磷酸铬铝基复合材料。采用TG-DSC和XRD等探讨了磷酸铬铝基体的固化特性和耐热性能,并研究了复合填料、纳米填料及热压工艺对材料力学性能的影响。结果表明,ZnO可以降低磷酸铬铝的固化温度并促进其晶型转变;复合填料Cr2O3和Al2O3可以提高材料的耐热性,当Cr2O3和Al2O3之比为7∶3且纳米Cr2O3加入量为5%时,复合材料的力学性能最好,其拉伸强度为95.2MPa,弯曲强度为190.02MPa。     

电沉积-热解法制备Cr2O3薄膜及其抗高温氧化性能

Cr2O3薄膜具有保护性,采用电沉积-热解法制备还未见报道.采用电沉积-热解法在304不锈钢表面制备Cr2O3薄膜,并将其于900℃高温氧化100 h,研究了电沉积溶液[Cr(NO3)3酒精]浓度、沉积电压对Cr2O3薄膜抗高温氧化性能的影响,分析高温氧化样的组织结构.结果表明:电沉积-热解法制备的Cr2O3薄膜显著提高了304不锈钢的抗高温氧化性能;沉积电压为25 V,电沉积溶液浓度为0.10 mol/L条件下制备的Cr2O3薄膜抗高温氧化性能最佳.     

Zn2+、Cr3+掺杂对水热合成纳米CoAl2O4尖晶石色料的影响

以CoCl2·6H2O、ZnCl2、AlCl3和CrCl3·6H2O为原料,采用水热法合成了CoAl2O4(AB2O4)尖晶石型纳米钴蓝色料.采用色度分析、X射线衍射(XRD)、透射电镜(TEM)以及高分辨透射电镜(HRTEM)等研究了A位掺杂Zn2+和B位掺杂Cr3+时不同掺杂量以及不同水热合成温度对样品呈色、晶相组成及CoAl2O4尖晶石的晶粒大小、发育程度和晶面间距的影响.结果表明,掺杂Zn2+、Cr3+所得固溶体型钴蓝色料晶粒发育均不完整,颗粒较于相同水热条件下获得的未掺杂样品更细小.A位掺杂Zn2+可降低CoAl2O4色料的合成温度,在230℃便能制得呈色较佳的Co0.95Zn0.05Al2O4钴蓝色料.随着Zn2+掺杂量的增加,合成产物由蓝色转为绿色,且呈色逐渐变浅.B位Cr3+掺杂则随着掺杂量的增加,产物从蓝色逐步转为绿色,但呈色逐渐变深.就两者相比较,A位掺杂Zn2+更有利于色料明度值的提高而呈色鲜亮.     

Determination of inlet transmission and conversion efficiencies for in situ measurements of the nocturnal nitrogen oxides, NO3, N2O5 and NO2, via pulsed cavity ring-down spectroscopy

Pulsed cavity ring-down spectroscopy is a highly sensitive method for direct absorption spectroscopy that has been applied to in situ detection of NO3, N2O5 and NO2 in the atmosphere from a variety of platforms, including ships, aircraft, and towers. In this paper, we report the development of schemes to significantly improve the accuracy of these measurements. This includes the following: (1) an overall improvement in the inlet transmission efficiencies (92 +/- 2% for NO3 and 97 +/- 1% for N2O5) achieved primarily through a reduction in the inlet residence time; and (2) the development of a calibration procedure that allows regular determination of these efficiencies in the field by addition of NO3 or N2O5 to the inlet from a portable source followed by conversion of NO3 to NO2. In addition, the dependence of the instrument's sensitivity and accuracy to a variety of conditions encountered in the field, including variations in relative humidity, aerosol loading, and VOC levels, was systematically investigated. The rate of degradation of N2O5 transmission efficiency on the inlet and filter system due to the accumulation of inorganic aerosol was determined, such that the frequency of filter changes required for accurate measurements could be defined. In the absence of aerosol, the presence of varying levels of relative humidity and reactive VOC were found to be unimportant factors in the instrument's performance. The 1 sigma accuracy of the NO3, N2O5, and NO2 measured with this instrument are -9/+12, -8/+11, +/- 6%, respectively, where the -/+ signs indicate that the actual value is low/high relative to the measurement. The largest contribution to the overall uncertainty is now due to the NO3 absorption cross section rather than the inlet transmission efficiency.     

Simultaneous stratospheric gas and aerosol retrievals from broadband infrared occultation measurements

The inversion method for simultaneous gas (O3, NO2, HNO3, N2O, CH4, H2O, CFC-11, CFC-12, N2O5, and ClONO2) and aerosol retrievals from broadband continuous IR spectra of occultation measurements is described. Both gas and aerosol physical modeling with consideration of the multicomponent character of aerosol and polar stratospheric clouds (PSCs) are used to minimize the difference between measured and modeled transmittance spectra under smoothness constraints imposed on particle-size distributions for each PSC component and positive constraints on all gas and aerosol parameters. The method is tested by numerical simulations in which synthetic occultation measurements inherent to the improved limb atmospheric spectrometer are used. The study reveals that the method has significant advantages over other approaches based on offset or gas-window-channel aerosol correction for accurate gas retrievals and provides additional information on the particle-size composition, volume density, and chemical component character of PSCs.     

Extent of oxidation of Cr(III) to Cr(VI) under various conditions pertaining to natural environment

Calculations show that oxidation of chromium oxide (Cr2O3) by oxygen and oxidation of chromium hydroxide (Cr(OH)3) by manganese dioxide (MnO2) are thermodynamically feasible in both aerobic and mildly anoxic environments. Experiments were carried out to determine the rate and extent of chromium oxidation under various conditions, i.e., when Cr2O3 was heated in the presence of oxygen, when Cr(OH)3 and MnO2 mixtures were suspended in aerobic or anoxic aqueous media at various pH values, when Cr(OH)3 and MnO2 mixtures interacted in moist aerobic conditions and when chromium assumed to be Cr(OH)3 and manganese assumed to be MnO2 interacted in the presence of competing electron donors/acceptors, as is the case in chromium-contaminated sludge. Results indicate that trivalent chromium in Cr2O3 could be readily converted to hexavalent chromium at a temperature range of 200-300 degrees C, with conversion rates of up to 50% in 12 h. In aqueous media, Cr(OH)3 was slowly converted to dissolved Cr(VI) in the presence of MnO2, both in aerobic and anoxic conditions, with conversion rates of up to 1% in 60 days. In moist aerobic conditions and in the presence of MnO2, Cr(OH)(3) slowly converted to hexavalent chromium, with up to 0.05% conversion observed in 90 days. Chromium oxidation also occurred in sludge samples, especially under aerobic conditions. However, such transformation was found to be transitory, with the Cr(VI) formed being ultimately reduced back to Cr(III) due to the presence of various reducing agents in the sludge. Nevertheless since up to 17% conversion of Cr(III) to Cr(VI) occurred in sludge under aerobic conditions by 30 days, there is real danger under field conditions of spreading Cr(VI) pollution due to possible intervening rainfall, runoff and percolation.     

Cr2O3对Al2O3基渣系黏度的影响

铝热还原制备铜铬合金时,合金中会存在气孔以及Al2O3、Cr2O3等夹杂物,采用电渣重熔工艺可有效去除气孔及夹杂物等缺陷。采用内柱体旋转法测量了不同组成的CaO-Al2O3-Cr2O3、CaO-Al2O3-CaF2-Cr2O3渣系的黏度,采用XRD技术分析了高温熔炼渣的物相,并计算了各渣样的黏流活化能。研究结果表明,当碱度不变时,随着CaO-Al2O3中Cr2O3含量的增加,渣样的黏度逐渐降低。当Cr2O3含量为4%时,下降的趋势很大,当Cr2O3含量为2%时黏度下降趋势平缓,当渣系中Cr2O3含量较高时会出现Ca3Al2O6等高熔点相,造成渣黏度增大。CaO-Al2O3-CaF2-Cr2O3渣的高温黏度较低,1500℃时渣样的粘度均小于0.1Pa.s。渣系的黏流活化能变化趋势与渣样的黏度值变化趋势一致。     

碳热还原法制取碳化铬、金属铬的热力学分析

分析了以Cr2O3和C为原料用碳热还原法制取Cr3C2和金属铬的热力学原理.结果表明, Cr2O3的碳热还原反应机理有2种,即主要依靠CO/CO2传质的气-固反应以及碳与Cr2O3之间固相扩散传质的固-固反应.前者的反应温度低于后者,何种反应机理占主导地位取决于Cr2O3和C的初始混合态.无论制取Cr3C2还是金属铬,最好都在真空气氛下进行,制取Cr3C2的反应温度比制取金属铬的低,制取金属铬的真空度不宜太高.     

Electrical Conductivity of Sintered Chromia Mixed with TiO2, CuO and Mn-Oxides

The electrical conductivity of sintered Cr2O3 mixed with 2% and 5% （in molar fraction） TiO2 or CuO was investigated in the temperature range 500-900℃ in air and in At/4 vol. pct H2 atmospheres. The effect of different Mn-oxides on the electrical conductivity of Cr2O3 was also studied under the same conditions. From the conductivity measurements it is established that additions of TiO2 change the defect structure of Cr2O3 and the effect of TiO2 on the electrical conductivity is controlled by TiO2 concentration as well as temperature and O2 partial pressure of the surrounding atmosphere. The conductivity of Cr2O3 increased in air and decreased in the At/H2 atmosphere by CuO additions. The effect of CuO was discussed with possible changes in the defect concentration in Cr2O3. Mixing of Cr2O3 with different Mn-oxides at the same Mn to metal atom fraction decreased the conductivity in air and in Ar/H2 atmospheres. No clear correlation between the spinel fraction and the changes in conductivity could be found.     

TiO_2-Fe_3O_4/MIL-101(Cr)磁性复合光催化材料的制备及其光催化性能

采用原位水热法合成了TiO_2-Fe_3O_4/MIL-101(Cr)磁性复合光催化材料,利用XRD、SEM、UV-Vis DRS、BET和磁学测量系统对复合光催化材料的结构和性能进行了表征,并以亚甲基蓝(MB)为模拟污染物,研究了该复合光催化材料的可见光催化活性,并考察了光催化材料的稳定性。结果表明:巯基官能化的Fe_3O_4和TiO_2与MIL-101(Cr)结合成功,复合后的TiO_2-Fe_3O_4/MIL-101(Cr)光催化材料的可见光响应范围得到明显拓宽;当TiO_2的添加量为400mg时所制得的磁性复合光催化材料具有相对较好的光催化降解效果,经过120min光照后,对MB的去除率高达80%;该磁性复合光催化材料具有良好的稳定性和磁分离性能。     

涡街流量计在四氧化二氮加注系统中的腐蚀产物分析

航天发射场加注库房数字式涡街流量计在四氧化二氮加注系统中长期使用,会致使其表面形成一定的腐蚀产物,改变其精度与准确性,进而影响加注量.为探讨其腐蚀产物的成分及形成机理,采用FEI场发射电子扫描电镜(SEM)、能谱分析仪(EDAX)和X射线光电子能谱仪(XPS)分别对腐蚀产物的表面形貌、组成含量及其存在形态进行了表征.结...     

C@K2Ti6O13分级纳米材料对Cr(VI)的吸附去除

Cr(VI)具有非常大的生物毒性, 去除溶液中的Cr(VI)是当前的一个研究热点。本研究制备了C@K₂Ti₆O₁₃分级纳米材料, 并用不同表征手段对材料的物相和结构等进行表征, 进一步探究了初始pH、吸附时间、离子强度等对C@K₂Ti₆O₁₃复合纳米结构吸附Cr(VI)的影响。实验结果表明C@K₂Ti₆O₁₃复合纳米结构对Cr(VI)有较强的吸附能力, 1 h内去除率能够达到50%以上, 其吸附动力学符合准二级动力学模型, 吸附热力学符合Langmuir等温吸附模型, 表明这种分级纳米材料在环境治理方面应用潜力巨大。     

New method for simultaneous gas and aerosol retrievals from space limb-scanning spectral observation of the atmosphere

This study concerns the development of a new inversion method for simultaneous gas and aerosol retrievals in the upper layers of the atmosphere from limb-viewing multiwavelength-transmission infrared measurements. In this method, concentrations of gas species such as O3, NO2, HNO3, N2O, CH4, and H2O, and spectral dependences of the aerosol extinction coefficient are retrieved simultaneously. When this is done, smoothness constraints on the desired spectral dependencies of the aerosol extinction coefficient are used as an a priori assumption. The method is used in the treating of synthetic transmission spectra of the Improved Limb Atmospheric Spectrometer, which is based on the solar occultation technique and was on board the Advanced Earth Observing Satellite. A set of numerical tests shows the efficiency of the method.