气体渗氮对F92钢在700 ℃空气中氧化行为的影响

利用扫描电镜(SEM)、能谱分析(EDS)、X射线衍射分析(XRD)研究了F92钢供货态和渗氮后在700 ℃静态空气中的高温氧化行为,阐述了气体渗氮对F92钢氧化行为的影响。研究表明,渗氮后F92钢表面形成了氮的过饱和膨胀铁素体相和CrN相。供货态F92钢表面生成了薄且致密的(Cr, Fe, Mn)₂O₃和MnCr₂O₄氧化层,具有良好的保护性。此外,供货态F92钢表面有两种瘤状氧化物生成,一种由连续的Fe₂O₃构成,另一种独立的由外层Fe₂O₃和内层富Cr的(Cr, Fe, Mn)₃O₄组成。渗氮加剧了F92钢的氧化,基体内部观察到了内氧化区。渗氮试样表面氧化膜呈双层结构,其中,外层为Fe₂O₃,内层为富Cr的Fe-Cr氧化物。F92钢渗氮过程中形成的膨胀氮过饱和铁素体相和CrN相以及氧化过程中析出的CrN沉淀相降低了铬的活性,阻碍了有保护性的富铬氧化物的生成,从而导致抗氧化性能的下降。     

The decomposition of NdPO4 during mechanical milling

The decomposition reactions of neodymium phosphate, NdPO₄, during mechanical milling (MM) have been studied. It has been found that under optimum conditions, NaOH, Ca(OH)₂, CaO with CaCl₂, and CaO with Ca(OH)₂ decomposed NdPO₄ completely, producing respectively Nd(OH)₃ with Na₃PO₄, Nd(OH)₃ with Ca₅(PO₄)₃(OH), NdOCl with Ca₅(PO₄)₃Cl and Nd₂O₃ with Ca₅(PO₄)₃(OH). CaO by itself caused partial decomposition of NdPO₄ to Nd₂O₃, with the formation of calcium neodymium phosphate oxide, Ca₈Nd₂(PO₄)₆O₂. No chemical reactions occurred between NdPO₄ and CaCl₂, NaCl or Na₂CO₃ during milling. Powder X-ray diffractometry and transmission electron microscopy have been used to characterize the decomposition products. The Gibbs free-energy changes of all the reactions under study are calculated. It appears that the free-energy changes at room temperature (25 °C) and ambient pressure (1 atm) are crucial in determining whether reactions can occur during MM.     

Cu-25Sn-10Ti活性钎焊SiO2f/SiO2复合材料与Invar合金

采用Cu-25Sn-10Ti钎料钎焊SiO_2f/SiO₂复合材料与Invar合金,研究了界面组织结构及其形成机理,分析了不同钎焊保温时间下界面组织对接头性能的影响.结果表明,在钎焊温度880℃,保温时间15 min的工艺参数下,接头在SiO_2f/SiO₂复合材料侧与Invar合金侧均形成了连续的界面反应层,界面整体结构为Invar合金/Fe₂Ti+Cu(s,s)+(Ni,Fe,Cu)₂TiSn/Cu(s,s)+Cu₄₁Sn₁₁+CuTi/TiSi+Ti₂O₃/SiO_2f/SiO₂复合材料.在钎焊温度一定时,随着保温时间的延长,复合材料侧TiSi+Ti₂O₃反应层厚度逐步增加,Fe₂Ti颗粒逐步呈大块状连续依附其上,接头强度先增大后减小.当钎焊温度880℃,保温时间15 min时,接头室温抗剪强度达到11.86 MPa.     

Fabrication of Bulk (Fe,Cr)_3Al/Al_2O_3 Intermetallic Matrix Nanocomposite Through Mechanical Alloying and Sintering

In the present study,(Fe,Cr)_3Al/20 vol% Al_2O_3 nanocomposite was prepared through mechanochemical reactions during ball milling and successfully bulked using a combination of cold isostatic press and sintering at 1400 ℃ for 1 h. Two processing approaches were utilized to produce(Fe,Cr)_3Al/Al_2O_3 nanocomposite: The first was milling of Fe, Cr,Al and Fe_2O_3, while the second one was milling of Fe, Cr, Al and Cr_2O_3, both in stoichiometric condition, to synthesize(Fe,Cr)_3Al/20 vol% Al_2O_3. Structural changes of powder particles during mechanical alloying were studied by X-ray diffraction. The microstructure and the morphology of powder particles and bulk samples were also studied by scanning electron microscopy and transmission electron microscopy. Microstructural analysis showed that mechanochemical reactions took place during milling, and nanometric Al_2O_3 was uniformly distributed in the matrix. The results also showed that the second approach required a considerably higher milling time to produce(Fe,Cr)_3Al/Al_2O_3 nanocomposite, as compared to the first one. For this reason, bulk samples were produced from the synthesized nanocomposite in the first approach. The microstructure of the sintered samples consisted of a network structure of(Fe,Cr)_3Al and Al_2O_3 phases with superior mechanical properties.     

Preparation and electrochemical performance of nanosized Co3O4 via hydrothermal method

The hydrotalcite-type cobalt compounds were prepared through oxidation of Co（OH）2 gel using NH4OH as precipitating agent and H2O2 as oxidant. These hydrotalcite-type cobalt compounds were transformed into Co3O4 through hydrothermal decomposition with nanostructural deformation. The precursor and product were characterized by Fourier-transform infrared（FT-IR） spectrum, X-ray diffractometry（XRD） and transmission electron microscopy（TEM）. The electrochemical performances of as-prepared nanosized Co3O4 as anode materials in lithium-ion batteries were tested by charge-discharge test in the voltage range of 0-3.0 V. The influence of morphology of Co3O4 particle on the capacity and cycling performance was studied. The results show that the shape and size of the final product can be controlled by altering cobalt sources. The irregular cubic Co3O4 with the average particle size of about 10 nm shows the best electrochemical performance. After 10 charge-discharge cycles, the specific charge capacity retains 555 mA.h/g.     

Structure and electrochemical properties of Li(Ni0.5Mn0.5)1-xTixO2 prepared by one-step solid state reaction

The layered compound Li(Ni_0.5Mn_0.5)_1-xTi_xO₂ powders were prepared with Ni(OH)₂, MnCO₃, Li₂CO₃ and TiO₂ by one-step solid state reaction. The effect of doping Ti on the structure and electrochemical properties was studied. The XRD results indicate that the powders with 0≤x≤0.05 have good layered structure and trace of impurity appears in the samples with x≥0.1. The SEM photographs show that the particle size distributes homogeneously and the sample with x=0.15 has larger particle size than other samples. The charge-discharge tests show that Li(Ni_0.5Mn_0.5)_0.95Ti_0.05O₂ synthesized at 800 °C for 36 h exhibits good electrochemical properties. It firstly delivers 173 mA·h/g and maintains 90% of the initial discharge capacity after 30 cycles. The cyclic voltammetry and differential capacity vs voltage curves show that the major oxidation and reduction peaks are around 3.95 V and 3.75 V, respectively, assigned to Ni²⁺/Ni⁴⁺ oxidation-reduction process. A weak peak around 4.5 V is found during the oxidation process in the first cycle, which can be regarded as the main reason of the large drop of discharge capacity in the initial cycle.     

Peculiarities of the R3(Fe,Si)29 phase formation in the Sm---Fe---Si system

The phase content of the Sm(Fe_1−xSi_x)_y alloys (0.05≤x≤0.15; 8.5≤y≤12) has been studied by X-ray diffraction using micromonocrystals. The compounds Sm₂(Fe,Si)₁₇, Sm(Fe,Si)₁₂ and a novel Sm₃(Fe,Si)₂₉ compound with a monoclinic unit cell are found. The lattice parameters of Sm₃(Fe,Si)₂₉ are: a=1.056 nm, b=0.850 nm, c=0.966 nm, β=96.8°. This compound forms as a result of a solid state transformation from the high-temperature Sm₂(Fe,Si)₁₇ phase. Diffuse effects observed in rocking photographs suggest transition structures arising from this transformation. The Curie temperatures of Sm₃(Fe,Si)₂₉ vary in the interval 496–521 K.     

Einkristall-Röntgenstrukturanalyse und magnetische eigenschaften von Ba3YRu2O9, Ba3GdRu2O9 und Ba3YbRu2O9

Single crystals of (I) Ba₃YRu₂O₉, (II) Ba₃GdRu₂O₉ and (III) Ba₃YbRu₂O₉ were obtained by high temperature solid state reactions and examined by X-ray analysis. They crystallize with hexagonal symmetry, space group D_{6h⁴-P63/mmc}, with (I) A = 5.987 Å, C = 14.464 Å; (II) A = 5.895 Å, C = 14.592 Å; (III) A = 5.858 Å, C = 14.432 Å; Z = 2. The crystal structures belong to the 6L perovskites. The magnetic behaviour was investigated between 77 and 650 K using a Faraday balance. The magnetic susceptibility of (I) shows the characteristic behaviour of an Ru₂O₉ face-shared double octahedron, with a Neél temperature T_N = 220 K. The compounds (II) and (III) comply with the Curie-Weiss law, indicating the oxidation state Ru⁴⁺.

Zusammenfassung

(I) Ba₃YRu₂O₉, (II) Ba₃GdRu₂O₉ und (III) Ba₃YbRu₂O₉ wurden mit Hilfe von Hochtemperatur-Festoffreaktionen einkristallin dargestellt und röntgenographisch untersucht. Sie kristallisieren hexagonal, in der Raumgruppe D_{6h⁴ - P63/mmc}, mit (I) A = 5,987 Å, C = 14,464 Å; (II) A = 5,895 Å, C = 14,592 Å; (III) A = 5,858 Å, C = 14,432 Å; Z = 2. Die Kristallstrukturen gehören zur Klasse der 6L-Perowskite. Ihr magnetisches Verhalten wurde mit der Faradaymethode zwischen 77 und 650 K untersucht. Die magnetische Suszeptibilität von (I) zeigt das typische Verhalten von Substanzen mit isolierten Ru₂O₉-Doppeloktaedern mit einer Neél-Temperatur von T_N = 220 K. Die Verbindungen (II) und (III) erfüllen das Curie-Weiss-Gesetz und weisen auf Ru⁴⁺ hin.     

Structural, magnetic and magnetostrictive studies of Tb0.27Dy0.73(Fe1 − xAlx)2

Measurements of magnetic properties, X-ray diffraction and magnetostriction were made on Tb_0.27Dy_0.73(Fe_{1 − x}Al_x)₂ (x = 0.1, 0.2, …, 0.7) compounds. It was found that the system has the cubic MgCu₂ structure over almost the whole (Fe,Al) concentration range investigated, except for a narrow intermediate range (x = 0.4–0.6) where the hexagonal MgZn₂ structure appears. With increasing Al content x, the lattice constant a increases linearly with x. The first replacement of Fe results in a marked decrease in the Curie temperature, which is followed by a slight decrease in T_C with x. A linear decrease in magnetostriction of |λ_| − λ| at room temperature with x was also observed from 1530 × 10⁻⁶ for x=0 to 36×10⁻⁶ for x=0.3. The saturation magnetization σ_s exhibits a complex concentration dependence in the Tb_0.27Dy_0.73(Fe)_{1 − x}Al_x)₂ system: in the range x < 0.5, σ_s increases linearly with x and, for x = 0.5–0.6, σ_s decreases and then increases again. An enhancement of the magnetic ‘hardness’ in this system was also observed at low temperature.     

Thermoelectric properties of Fe0.98Co0.02Si2 with ZrO2 and rare-earth oxide dispersion by mechanical alloying

The n-type Co-doped β-FeSi₂ (Fe_0.98Co_0.02Si₂) with dispersion of several oxides, such as ZrO₂ or several rare-earth oxides (Y₂O₃, Nd₂O₃, Sm₂O₃ and Gd₂O₃), was synthesized by mechanical alloying and subsequent hot pressing. The effects of these oxide dispersions on the thermoelectric properties of Fe_0.98Co_0.02Si₂ were investigated. ZrO₂ was decomposed in the β phase, and the ZrSi and -FeSi phases, which are metallic phases, were formed in the samples with ZrO₂ addition. The Seebeck coefficient and the electrical resistivity were significantly decreased with increasing amount of ZrO₂, indicating that a part of the Zr atoms was substituted for Fe atoms in the β phase. In the case of the samples with rare-earth oxide addition, a decomposition of a large amount of these added oxides did not occur. However, the rare-earth oxide addition caused a slight increase in the amount of the phase. The Seebeck coefficient was significantly enhanced by the rare-earth oxide addition especially in the low temperature range. These facts indicated that a small amount of rare-earth oxides was decomposed in the β phase, and rare-earth elements were substituted for Fe atoms as a p-type dopant, resulting in the decrease in the carrier concentration. The rare-earth oxide addition was also effective in reducing the thermal conductivity.     

Oxidation behavior of the (Cu78Y22)98Al2 bulk metallic glass containing Cu5Y-particle composite at 400–600 °C

The oxidation behavior of the (Cu₇₈Y₂₂)₉₈Al₂ bulk metallic glass containing 55% Cu₅Y particles (CYA-composite) was studied over the temperature range of 400–600 °C in dry air. The results generally showed that the oxidation kinetics of the composite obeyed a two-stage parabolic-rate law, with its steady-state parabolic-rate constants (k_p values) increased with temperature. In addition, the oxidation rates of the composite were significantly lower than those of the polycrystalline Cu–20%Y alloy. The scales formed on the composite consisted mostly of hexagonal-Y₂O₃ (h-Y₂O₃) and minor CuO, while significant amounts of Cu₂O and CuO, with minor amounts of Y₂O₃ were detected for the Cu–20%Y alloy. It was found that the absence of Cu₂O is responsible for the slower oxidation rates of CYA-composite.     

Formation and chemical leaching effects of nonequilibrium Al0.6(Fe25Cu75) alloy powder produced by rod milling

The formation and chemical leaching effects of a nonequilibrium Al_0.6(Fe₂₅Cu₇₅)_0.4 powder produced by rod milling is described. X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and vibrating sample magnetometry were used to characterize both the as-milled and leached specimens. After 400 h of milling, only the bcc AlFe phase with an amorphous phase was detected in the XRD patterns. The crystallite size for the bcc AlFe phase (110) after 400 h of milling was about 5.3 nm. The peak temperature and the crystallization temperature of the as-milled powders were 448.7 and 428.0 °C, respectively. Al atoms leaching from the as-milled bcc AlFe powders in the L1 condition did not alter the diffraction pattern significantly, even though Al atoms had been removed. After the L1 specimen was annealed at 500 °C for 1 h, the bcc AlFe phase transformed to the fcc Cu, Fe, and CuFe₂O₄ phases. The peak widths of L1 and L2 specimens were similar, but became broader than that of the as-milled powder. The saturation magnetization decreased with increasing milling time, and a value of 10.4 emu/g was reached after 400 h of milling. After cooling the specimen from 750 °C, the magnetization slowly increased at approximately 491.4 °C, indicating that the bcc AlFe phase had transformed to the fcc Cu and Fe phases.     

钼酸钠和三乙醇胺对Q235碳钢小孔腐蚀的抑制作用

通过动电位扫描,微区电位扫描,电化学阻抗谱及XPS等技术,考察了Na₂MoO₄和三乙醇胺 (TEA) 复配缓蚀剂对Q235碳钢孔蚀的抑制作用。结果表明：Q235碳钢在0.02 mol/L NaCl+0.1 mol/L NaHCO₃溶液中,适量的Na₂MoO₄与TEA复配对其孔蚀的抑制作用要优于单独使用Na₂MoO₄对孔蚀的抑制效果。在外加恒电位为0.3 V时,在实验溶液中碳钢表面有活性点被激活,Na₂MoO₄+TEA复配缓蚀剂能够明显抑制表面活性点的生成,并且能使形成的活性点的电位峰值迅速降低,抑制其向腐蚀小孔的转化。在加有Na₂MoO₄+TEA复配缓蚀剂的实验溶液中形成的缓蚀膜主要成分为Fe₂(MoO₄)₃,Fe₂O₃和TEA,三乙醇胺的吸附可以改善钼酸盐缓蚀膜的致密性,进一步提高缓蚀性能。     

Super304H奥氏体不锈钢的高温抗氧化性能

对Super304H奥氏体不锈钢在550～800℃进行高温氧化试验,结合氧化动力学规律去研究Super304H奥氏体不锈钢的氧化机理。结果表明,Super304H奥氏体不锈钢在550～800℃氧化质量增加曲线遵循抛物线规律,在750～800℃时60 h以内氧化质量增加趋势最明显,100 h后质量增加高达0.005 mg·mm^-2。在550～750℃逐渐生成致密的氧化膜,主要由Cr₂O₃和Fe_3-xCr_xNiO₄混合氧化物和少量CuCrMnO₄构成。升高温度会促进Cr的选择性氧化,使得Cr₂O₃保护膜开裂,800℃时暴露出的Fe基体与氧原子反应生成瘤状Fe₃O₄,氧化膜厚重并伴有剥落现象。应变速率为3.2×10^-4 s^-1时,不锈钢的抗拉强度随氧化温度升高而降低,600℃的抗拉强度最大,达350 MPa; ...     

加热温度对10CrNiCuSi钢氧化铁皮的影响

为改善10CrNiCuSi船板钢表面质量粗糙的问题,采用电阻炉开展了1100~1300 ℃高温氧化试验,利用弯曲试验评价了氧化铁皮的剥离性,并研究了不同温度下氧化铁皮的演变规律。结果表明,随着加热温度的升高,氧化速率增大,氧化层厚度明显增加。氧化铁皮主要由Fe₂O₃、Fe₃O₄、FeO和内氧化层组成,而内氧化层主要由FeNiCu、Fe₂SiO₄和FeO相组成。加热过程中Fe₂SiO₄/FeO共晶液相的产生对氧化铁皮的剥离性具有重要影响。在1100 ℃和1150 ℃条件下,内氧化层中的Fe₂SiO₄呈现颗粒状或块状弥散分布,氧化铁皮与基体之间界面平直,氧化铁皮易于剥离;在1200、1250和1300 ℃条件下,Fe₂SiO₄-FeO或Fe₂SiO₄发生熔化形成液相渗入基体和氧化铁皮中,造成界面粗糙,而锚状FeNiCu相与基体及氧化铁皮具有较好的结合力,两者的协同作用造成氧化铁皮难于剥离。因此在1100 ~1150 ℃条件下去除氧化铁皮较为合适。     

Mechanical properties and oxidation behaviour of two-phase iron aluminium alloys with Zr(Fe,Al)2 Laves phase or Zr(Fe,Al)12 τ1 phase

Two-phase Fe-rich Fe–Al–Zr alloys have been prepared consisting of binary Fe–Al with a very low solubility for Zr and the ternary Laves phase Zr(Fe,Al)₂ or τ₁ phase Zr(Fe,Al)₁₂. Yield stress, flexural fracture strain, and oxidation behaviour of these alloys have been studied in the temperature range between room temperature and 1200 °C. Both the Laves phase and the τ₁ phase act as strengthening phases increasing significantly the yield stress as well as the brittle-to-ductile transition temperature. Alloys containing disordered A2+ ordered D0₃ Fe–Al show strongly increased yield stresses compared to alloys with only A2 or D0₃ Fe–Al. The binary and ternary alloys with about 40at.% Al and 0 or 0.8at.% Zr show the effect of vacancy hardening at low temperatures which can be eliminated by heat treatments at 400 °C. At higher Zr contents this effect is lost and instead an increase of low-temperature strength is observed after the heat treatment. The increase of the high-temperature yield strength of Fe-40at.% Al by adding Zr is much stronger than by other ternary additions such as Ti, Nb, or Mo. Tests on the oxidation resistance at temperatures up to 1200 °C indicate a detrimental effect of Zr already for additions of 0.1at.%.     

Spectroscopy, magnetism and non-radiative processes in heteronuclear Cu:Pr squarate; [Pr2Cu(C4O4)4(H2O)16]·2H2O

In the present work, the spectroscopic and magnetic properties of heteronuclear Cu:Pr squarate are reported. Single crystals of [Pr₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O were obtained by reaction of squaric acid, praseodymium chloride and copper chloride in water solution according to the procedure described earlier. The crystals of title compound are isomorphic with [La₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O crystal, where squarate anions participate as bridging ligands between metal ions.

The UV region of absorption spectra of the title compound is dominated by C–T band of Cu(II), f–d transition of Pr(III) and internal π–π*(A_1g→E_u) and π–π*(A_1g→E_g) ligand transitions. In visible and IR regions, t_2g–e_g of copper Cu(II) as well as ³H₄→³P_J, ¹D₂, ¹G₄, ³F_J, ³H₆ Pr(III) transitions at 293 and 4 K were recorded. At low temperature splitting given by Jahn–Teller effect can be observed. Significant anisotropy of d–d transitions intensities confirms well the Jahn–Teller effect, too. Unexpectedly high intensity of ³H₄→¹G₄ transition is probably due to the intensity borrowing from the Cu (II) d–d transition.

The ³P₀ and ¹D₂ emission of Pr(III) in the [Pr₂Cu(C₄O₄)₄(H₂O)₁₆]·2H₂O crystals is quenched even at 77 K. Whereas emission of appropriate polynuclear europium squarate was detected. The pathways of excited state quenching by e_g levels of Cu(II), multhiphonon relaxation and concentration quenching can be considered in the system under studies. Magnetic susceptibility measurements were carried out in 300–1.7 K temperature range and are discussed in relation to the structure.

Effect of the polymeric structure on spectroscopic behaviour is presented. Selectivity of polymeric europium squarate in vitro test for different tumor cells is shown.     

Ordering in the sublattices of Fe3Al during the phase transformation B2↔D03

The temperature dependence of the iron concentrations in the individual sublattices of hyperstoichiometric binary Fe₇₂Al₂₈ and ternary Fe₆₈Al₂₈Cr₄ alloys were obtained from X-ray diffraction data measured in a high temperature vacuum chamber during linear heating around the phase transformation B2↔D0₃. A method for the processing of the diffraction pattern based on the splitting of the diffraction lines of the structure D0₃ into three groups is presented. Applying this method it was found that the structure B2 was not well developed in both samples. The maximum value of c_C≈0.8 gives S_B2 equal to 0.4 and 0.3 for binary and ternary alloy, respectively. The D0₃-order was not well developed too, because structure D0₃ arises from the structure B2. D0₃-ordering, i.e. redistribution of atoms within the sublattices A and B, is given only by the total number of iron atoms in these sublattices before the phase transformation B2↔D0₃.     

基于热力学计算的水工况对耐热钢高温氧化行为影响

基于热力学计算方法,对6种不同的水工况条件下的高温氧分压进行了计算和对比.计算结果显示,TP347H和T91两种材料在570℃时高温氧化产物类型转变的临界氧分压约为1.0×10-15,而常规的加氧工况OT(1)、纯水工况、还原性全挥发处理工况AVT(R1)在此条件下的氧分压均高于1.0×10-10,因此认为常规的加氧工...     

NiCrAlY/Al-Al2O3/Ti2AlNb高温抗氧化和力学性能研究

采用电弧离子镀技水在NiCrAlY涂层与O相Ti₂AlNb合金之间沉积不同Al:Al₂O₃比例的Al-Al₂O₃薄膜作为扩散阻挡层.研究了900℃下恒温氧化500 h后NiCrAlY/Al-Al₂O₃/Ti₂AlNb体系中Al-Al₂O₃层阻挡合金元素互扩散的行为,以及对涂层氧化动力学曲线的影响.结果表明,没有添加扩散阻挡层的NiCrAlY/Ti₂AlNb体系,涂层和基体之间的元素互扩散十分严重,涂层丧失抗氧化能力;而添加扩散阻挡层的材料体系,涂层和基体之间的元素互扩散受到抑制,涂层的长期抗高温氧化性能得到提高.对于3Al-Al₂O₃,1Al-Al₂O₃和0Al-Al₂O₃ 3种扩散阻挡层,综合比较材料体系的抗氧化性能、阻挡层阻挡涂层和基体元素互扩散能力、以及涂层和基体之间结合力,当1Al-Al₂O₃薄膜作为扩散阻挡层时,材料性能最优异.同时,本文利用扩散阻挡系数简洁定量地表示出不同Al:Al₂O₃比例阻挡层的阻挡扩散能力.