ZrO2/Al2O3复相陶瓷的制备及性能研究

本文以工业用ZrO2和α-Al2O3微粉为原料,通过干压成型和常压烧结工艺制备ZrO2/Al2O3复相陶瓷.通过检测复相陶瓷的体积密度、显气孔率、常温抗折强度、烧后线变化率和热震稳定性,研究不同α-Al2O3微粉加入量及添加剂Y2O3对ZrO2/Al2O3复相陶瓷烧结性能、常温强度、热震稳定性及微观结构的影响,并通过SEM方法对烧后试样的微观结构进行表征.结果表明:系统配料中加入Al2O3会降低ZrO2/Al2O3复相陶瓷的致密度,常温强度随着Al2O3加入量增大而呈现先增大后减小趋势,然而热震稳定性有一定程度改善.Y2O3作为一种助烧剂可以促进ZrO2/Al2O3复相陶瓷结构内晶粒长大,加入Y2O3有利于增强复相陶瓷的烧结性.     

超重力场中熔融铸造透明YAG陶瓷的新技术

以超重力技术结合燃烧合成熔融铸造方法制备钇铝石榴石(vtnium aluminum garnet,YAG)透陶瓷材料,以Al/NiO/Y2O3为反应剂,诱发各组元间的燃烧合成反应后获得陶瓷(YAG)和金属(Ni)的混合熔体产物,随后利用2种熔体的密度差异,在超重力场中实现陶瓷熔体和金属熔体的彻底分离和陶瓷的快速凝固,制备出YAG透明陶瓷材料.目前,所制备的YAG透明陶瓷相对密度最高达到99.30%,晶粒尺寸30～50 μm,并具有半透明效果.进一步优化超重力场与燃烧合成过程的耦合,有望发展成为一种快速制备透明陶瓷材料的新技术.     

燃烧合成复合陶瓷制备及固化过程温度场模拟

基于燃烧合成技术,在SHS铝热剂燃烧体系中添加ZrO2组元,采用超重力离心技术,制备出了Al2O3/YSZ共晶复合陶瓷板材.通过测定陶瓷熔体表层、石墨模具温度随时间的变化,结合有限元方法,对陶瓷熔体的固化过程温度场进行了有限元数值模拟分析.结果表明:随着复合陶瓷熔体冷却速度的降低,气孔与宏观裂纹等缺陷消失,晶粒形貌也由棒状共晶团转化为胞状共晶团.     

固相反应法制备透明多晶YAG陶瓷

采用高纯α-Al2O3和Y2O3作为原料并由固相反应法合成了钇铝石榴石(yttrium aluminum garnet,YAG)透明多晶陶瓷.α-Al2O3和Y2O3的摩尔比为5∶3,并添加0.5%(质量分数)正硅酸乙脂为烧结助剂的混合粉体经球磨后,在1 400℃空气中煅烧,经成形并在1 750℃真空烧结4h制备得到透明YAG陶瓷.1 850℃真空烧结4h的YAG陶瓷晶粒粗大,晶界宽化,晶界处有共晶相YAlO3相和α-Al2O3相存在.     

YSZ/MgAl_2O_4复合粉末的合成及其材料的烧成活化能

采用共沉淀法在1100℃制备了70%(体积分数,下同)氧化钇稳定氧化锆[xY2O3+(1-x)ZrO2,x=0.02,0.03,0.04,in mole,yttria stabilized zirconia,YSZ]-30%镁铝尖晶石(MgAl2O4)复合粉体,2种原始粉料的配料各为70%和30%,并在1200～1500℃常压烧成制备了陶瓷材料。结果表明:在制得的所有粉末中,未发现单斜相ZrO2;2YSZ(0.02Y2O3+0.98ZrO2,摩尔分数,下同)/MgAl2O4和3YSZ/MgAl2O4这2种粉体中的ZrO2为四方相多晶氧化锆;而4YSZ/MgAl2O4粉末中的ZrO2相为全稳定立方氧化锆。对于1500℃烧结制备的陶瓷材料,2YSZ/MgAl2O4块体中的ZrO2相为部分稳定氧化锆;而3YSZ/MgAl2O4和4YSZ/MgAl2O4块体中的ZrO2相为全稳定氧化锆。(2～4)YSZ/MgAl2O4复相陶瓷的活化能为(623±80)kJ/mol。     

机床用Al_2O_3/TiB_2复相陶瓷刀具材料的研究

以α-Al2O3和TiB2为主要原料,采用真空热压烧结工艺制备机床用Al2O3/TiB2复相陶瓷刀具材料。测试和分析了烧结样品的相对密度、弯曲强度、断裂韧性、硬度值、相组成以及显微结构。结果表明,当α-Al2O3添加量为75 wt%,微米TiB2添加量为20 wt%时,所制备的Al2O3/TiB2复相陶瓷刀具材料性能最佳,其相对密度值为98.8%,弯曲强度为606.25 MPa,断裂韧性为4.85 MPa·m1/2,硬度值为26.55 GPa。最佳样品的主晶相为刚玉(Al2O3)和硼化钛(TiB2),次要晶相为氧化钇(Y2O3)。     

激光近净成形Al_2O_3–YAG复合陶瓷薄壁件微观组织与力学性能分析

采用同轴输送Al2O3–Y2O3粉末激光近净成形方法进行复合陶瓷薄壁件成形实验,使用扫描电子显微镜,X射线衍射及电子探针显微分析仪对成形薄壁样件微观组织、物相组成及元素含量进行检测,通过压痕法测量样件显微硬度与断裂韧性。结果表明:同轴输送Al2O3–Y2O3粉末激光近净成形可得到Al2O3–YAG复合陶瓷件,主要由α-Al2O3和YAG两相组成,但同时存少量亚稳态YAP或YAM相;薄壁样件内部主要由粗大的富YAG初生相和Al2O3/YAG交错生长的网状共晶组织组成,成形过程中Al2O3较易挥发,不同高度位置重熔次数影响Al相对挥发量,导致两相比例不同,由顶部到底部,富YAG初生相尺寸和比例增大,成形过程中,高温促使亚稳相向YAG转化加剧这一现象;压痕法测量样件显微硬度为16 GPa,断裂韧性为2.89 MPa·m1/2,说明该方法可得到性能较好的陶瓷件。     

Y_2O_3-Al_2O_3粉体固相反应制备Y-Al-O体系陶瓷的对比研究

研究了摩尔比n(Y2O3):n(Al2O3)分别为2:1、1:1和3:5的粉体在不同温度发生的相变及其高温烧结的陶瓷。Y2O3-Al2O3粉体经球磨后在1750℃真空烧结制备陶瓷。用差热-热重、X射线衍射及扫描电子显微镜表征制备的Y2O3-Al2O3材料。结果表明:在低于800℃时,Y2O3-Al2O3之间未发生反应;在1000℃煅烧后,出现Y4Al2O9(YAM)相;1200℃煅烧后,出现YAlO3(YAP)相和钇铝石榴石(yttrium aluminumgarnet,YAG)相。n(Y2O3):n(Al2O3)=3:5粉体在1400℃煅烧后生成YAG纯相。n(Y2O3):n(Al2O3)=2:1、3:5粉体烧结的陶瓷的物相分别为YAM相和YAG相,其相对体积密度分别为97.8%和99.95%,n(Y2O3):n(Al2O3)=1:1粉体烧结陶瓷的物相为多相共存,3种配比制备陶瓷断口的形貌差别较大。     

添加MgO对不同SiO2含量的ZrO2-Al2O3-SiO2陶瓷烧结的影响

以高纯石英砂、α-Al2O3、ZrO2为原料,MgO为添加剂(添加质量分数分别为0、1%、2%、3%),经研磨、造粒、成型,并在1 600℃烧结2 h后获得了SiO2含量(w)分别为4%、8%、12%的ZrO2-Al2O3-SiO2系陶瓷试样。采用XRD、SEM对试样进行物相和显微结构的分析。结果表明:1)所制备的ZrO2-Al2O3-SiO2陶瓷的主要物相是单斜氧化锆、莫来石和刚玉,随着SiO2含量(w)由4%增加到12%,SiO2与Al2O3反应生成的莫来石量增加,体积膨胀效应越发明显,导致烧结试样的致密度降低;2)添加MgO促进了ZrO2-Al2O3-SiO2陶瓷的烧结,在SiO2含量为4%(w)的陶瓷中加入1%(w)的MgO时,烧结试样的致密度最大,其相对密度达到90.49%,体积密度为3.90 g·cm-3。     

3Y-TZP/Al_2O_3复合粉末的相变研究

采用化学共沉淀法制备了 3Y -TZP/Al2 O3纳米级复合粉末 ,研究了Al2 O3含量和煅烧温度对粉末的相结构和ZrO2 晶格常数的影响 .研究表明 :80 0℃ ,1h煅烧的复合粉末只出现t-ZrO2 相 ,不出现Al2 O3的任何晶相 ,当Al2 O3质量分数不大于 10 %时 ,ZrO2 晶格常数随Al2 O3含量增加而减小 ,但当Al2 O3质量分数为 2 0 %时 ,ZrO2 晶格常数反而略有增大 ;当温度升至 12 0 0℃时 ,开始形成α -Al2 O3,Al2 O3对ZrO2 晶格常数的影响减小 ;当温度达到 14 5 0℃时 ,完成了向α-Al2 O3的转变 ,故Al2 O3不再对ZrO2 晶格常数产生影响 .     

Preparation and properties of poly(Nε,Nε-dicarboxymethyl-l-lysine)

A new ampholytic homopolypeptide, $\text{poly}\text{(N}{}^{\mathrm{\epsilon }}\text{,N}{}^{\mathrm{\epsilon }}\text{-}\text{dicarboxy-methyl-}\text{l}\text{-lysine}\text{)}$, which has one tertiary amino and two carboxyl groups in the side chain has been derived from a hydrochloride salt of poly(L-lysine). The polymer in aqueous solution seems to be in the coil form with locally extended structure (LES) at neutral pH. In both the acidic and alkaline regions, the molar ellipticity of the polymer changes as a result of change in net charge on the side chain. The conformational changes may be from the coil with LES to other coiled forms. 5–7 M NaClO₄ and 80% aqueous methanol induce the α-helix in the polymer at neutral pH. Divalent cations, Cu²⁺ and Ca²⁺, do not induce any remarkably ordered structures such as α-helix or β-structure in the polymer in aqueous solution at any pH. Ultraviolet absorption studies show an absorption peak of the polymer-Cu²⁺ complex near 240 nm. Dependence of the peak intensity on pH at various q values ($\text{q =}\text{[}\text{Cu}{}^{\mathrm{2+}}\text{]}\text{[}\text{residue}\text{]}$) indicates the two steps of the complex formation. At q less than 0.64, the formation is described only with the first step. An average coordination number for Cu²⁺ at the first step was calculated to be about 2 by the method of Mandel and Leyte. The association constant of Cu²⁺ with the residue at the step was determined from the absorption data to be far smaller than that for the Cu²⁺-EDTA complex. The second step of the formation occurs in the case of large q but the absorption data for the second step cannot be obtained exactly due to precipitation.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

Participation of lewis base on vinyl chloride polymerization with Al(C2H5)3CCl4 catalyst system

The polymerization of vinyl chloride has been investigated using an $\text{Al}\text{(}\text{C}{}_2\text{H}{}_5\text{)}{}_3\text{CCl}{}_4$ catalyst system in the presence of various Lewis bases. Effective Lewis bases are γ-butyrolactone, diglyme and diethylenetriamine which are multidentate. The rate of polymerization is dependent not only on the basicity of the Lewis base used but also on a coordination number of one. The latter is the predominant factor. For the effect of polymeric amines, a tentative hypothesis is discussed.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

Synthesis and Characterization of Ti0.33Ta0.33Nb0.33C and Ti0.33Ta0.33Nb0.33CxN1-x Whiskers

Ta_0.33Ti_0.33Nb_0.33C and Ta_0.33Ti_0.33Nb_0.33C _x N_{1− x} whiskers were synthesized via a carbothermal vapor-liquid-solid growth mechanism in the temperature range 900°-1450°C in Ar or N₂. The optimum temperature was 1250°C. Whiskers were obtained in a yield of 70-90 vol%. The whiskers were 0.5–1 µm in diameter and 10–30 µm in length. The starting materials that produced the highest whisker yield were: TiO₂, Ta₂O₅, Nb₂O₅, C, Ni, and NaCl. C was added to reduce the oxides, and Ni to catalyze whisker growth. NaCl was used as a source of Cl for vapor-phase transportation of Ta and Nb oxochlorides and Ti chlorides to the catalyst. The catalyst metal was recycled several times during the synthesis and was transported as NiCl₂( g ) according to thermodynamic calculations. The rate of formation and the chemical composition of the whiskers depended on the synthesis temperature, the choice of catalyst, and the atmosphere. At low temperatures, the whiskers were enriched in Nb and Ta, whereas the Ti content increased with increased synthesis temperature.