Chemical quenching and inhibition of positronium in Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

The pore structure of Cr2O3/Al2O3 catalysts and the surface chemical properties of these pores were characterized by positron lifetime and coincidence Doppler broadening (CDB) measurements. Four lifetime components could be resolved from the positron lifetime spectrum, with two long lifetime components and two short lifetime components. The two long lifetimes τ4 and τ3 are attributed to ortho-positronium (o-Ps) annihilation in large pores and microvoids, respectively. With increasing Cr2O3 content, both τ4 and its intensity I4 show sharp decrease, while τ3 and its intensity I3 keep nearly unchanged. The Doppler broadening S parameters also show sharp decrease with increasing Cr2O3 content. Detailed analysis of the CDB spectrum reveals that the parapositronium (p-Ps) intensity also decreases with increasing Cr2O3 content. This indicates that the change of o-Ps lifetime τ4 is due to the chemical quenching by Cr2O3 but not spin-conversion of positronium. The decrease of o-Ps intensity I4 indicates that Cr2O3 also inhibits positronium formation.     

Influence of target-substrate distance and sputtering power on chromium oxide films prepared by medium-frequency magnetron sputtering

Chromium oxide films were deposited on Si (100) substrates by medium-frequency (MF) unbalanced magnetron sputtering at different target-substrate distances D _TS (60, 100, 120 mm) and sputtering power (2.8, 5.6, 11.2 kW), respectively. The structure, surface morphologies, and microhardness of the chromium oxide films were examined by X-ray diffraction (XRD), atomic force microscopy (AFM), and microhardness tester. The results indicate that elevated MF sputtering power can improve the crystallization of the films; The D _TS value affects the structure of the films by changing the preferential orientation from CrO₃ (221) to Cr₂O₃ (116); The microhardness of the chromium oxide films is found to increase with the sputtering power. For preparing the Cr₂O₃-dominated films with comparatively high-performance, the optimized condition is the target-substrate distance of 100 mm and MF sputtering power of 11.2 kW.     

Wear properties of NiAl based materials

The NiAl based materials including NiAl-TiC-Al2O3 composite,NiAl-Cr(Mo)-Hf-Ho eutectic alloy and NiAl-Cr(Mo)-CrxSy in situ composite were fabricated and their wear properties were tested at different temperatures.The results revealed that the NiAl-TiC-Al2O3 composite,NiAl-Cr(Mo)-Hf-Ho eutectic alloy and NiAl-Cr(Mo)-CrxSy in situ composite exhibited the excellent wear properties between 700℃ and 900℃.The microstructure observations exhibited that the self-lubricant films formed on the worn surfaces during the dry sliding test at high temperature,which decreased the wear rate and friction coefficient significantly.TEM observation on the self-lubricant film revealed that it was mainly comprised by ceramic amorphous and nanocrystalline.Compared with the NiAl-TiC-Al2O3 composite,the NiAl-Cr(Mo)-CrxSy in situ composite has lower friction coefficient at low temperature.Such phenomena may be ascribed to the addition of sulfide which contributes much to the formation of self-lubricant,and moreover the TiC addition increase the strength of NiAl based material and its wear resistance.     

Effect of FeO on the formation of spinel phases and chromium distribution in the CaO-SiO2-MgO-Al2O3-Cr2O3 system

Synthetic slag samples of the CaO-SiO₂-MgO-Al₂O₃-Cr₂O₃ system were obtained to clarify the effect of FeO on the formation of spinel phases and Cr distribution. X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS), as well as the thermodynamic software FactSage 6.2, were used for sample characterization. The results show that the addition of FeO can decrease the viscosity of molten slag and the precipitation temperatures of melilite and merwinite. The solidus temperature significantly decreases from 1400 to 1250°C with the increase of FeO content from 0wt% to 6wt%. The addition of FeO could enhance the content of Cr in spinel phases and reduce the content of Cr in soluble minerals, such as merwinite, melilite, and dicalcium silicate. Hence, the addition of FeO is conducive to decreasing Cr leaching.     

Comparative study on the corrosion behavior of X52, 3Cr,and 13Cr steel in an O2-H2O-CO2 system:products,reaction kinetics,and pitting sensitivity

The corrosion behaviors of X52, 3Cr low-alloy steel, and 13Cr stainless steel were investigated in an O₂-H₂O-CO₂ environment at various temperatures and O₂-CO₂ partial-pressure ratios. The results showed that the corrosion rates of X52, 3Cr, and 13Cr steels increased with increasing temperature. The corrosion rates slowly increased at temperatures less than 100℃ and increased sharply when the temperature exceeded 100℃. In the absence of O₂, X52, 3Cr, and 13Cr exhibited uniform corrosion morphology and FeCO₃ was the main corrosion product. When O₂ was introduced into the system, various forms of Fe₂O₃ appeared on the surface of the samples. The Cr content strongly influenced the corrosion resistance. The 3Cr steel with a low Cr content was more sensitive to pitting than the X52 or 13Cr steel. Thus, pitting occurred on the surface of 3Cr when 1.25 MPa of O₂ was added; this phenomenon is related to the non-uniform distribution of Cr in 3Cr.     

FeO影响CaO-SiO_2-MgO-Al_2O_3-Cr_2O_3体系中含铬尖晶石晶体析出的热力学分析

不锈钢渣中的铬以尖晶石矿物相状态赋存时不易溶出,有利于钢渣的资源化利用。本文基于熔体非平衡凝固理论,采用热力学数据库FactSage 7.0研究了FeO添加量对CaO-SiO_2-MgO-Al_2O_3-Cr_2O_3不锈钢渣体系中尖晶石晶体析出温度、析出量、化学组成及铬元素赋存状态的影响规律。模拟计算结果表明,尖晶石晶体为高温析出相,主要由MgCr_2O_4和FeCr_2O_4组成;随着FeO添加量不断增多,尖晶石晶体的析出温度逐渐降低,其最终析出量逐渐增加,析出物中FeCr_2O_4所占比例增加而MgCr_2O_4相对减少;铬元素的赋存状态未受FeO添加量变化影响,仍以尖晶石固溶体形式存在。     

Flow-injection microcolumn on-line preconcentration for the determination of chromium (VI)

A rapid and sensitive on-line preconcentration method for spectrophotometric determination of chromium (VI) in nature water is described. Preconcentration and determination are based on (i) the quantitative and fast adsorption of chromium (VI) on the high surface area nanometer-size TiO₂ (anatase) powders, which prepared by a sol-gel method from hydrolysis of TiCl₄ and (ii) the quantitative and reproducible elution of Cr (VI) by 2.0 mol·L⁻¹ HCl. A mini-column system for preconcentration is developed, Cr(VI) on the mini-column is eluted and merged with a stream water and DPCB (1,5-diphenylcarbazide) as the chromogenic reagent. The proposed system permits throughputs of 6 sample h⁻¹ (0.001 μg·mL⁻¹ Cr(VI)) or 20 sample h⁻¹ (0.1 μg·mL⁻¹ Cr(VI)). The preconcentration factor is 55. The detection limit is 0.8 ng · mL⁻¹ Cr(VI). The reproducibility is satisfactory with a relative standard deviation of less than 3.35% (0.01 μg·mL⁻¹ Cr(VI),n=5). Supported by the National Natural Science Foundation of China Ma Wanhong: born in 1961, Ph. D. Graduate student, Associate professor     

氯化锌改性玉米秸秆生物炭对Cr(Ⅵ)的吸附特性研究

为了提高对废水中Cr （Ⅵ）的去除效率,获得高效且成本低廉的吸附剂,以农业废弃物玉米秸秆为原材料制备生物炭,并采用氯化锌对其进行改性。实验表明,在固液比为2 g/L、pH为2、Cr （Ⅵ）溶液初始质量浓度为100 mg/L、吸附时间为6 h时,最佳改性剂比例条件下改性炭的去除率能够达到99.3%,比未改性的生物炭高73.7%。此外,考察了单一因素改性剂比例、溶液pH、吸附温度、离子强度对吸附效果的影响。同时研究了改性炭对Cr（Ⅵ）的吸附动力学和吸附等温线。结果说明该吸附是自发、熵增的吸热过程且吸附反应符合准二级动力学方程和Langmiur等温模型,最大饱和吸附容量为72.46 mg/g。通过扫描电镜（scanning electron microscopy）、傅里叶红外光谱（Fourier transform infrared spectroscopy）、X射线衍射（X-ray diffraction）等方法对原炭（biochar）和改性生物炭（modified biochar）进行表征,分析表明改性炭微孔结构明显,表面粗糙,吸附位点增加,芳香化程度提高,从而提高了吸附性能,且锌以氢氧化物颗粒形式存在于生物炭表面。     

镍基合金CMSX-4在3.5wt.% NaCl溶液中的腐蚀行为

研究二代镍基合金CMSX-4在质量分数为3.5% NaCl溶液中的腐蚀行为,对该类合金在海洋性环境条件下的应用具有深远意义。通过动电位极化方法研究室温条件下镍基合金CMSX-4在3.5 wt.% NaCl溶液中的电化学行为,利用扫描电子显微镜（SEM）、能谱分析仪（EDS）和X射线光电子能谱仪（XPS）对合金表面阳极腐蚀产物进行微观形貌观察及成分分析。研究表明,CMSX-4合金具有一定的钝化能力,钝化区间比较宽广;在镍基合金CMSX-4表面上形成的腐蚀产物可大致分为两层,表层主要由Ni （OH）₂、Cr （OH）₃、Co （OH）₂和Al （OH）₃等氢氧化物组成,内层主要分布着NiO、Al₂O₃、CoO、Cr₂O₃和CrO₃等氧化物及组成合金基体的各种金属;由Ni （OH）₂和Cr （OH）₃等氢氧化物组成的腐蚀产物膜外层能够在腐蚀介质和金属之间产生较好的屏蔽效果;构成腐蚀产物膜内层的NiO、Al₂O₃、Cr₂O₃和CrO₃等氧化物有利于产物膜内层与外层之间建立一定的空间电荷区,对稳定腐蚀产物内层有很大帮助。研究表明CMSX-4合金在海洋性环境中具有一定的耐蚀性能。     

High-temperature frictional wear behavior of MCrAlY-based coatings deposited by atmosphere plasma spraying

Al₂O₃-Cr₂O₃/NiCoCrAlYTa coatings were prepared via atmosphere plasma spraying (APS). The microstructure and phase composition of the coatings were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), laser confocal scanning microscopy (LSCM), and transmission electron microscopy (TEM). The dry frictional wear behavior of the coatings at 500℃ in static air was investigated and compared with that of 0Cr25Ni20 steel. The results show that the coatings comprise the slatted layers of oxide phases, unmelted particles, and pores. The hot abrasive resistance of the coatings is enhanced compared to that of 0Cr25Ni20, and their mass loss is approximately one-fifteenth that of 0Cr25Ni20 steel. The main wear failure mechanisms of the coatings are abrasive wear, fatigue wear, and adhesive wear.     

Transition-metal-doped Fe2O3 nanoparticles for oxygen evolution reaction

Hematite(α-Fe_2O_3)has been extensively studied as a promising photocatalyst,with the capacity to split water under visible light.To tune its electronic structure and improve the performance for oxygen evolution reaction(OER),high-quality single crystals ofα-Fe_2O_3nanoparticles were synthesized and doped by various transition metals(M=V,Cr,Mn,Zn,Co,Ni,Cu,Nb,Mo,Ti)by a molten-salt flux method.Optical,electronic and catalytic properties of transition-metal-dopedα-Fe_2O_3(TM-dopedα-Fe_2O_3)have been systematically investigated.Cobalt has been identified as the best dopant forα-Fe_2O_3,reducing the OER overpotential by 0.16 V with respect to the undoped.     

One-step disposal of Cr (Ⅵ)-bearing wastewater by natural pyrrhotite

Cr(VI)-bearing wastewater can be treated by natural pyrrhotite which is used for reductant to reduce Cr(VI) and precipitant to precipitate Cr(III) simultaneously. The disposal products can be divided into three parts in the beakers, namely supernatant in the upper part, the yellowish colloidal precipitates in the middle part and the pyrrhotite in the lower part. The content of total Cr=Cr(VI)+Cr(III) in the supernatant liquid is 0.06 mg/L, which is lower than 1.5 mg/L of the discharge standard of China and near to 0.05 mg/L of the standard of potable water. This one-step disposal composing of both reduction and precipitation which is traditionally divided into two independent steps called reducing technology and precipitating technology respectively. The new method is of obvious economic advantage and favourable to decreasing surplus mud derived from adding Ca(OH)₂ to precipitate Cr(III) traditionally so as to avoid recontamination. In fact, sodium sulfite (Na₂SO₃) used in disposal of Cr(VI) was traditionally produced from natural mineral of pyrrhotite (FeS). One molecule of FeS is 4 times more than that of Na₂SO₃ from a view point of rational use of mineral resources. Therefore the prospective of application of the one-step disposal of Cr(VI) method is full of promise.     

镀锡钢板铬酸盐钝化膜的X射线光电子谱分析

使用X射线光电子能谱(XPS)全元素扫描分析方法对镀锡钢板铬酸盐钝化膜的成分进行了分析研究.结果表明,组成钝化膜的主要元素为Cr,O,Sn和C.通过Ar+溅射对钝化膜进行深度剖析表明,C元素来自于表面的污染而不是膜层本身;Cr和O元素随着Ar+溅射的进行含量逐渐降低,而Sn元素的含量却逐渐增加.溅射约360 s后,Sn元素的含量已达到了80%以上,此时所对应的钝化膜的厚度约为20 nm.通过窄幅扫描对钝化膜的相组成进行了分析,结果表明钝化膜主要由Cr(OH)3,Cr2O3,Sn及其氧化物构成.     

Carbothermal reduction process of the Fe-Cr-O system

Understanding the reduction behaviors and characteristics of the end products of Fe-Cr-O systems is very important not only for maximizing the recovery of metals from stainless steel dust but also for the subsequent reuse in metallurgical process. The present work first predicted the possible products thermodynamically when FeCr₂O₄ was reduced by C. The reduction behaviors by graphite of three kinds of Fe-Cr-O systems, i.e., FeCr₂O₄, Fe₂O₃+Cr₂O₃, and Fe+Cr₂O₃, were then investigated in 1350–1550℃. Further, the microstructures of final products and element distribution conditions were examined. The results suggest that, thermodynamically, the mass of products for the carbothermal reduction of FeCr₂O₄ is a strong function of temperature, and the initial carbon content is used. More Fe-Cr-C solution and less residual carbon content are obtained at higher temperatures and lower n_C:n_O ratios (the initial molar ratio of C to O in the sample). Experimental data show that the sample amount tends to affect the reduction rate, and the residual carbon content strongly depends on n_C:n_O. With regard to the phases present in products during the reaction process, metal carbides tend to form in the initial stage, whereas Fe-Cr-C solution forms when the degree of reduction is sufficiently high.     

Ni/α-Al2O3催化剂上甲烷水蒸气重整本征动力学

在消除扩散影响的条件下，在装填工业Ni/α-Al₂O₃催化剂的微分反应器内进行了甲烷水蒸气重整的本征动力学研究。实验证明在低产物浓度时H_2, CO和CO₂为主要产物，且两者的生成速率均与CH₄分压成正比，同时CO的生成速率与CO₂分压成正比关系，而CO₂的生成速率与H₂O分压成正比关系。考虑了5种可能的模型推导了本征动力学方程，通过参数估计和模型比较确定了比较满意的甲烷水蒸气重整本征动力学方程。     

Sintering behavior of Cr in different atmospheres and its effect on the microstructure and properties of copper-based composite materials

Copper matrix composites consisting of chromium (Cr) or ferrochrome (Cr-Fe) as strengthening elements and molybdenum disulfide as a lubricant had been sintered in nitrogen and hydrogen atmosphere, respectively. Their morphology and energy-dispersive X-ray spectrometry (EDS) analysis showed that serious interaction occurred between MoS₂ and Cr (or Cr-Fe) particles when the samples were sintered in hydrogen atmosphere. Chromium sulfide compound (Cr_xS_y) was formed as a reaction product, which decreased the density and strength of the composites remarkably. This interaction was inhibited when the samples were sintered in nitrogen atmosphere; thus, the mechanical properties of the composites were improved.     

Modulation of active Cr(III) complexes by bath preparation to adjust Cr(III) electrodeposition

The preparation process of the Cr(III) bath was studied based on a perspective of accelerating the formation of active Cr(III) complexes. The results of ultraviolet-visible absorption spectroscopy (UV-Vis) and electrodeposition showed that active Cr(III) complexes in the bath prepared at room temperature in several days were rare for depositing chromium. The increase of heating temperature, time, and pH value during the bath preparation promoted the formation of active Cr(III) complexes. The chromium deposition rate increased with the concentration of active Cr(III) complexes increasing. Increasing the heating temperature from 60 to 96℃, the chromium deposition rate increased from 0.40 to 0.71 μm/min. When the concentration of active Cr(III) complexes increased, the grain size of Cr coatings increased, and the carbon content of the coating decreased. It is deduced that Cr(H₂O)₄(OH)L2+ (L is an organic ligand, and its valence is omitted) is a primary active Cr(III) complex.     

Vapor phase codeposition of Cr and Si on Nb-base in situ composites by pack cementation process

In order to identify suitable halide activators and pack compositions for codepositing Cr and Si to form diffusion coatings on Nb-base in situ composites by the pack cementation process, thermochemical calculation was taken to analyze the vapor pressure of halide species generated at high temperatures. NH4Cl, NaF and CrCl3·6H2O were selected as the halide salts. The results of thermochemical calculations suggested that the pack powder mixtures, which contained Cr, Si, halide salts and Al2O3, may be activated by NH4Cl and NaF. According to the thermochemical calculations, the pack powder mixture of 12Cr-6Si-5NH4Cl-77Al2O3 (wt%) activated by NH4Cl was formulated and coating deposition experiments were carried out at 1200 and 1300℃. With adequate control of pack compositions and deposition conditions, it was found that codeposition of Cr and Si could indeed be achieved at these temperatures. The coating has a three-layer structure, of which was mainly composed of Cr2(Nb,X) (X represents Ti and Hf elements), Nb5Si3 and (Nb,Cr)3Si. Then the kinetics of coating growth process affected by temperature was studied. The experimental results of the oxidation showed that the coating can efficiently prevent substrate from oxidizing.     

Degradation of organic pollutants by a Co3O4-graphite composite electrode in an electro-Fenton-like system

A novel composite electrode was constructed by pressing together Co3O4 and graphite and it was used as the cathode in an electro-Fenton-like (EFL) system. The poor electron transport characteristic of Co3O4 was overcome by incorporating graphite. In situ electro-catalytic generation of hydroxyl radicals (·OH) occurred at high current efficiencies from pH 2-10, extending the traditional Fenton reaction pH range. Cyclic voltammetry and AC impedance spectrometry were used to characterize the composite electrode. The ability of the EFL system to degrade organic compounds was investigated using sulforhodamine B (SRB) and 2,4-dichlorophenol (2,4-DCP) as probes. Decoloration of SRB (1.0×10-5 mol/L) was complete (100%) in 150 min and SRB was effectively degraded from pH 2-10. The decomposition of SRB was studied using Fourier transform infrared spectroscopy (FT-IR) and total organic carbon (TOC) analysis and results indicated that the final degradation products were carbon dioxide, carboxylic acids and amines. The EFL system also decomposed 2,4-DCP and the degradation was 98.6% in 240 min. Electro-catalytic degradation of SRB occurs by a ·OH mechanism. After 5 times reused, the degradation rate of SRB did not significantly slow down. The electrode shows excellent potential for use in advanced oxidation processes (AOPs) used to treat persistent organic pollutants (POPs) in wastewater.     

壳聚糖螯合铬(Ⅵ)的稳定常数测定及螯合效果分析

为了考察壳聚糖（CTS）对重金属离子铬(VI)的螯合性能,利用紫外分光光度法对壳聚糖螯合铬(VI)的机理进行了研究,测定了不同c(Cr6+)/c(-NH3+)浓度比下壳聚糖-铬(Ⅵ)螯合物的紫外吸收光谱,确定了螯合物的配位比并计算了稳定常数。结果表明：壳聚糖对铬(VI)具有螯合作用,在不同壳聚糖氨根配体浓度下,当c(Cr6+)/c(-NH3+)≥0.5时,螯合反应达到平衡;壳聚糖中主要配体-NH2基团与铬(VI)按物质的量比2:1形成螯合物,壳聚糖铬(VI)螯合物的稳定常数为1.212×108。通过实验考察了壳聚糖用量、体系pH值对壳聚糖螯合铬(Ⅵ)离子效果的影响。结果表明：壳聚糖用量为0.15 g·L-1,反应酸碱度为pH=4的弱酸环境时,铬(VI)离子去除率可达到87.5%。