高能球磨结合SPS技术制备Al2O3-TiC复合材料及其性能研究

以TiO₂、Al、C(石墨)为原料,首先采用高能球磨引导铝热反应合成了Al_2O3-TiC 纳米复合粉体,然后采用放电等离子体烧结纳米复合粉体制备了Al₂O₃-TiC复合材料.结果表明,在氩气氛围下高能球磨3h后,原料粉末就发生了铝热反应,合成的Al₂O₃-TiC复合粉体粒子尺寸大约在100nm左右.采用SPS技术在1450℃保温4min烧结的试样致密度达99.6%,并且结构精细(大部分晶粒<1μm),两相分布比较均匀,有较好的力学性能和电导性能,抗弯强度为650±21MPa.,硬度为19.1±0.2GPa,断裂韧性为4.5±0.2MPa·m^1/2,电导率为2.3828×105Ω^-1·m^-1.     

SPS界面反应增强机制调控的软磁复合材料磁性能和电阻率

设计软磁复合材料(SMCs)的绝缘层要兼顾软磁性能和电阻率。本研究以Fe/Ni_0.5Zn_0.5Fe₂O₄复合体系为例, 研究界面MnO₂氧化剂对样品软磁性能和电阻率的影响, 揭示提高软磁性能和电阻率的SMCs界面放电等离子烧结(SPS)氧化还原机制。采用球磨法制备添加0、0.1wt%、0.3wt%、0.5wt%和1.0wt% MnO₂的核壳结构Fe@Ni_0.5Zn_0.5Fe₂O₄(MnO₂)复合粉末, 随后SPS烧结制备Fe/Ni_0.5Zn_0.5Fe₂O₄(MnO₂)块体SMCs样品, 通过扫描电镜(SEM)、X射线衍射(XRD)表征该样品的结构特征, 用精密电阻测试仪和振动样品磁强计测试该样品的电阻率和磁性能。研究发现, 添加0.5wt% MnO₂的Fe/Ni_0.5Zn_0.5Fe₂O₄(MnO₂)块体SMCs样品比未添加样品电阻率提高33.7%、饱和磁化强度提高6.9%。研究结果表明, SPS烧结增强SMCs界面快速氧化还原反应, MnO₂氧化剂的添加使界面铁氧体离子浓度变化, 降低了B位电子跃迁频率, 提高有效波尔磁子数及B-B磁超交换作用, 表现出同时提高SMCs的软磁性能和电阻率的多重效应。     

Synthesis of Aluminium-Cementite Metal Matrix Composite by Mechanical Alloying

Cementite powder was prepared from elemental iron and graphite powder by mechanical alloying (MA) in a specially built dual-drive planetary mill. The phase evolution, particle-size distribution, and morphology of particles were studied during 40 hours grinding period. X-ray diffraction (XRD) shows formation of cementite and other iron carbides along with elemental iron after milling, whereas after annealing only cementite is present. Initially particle size increases with milling due to ductility of iron powder and then reduces with further milling.

Al-cementite composite was synthesized by mixing cementite with Al powders, and then by hot pressing or cold compaction and sintering. XRD analysis of Al-Fe₃C composite shows Fe₃C, FeAl, Al, and other iron carbides along with Al₄C₃ after sintering. Scanning electron microscope (SEM) micrograph of hot-pressed samples shows excellent compatibilility between Al matrix and cementite particles.     

A STUDY ON THE THERMAL STABILITY TO 1000°C OF VARIOUS CARBON ALLOTROPES AND CARBONACEOUS MATTER BOTH UNDER NITROGEN AND IN AIR

The thermal behavior of graphite, C₆₀ fullerene, fullerene black (carbon soot containing fullerenes), extracted fullerene black and diamond has been analyzed to 1000°C by TGA-DTA (thermogravimetric analysis and differential thermal analysis) under a nitrogen flow at a heating rate of 20°C/min. Very small weight losses have been recorded in the case of graphite and diamond. Furthermore no diamond graphitization has been observed. The sublimation of pure C₆₀ and the fullerene fraction of fullerene black (both pristine and extracted) has been observed and discussed.

The combustion reaction in air flow of graphite, C₆₀ and C₇₀ fullerenes, fullerene black (both unextracted and extracted), carbon nanotubes and diamond has been studied by TGA-DTA at a heating rate of 20°C/min. C₇₀ fullerene and fullerene black have been found to be the most reactive carbon materials with O₂. The role played by C₇₀ in the degradation of fullerites has been discussed. Among the carbon materials examined, the best resistance to O₂ attack has been shown by diamond and carbon nanotubes. The behavior of graphite is intermediate between diamond and fullerene blacks. The behavior of C₆₀ fullerene appears closer to that of graphite although it appears to be more reactive with O₂. Samples of graphite and carbon blacks N375 and N234 have been studied by TGA-DTA in air flow before and after a radiation treatment with neutrons or γ radiation. The effect of the radiation damage in the combustion reaction of these carbon materials has been discussed.     

AN FT-ICR STUDY ON LASER ABLATION OF GRAPHITE AND CARBON BLACK TARGETS: COSMOCHEMICAL IMPLICATIONS

Graphite and carbon black samples were laser ablated in an FT-ICR (Fourier transform-ion cyclotron resonance spectrometer) by Nd-YAG laser under high vacuum in conditions recalling those existing in the interstellar medium. It is shown that graphite gives a regular sequence of polyyne and cyclopolyyne chains from C₁₀ to C₂₇ and additionally produces 2% of C₆₀ fullerene. When carbon black is used in place of graphite under the same conditions, no C₆₀ fullerene was produced and also the sequence of polyyne species generated was very irregular. If really carbon black structure and elemental composition approaches more closely than pure graphite the structure of the carbon dust, we can predict that C₆₀ fullerene should not be produced from the thermal decomposition of this dust in high vacuum.     

Structural Analogies and Differences Between Graphite Oxide and C60 and C70 Polymeric Oxides (Fullerene Ozopolymers)

A brief survey of the chemical structural analogies and differences between graphite oxide and fullerene ozopolymers or polymeric fullerene oxides (PFO) is presented. Graphite oxide is the product of oxidation of graphite prepared with strong oxidizing agents while PFO is the products formed by prolonged ozonation of C₆₀ or C₇₀ in solution. Notwithstanding the different starting substrates and oxidation conditions, elemental analyses, FT-IR spectroscopy and ¹³C-NMR spectroscopy suggest a very similar chemical structure for graphite oxide and PFO. A further analogy is the possibility to perform reduction or oxidation reactions on both substrates considered. Graphite oxide and PFO have also in common the ability to act as ion exchangers and as metal ion binders. Even the thermal behavior is comparable. However, X-ray powder diffraction has confirmed that graphite oxide still has a layered structure derived from graphite but with the graphene sheets at much bigger distance from each other due to the intercalation of oxidized groups and solvent molecules, while PFO do not show at all any sign of layered structure either from the X-ray spectra and also by its behavior in solution which is strikingly different from that shown by graphite oxide.     

Characterization of mechanically alloyed ternary Fe–Ti–Al powders

The effects of Ti-substitution for Fe in the Fe₃Al system on the mechanical alloying process were investigated. For this purpose, blended elemental powders with the following nominal compositions (at.%): Fe₇₅Al₂₅, Fe₇₀Ti₅Al₂₅, Fe₆₅Ti₁₀Al₂₅, Fe₆₀Ti₁₅Al₂₅, were mechanically alloyed in a high energy attritor-type ball milling system for up to 100 h. The structural evolution in these powders was characterized by scanning electron microscopy, differential thermal analysis and X-ray diffraction techniques. It was found that elemental powders were progressively transformed into nanocrystalline solid solutions during mechanical alloying. The addition of Ti in the powders shortened the milling time for solid solution formation. With increasing Ti content, the grain size of the solid solutions decreased, but the lattice parameter increased. Upon heating, the milled powders were transformed into ordered (Fe,Ti)₃Al intermetallic compounds in an extended range of temperature (from 350 to 500°C). Ti addition enhanced the occurrence of DO₃ ordering in heated powders.     

Synthesis of Bulk Nano-Al2O3 Dispersed Cu-Matrix Composite Using Ball Milled Precursor

Kinetics of solid-state reduction reaction during ball milling of CuO-Al and CuO-prealloyed Cu(Al) powder blends in dry and wet condition has been investigated by using X-ray diffraction (XRD), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM) techniques. Direct reduction of CuO by Al has resulted into Al₂O₃ dispersed Cu-matrix composite through a self-propagating reaction only during milling in dry condition. However, indirect reduction of CuO by prealloyed Cu(Al) resulted into formation of nano-Al₂O₃ dispersed Cu-matrix composite either by continued ball milling in dry condition or by subsequent thermal treatment of wet milled powder precursor. The influence of milling conditions, that is, milling speed, and milling media, on the occurrence of reduction of CuO by elemental Al or Al in prealloyed Cu(Al) during ball milling have been explained by considering their effects on the rise of powder temperature due to collisions between balls and powder particles, and the rate of reduction of ignition temperature of the reaction due to microstructural refinement. TEM investigation has revealed that the size of Al₂O₃ particles in the composite power blend formed by the indirect reaction route (CuO-prealloyed Cu(Al)) is much finer than the same in case of direct reaction route (CuO-Al). It is suggested that the kinetics of the reduction reaction in the indirect reaction route is relatively sluggish in nature and amenable to processing of large amount of nano-Al₂O₃ dispersed Cu-matrix composite powder for industrial purpose.     

FORMATION OF FULLERENES AND CARBON CLUSTERS BY LASER IRRADIATION OF POLYMERIC FULLERENE OXIDE (FULLERENE OZOPOLYMER)

Polymeric fullerene oxide (PFO) prepared by prolonged ozonation of C₆₀ fullerene has been laser irradiated and the resulting products formed have been studied by ion cyclotron resonance mass spectrometry. It has been found that PFO produces a complete set of carbon clusters from C₆₀ up to C₁₆₄. The mechanism of formation of this set of fullerenic clusters implies necessarily a laser-induced carbonization step of the PFO substrate. Once the PFO target has been changed into the opportune carbon nanostructure by the laser radiation, the sequence of fullerene carbon clusters has been produced.     

粉末冶金(FeNiMnAl_(x))_(50)Cu_(50)中熵合金的微观组织与力学性能EI北大核心CSCD

对物理法制备的再生铜合金粉末进一步合金化,通过机械合金化(MA)结合放电等离子烧结(SPS)的方法制备了(Fe_(40)Ni_(40)Mn_(20))_(50)Cu_(50),(Fe_(38)Ni_(38)Ni_(38)Mn_(19)Al_(5))_(50)Cu_(50),(Fe_(36)Ni_(36)Mn_(18)Al_(10))50 Cu_(50)和(Fe_(32)Ni_(32)Mn_(16)Al_(20))_(50)Cu_(50)四种中熵合金块体,并研究了Al元素的含量对中熵合金微观组织与力学性能的影响。结果表明:在高能球磨60 h之后合金粉末完成合金化,四种中熵合金粉末均形成单一FCC相的过饱和固溶体且有微量WC杂质。经SPS烧结后,(Fe_(40)Ni_(40)Mn_(20))_(50)Cu_(50),(Fe_(38)Ni_(38)Mn_(19)Al_(5))_(50)Cu_(50)和(Fe_(36)Ni_(36)Mn_(18)Al_(10))50 Cu_(50)形成了由富Cu的FCC1相和富Fe-Ni的FCC2相组成的双相FCC结构,并具有超细晶+微米晶的多尺度结构;而(Fe_(32)Ni_(32)Mn_(16)Al_(20))_(50)Cu_(50)由富Cu的FCC主相和少量富Fe-Mn的FCC2相及富Ni-Al的BCC相(B2)组成。随着Al含量的提高,四种中熵合金的塑性逐渐降低,而强度和硬度逐渐提高。(Fe_(40)Ni_(40)Mn_(20))_(50)Cu_(50)合金的压缩屈服强度、抗压强度和维氏硬度分别为878 MPa,1257 MPa和248.5HV。与(Fe_(40)Ni_(40)Mn_(20))_(50)Cu_(50)相比,(Fe_(32)Ni_(32)Mn_(16)Al_(20))_(50)Cu_(50)的压缩屈服强度和硬度分别提高了50.1%和50.4%,断裂应变由19.55%下降至8.31%。     

机械合金化-放电等离子烧结Al2Cu颗粒增强Al基复合材料的制备

以Al粉和Cu粉为原料,采用机械合金化(MA)和放电等离子烧结(SPS)工艺,原位合成了致密的Al₂Cu/Al块体复合材料,着重研究了MA过程中粉末的形貌、尺寸和物相结构的变化以及SPS后复合材料的微观组织和力学性能。结果表明: 在MA过程中,随着MA时间延长,部分Cu原子逐渐固溶于Al原子晶格中,形成均匀过饱和的固溶体Al(Cu);在SPS过程中,Cu从过饱和固溶体中析出并与Al反应形成Al₂Cu颗粒,且弥散分布于Al基体中,形成Al₂Cu/Al复合材料;Al₂Cu/Al复合材料的致密度高达98.7%,室温下的压缩断裂强度为611.3 MPa,延伸率为9.6%,具有良好的力学性能。     

石墨/TiO2复合光催化剂的制备和性能

以石墨和纯的TiO₂为原料,采用球磨工艺制备了石墨/TiO₂复合光催化剂。使用XRD、SEM、TEM、XPS和DRS等手段对其性能进行了表征。以甲基橙为模拟污染物,研究了石墨掺入量、球磨时间对复合光催化剂光催化活性的影响。结果表明,石墨/TiO₂复合光催化剂具有锐钛矿结构,球磨后TiO₂(101)面的衍射峰宽化并右移,TiO₂成为200 nm左右的不规则球状颗粒,在其表面均匀分布着石墨。TiO₂晶粒的Ti-O键的结合能变高,且表面有缺陷产生,使其在可见光区具有显著的吸收。石墨掺入量为5%、球磨时间为12 h的石墨/TiO₂样品对甲基橙具有优异的光催化降解效果,在70 min的降解时间内甲基橙的降解去除率可达95.08%。石墨/TiO₂复合光催化剂的光催化反应速率常数k为0.043035 min^-1,是纯TiO₂的2.64倍。     

Mechanical alloying and microstructure of a Nb–20% V–15% Al alloy

A niobium-based alloy with 20% V–15% Al (at.%) was synthesized by mechanical alloying of elemental powders. During milling, the splitting of Nb X-ray peaks into two components was observed. Each component was found to correspond to a niobium solid solution (Nb_I and Nb_II) with a different lattice parameter. The intensities of Nb_I peaks on X-ray diffraction patterns decreased with the milling time and disappeared completely after 180 h of milling while the intensities of Nb_II peaks gradually increased. The powders were hot pressed and microstructural and phase analyses of the consolidated material were carried out. The microstructure consisted of Nb solid solution, Nb₃Al-base intermetallic with the A15 crystal structure and dispersoid Al₂O₃. Also an unexpected, detrimental, Nb₂Al-base σ phase was found. The volume fraction of the σ phase depended on the temperature of consolidation.     

ON THE MECHANISM OF CARBON CLUSTERS FORMATION UNDER LASER IRRADIATION. THE CASE OF DIAMOND GRAINS AND SOLID C60 FULLERENE

It is shown by FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry that carbon clusters considered to be the superior homologues of C₆₀ fullerene are formed by laser irradiation of both synthetic diamond grains or from pure C₆₀ fullerene crystals. The surfaces of the laser irradiated diamond or C₆₀ have been examined by Raman spectroscopy. In the case of diamond the Raman spectrum suggests the superficial formation of mixed carbon nanostructures consisting of disordered graphite, fullerenic nanostructures, onion-like carbon nanostructures and diamond-like carbon. Based on the Raman spectra of the surface and on data taken from the phase diagram of carbon, it is shown that the graphitization is needed in order to produce fullerenes from diamond under laser ablation conditions. In the case of C₆₀ fullerene, it is shown by Raman spectroscopy that the laser irradiation of the crystals causes initially their photopolymerization and after further irradiation their transformation into disordered graphite. Based on these results and on a literature survey on the formation of fullerenes from more than 15 completely different substrates, it is concluded that fullerenes are formed always when laser ablation leads to a graphitization of the laser-irradiated substrate. Some astrochemical implications of the conclusions have been discussed.     

Synthesis of MoSi2–Al2O3 nanocomposite by mechanical alloying

MoSi₂–Al₂O₃ nanocomposite was synthesized by mechanical alloying (MA) of MoO₃, SiO₂ and Al powder mixture. The structural evolution of the powders was studied by X-ray diffraction (XRD). Both β-MoSi₂ and -MoSi₂ were obtained after 3 h of milling. The spontaneous formation of β-MoSi₂ during milling proceeded by a mechanically induced self propagating reaction (MSR), analogous to that of the self propagating high temperature synthesis (SHS). After 70 h of milling the β-phase transformed to -phase. The crystallite size of -MoSi₂ and Al₂O₃ after milling for 100 h was 12 and 17 nm, respectively. Residual Mo and Si in the 3 and 70 h milled samples formed β-MoSi₂ and Mo₅Si₃ during heating at 1000 °C, respectively.     

Study of the Submerged Electric Arc in Hexane in Presence of C60 Fullerene

The effect of the electric arc between graphite electrodes submerged in n-hexane solutions of C₆₀ fullerene has been studied by electronic absorption spectroscopy, liquid chromatographic analysis (HPLC-DAD), and FT-IR spectroscopy. The experimental results show that C₆₀ does not appear able to inhibit the polyynes' formation at the concentration used. Polyynes are formed in large amounts as usual from the graphite arc, and polycyclic aromatic hydrocarbons have been detected as by-products. Prolonged arcing causes the disappearance of C₆₀ from the solution. There is experimental evidence that C₆₀ undergoes radical addition reactions during the early stages of arcing.     

Elevated temperature creep behavior of three rapidly solidified Al-Fe-Si materials containing Cr, Mn, or Mo

Research on the high temperature creep behavior of three rapidly solidified Al-Fe-X-Si (where X = Cr, Mn or Mo) dispersion strengthened materials with three different alloying compositions has been conducted. Firstly, microstructural examinations have been carried out on the as-received, thermally treated and tested samples. The microstructure consists of a fine Al matrix embedding small round-shaped Al₁₂(Fe,X)₃Si and Al₁₃(Fe,X)₄ dispersoids. Grain sizes ranging from 0.85 to 1.45 μm and dispersoid sizes ranging from 45 to 54 nm were observed. Secondly, tensile tests were performed at high temperature from 573 to 823 K at strain rates ranging from 2.5×10⁻⁶ to 10⁻²s⁻¹. The experimental data exhibited high apparent stress exponent, n_ap, and high activation energy, Q_ap. The rnicrostructure remained stable and fine after testing. The results are analyzed by means of various models used in the literature.     

ZrO2(Y2O3)含量对双峰晶粒度分布Mo-12Si-8.5B-ZrO2(Y2O3)复合材料力学性能的影响

多相Mo-12Si-8.5B合金是一种很有应用前景的高温结构材料,为了同时提高Mo-12Si-8.5B合金的强度和韧性,提出了采用纳米ZrO₂(Y₂O₃)强韧化具有双峰晶粒度分布Mo-12Si-8.5B复合材料的方法。首先采用溶胶-凝胶和高温氢还原法制备了纳米Mo-ZrO₂(Y₂O₃)复合粉末,然后以纳米Mo-ZrO₂(Y₂O₃)粉末和微米Mo粉末为原材料,采用放电等离子烧结(SPS)技术制备了具有双峰晶粒度分布的Mo-12Si-8.5B-ZrO₂(Y₂O₃)复合材料。结果表明,随着ZrO₂(Y₂O₃)含量的增加,制备的Mo-ZrO₂(Y₂O₃)纳米粉末的粒度和烧结体相对致密度均逐渐减小,ZrO₂(Y₂O₃)含量小于2.5wt%时,烧结体的相对致密度均大于98.1%。当ZrO₂(Y₂O₃)含量为1.5wt%和2.5wt%时,复合材料具有较高的硬度(9.76~9.98 GPa),抗弯强度(672~678 MPa)和断裂韧性(12.68~12.82 MPa·m1/2)。Mo-12Si-8.5B-ZrO₂(Y₂O₃)复合材料中Mo晶粒细化、粗细Mo晶粒的晶界强化和纳米ZrO₂(Y₂O₃)颗粒第二相强化是提高硬度和抗弯强度主要原因;复合材料中粗晶粒Mo和纳米ZrO₂(Y₂O₃)有助于断裂韧性的提高,材料的增韧机制主要是裂纹偏转和裂纹桥接。      

Microstructure characterization in cryomilled Al 5083

Nanocrystalline metals and alloys processed by severe plastic deformation (SPD) generally have improved mechanical strength compared with conventionally processed materials. In this work, we survey the microstructure of an Al 5083 alloy prepared by ball-milling powders at cryogenic temperatures (cryomilling) then consolidated by hot-isostatic pressing (HIPing) and extrusion into cylindrical billets. After milling, the particles are comprised of nanocrystalline grains, which are maintained following extrusion. We identify MgO, Al₆(FeMnCr), Al(MnFe)Si, AlCrMg, Mg₂Si, and SiO₂ phases as precipitates or dispersoids in the microstructure. This synthesis method results in a yield strength that is approximately twice that of typical wrought Al 5083 alloys. We find that the microhardness is essentially unchanged after annealing at temperatures up to 0.8T_m. The influence of the components of the microstructure on the measured mechanical properties is discussed.     

压铸(Al63Cu25Fe12)p/AZ91复合材料的组织、性能和热处理特征

在CO2/SF6气氛保护下,采用压铸的方法将-200目的Al63Cu25Fe12准晶粉末注入到熔融的AZ91镁合金中,于720℃和一定的压力下保压30min,制备了新型的(Al63Cu25Fe12)p/AZ91镁基复合材料.结果表明,在复合过程中,准晶相分解出的自由Cu向基体扩散并与基体中的Al发生反应,生成的金属间化合物分布在准晶颗粒周围,同时Mg向颗粒中浸渗填充到颗粒的孔隙中;复合材料具有不同于基体镁合金的固溶时效特征,需要更长的时间才能达到时效峰值;复合材料经过热挤压和热处理后的力学性能显著提高,抗拉强度从AZ91铸态材料的189.54MPa提高到359.38MPa,但塑性有所降低.