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1.
Water-atomized iron and steel powder is commonly used as the base material for powder metallurgy (PM) of ferrous components. The powder surface chemistry is characterized by a thin surface oxide layer and more thermodynamically stable oxide particulates whose extent, distribution, and composition change during the sintering cycle due to a complex set of oxidation–reduction reactions. In this study, the surface chemistry of iron and steel powder was investigated by combined surface and thermal analysis. The progressive reduction of oxides was studied using model sintering cycles in hydrogen atmospheres in a thermogravimetric (TG) setup, with experiments ended at intermediate steps (500–1300°C) of the heating stage. The surface chemistry of the samples was then investigated by means of X-ray photoelectron spectroscopy (XPS) to reveal changes that occurred during heating. The results show that reduction of the surface oxide layer occurs at relatively lower temperature for the steel powder, attributed to an influence of chromium, which is supported by a strong increase in Cr content immediately after oxide layer reduction. The reduction of the stable oxide particulates was shifted to higher temperatures, reflecting their higher thermodynamic stability. A complementary vacuum annealing treatment at 800°C was performed in a furnace directly connected to the XPS instrument allowing for sample transfer in vacuum. The results showed that Fe oxides were completely reduced, with segregation and growth of Cr and Mn oxides on the particle surfaces. This underlines the sequential reduction of oxides during sintering that reflects the thermodynamic stability and availability of oxide-forming elements.  相似文献   

2.
For the consolidation of steel parts manufactured by powder metallurgy (PM) techniques, removal of the surface oxides covering metallic powder particles is a necessary prerequisite. In PM steels with conventional compositions, reduction of the oxides is easily achieved in traditional sintering furnaces. However, processing steels containing alloying elements with a high oxygen affinity represents a big challenge that requires a deeper understanding of the chemical processes occurring during sintering. In the present work, thermogravimetry analysis coupled with mass spectrometry is used to describe the oxidation/reduction phenomena that take place when sintering steel powders and how these processes are modified by the addition of admixed particles containing oxygen-sensitive elements. Carbothermal reduction processes are studied using pure oxides (Fe2O3, MnO2, Cr2O3 and SiO2) as well as water-atomized Fe powders mixed with small amounts—4 mass/%—of Cr, Mn and Si powders or Fe–Mn–Si–(Cr) master alloy powders. The results show that there is an oxygen transfer from the base iron particles to the oxidation-sensitive elements—“internal getter effect”—taking place mostly through the gas phase. Different alloying elements (Cr, Mn, Si) show different temperature ranges of susceptibility to oxidation. Combination of these oxygen-sensitive alloying elements in the form of a master alloy powder reduces their sensitivity to oxidation. Also, the use of master alloys promotes the concentration of the oxides on the surface of the alloying particles and not in the grain boundaries of the surrounding iron particles—as occurs when using Mn carriers—which should have a beneficial impact on the final mechanical performance.  相似文献   

3.
Silicon powder is vulnerable to oxidation due to its high surface activity. The as‐prepared Si powder is characterized by X‐ray photoelectron spectroscopy spectra coupled with an oxygen nitrogen analyzer, revealing that oxygen impurities mainly consist of Si oxides but with a small amount of free oxygen. The stable oxide films can deteriorate the properties of sintered materials since they cannot be removed during sintering process. The cleaning of these oxides by a single‐HF solution is not straightforward and efficient due to the large surface tension. To remove the oxygen, a more efficient way with the addition of ethanol to a HF solution has been proposed. The addition of a moderate percent of ethanol can decrease the water contact angle and then improve the cleaning efficiency. Importantly, the resulting Si powder possesses good dispersity, uniformity and fluidity. However, excess hydrofluoric acid suppresses oxide removal. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

4.
The change in reactivity for nanostructured iron oxide within mesoporous silica materials is demonstrated. Iron oxides were incorporated into the pore system of MCM‐41 and MCM‐48 silica materials and characterized by powder X‐ray diffraction and nitrogen physisorption. Iron oxide shows significant changes in the reducibility by hydrogen compared to comparable bulk iron oxide phases. Partially reduced iron oxides within the mesoporous host were characterized by X‐ray absorption spectroscopy and SQUID measurements.  相似文献   

5.
制备了有序介孔氮掺杂碳负载三氧化铁,有效降低了氧还原的过电势。通过扫描电子显微镜、透射电子显微镜、氮气吸附-脱附测试、粉末X射线衍射、X射线光电子能谱、拉曼光谱等技术表征了所制备的催化剂的物理化学性质。此外,用旋转圆盘电极测试了其在碱性条件下对氧还原反应的催化活性和选择性。实验结果表明:氮气热解后铁以三氧化二铁的形式负载于有序介孔氮掺杂碳中,其比表面积达到755 cm^2·g^-1。拉曼和X射线光电子能谱结果表明,加入铁前驱体后所制备的催化剂石墨化程度有所提升、阻抗降低、导电性增加。在碱性条件下,Fe2O3@NC催化剂呈现出4电子氧还原反应,其起始电位(-0.01 V vs Ag/AgCl)和半波电位(-0.13 V vs Ag/AgCl)与商用20%Pt/C相当。此外,该催化剂具有较好的抗甲醇性能且其恒电压稳定性优于商用Pt/C。Fe2O3@NC催化剂用于锌-空电池放电测试,其放电功率可以达到88 mW·cm^-2,是商用Pt/C的1.29倍。  相似文献   

6.
High‐strength dual phase steels readily exhibit bad galvanizability and coating defects because of selective oxides formed on steel surface during the annealing process prior to galvanizing. To investigate selective oxidation of alloying elements and their effects on glavanizability, a high‐strength dual phase steel was annealed with soaking duration for 45, 90, and 120 s, respectively, and then galvanized using a hot‐dip simulator. Field‐emission scanning electron microscopy characterization revealed that when dual phase steel was soaked for 45 s, selective oxides mainly precipitated along grain boundaries, while only a few of the oxides formed on grains. With soaking duration increased, oxides were so dense that nearly all steel surface was covered, leaving little bare area of the steel surface. Further XPS analysis showed that selective oxides mainly consisted of MnO and Cr2O3. In addition, the chemical nature of oxides did not change at all although soaking duration prolonged. Scanning Auger microprobe depth profiles presented that Mn had a much higher tendency to segregate than Cr and Mo. Oxygen penetration depth to subsurface was promoted as soaking duration increased. The formation of interfacial inhibition layer was founded to be greatly influenced by the density and size of surface oxides. The widely spaced small oxides had virtually no adverse effect on wettability because of aluminothermic reduction of oxides by the bath dissolved Al. As the oxides became dense and considerably big, the grains of the inhibition layer in some certain zones became coarse and the galvanizability tended to deteriorate. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

7.
A constant pH precipitation method has been applied to obtain solids with Ni/Fe molar ratios of 2/1, 3/2, 1/1, 2/3, and 1/2. In all cases, a phase with the hydrotalcite‐like structure is obtained, containing NiII and FeIII in the brucite‐like layers and carbonate in the interlayer, and, for samples with a Ni/Fe molar ratio lower than 2/1, amorphous hydrated iron oxides, undetected by X‐ray diffraction, are also formed. The solids have been characterized by element chemical analysis, powder X‐ray diffraction, differential thermal analysis, thermogravimetric and differential thermogravimetric analysis, FT‐IR spectroscopy, temperature‐programmed reduction and assessment of specific surface area by nitrogen adsorption at ?196 °C. In all cases reduction leads to zero‐valent state for the metals, reduced nickel particles probably favouring reduction of FeIII species; the specific surface area increases with the iron content, probably due to the amorphous nature of the hydrated iron oxides formed. Calcination at 1200 °C in air leads to well crystallized solids, formed by NiFe2O4 spinel and, additionally, rocksalt‐type NiO for Ni/Fe ratios larger than 1/2. In this way, solids with tailored compositions of these two phases can be prepared.  相似文献   

8.
The identification of catalytically active sites (CASs) in heterogeneous catalysis is of vital importance to design and develop improved catalysts, but remains a great challenge. The CASs have been identified in the low‐temperature selective catalytic reduction of nitrogen oxides by ammonia (SCR) over a hollandite manganese oxide (HMO) catalyst with a rod‐shaped morphology and one‐dimensional tunnels. Electron microscopy and synchrotron X‐ray diffraction determine the surface and crystal structures of the one‐dimensional HMO rods closed by {100} side facets and {001} top facets. A combination of X‐ray absorption spectra, molecular probes with potassium and nitric oxide, and catalytic tests reveals that the CASs are located on the {100} side facets of the HMO rods rather than on the top facets or in the tunnels, and hence semi‐tunnel structural motifs on the {100} facets are evidenced to be the CASs of the SCR reaction. This work paves the way to further investigate the intrinsic mechanisms of SCR reactions.  相似文献   

9.
Surface oxidation of Fe‐19Cr‐17Ni, Fe‐19Cr‐18Ni‐1Al and TiC‐enriched Fe‐19Cr‐18Ni‐1Al alloys was investigated by photoelectron spectroscopy (PES). The experiments were conducted at 323 K in pure O2 (2.7 × 10?6 mbar). Composition and morphology of the nanoscale surface oxides were determined quantitatively by inelastic electron background analysis. Moreover, use of synchrotron radiation facilities were necessary to obtain improved sensitivity for studying minor alloying elements such as Al and Si. The results indicate oxygen‐induced segregation of Al, which significantly hinders the oxidation of the major alloying elements Fe and Cr. Ti remains in its inert carbide form. The relative concentration of Fe within the oxide layer was found to increase with the oxide‐layer thickness, indicating greater mobility of Fe relative to other alloying elements. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

10.
The adsorption of 3‐aminopropyltrimethoxysilane thin films on Fe? 18Cr? 7Mn? 3Ni (austenitic stainless steel) was investigated by X‐ray photoelectron spectroscopy (XPS) and inelastic electron background analysis. The bonding and morphology of the films were strongly dependent on the surface hydroxyl concentration, which was controlled by the oxidation pretreatment of the substrate. In particular, an aminopropylsilane (APS) monolayer with high degree of bonding to the substrate was obtained on an electrochemically passivated surface with very high hydroxyl concentration. On the other hand, the deposition of weakly bound APS clusters was observed on substrates having relatively low hydroxyl concentrations. The adsorption occurred initially via hydrogen bonding, whereas heating to 373 K resulted in the formation of covalent Si? O? M bonds at the silane/metal oxide interface. The results of this study provide insight into the interaction between silanes and stainless steels surfaces, and can be applied for functionalization of stainless steel materials in an extensive range of applications. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

11.
选择性刻蚀制备铜锰复合氧化物及其CO催化氧化性能   总被引:1,自引:0,他引:1  
石磊  胡臻浩  邓高明  李文翠 《催化学报》2015,(11):1920-1927
由于在工业、环保和能源等诸多领域的潜在应用,低温CO催化氧化催化剂的研发引起了广泛关注.尽管贵金属表现出优越的CO氧化活性和稳定性,但是其有限储量和高昂价格一直限制着它们的实际应用.铜锰氧化物是著名的霍加拉特催化剂的主组分,价格低廉,催化氧化CO活性高,可高效替代贵金属催化剂.大量研究已证实, CO在铜锰氧化物上的氧化遵循氧化-还原机理,因此调变铜锰氧化物催化剂的氧化-还原性能对于改善其CO氧化活性至关重要.本文报道了一种简单的选择性刻蚀技术,即在铜、锰前驱物共沉淀过程中引入氨水作为刻蚀剂,利用氨水与铜离子的强络合作用选择性刻蚀铜组分,调变铜锰氧化物的铜锰比,有效改善了铜锰氧化物的氧化-还原特性,从而提高了其CO氧化性能. X射线粉末衍射(XRD)测试结果表明,初始制备的样品结晶弱,主要物相包含铜锰复合氧化物和氧化锰,此外还存在少量碳酸锰.不同浓度氨水刻蚀几乎未改变铜锰氧化物的物相组成.透射电子显微(TEM)照片中几乎没有发现晶格相,进一步证实这些铜锰氧化物的弱结晶本质.扫描电子显微(SEM)照片显示初始制备的铜锰复合氧化物主要由1.5?m左右的球形颗粒堆积而成,氨水刻蚀后颗粒形状变得不规则,表面更加粗糙,样品比表面积也从刻蚀前的85 m2/g增加到139 m2/g.理论上,氨水与铜的络合作用更强,样品主体和表面组成分析结果显示,随着氨刻蚀量增加,铜含量逐步降低,这清晰证实了氨有效地选择性刻蚀了铜组分. 进一步运用X射线光电子能谱(XPS)、氢程序升温还原(H2-TPR)、CO程序升温还原(CO-TPR)和氧程序升温脱附(O2-TPD)等测试手段表征了铜锰氧化物的氧化和还原特性,特别是氨刻蚀后催化剂氧化-还原性能. XPS分析显示铜锰氧化物中铜和锰物种的氧化态分别为+2和+3,氨刻蚀并没有改变两物种的氧化态. H2-TPR和CO-TPR证实氨刻蚀有效促进了铜锰氧化物中晶格氧从锰到铜物种的迁移,氨刻蚀同时还增强了与铜和锰键合的晶格氧物种的反应活性. O2-TPD结果进一步表明,氨刻蚀显著改善了铜锰氧化物中与铜键合晶格氧的释放.综合来看,氨刻蚀可有效促进铜锰氧化物的晶格氧迁移、释放和反应等氧化-还原特性. CO氧化反应研究显示,氨刻蚀大幅度促进了铜锰氧化物的催化活性.当反应温度在30?C时,相比于初始制备的铜锰氧化物催化剂,氨水刻蚀的样品上CO转化率提高了30%,达到90%转化率时的温度降低了20?C.关联催化剂结构表征和CO氧化性能数据发现,以表面Cu量归一化的CO氧化反应速率与催化剂的氧化-还原性能正相关.这一结果清晰证实氨刻蚀能显著改善铜锰氧化物的氧化-还原特性,进而有效促进其CO氧化活性.  相似文献   

12.
Removal of the native surface oxide from steel is an important initial step during vacuum brazing. Trace and alloying elements in steel, such as Mn, Si, and Ni, can diffuse to the surface and influence the deoxidation process. The detailed surface chemical composition and grain morphology of the common stainless-steel grade 316L is imaged and spectroscopically analyzed at several stages of in-vacuum annealing from room temperature up to 850°C. Measurements are performed using synchrotron-based X-ray photoemission and low-energy electron microscopy (XPEEM/LEEM). The initial native Cr surface oxide is amorphous and unaffected by the underlying Fe grain morphology. After annealing to ~700°C, the grain morphology is seen at the surface, persisting also after the complete oxygen removal at 850°C. The surface concentration of first Mn and then Si increases significantly when annealing to 500°C and 700°C, respectively, while Ni and Cr concentrations do not change. Mn and Si are not located only in grain boundaries or clusters but are distributed across over the surface. Both Mn and Si appear as oxides, while Cr oxide becomes metallic Cr. Annealing from 500°C up to 850°C leads to the removal of first the Mn and then Si oxides from the surface, while Cr and Fe are completely reduced to metals. Deoxidation of Cr occurs faster at the grain boundaries, and the final Cr metal surface content varies between the grains. The findings are summarized in a general qualitative model, relevant for austenite steels.  相似文献   

13.
Amorphous aluminophosphate (AlP) and metal‐aluminophosphates (MAlPs, where M=2.5 mol%Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesis of jasminaldehyde through the aldol condensation of n‐heptanal and benzaldehyde were investigated. The nitrogen adsorption‐desorption isotherms showed that the microporosity exhibited by the aluminophosphate was changed to a mesoporous and macroporous structure which depended on the metal incorporated, with a concomitant change in the surface area. Temperature‐programmed desorption of NH3 and CO2 revealed that the materials possessed both acidic and basic sites. The acidic strength of the material was either increased or decreased depending on the nature of the metal. The basicity was increased compared to AlP. All the materials were X‐ray amorphous and powder X‐ray diffraction studies indicated the absence of metal oxide phases. The Fourier transform infrared analysis confirmed the presence of phosphate groups and also the absence of any M‐O moieties in the materials. The selected organic reaction occurred only in the presence of the AlP and MAlPs. The selectivity for the jasminaldehyde product was up to 75%with a yield of 65%. The best conversion of n‐heptanal with a high selectivity to jasminaldehyde was obtained with FeAlP as the catalyst, and this material was characterized to have less weak acid sites and more basic sites.  相似文献   

14.
It is well known that there is a critical relationship between the surface composition and catalytic performance for a bimetallic catalyst. However, in most cases, the surface composition is obviously different from that of the bulk. Moreover, the surface is normally reconstructed under reaction conditions. In this personal account, our recent progresses in determining the surface compositions of oxide supported bimetal catalysts by high‐sensitivity low energy ion scattering spectroscopy (HS‐LEIS) and X‐ray photoemission spectroscopy (XPS) are summarized. Phase diagrams of the surface compositions under various conditions as a function of the bulk composition are established and compared. It is found that oxidation induces de‐alloying and enrichment of PdO, CuO, SnO2 on the surface, while H2 reduction results in re‐alloying. The addition of the second component not only modifies the nature of the active site, but also varies the dispersion of the active components. The support effects are discussed. The compared studies reveal that HS‐LEIS can achieve a more reliable surface composition for oxide supported catalysts.  相似文献   

15.
The initial oxide state of powder is essential to the robust additive manufacturing of metal components using powder bed fusion processes. However, the variation of the powder surface oxide composition as a function of the atomizing medium is not clear. This work summarizes a detailed surface characterization of three 316L powders, produced using water atomization (WA), vacuum melting inert gas atomization (VIGA), and nitrogen atomization (GA). X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy analyses were combined to characterize the surface state of the powders. The results showed that the surface oxides consisted of a thin (~4 nm) iron oxide (Fe2O3) layer with particulate oxide phases rich in Cr, Mn, and Si, with a varying composition. XPS analysis combined with depth-profiling showed that the VIGA powder had the lowest surface coverage of particulate compounds, followed by the GA powder, whereas the WA powder had the largest fraction of particulate surface oxides. The composition of the oxides was evaluated based on the XPS analysis of the oxide standards. Effects of Ar sputtering on the peak positions of the oxide standards were evaluated with the aim of providing an accurate analysis of the oxide characteristics at different etch depths.  相似文献   

16.
A new high‐temperature, hybrid, phase‐transition material, 1‐methylpiperidinium tetrabromozincate ( 1 ), that shows a reversible transition at 345 K was synthesized. Differential scanning calorimetry and specific heat capacity measurements confirmed this reversible transformation with a large heat hysteresis of 25 K, which describes a typical first‐order phase transition in 1 . The dielectric constant exhibited a steplike anomaly and showed high and low dielectric states in the high‐ and room‐temperature phases, respectively, and therefore, this hybrid might be considered as a potential switchable dielectric material. The variable‐temperature powder X‐ray diffraction patterns displayed remarkable shifts between the experimental patterns at the two different phases. Single‐crystal X‐ray diffraction analyses at various temperatures revealed that the origin of this transformation could be attributed to disordering of the bromine atoms in the anion and the nitrogen atom of the cation. The cation also assumed a conformational change, which was likely induced by the disordered nitrogen atom. The conformational onset of the transformation of the cation from a planar conformer into a relaxed chair also occurred upon decreasing the temperature below transition point; thus, the combined order–disorder and conformational change induced the structural transformation and the change in symmetry.  相似文献   

17.
The liquid precipitation method using zinc acetate dihydrate was applied for the synthesis of uniform and spherical ZnO nanoparticles. The ultrafine zinc oxid was prepared in a water‐ethanol mixture solution. The solution containing zinc cation was soluble in water. The surface‐active agent triethanolamine (TEA) was soluble in ethanol. Then alkali precipitated by adding n‐propylamine. The spherical zinc oxide particle morphology was found to be highly dependent on the zinc salt concentration, ethanol‐water ratio, and the surface‐active agent additive. The process can produce white ZnO powder of 50–90 nm in size. The morphology of zinc oxide showed a powder shape by transmission electron microscopy (TEM), the crystallization phase structure of zinc oxide by X‐ray diffraction (XRD), and the zinc oxide remaining by using an organic analysis by infrared spectroscopy (IR).  相似文献   

18.
Low‐molecular‐weight organic additives such as stearic acid are commonly used as surface additives in powder injection moulding (PIM). It is therefore important to know how the additives interact with the surface of the powder used. In this study, such interactions are studied by means of controlled adsorption of carboxylic acids on the oxides of interest. The oxides are prepared by oxidation of flat samples of Fe, Cr, Mn and Si. Surface chemical characterization is done by means of XPS, the main approach on flat samples being a comparison of angle‐resolved analysis and the use of the Tougaard nanostructure analysis technique. Taking advantage of this comparison, the Tougaard method is then applied in the evaluation of XPS analyses of stainless‐steel powder with adsorbed stearic acid. In addition, time‐of‐flight SIMS analysis is used to verify the adsorption of stearic acid on the powder surface. It is shown that Tougaard nanostructure analysis can be used for determining the thickness of an organic layer on particulate material. The layer thickness of adsorbed stearic acid was estimated to be ~20 Å, corresponding to monolayer adsorption. Time‐of‐flight SIMS analysis verified the adsorption of stearic acid on the powder surface. From the XPS analysis of flat samples it was determined that the use of the metal/oxide universal cross‐section in Tougaard nanostructure analysis best described the increased background due to adsorption of carboxylic acids, and that information about molecular orientation could be gained. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

19.
A simple method was adopted in which ultrathin cerium oxide nanoplates (<1.4 nm) were synthesized to increase the surface atomic content, allowing transformation from a face‐centered cubic (fcc) phase to a body‐centered tetragonal (bct) phase. Three types of cerium oxide nanoparticles of different thicknesses (1.2 nm ultrathin nanoplates, 2.2 nm nanoplates, and 5.4 nm nanocubes) were examined using transmission electron microscopy and X‐ray diffraction. The metastable bct phase was observed only in ultrathin nanoplates. Thermodynamic energy analysis confirmed that the surface energy of the ultrathin nanoplates is the cause of the remarkable stabilization of the metastable bct phase. The mechanism of surface energy regulation can be expanded to other metallic oxides, thus providing a new means for manipulating and stabilizing novel materials under ambient conditions that otherwise would not be recovered.  相似文献   

20.
The oxidative photocyclization reactions of olefins that contain 1H‐phosphindole or dibenzophosphole substituents have been applied to the synthesis of P/N‐bi‐heterosubstituted dimeric helicenes, as well as of new [6]‐ and [8]phosphahelicenes. In these photocyclization processes, the configuration of the stereogenic phosphorus center dictates the sense of helical chirality. Thus, by starting from enantiomerically pure P‐menthylphosphole‐oxide units, this method affords enantiopure helical compounds. The helical phosphine oxides were characterized by X‐ray diffraction. After reduction of the phosphine‐oxides, the corresponding helical phosphines have been used as ligands in transition‐metal complexes. The X‐ray crystal structure of a gold chloride complex of a [6]helicene is reported.  相似文献   

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