PEG对A1203陶瓷凝胶注模成型坯体表面起皮的抑制研究

采用凝胶注模工艺制备Al2O3,陶瓷过程中,在单体和交联剂的预混溶液中加入适量的聚乙二醇(PEG),能有效克服单体聚合的氧阻聚问题,从而消除陶瓷坯体的表面起皮现象.本文研究了PEG的用量对氧化铝粉体的分散特性、浆料的粘度以及坯体表面形态等影响,并初步讨论了PEG对凝胶化过程中氧阻聚效应的抑制作用.     

95氧化铝瓷凝胶注模浆料的制备及氧阻聚的抑制

本文研究95氧化铝瓷凝胶注模成型中浆料的流变性.分析了pH值、分散剂用量、球磨时间对浆料粘度的影响.采用L_9(3~4)正交试验,制备出固相含量为58 vol;,粘度为110 mPa · s的95氧化铝瓷浆料.针对表面氧阻聚,本文通过表面改性的方法,既不增加坯体内有机物的含量,也不降低坯体的强度,使坯体表面不起皮、不剥落.结果显示:通过坯体性能参数和显微结构的比较,凝胶注模的95氧化铝瓷坯体性能均优于热压铸成型的坯体性能.     

Al_2O_3陶瓷坯体的激光加工性能研究

本文系统研究了凝胶注模成型的Al2O3陶瓷坯体在CO2激光作用下的加工性能。陶瓷坯体的激光加工性能受许多工艺参数影响。对固相含量、粉体粒度、水分含量等参数对陶瓷坯体的加工效率的影响进行实验研究。通过调整工艺参数,获得最佳的陶瓷坯体的激光加工工艺参数。     

注凝成型制备氧化锆增韧氧化铝陶瓷

采用低毒单体N,N-二甲基丙烯酰胺(DMAA)制备了氧化锆增韧氧化铝(ZrO2/Al2O3,ZTA)陶瓷,氧化铝与氧化锆的质量比为3∶1,浆料的固相体积分数为50 vol%。讨论了不同干燥方式对干燥速率以及坯体性能的影响,研究了不同成型温度对坯体性能的影响。通过研究发现,在湿热烘箱中干燥的坯体强度最高,成型温度应控制在65℃附近。通过对不同单体含量的坯体烧结后陶瓷性能的对比,发现单体的加入量为10wt%左右较好,通过与干压成型陶瓷性能的对比,发现注凝成型得到的陶瓷强度和韧性分别提高了42.2%和23.5%,达到640 MPa和6.3MPa.m1/2,通过扫描电镜图片分析发现,注凝成型制得的陶瓷结构更均匀。     

聚乙二醇用于注凝成型ZrO2坯体干燥研究

研究了注凝成型ZrO2坯体在聚乙二醇(PEG)溶液中的干燥过程,结果证明,随着PEG溶液浓度的增加,坯体脱水速度加快,平衡时残余水分降低;坯体固相含量越低,在PEG溶液中的脱水速度越快,干燥时间越短;随坯体尺寸增加,脱永速度降低,平衡时残余水分增高;注凝成型ZrO2坯体先在PEG溶液中脱水至平衡状态,再放置到空气中干燥,可以避免变形、开裂等缺陷的产生.     

凝胶注模成型Al2O3陶瓷的显微结构及力学性能研究

以Al2O3粉为原料,TiO2+MgO为烧结助剂,琼脂糖为单体,聚丙烯酸铵为分散剂,利用凝胶注模及无压烧结工艺制备了Al2O3陶瓷.研究了琼脂糖固化机制、烧结助剂作用机理以及琼脂糖含量对Al2O3陶瓷坯体及烧结体的显微结构及力学性能的影响规律.试验结果表明,琼脂糖利用内部氢键的结合,形成三维网络状结构,将Al2O3粉原位凝固成型.TiO2+MgO烧结助剂使材料实现了液相烧结机制,有利于降低材料的烧结温度及促进致密化进程.随着琼脂糖含量增加,坯体的致密度、坯体及烧结体的抗弯强度均呈先增大后减小趋势.当琼脂糖含量为0.5wt;时,Al2O3陶瓷的抗弯强度达到最大值.     

溶胶凝胶法制备耐高温SiZrOC陶瓷纤维

以二氯氧化锆(ZrOCl2)为锆源,利用其与硅氧烷单体(正硅酸乙酯TEOS和二甲基二乙氧基硅烷DMDES)的溶胶凝胶反应,获得了聚硅锆氧碳(PZSO)凝胶纤维,并通过改变ZrOCl2和水的加入量优化了体系的纺丝性能.PZSO凝胶纤维经干燥和热解获得了SiZrOC陶瓷纤维,在1000℃保持高的陶瓷产率(84.7wt;).扫描电镜观察SiZrOC纤维表面均匀光滑致密,并保持了热解前PZSO纤维的圆形截面结构.红外光谱分析显示纤维中Zr连入Si-O四面体,表明通过ZrOCl2,TEOS和DMDES的共缩聚反应形成了=Zr-O-Si;桥键.这种SiZrOC陶瓷纤维在氩气气氛中高温热处理到1500℃失重小于5wt;,表明它在高温环境下具有优异的高温稳定性.     

光固化树脂基陶瓷单层成型工艺研究

在陶瓷光固化三维成型工艺中,单层成型效果对坯体堆积成型起着决定性作用.文章主要研究在单层坯体打印成型中,光源波长、扫描速度、光照时间和光源的照射距离对成型件质量和精度的影响.实验结果表明,光源波长越接近引发剂吸收波长范围,固化效果越好;光源的曝光量达到临界曝光量时,浆料才能发生完全固化;随着扫描速度的不断增大,陶瓷坯体的硬度不断降低,固化厚度逐渐减小,当扫描速度很大时,坯体表面致密度极低,组织样貌变得疏松.此外,紫外光源的照射距离对坯体的成型质量没有影响.     

快速冷冻干燥法制备多孔氧化硅陶瓷

为制备氧化硅多孔陶瓷,尝试了快速冷冻干燥法,探索了氧化硅浆体的分散剂和pH值对孔结构的影响.结果表明:使用0.1wt;六偏磷酸钠作为分散剂时,孔壁处团聚现象明显;改用聚甲基丙烯酸钠团聚显著减少.主要原因是氧化硅表面的Si-OH可能与六偏磷酸钠络合成Si-Na4P6O18-,但其在水中易断裂,减弱了颗粒之间排斥力,未能抑制团聚;而聚甲基丙烯酸钠吸附在氧化硅表面,可能形成Si-C4H5O2等空间位阻抑制团聚.在聚甲基丙烯酸钠的基础上再调节浆体pH值至～10使氧化硅的zeta电位达到～-60 mV,可更好抑制团聚.综上所述冻干法适合制备开口通孔结构的多孔氧化硅陶瓷.     

有机前驱体法裂解制备SiBCN陶瓷及其表征

采用固态核磁共振(NMR)为主要研究手段,FT-IR,XRD等作为辅助方法对陶瓷前驱体高温裂解制备的SiBCN陶瓷的结构进行分析和表征.研究表明SiBCN陶瓷是非晶结构,并且SiBCN陶瓷结构中存在Si四面体结构,与非晶的氧化硅中硅氧四面体的结构相类似;SiBCN陶瓷前驱体中C-C键,Si-C键,Si-N键以及C-B-C键经过高温裂解后保留在SiBCN陶瓷结构中;SiBCN陶瓷中的硼原子与其它原子形成的是平面三角结构,但是前驱体向陶瓷转化过程中,由于季碳的产生,空间位阻增大,围绕中心碳发生了偏转以降低产生季碳造成的应力增大,这样的偏转改变了一部分硼的空间结构,使硼原子不在一个平面内而使化学位移发生改变.     

Inferences about structure of aluminosilicates from viscosity data

Replacement of two cations of silica by two cations of alumina and one of baria in barium silicate glasses raises the strain, annealing and softening points even though the number of non-bridging oxygen atoms is unchanged. This observation is difficult to explain unless one postulates that a large moiety such as the S₈ unit (described herein) moves as a whole during any flow process in this temperature range. The dependence of the strain point on the excess baria in a series of glasses having a constant number of non-bridging oxygens and constant alumina suggests that the negative charges of the alumina sites are balanced preferentially by barium ions rather than alkali ions.     

水系流延技术制备95氧化铝陶瓷基片的研究

本论文采用水系流延技术制备了95氧化铝陶瓷基片,主要对浆料中各种添加剂的作用作了系统研究.分散剂通过与无机粉料的吸附,提供双重稳定效应使浆料具有较好的分散性,实验中分散剂PAA(聚丙烯酸)最佳的用量为0.5wt;.粘结剂PVA(聚乙烯醇)最佳用量为4.5wt;.塑化剂PEG(聚乙二醇)的加入可以降低粘结剂的玻化温度,提高坯片柔韧性.塑化剂与粘结剂的用量比值(R)在1～1.2之间为宜.最终获得了具有一定强度、韧性、表面光滑的坯片,烧结出密度为3.785g/cm395氧化铝陶瓷基片.     

Effect of alumina on enthalpy of mixing of mixed alkali silicate glasses

The enthalpy of mixing of mixed alkali (Na₂O and K₂O) silicate glasses containing various concentrations of alumina was determined using an ion-exchange equilibrium method. For glasses with a constant alkali concentration, the enthalpy of mixing was found to become less negative with alumina addition. Consistent with our previous results on the enthalpy of mixing of alumina-free mixed alkali silicate glasses, the magnitude of enthalpy of mixing exhibited a good correlation with the molar volume mismatch of the corresponding two single alkali glasses as well as with the extent of conductivity mixed alkali effect, e.g. excess activation energy of conductivity, ΔE. The reduction of the magnitude of the enthalpy of mixing with alumina addition can be attributed to the reduction of non-bridging oxygen and ionic field strength. Combining the present results with results obtained earlier, the magnitude of the enthalpy of mixing for all mixed alkali (Na₂O and K₂O) silicate glasses with and without alumina was expressed by a simple function of a modified Tobolsky parameter, which takes into account the alkali concentration and the difference in cation-to-effective anion distances. The enthalpy of mixing data of the mixed alkali glasses was then compared with reported experimental data on the conductivity of mixed alkali aluminosilicate glasses. What appears to be conflicting experimental data can be understood in terms of the magnitude of the enthalpy of mixing and we can conclude that the mixed alkali effect is closely correlated with the negative enthalpy of mixing.     

Photo-quenched of the luminiscence signal in Co(II)-doped alumina prepared by the sol-gel method

Co(II)-doped alumina monoliths prepared by the sol-gel method were laser irradiated producing fluorescence. The intensity of this defect-induced fluorescence was exponentially reduced with the irradiation time to practically disappear. The rate the fluorescence intensity decays was modeled as a double exponential function of the irradiation time; the characteristic times associated with the decays are in the range of seconds. The suppression of the luminescence was associated with the local heating produced by the highly focused laser beam in a small area (≈ 2 μm in diameter) on the sample. This heating process reduces physical (grain boundaries and surface states) and chemical (oxygen vacancies) defects present in the sol-gel samples. Some residual fluorescence still remains after long periods of illumination. The characteristic times for alumina samples are compared with those obtained for other metal oxides prepared also by the sol-gel method.     

Preparation and properties of alumina-organic compound aerogels

A wet alumina gel was obtained by cross-linking alumina sol particles from a hydrolyzed aluminum alkoxide with hexamethylene diisocyanate. The alumina gel cross-linked with hexamethylene was supercritically dried in a CO₂ extractor. The bulk density of the dried alumina-hexamethylene was one-third that of an alumina aerogel. Boehmite phase was observed in the dried alumina-hexamethylene aerogel. Needle-like texture was observed in the alumina-hexamethylene fired at a temperature of 1200°C for 5 h. The specific surface area of the dried alumina-hexamethylene aerogel was found to be less than that of the alumina aerogel, while its pore sizes were larger. The aerogel had a larger specific surface area after firing at 1200°C for 5 h. This larger surface area was attributed to a θ-phase in the alumina-hexamethylene aerogel, while the alumina aerogel had an -phase at that temperature. It is concluded that the temperature of the a phase transformation in the alumina-hexamethylene aerogel was higher than in the alumina aerogel. This difference was attributed to the lower packing density resulting from the addition of an organic compound, the existence of boehmite crystallites and the needle-like texture.     

聚乙二醇分子量对其分散多壁碳纳米管能力的影响

本文研究了聚乙二醇(PEG)分子量对其分散多壁碳纳米管(MWNTs)能力的影响。PEG解团聚的能力与分子量的关系不是单调递增的,而是先降低后增加,存在一个最低点,这与其解团聚路线有关。PEG分散的MWNTs对时间和电解质的稳定性都随着分子量的增加而增加,但是对温度的稳定性却随着分子量的增加而减小。     

氧化锆凝胶注模工艺研究

采用凝胶注模成型超细粒度氧化锆陶瓷.使用小分子型分散剂PBTCA(2-磷酸丁烷1,2,4-三羧酸)制备高固相、低粘度浆料.探讨了分散剂含量、单体与交联剂的比例及引发剂的含量对生坯及氧化锆陶瓷性能的影响.结果表明:当固相含量为50vol;,分散剂加入量为0.2wt;,浆料的粘度为0.86 Pa·s.且当单体和交联剂的比例为15∶1、引发剂的加入量为2.5wt;时,生坯抗弯强度为29.56 MPa;经1520℃烧结后,氧化锆陶瓷体积密度和抗弯强度分别达到5.96 g/cm3和828.46 MPa.通过SEM进行断面观察,其结构均匀致密.