熔体浸渍技术制备SiCp/AlN复合材料

采用熔体浸渍技术，研究了在高纯氮气氛下Al—Mg—Si合金反应浸渍碳化硅预形体制备SiCp／AlN复合材料．借助XRD，SEM／EDS，EMPA等测试手段检测了产物的物相组成，观察了材料的微观形貌，并对复合材料微区成分进行了分析。结果表明：1200℃下，在氮气气氛中用Al—Mg—Si合金反应浸渍碳化硅形成了SiCp／AlN复合材料。在氮化温度下，Al—Mg—Si合金中的Mg元素极易蒸发，与气氛中的微量氧发生反应，起到深脱氧作用，而Si元素的存在使Al—Si熔体容易浸渍渗透进入SiC预形体中，同时氮化反应生成AIN，形成了以AIN／Si为三维骨架，SiC呈孤岛状结构的SiCp／AlN复合材料。生长前沿氮化铝以胞状方式生长，胞内由呈放射状生长排列的柱状晶氮化铝构成，柱晶之问有大量的通道间隙，Si元素在胞内呈不均匀分布，胞边缘部分的硅含量明显高于胞中心部分，这与柱状氮化铝的生长机理有关。     

MgO对Al-Zn-Si合金直接熔融氧化的影响

为了抑制熔融铝合金直接氧化过程中的胞状生长,优化复合材料的组织结构,通过热重实验,研究了在熔融Al-Zn-Si合金表面覆盖MgO引发剂对其氧化生长过程的影响.结果表明:MgO能显著缩短铝合金熔融氧化过程的孕育期及Al2O3/Al复合材料的生长时间,有助于复合材料以光滑方式进行氧化生长.Al2O3/Al复合材料结构的不同区域出现均匀度和致密度不同的现象,是Al-Zn-Si和Al-Mg-Si合金不同氧化生长机制共同作用的结果.     

界面反应对铝熔体定向渗透氮化过程的影响

将外形尺寸为φ15 mm×10 mm的一级工业纯铝锭(w(Al)=99%)6.5 g放入石墨坩埚内,在其四周及底部填充氧化铝粉阻生剂,采用粒度均为1～0.5 mm、固定量均为3 g的电熔镁砂(w(MgO)=95%)、镁铝尖晶石(31.9%MgO,58.1% Al2O3)和电熔刚玉(w(Al2O3>)=95%)3种颗粒作为填充剂,分别与占铝锭质量10%的金属Mg粉(w(Mg)=99%)混合后,松散堆积在铝锭表面上,在1 200℃氮气气氛中处理10 h.利用XRD、SEM、EPMA及OM分析了反应后得到复合材料的物相组成和显微结构,研究了定向金属氮化制备氮化铝基复合材料过程中金属铝熔体和填充剂间的界面反应对渗透氮化的影响.结果表明:1 200℃下,镁砂与铝熔体剧烈反应生成大量镁,促进了铝熔体的渗透和氮化过程;镁铝尖晶石与铝熔体反应明显减弱,但生成少量的镁,也在一定程度上有利于渗透和氮化过程;相比之下,刚玉与熔体界面反应消耗了反应体系的镁,影响了铝熔体的渗透,但渗入铝的氮化较为完全,且复合材料结构致密.     

Zr-Si合金熔渗改性C/C复合材料的微观结构及耐高温氧化机理研究

采用Zr-Si合金在较低温度下熔渗制备了不同密度的C/C-ZrC复合材料,研究了不同密度C/C多孔体的熔渗行为以及不同密度复合材料的相组成和微观形貌,并且在1 500℃下对其静态氧化行为进行了研究。结果表明:中等密度多孔体熔渗较为理想,气孔率仅为4.78%。随着原材料密度的增加,C/C-ZrC复合材料密度增量相应下降。物相分析显示,C/C-ZrC复合材料由C,ZrC,Zr和Zr_2Si组成,未发现SiC相的存在。微观结构解析表明,反应生成的ZrC陶瓷相主要集中在网胎层,合金除与C基体反应生成ZrC层外,在熔体内部也有部分ZrC析出。论文从界面反应以及元素扩散的角度探讨了熔渗机理。C/C-ZrC复合材料在1 500℃静态氧化后的产物主要包括单斜相ZrO_2和非晶态SiO_2,未能形成致密氧化膜,改性后的样品失重率随着熔渗增重增大而减小。     

氮化烧成铝–方镁石–刚玉复合材料的显微结构和反应机理

在刚玉(电熔刚玉、板状刚玉)–高纯镁砂中加入质量分数分别为0、4%、6%、10%的铝粉,在碳管炉1 600℃氮气气氛下制备Al–Mg O–Al_2O_3复合材料。结果表明:烧后试样的主晶相为刚玉和镁铝尖晶石固溶体,基质是由镁铝尖晶石固溶体、氮化铝、Al ON和Mg Al ON等增强相组成的复合结构。随铝粉含量增加,Al N、Al ON和Mg Al ON含量增加且存在未反应的铝粉。铝粉氮化机理为Al反应生成Al N,Al N与Al_2O_3固溶形成Al ON相,氧化镁或新形成的尖晶石与Al ON相固溶形成Mg Al ON相。建立了金属铝粉氮化反应模型,反应模型呈明显的环状结构:内层产物为未反应的铝和反应后形成的微孔;中间层产物为氮化铝和阿隆的复合结构;外层环带状产物为阿隆和镁阿隆的复合结构。电熔刚玉颗粒部分参与反应形成环带状镁铝尖晶石固溶体。     

气氛对TiO_2碳热还原氮化反应的影响

为研究反应气氛对TiO_2碳热还原氮化反应产物相的影响,以电极石墨和锐钛矿型钛白粉为原料,分别在nTi∶nC为1∶2. 1、1∶3、1∶4的配碳量下配料,在1 550 K的反应温度下分别进行流动氮气、空气中埋碳、流动氮气中埋碳三种不同气氛下的碳热还原氮化反应。依据热力学计算得出的Ti-C-O-N体系不同相的稳定存在区域,并利用SEM、EDS和XRD等研究了产物的化学矿物组成、微观组织形貌,以探讨气氛对反应的影响机制。结果表明:在流动氮气中埋碳的气氛下反应时,较之目前常见的流动氮气、空气中埋碳等气氛下的反应更彻底,氮化率更高,是一种高效、节能的新型反应条件。在流动氮气中埋碳的气氛下反应时,n_(Ti)∶n_C=1∶3为反应的最佳配碳量,此时的试样表面生成了TiN_(0. 93)、Ti(C_(0. 4),N_(0. 6))等钛族非氧化物。     

反应熔渗C_f/(ZrB_2)-ZrC-SiC超高温陶瓷基复合材料的优化制备及性能

受熔渗动力学控制,常规反应熔渗制备的超高温陶瓷基复合材料易存在纤维/界面损伤,基体大尺寸金属残留等问题,严重影响复合材料性能。近年来,中国科学院上海硅酸盐研究所建立了基于溶胶-凝胶预成型体孔隙结构设计的超高温陶瓷基复合材料反应熔渗新方法,揭示了预成型体孔隙结构对复合材料基体分布、界面损伤及性能的影响规律;发现反应熔渗超高温陶瓷基复合材料界面锆元素聚集现象,并首次提出反应-类熔融界面损伤机制;提出准连续ZrC界面保护结构设计思路,有效缓解了反应熔渗纤维/界面损伤,实现反应熔渗C_f/(ZrB_2)-ZrCSiC超高温陶瓷基复合材料性能大幅提升。     

原位合成Al2O3-TiN复合材料的结构特征

以纯度均为99%(质量分数)的板状刚玉,α-Al2O3微粉、TiO2微粉及金属铝粉为原料,经机械复合法制样后在流动氮气下利用常压铝热还原原位反应烧结的方法制备了Al2O3-TiN复合陶瓷材料.分析了不同的TiN生成量、烧结温度对试样的力学性能及显微结构的影响.结果表明:生成的TiN含量在10wt%的试样经过1500℃保温3 h后复合材料体积膨胀率为3.27%,体积密度为2.85g/cm3、显气孔率28.73%、抗折强度23.81 MPa.显微结构分析表明,无压烧结作用下,铝热还原氮化反应并未发生典型的烧结过程,烧结温度、TiN的自身性质、反应的强放热以及TiN和Al2O3线膨胀系数之间的差别严重影响了复合材料的烧结致密化.     

SiCp/Al复合材料的自发熔渗机理

以Mg为助渗剂,采用液态铝自发熔渗经氧化处理的SiC粉体压坯的方法,制备出高增强体含量的SiCp/Al复合材料.通过考察铝液在SiC粉体压坯中的渗入高度与温度、时间的关系来研究铝液的熔渗机理,并对SiCp/Al复合材料进行X射线衍射、能量散射谱和金相分析.结果表明:在熔渗前沿发生的液-固界面化学反应促进两相润湿,毛细管力导致铝液自发渗入到SiC多孔陶瓷中;熔渗高度与时间呈抛物线关系.熔渗激活能为166 kJ/mol,这表明渗透过程受界面反应控制.经氧化处理的SiC粉体均匀地分布在金属基体中,其轮廓清晰.在SiCp/Al复合材料中未发现Al4C3的存在.     

碳纤维增强超高温陶瓷基复合材料的多相反应制备与抗烧蚀性能

为提高C/C复合材料在2000℃以上有氧环境中的抗氧化烧蚀性能,本研究采用ZrB₂浆料浸渍、ZrC-SiC前驱体浸渍裂解与Si-Zr10共晶合金反应熔渗复合工艺制备了C/C-SiC-ZrB₂-ZrC复合材料,细致研究了复合材料在熔渗过程中的基体微观结构演变机理及其力学性能和抗烧蚀性能。结果表明,在反应熔渗结束后的降温阶段,部分ZrC陶瓷与残余Si熔体通过原位固-液反应转化为ZrSi₂和SiC,生成的亚微米级SiC颗粒均匀镶嵌于ZrC-ZrSi₂二元混合物中,最终形成ZrC-ZrSi₂-SiC三相混合微区。制备的C/C-SiC-ZrB₂-ZrC复合材料密度为3.18 g/cm³,开孔率为2.77%,其弯曲强度和弯曲模量分别为121.46±13.77 MPa和21.78±5.56 GPa。在其断口处能观察到较长且较多的单丝纤维拔出以及明显的界面脱黏,这表明复合材料的失效方式为韧性断裂。经2000℃,300 s的大气等离子体烧蚀,复合材料表...     

Microstructural evolution in MgOp/AlN composites

MgO_p/AlN composite has been fabricated by directed melt nitridation of pure Al block covered with a powder mixture of 0.5–1 mm magnesia particles and 0.075–0.15 mm chemically pure magnesium powder in flowing N₂ in the range of 900–1200 °C. The extent of Al nitridation and the depth of Al penetration into the MgO particles increases with temperature. The phase composition in the matrix from metal rich to ceramic rich can be adjusted by controlling processing temperature. A multilayer microstructure of MgO/MgAl₂O₄/AlN surrounds the MgO particles due to the interface reaction. The thickness of each layer in this structure varies with processing parameters such as the temperature and local Mg concentration, depending on the influence of these processing parameters on the interface reaction of MgAl₂O₄ formation and Al nitridation.     

Evolution mechanism of MgAlON in the Al-Al2O3–MgO composite at 1800 °C in flowing nitrogen

The Al-Al₂O₃–MgO composite was calcined at 1800 ℃ in flowing nitrogen, using fused corundum, tabular alumina, activated α-Al₂O₃, high purity magnesia and metal aluminum powder as raw materials and magnesium aluminate sol as binding agent. The calcined sample was characterized and analyzed by XRD, SEM and EDS, and evolution mechanism of MgAlON was studied. Formation mechanism of MgAlON can be described as follows. At elevated temperatures in flowing nitrogen, Al(g)/Al₂O(g) diffuses and transfers along pores or gaps in the Al-Al₂O₃–MgO composite, being nitrided as AlN, and then AlN reacts with Al₂O₃-rich spinel to form granular MgAlON. In gas-gas reaction system, Al(g)/Al₂O(g), N₂(g), Mg(g) and O₂(g) react to form flake MgAlON.     

Preparation of aluminum nitride by combustion of a Mg-Al alloy

Aluminum nitride (AlN) was synthesized by combustion of spherical Mg–Al alloy particles in air. Alloy powder was freely poured on a sample table, which formed a cone with a diameter of 1-2 cm. A commercial electro-thermal furnace was used to ignite the cone to start the synthesis. During the combustion, the temperature was measured and the actual burning process was recorded by a video camera. The morphology and phase makeup of the raw powders and the synthesized AlN powders were analyzed by scanning electron microscopy and X-ray diffraction. The thermodynamic properties and ignition temperatures were studied using differential scanning calorimetry and thermogravimetric analysis. Moreover, the effects of the Mg–Al alloy particle size (212.8 μm, 124.1 μm, 61.1 μm, and 29.5 μm) on the morphology of AlN were investigated. The results show that the combustion of Mg greatly promoted the nitridation of Al and that Al in both large and small alloy particles could be completely converted into AlN. The combustion products of the alloy consisted of two different layers: an upper white layer containing MgO and a lower black layer containing AlN. More AlN whiskers formed when small particles were used. However, very small Mg–Al alloy particles hindered the formation of AlN whiskers.     

逆反应烧结制备碳化硅/氮化硅复合材料的工艺

制备Si3N4／SiC复合材料的常规反应烧结是以Si和SiC为原料进行氮化烧结,而逆反应烧结是以Si3N4和SiC为原料,首先使Si3N4反向反应为活性氧化物后再进行烧结。建立逆反应烧结工艺制备Si3N4／SiC复合材料的热力学基础。确定了Si3N4先于SiC氧化;氧化产物可以是SiO2,也可以是Si2N2O;形成的SiO2氧化膜不会与基体材料反应;在膜与基体之间可能生成Si2N2O。论证了逆反应烧结的热力学可行性。通过6个烧结实验,证实了其热力学分析的正确性,并从工艺参数与密度变化、残氮率和比强度等关系筛选出最佳的烧结工艺参数。     

Low‐Temperature Synthesis of Aluminum Nitride from Transition Alumina by Microwave Processing

Aluminum nitride (AlN) was synthesized by carbothermal reduction and nitridation method from a mixture of various transition alumina powders and carbon black using 2.45 GHz microwave irradiation in N₂ atmosphere. We achieved the synthesis of AlN at 1300–1400°C using 2.45 GHz microwave irradiation for 60 min. Our results suggest that θ‐Al₂O₃ is more easily nitrided than γ‐, δ‐, and α‐Al₂O₃. On the other hand, nitridation ratio of samples synthesized in a conventional furnace under nitrogen atmosphere were zero or very low. These results show that 2.45 GHz microwave irradiation enhanced the reduction and nitridation reaction of alumina.     

Effect of nitriding atmosphere on the morphology of AlN nanofibers from solution blow spinning

High purity AlN fiber is a promising thermal conductive material. In this work, AlN fibers were prepared using solution blow spinning followed by nitridation under N₂ or NH₃ atmosphere. Soluble polymer, such as polyaluminoxane, and allyl-functional novolac resin were adopted as raw materials to form homogeneous distribution of Al₂O₃ and C nanoparticles within the fibers, which could inhibit the growth of alumina crystal and promote their nitridation process. The effect of nitriding atmosphere on the fiber morphology was investigated. XRD results showed that complete nitridation was achieved at 1300 °C in the NH₃ or at 1500 °C in the N₂ atmosphere. Hollowed fiber structure was observed when fiber was nitrided in N₂ at high temperature, which was caused by gaseous Al gas diffusion, and this phenomenon was eliminated in NH₃ atmosphere. The nitridation mechanisms in different atmosphere were analyzed in detail. It was demonstrated that the nitridation of Al₂O₃ fibers in the NH₃ atmosphere offered the favored AlN morphology and chemical quality. Flexible AlN fiber with O content of 0.7 wt% was achieved after nitriding in NH₃ at 1400 °C. The high quality AlN can be used in thermal conductive composite materials.     

Reaction Synthesis of Aluminum Nitride–Boron Nitride Composites Based on the Nitridation of Aluminum Boride

Aluminum nitride–boron nitride (AlN–BN) composites were prepared based on the nitridation of aluminum boride (AlB₂). AlN powder was added to change the BN volume fraction in the obtained composites. Thermogravimetry–differential thermal analysis (TG-DTA), X-ray diffractometry, and the nitridation ratio were used to investigate the nitridation process of AlB₂. At ∼1000°C, a sharp exothermic peak occurred in the DTA curve, corresponding to the rapid nitridation of aluminum in AlB₂. On the other hand, the nitridation of the transient phase, Al_1.67B₂₂, was very slow when the temperature was <1400°C. However, the nitridation speed obviously accelerated at temperatures >1600°C. The pressure of the nitrogen atmosphere was also an important factor; high nitrogen pressure remarkably promoted nitridation. Treatment at 2000°C was disadvantageous for nitridation, because of the rapid formation of a dense surface layer that inhibited nitrogen diffusion into the specimen interior. Three specimens, with 5 wt% Y₂O₃ additive and different BN contents, were prepared by pressureless reactive sintering, according to the determined sintering schedule. Electron microscopy (scanning and transmission) observations revealed that the in-situ -formed BN flakes were homogeneously and isotropically distributed in the AlN matrix. A schematic mechanism for microstructural formation was developed, based on the results of nitridation and the microstructural features of the obtained composites. The obtained composites, with a low BN content, exhibited a high bending strength, comparable to that of reported hot-pressed AlN–BN composites.     

Combustion Synthesis of AlON–BN Composites under Low Nitrogen Pressure

Hexagonal boron nitride (hBN) and aluminum oxinitride (AlON) composites were synthesized by combustion reaction of powder mixtures of Al–B₂O₃–AlN systems under a low pressure of nitrogen gas (0.5 MPa). Explosive combustion reaction of Al–B₂O₃ systems under the same nitrogen pressure produced alumina, aluminum borate, AlN, and AlON depending on the binary mixing ratio, but no trace of BN phases could be identified. Most of the elemental boron product remained unreacted and amorphous. On the other hand, AlN addition as a diluent in the range of 15–30 wt% was effective in producing hBN phase and forming AlON–BN composites. In the composition range of the ternary mixture of Al, B₂O₃, and AlN, where significant BN formation was identified, the primary role of AlN was to react with B₂O₃ to produce BN and α-Al₂O₃. The temperature profile obtained during the combustion reaction by a thermocouple imbedded in the middle of the powder bed revealed that the initial nitridation reaction of aluminum metal provides the heat required for the combustion reaction, creating a state of a "chemical oven." The reaction product, α-Al₂O₃, reacted subsequently with AlN to produce AlON phases to give final AlON–BN composites. The combustion reaction was highly unstable and followed a mixed mode with a regularly reversing spinning mode for aluminum nitridation reaction in the surface region and an oscillatory mode for the BN formation reaction in the subsurface region.     

Preparation of nanometer AlN powders by combining spray pyrolysis with carbothermal reduction and nitridation

Nanometer AlN powders were prepared by combining spray pyrolysis with carbothermal reduction and nitridation (CRN). The aluminum oxide/carbon composite powders prepared by spray pyrolysis from a sucrose spray solution were several microns in size, with hollow and porous structures. Precursor powder with 67 wt% carbon content was transformed into phase-pure AlN powder by CRN at temperatures above 1,400 °C. The hollow-structured AlN powder was ground to 20 nm mean size by simple milling.     

Nitridation reaction of aluminum powder in flowing ammonia

AlN powder was prepared by the nitridation of metal Al in flowing NH₃. The effects of reaction temperature and the temperature gradient of the reaction zone on the nitridation of Al were investigated. Comparative analysis of products formed in different reaction zones and reaction temperatures suggested that the nitridation reaction of liquid Al particles in flowing NH₃ was through the following mechanisms: NH₃ dissociated into reactive nitrogen (N) and hydrogen (H) radicals at the surface of Al particles. N reacted with Al to form AlN, while H promoted the decomposition of NH₃, which provided enough energy for the dissociation of NH₃. All of the experimental results had been discussed on the basis of this model, which indicated high reaction temperature or positive temperature gradient was favorable for the nitridation of Al.