Experimental and DFT study on cerium inclusions in clean steels

To provide insights into deforming Ce-O-S-Al inclusions in steels and improving the mechanical properties,the evolution process of such harmful inclusions in clean steels was investigated by thermodynamic calculation,metallographic examination and first-principles calculation in this paper.For the tested IF steel,the thermodynamic analysis results are consistent with the calculated formation enthalpy.After Ce addition,the inclusions are transformed from Al₂O₃and TiN-Al₂TiO₅-Al₂O₃to Ce2O₃,Ce₂O₂S,CeAlO₃,TiN-Al₂TiO₅-Ce₂O₃and TiN-Al₂TiO₅-Ce₂O₂S composite inclusions,which can be confirmed by metallographic examination.The elastic constants were calculated,and the bulk modulus,Young's modulus,shear modulus and Poisson's ratio were evaluated by the Voigt-Reuss-Hill(VRH)approximation.All inclusions except Ce₂O₃show apparent brittleness.TiN,Al₂O₃,Al₂TiO₅and CeAlO₃present much higher hardness than iron matrix,while the hardness of Ce2O₃or Ce₂O₂S is close to that of iron matrix.The thermal expansion coefficients of Ce₂O₃and CeAlO₃are close to that of iron matrix,whereas,Ce₂O₂S inclusion has largely different thermal expansion coefficient from iron matrix and may deteriorate the steel performance at higher temperatures.The relatively small differences between Ce inclusions and iron matrix in terms of hardness,toughness,brittleness,and thermal expansion coefficient can explain the improvement of the mechanical properties of the tested steel.     

Dysprosium cerate nanostructures:facile synthesis,characterization,optical and photocatalytic properties

A facile approach was developed to prepare Dy_2Ce_2O_7 nanostructures. Dy_2Ce_2O_7 nanostructures were prepared by applying cerium(IV) ammonium nitrate and dysprosium nitrate as Ce and Dy precursors. It was found that the kind of connecting agent, space-filling template and chelating agent were significant factors for the control in shape and size. Transmission electron microscopy(TEM), X-ray diffraction(XRD), diffuse reflectance UV-vis spectroscopy(DR-UV-vis), field emission scanning electron microscopy(FESEM), photoluminescence spectroscopy(PL) and energy dispersive X-ray microanalysis(EDX) techniques were applied to characterize the Dy_2Ce_2O_7 nanostructures and investigate their optical characteristics. To examine the photocatalytic activity of as-produced Dy_2Ce_2O_7 nanostructures, the photocatalytic degradation of erythrosine dye as water pollutant was carried out. The results of the photocatalytic investigations suggest as-obtained nano-sized Dy_2Ce_2O_7 product as a new, proper and efficient candidate for photocatalytic usages under UV illumination.     

Effect of Cerium on Microstructures of Hard Alloys

Microstructures and crack extending characteristic of the YG8R,YT5R and YT14R hard alloysadding a trace cerium were studied by AEM and HVEM with a tensile holder.In the hard alloys addingcerium,the compounds of Ce_2O_3 or Ce_2O_2S could be formed,extending of stacking faults and transforma-tion from fcc Co to hcp Co were suppressed,volume fraction of fcc Co in the alloys was increased,andstrength of Co and(TiW)C phases and grain boundaries were raised.Plastic deformation in Co phase nearedges of the tensile cracks was more strong,and the tensile cracks could pass through some smaller WCgrains.     

贵金属/铈锆铽固溶体催化剂的制备与台架性能评价

用Ce0.6Zr0.3Tb0.1O2作为储氧材料,分别制备了实尺寸的全钯三效催化剂和双层钯、铂、铑三效催化剂。为作对比,同时制备了含商用铈锆固溶体的双层钯、铂、铑三效催化剂。在发动机台架上对所制备的催化剂进行了活性评价。3种催化剂具有较高的三效催化活性,在交叉点附近对CO和NOx的转化率接近100%,对THC的转化率接近90%。双层催化剂和单层全钯催化剂相比,不仅在富燃区具有较高的NOx转化率,而且具有较低的起燃温度。含Ce0.6Zr0.3Tb0.1O2固溶体的双层催化剂的性能优于含商用铈锆固溶体的催化剂。     

Pitting corrosion behavior of cerium treated HSLA steel induced by sulfide inclusions in 3.5 wt% NaCl solution

Pitting corrosion behavior of Ce treated HSLA steels induced by sulfide inclusions in 3.5 wt% NaCl solution was investigated with potentiodynamic polarization and immersion corrosion test.The results show that Ce added steels exhibit better pitting corrosion resistance with lower corrosion current density and bigger pitting potential compared with steel without Ce,which is mainly attributed to optimized characteristics of spherical Ce-oxysulfide inclusions with less number density,smaller average size and lower pitting corrosion susceptibility.The spherical Ce₂O₂ S inclusions precipitated on the surface of CeAlO₃ inclusions in the Ce added steels induce pits with bigger opening mouth and shallow depth,reducing their tendency of extension to go deeper due to occlusion corrosion battery in the pitting holes.Furthermore,corrosion inhibitor Ce(OH)₃ generated by Ce₂O₂ S hydration can weaken electrochemical corrosion of the matrix micro-region around the pits.To avoid harmful bigger inclusions,Ce content in steels should be regulated within reasonable range,0.015 wt% Ce in present steels effectively modified inclusions to acquire the best pitting corrosion resistance of the steels.     

Effects of cerium addition on solidification structure and mechanical properties of 434 ferritic stainless steel

Effects of Ce refiners on the solidification structure and the mechanical property of ferritic stainless steel were investigated, the corresponding mechanisms were also discussed. The results showed that the solidification of the ferritic stainless steel was remarkably refined with 0.011 wt.% Ce and 0.023 wt.% Ce refiners. Ce played a great role of inclusion modification and the shape and size of the inclusions were changed by adding Ce. And after adding rare earth Ce, great amounts of high-melting point rare earth Ce inclusions(Ce_2O_3 and Ce_2O_2S) were formed. The fracture mode of 434 ferritic stainless steel was typical cleavage fracture, however, the ductility and the toughness of ferritic stainless steel was remarkably enhanced with 0.011 wt.% Ce and 0.023 wt.% Ce refiner. But the solidification structure and the mechanical property of 434 ferritic stainless steel could not be improved with 0.034 wt.% Cerefiner.     

成分及第二相组织对球墨铸钢热疲劳性能的影响

利用正交试验、定量金相、热疲劳试验及回归分析等方法，研究了碳、硅、铜、铬及石墨与碳化物体积分数对球墨铸钢热疲劳性能的影响规律，并得到了其相应的定量关系式－回归方程，从而为热循环条件下工作的球墨铸钢的成分选择及组织控制提供了依据。研究表明，球状石墨及促进石墨化元素有利于其热疲劳性能的提高，而碳化物及反石墨化元素则削弱其疲劳性能。中还对这些影响因素进行了必要的分析讨论。     

Y2O3和La2O3对金属陶瓷内衬显微硬度和耐蚀性的影响

研究了钇、镧等添加物对金属陶瓷内衬显微硬度和耐蚀性的影响。结果表明:加入Y2O3、L a2O3和S iO2可使陶瓷层的孔隙度降低,一定程度上使耐蚀性增加。L a2O3对提高陶瓷层性能的效果比Y2O3要好。     

High activity of CeO_2-TiO_2 composites for deep oxidation of 1,2-dichloroethane

CeO_2-TiO_2 catalysts prepared by different methods were investigated for deep oxidation of 1,2-dichloroethane(DCE),as a typical representative of the chlorinated volatile organic compounds(CVOCs).Characterization analysis reveals that CeO_2-TiO_2 catalysts prepared by sol-gel and coprecipitation methods exhibit higher specific area,CeO_2 and TiO_2 particles are highly dispersed into each other and the reducibility and mobility of active oxygen species are obviously promoted due to the strong interaction between the two catalysts CeO_2 and TiO_2,resulting in higher catalytic activity for DCE oxidation to and less chlorinated byproduct.The high calcination temperature would lead to the formation of a new monoclinic phase Ce_(0.3)Ti_(0.7)O_2 and sintering,which is the main reason for the catalytic activity for DCE oxidation markedly decreases.     

Heterogeneous nuclei and graphite chemistry in flake and nodular cast irons

Nodular and flake graphite have been extracted from commercial cast irons and studied by a variety of techniques, including high voltage transmission electron microscopy. For nodular graphite the nuclei are (in these cast irons at least) 2 to 5 μm diam spherical particles of primarily CeCO₂, MgO, and Fe₂C₃. In addition the nuclei contain variously Ca, Al, P, S, and Si. The composition of the nuclei is highly variable, presumably dueto the highly nonequilibrium conditions under which they are formed. For flake graphite the nuclei are apparently sulfide particles, again of variable composition. They are spherical and approximately the same diameter as the nodular nuclei. Moreover, chemical analysis of flake and nodular graphites shows that there is a relatively high concentration of oxygen in solution in flake graphite but not in nodular graphite, which suggests oxygen is a growth modifier. Formerly with Harvey Mudd College     

Effect of template on catalytic performance of La_(0.7)Ce_(0.3)Ni_(0.7)Fe_(0.3)O_3 for ethanol steam reforming reaction

Perovskite-type oxides La_(0.7)Ce_(0.3)Ni_(0.7)Fe_(0.3)O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structure and physicochemical properties of the obtained oxides were investigated by scanning electron microscopy, X-ray diffraction, N_2 adsorption-desorption, Fourier transform infrared spectrometry, H_2 temperature-programmed reduction and H_2 temperature-programmed desorption, as well as X-ray photoelectron spectroscopy. The results show that the as-synthesized LCNF-CCT perovskite possesses large specific surface area and regular pore size distribution. In addition, the formation of additional oxygen vacancies on the surface favors the migration of lattice oxygen from the bulk phase to the surface and production of more metallic sites, thus improving the activity and resistance to carbon deposition of catalysts in ethanol steam reforming reaction.     

纯铜表面催渗渗铝及弥散强化研究

提出了用稀土合金CeCl3进行催渗的纯铜渗铝技术。采用渗铝—内氧化技术制备了Al2O3表面弥散铜基导电材料。研究了CeCl3合金催渗对渗铝层的影响和表面弥散层的显微组织及有关性能。结果表明:利用稀土合金CeCl3催渗的纯铜渗铝试样渗层厚度远高于同等工艺参数下未催渗的纯铜渗铝试样。内氧化后,能在渗铝层形成Al2O3弥散硬化层。     

Preparation and characterization of Ce_(1-x)Pr_xO_2 supports and their catalytic activities

In this work, the addition of praseodymium(Pr) into ceria as a mixed oxide support in a form of Ce_(1-x)Pr_xO_2(x = 0.01,0.025, 0.050, 0.075 and 0.10) was prepared using a co-precipitation method. The structural and textural properties of the synthesized supports were characterized by X-ray diffraction(XRD), N_2 adsorption-desorption, Raman spectroscopy, H_2-temperature programmed reduction(H_2-TPR) and H_2-chemisorption. Upon addition of Pr, XRD patterns and Raman spectra indicated an enlargement of ceria unit cell and the characteristics Raman broad peak at 570 cm~(-1) which was attributed to the existence of oxygen vacancies in the ceria lattice. This indicated that some Ce~(4+) ions in ceria were replaced by larger Pr~(3+) cations. To evidence the incorporation of Pr~(3+) cations into ceria lattice,X-ray absorption near edge structure(XANES) was employed. The results showed that the oxidation states of Ce in mixed oxide supports were slightly lower than 4+ while those of Pr were still the same as a precursor salt. Therefore, the incorporation of Pr~(3+) into ceria lattice would lead to strain and unbalanced charge and result in oxygen vacancies. The reducibility of Ce_(1-x)Pr_xO_2 mixed oxide supports was investigated by H_2-TPR and temperature-resolved X-ray absorption spectroscopy experiment under reduction conditions. XANES spectra of Ce L_3 edges showed a lower surface reduction temperature(Ce~(4+)to Ce~(3+)) of Ce_(0.925)Pr_(0.075)O_2 than that of CeO_2 which agreed with H_2-TPR results. H_2-chemisorption indicated that Pr promoted the dispersion of the metal catalyst on the mixed oxide support and increased the adsorption site for CO. For WGS reaction, 1% Pd/mixed oxide support had higher WGS activity than 1%Pd/ceria. The increase of WGS activity was due to the increase of Pd dispersion on the support and the existence of oxygen vacancies produced from incorporation of Pr into the ceria lattice.     

Effect of PdO_x structure properties on catalytic performance of Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst for CO,HC and NO_x elimination

Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst was pretreated in different atmosphere respectively, and characterized by CO chemical adsorption, XPS, HR-TEM, H_2-TPR, Raman, OSC and in situ DRIFTS to investigate the effect of the structure properties of PdO_x species on the catalytic performance for CO, HC and NO_x elimination. The results show that Pd/CZ catalyst pretreated in air atmosphere has higher oxidation activity of HC due to having high Pd dispersion and strong interaction between PdO_x and CZ support. Pd/CZ-H catalyst pretreated in reducing atmosphere exhibits better catalytic performance of NO_x elimination because of having relatively big Pd particle size, more Pd species in metallic state and higher concentration of oxygen vacancies. While for the Pd/CZ-RG catalyst pretreated in reactant atmosphere, strong adsorption of HC species on the surface of catalysts would lead to a part of active sites being covered, which inhibits HC and NO conversions.     

Ultrasonic nondestructive evaluation of matrix structures and nodularity in cast irons

The primary purpose of this research was to investigate the nondestructive ultrasonic wave response, in terms of acoustic velocities and attenuation of sound energy, in cast irons with different nodularities and matrix structures and its correlation with mechanical properties. The results indicated that the influences of matrix structures on the acoustic velocities were not apparent in the cast irons investigated. As to the nodularity, when graphites were largely spheroidal in shape (i. e., nodularity over 80 pct), the velocity of longitudinal waves propagation was about 5300 to 5500 m/s. The velocities seemed to decrease linearly down to nodularity of 25 pct, where velocity was approximately 4800 m/s. Below 25 pct nodularity, the values of acoustic velocity dropped rapidly to about 4000 to 4200 m/s. This represented the velocity of longitudinal waves propagation in gray cast iron, in which the graphites appeared in flake form. The analysis of the attenuation of ultrasonic amplitude indicated that when the nodularity of cast irons is low, the echo sound amplitude will decay more rapidly with respect to distance of echo sound travel. As to the matrix structures, ferritic, bainitic, ferritic-pearlitic (low pearlite content) and tempered martensitic matrix structures were found to have similar ultrasonic attenuation characteristics at the testing frequency of 2 MHz. A higher amount of pearlite (over 90 pct) or fresh martensite in the matrix of cast irons has resulted in faster attenuation of ultrasonic energy, with the fresh martensitic matrix being the fastest. At a testing frequency of 4 MHz, the attenuation of the ultrasonic amplitude in pearlitic and fresh martensitic matrices was found to be even greater than that of 2 MHz. However, other matrices exhibited similar attenuation behavior at both 2 and 4 MHz frequencies. The relationship between the mechanical properties of various cast irons and ultrasonic characteristics was also examined. JIA-MING SUEN, formerly Graduate Student, Department of Materials Engineering, Tatung Institute of Technology     

Effective removal of automobile exhausts over flower-like Ce1−xCuxO2 nanocatalysts exposed active {100} plane

This work elucidates the synthesis and characterization of copper ions incorporated ceria(Ce_(1-x)Cu_xO_2)nanocatalysts with 3 D flower-like and nanocrystalline morphology for the purification of automobile exhausts. XRD and Raman results confirm the presence of copper ions in ceria. The 3 D flower-like and nanocrystalline morphology exhibited by these catalysts were seen by FESEM images. HRTEM and SAED results confirm that(100) plane is dominantly presented in 3 D flower-like Ce_(1-x)Cu_xO_2 catalysts when compared to nanocrystalline morphology. The textural properties of synthesized catalysts was done with the help of N2 sorption study, which confirms that flower-like Ce_(1-x)Cu_xO_2 catalysts show high surface area and pore volume. The existence of Ce~(3+), Ce~(4+), Cu~+ and Cu~(2+) ions in the catalyst were examined by XPS and DR UV-Vis techniques. Oxygen storage capacity(OSC) of the catalysts was studied by H_2-TPR analysis. These characterization results elucidate the presence of dominant active sites(Ce~(3+), Ce~(4+), Cu~+and Cu~(2+)) and {100} plane in the flower-like morphology compared to nanocrystalline. The catalytic activity of synthesized Ce_(1-x)Cu_xO_2 catalysts was tested for removal of CO, HC_x and NO gases from automobile emission with respect to the copper content and morphology. The obtained results indicate that the presence of optimum amount of copper in ceria with flower-like morphology is essential for the removal of CO, HC_x and NO at low temperature via redox process, which is due to the presence of active sites on the dominant {100} plane.     

Microstructure and high-temperature properties of Fe-Ti-Cr-Mo-B-C-Y_2O_3 laser cladding coating

Fe-based composite coatings were fabricated on 5 CrNiMo die steel by laser beam melting a precursor mixture of ferrotitanium,ferrochromium,ferromolybdenum,B4 C and Y_2 O_3 powders.Micro structure and properties of the coatings were studied by X-ray diffraction(XRD),scanning electron microscopy(SEM),energy-dispersive spectrometer(EDS),resistance furnace and high-temperature tribometer.The results show that(Ti,Mo)C particles with flower-like and(Ti,Mo)B_2 with block-like shapes are in situ formed during laser cladding.Volume faction of multiple ceramic particles increases with the increasing of Y_2 O_3.The cumulative oxidation mass of the coating with 2 wt% Y_2 O_3 is decreased by one-third than that of the coating without Y_2 O_3.The oxidation layer of the coating with Y_2 O_3 is getting smooth.Meanwhile,high temperature wear volume loss of the coating with 2 wt% Y_2 O_3 is about 40% that of the coating without Y_2 O_3.The coating with 2 wt% Y_2 O_3 shows a smoother wear scar and few flat grooves are observed after high temperature wear test.     

Synthesis and Property of H2La2Ti3O10/CdS Layered Nanocomposite Photocatalyst

H2La2Ti3O10/CdS nanocomposite with er photoactivity was synthesized by a stepwise exchange process from H2La2Ti3O10, which was obtained by H^＋ -exchanging reaction of H2La2Ti3O10 with HCl other than the normally used HNO3. The pillaring process was investigated by XRD, TEM, FT-IR and BET methods. The photocatalytic decomposition of aniline was used as the model system to evaluate the photochemical properties of H2La2Ti3O10/CdS,H2La2Ti3O10 and K2La2Ti3O10. It is found that the photoactivity of layered H2La2Ti3O10 is greatly improved by the intercalation of CdS in the interlayer. In general, the excellent photoactivity of the H2La2Ti3O10/CdS nanocomposite might be attributing to the extremely small particle size of incorporated CdS and good contact between CdS and La2Ti3O10^2- layers. On the other hand, the coupling of two semiconductor particles with different energy gap is useful to achieve effective charge separation. In H2La2Ti3O10/CdS, a photo-generated electron can transfer from CdS to the La2Ti3O10^2- layer, while the holes remain in the CdS particles. This helps to diffuse the electrons and holes before reaching the interface, and the holes and electrons can be effectively captured by the electrolyte in the solution. Simuhaneously, the optimal operating condition of photodecomposition aniline was investigated.     

火焰喷涂热障陶瓷基复合涂层的新方法

介绍了用氧乙炔火焰在铜材表面喷涂Al_2O_3基复合耐热涂层的新方法——倾斜过渡和重熔。用电镜对涂层的显微结构进行了研究,着重分析了火焰喷涂陶瓷基复合涂层的扩散反应和液相烧结,以及晶粒细小等特征。还讨论了这些显微结构特征对涂层结合强度、耐热和抗热震性能等的影响。采用本工艺配方,对炼铁高炉渣口进行喷涂后,其使用寿命提高2倍以上。     

CSP流程薄板坯及热轧板卷氧化皮组织演变

 采用SEM和XRD方法对CSP冷轧冲压用钢薄板坯和热轧板氧化皮进行了研究。结果表明：覆盖在板坯表面的氧化皮对氧化性炉气的高温腐蚀有明显保护作用,均热前后Fe2O3:Fe3O4:FeO为5:35:60,新鲜基体腐蚀严重些,Fe2O3和Fe3O4含量增加到28%和64%;卷取后快冷钢的氧化皮以2层结构为主,Fe2O3:Fe3O4:FeO为6:31:63,缓冷钢的氧化皮中析出了弥散或薄片状的Fe相,Fe2O3:Fe3O4:FeO:Fe为8:73:15:4,二者厚度相差不大;卷取温度升高,快冷钢的Fe2O3和Fe3O4的含量略有降低,但缓冷钢中残余FeO含量明显减少,不利于酸洗。