ZrB2-玻璃陶瓷复合材料氧化分析

对ZrB₂-玻璃陶瓷复合材料氧化行为进行热力学分析,对氧化形成的氧化层进行物相分析和显微结构分析。结果表明：在1000°C-1400°C的反应温度范围内,ZrB₂氧化生成ZrO₂,B₂O₃玻璃相,氧化产物ZrO₂与SiO₂反应生成ZrSiO₄,当温度低于1177°C(1450K)时,氧化层主要包括ZrO₂,B₂O₃玻璃相,ZrSiO₄。当氧化温度超过1177°C(1450K)时,B₂O₃玻璃相蒸发,此时SiO₂玻璃相具有良好的流动性,氧化层主要包括ZrO₂,SiO₂玻璃相,ZrSiO₄。氧化过程中的反应产物B₂O₃玻璃相,ZrSiO₄和流动性良好的SiO₂玻璃相,均对氧气向基体的扩散均起到了良好的阻碍作用。     

ZrO_2纳米颗粒对Al-12.5%Si合金PEO陶瓷层微观形貌及热防护性能的影响

采用外加ZrO_2纳米颗粒的电解液体系在Al-12.5%Si合金表面制备ZrO_2-Al_2O_3-SiO_2三相PEO陶瓷层。利用SEM和XRD对陶瓷层微观结构和物相进行分析,并对其隔热及热冲击性能进行测试。结果表明:ZrO_2纳米颗粒显著提高了膜层的致密度和结合性,并有效减弱了Si元素对PEO成膜的抑制作用,提高了成膜速率;三相PEO陶瓷层的主要物相为SiO_2及高温稳定相α-Al_2O_3和c-ZrO_2,其独特的微结构和成分致使ZrO_2纳米颗粒改性的陶瓷层具有良好的热防护性能和热冲击性能。     

三元共晶成分Al2O3/YAG/ZrO2粉体及陶瓷的制备与组织性能研究

本文采用醇水共沉淀法制备了三元共晶成分Al₂O₃/YAG/ZrO₂粉体,在600-1350_oC温度范围煅烧后研究其物相转变过程。经1300_oC煅烧后Al₂O₃/YAG/ZrO₂共晶成分粉体的物相由α-Al₂O₃、c-ZrO₂和YAG构成,且具有α-Al₂O₃相包裹c-ZrO₂相的特殊结构。将煅烧粉体在1550_oC下热压烧结,制备具有内晶型结构的共晶成分Al₂O₃/YAG/ZrO₂复相陶瓷,其致密度、室温抗弯强度、断裂韧性和高温(1000_oC)抗弯强度分别为98.8%、420 MPa、3.69 MPa.m_1/2和464 MPa,并对复相陶瓷组织结构的形成机理进行了探讨。     

LZO/8YSZ双陶瓷热障涂层CMAS的腐蚀性能

为探究 La₂Zr₂O₇(LZO)涂层服役于 CMAS 环境中其微观结构、力学性能的变化及封阻渗透的原因,采用大气等离子制备了以 Al ₂O₃ 为基体的 LZO/ 8YSZ 双陶瓷热障涂层( TBCs) ,并辅以 8YSZ 单陶瓷 TBCs 作对比。 利用 XRD、SEM 和 EDS 研究了 8YSZ 和 LZO/ 8YSZ 单双陶瓷 TBCs 的相结构和微观组织;利用维式硬度计和 Image Pro plus 软件研究了腐蚀后的涂层硬度及渗透深度。 结果表明:1250 ℃ CMAS 腐蚀 12 h 后,LZO/ 8YSZ 双陶瓷 TBCs 中 LZO 反应厚度约为 57 μm;反应层物相以球状 ZrO₂ 和棒状 Ca₂La₈( SiO₄ ) ₆O₂ 为主,并伴有少量 CaAl ₂ Si ₂O₈ 和 M_gAl ₂O₄ 。 而 8YSZ 单陶瓷 TBCs 腐蚀深度约为 300 μm( 整个 8YSZ 层厚) ,截面变为以球状 m-ZrO₂ 为主的疏松结构。 腐蚀后 8YSZ、LZO 反应层硬度均有所增加,但提高的面内刚度未引发反应/ 未反应层间开裂。 LZO 陶瓷层作为双陶瓷 TBCs 牺牲防护层,依靠 La 同 CMAS 反应生成致密磷灰石(Ca₂La₈( SiO₄ ) ₆O₂ )的封阻作用,有效减少 CMAS 渗入,抑制了内部 8YSZ 的不稳定性。     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

空气反应钎焊ZrO2与GH3536接头组织与力学性能

采用Al₂TiO₅颗粒增强的Ag-CuO-Al₂TiO₅复合钎料,在钎焊温度为1050 ℃保温30 min工艺参数下,对ZrO₂陶瓷与GH3536合金进行了空气反应钎焊(RAB),分析了钎焊接头的界面结构及其形成机制;同时研究了接头在800 ℃氧化不同时间的组织演变规律及其对连接性能的影响。结果表明,钎焊过程中Al₂TiO₅颗粒分解产生Al₂O₃和TiO₂,TiO₂与ZrO₂陶瓷反应生成ZrTiO₄相。GH3536侧金属元素发生氧化形成尖晶石层,并分别与钎缝中的Al₂O₃、CuO反应,在钎缝中生成细密分布的NiAl₂O₄相及紧邻尖晶石层的团块状NiCuO₂相。ZrO₂/GH3536接头高温氧化1000 h后,钎缝中NiAl₂O₄呈团块状分布,Cr₂O₃薄层保持稳定;尖晶石层内部元素均匀化,厚度有明显增加。接头强度随着氧化时间的延长先降低后稳定在20 MPa。     

原位合成ZrO2/MgO膜层及自修复裂纹研究

微弧氧化熔融冷却成膜过程出现的裂纹将影响膜层的强韧性和磨损性能。本文利用ZrO₂自身的强韧性,采用原位合成制备具有自修复裂纹作用的ZrO₂/MgO膜层,研究原位合成的ZrO₂对膜层磨损性能的影响。研究发现,微弧氧化原位合成ZrO₂在高温放电通道发生相变产生体积膨胀氧化锆界面萌生微裂纹,抑制了成膜过程裂纹扩展从而实现自修复膜层裂纹的作用。通过控制锆源含量可以实现了对膜层中ZrO₂含量的调控,膜层中原位ZrO₂含量为32%,ZrO₂/MgO膜层裂纹呈现细小分散化,裂纹密度较传统膜层下降63.4%,摩擦系数减小53.4%,磨损量降低66.7%。研究认为,原位合成的ZrO₂在膜层制备过程的自修复裂纹和耐磨性的提高,可以降低摩擦系数和磨损量,改善ZrO₂/MgO膜层表面磨损性能。     

激光熔覆纳米 Al2O3颗粒增强 Ni 基合金涂层界面组织和高温热腐蚀性能

目的 研究纳米颗粒对 Ni 基合金涂层抗热腐蚀性能的影响。 方法 采用压片预置式激光熔覆工艺,制备了纳米 Al₂O₃ 颗粒增强的 NiCoCrAlY 合金涂层,对熔覆层界面区组织及裂纹进行了显微分析,进行了 1000 益 高温熔盐热腐蚀性能试验。 结果 加入纳米 Al₂O₃ 颗粒的激光熔覆涂层界面区未出现明显缺陷,其热腐蚀失重速率远远低于未加纳米颗粒的涂层,腐蚀表面未出现严重的隆起和剥落,腐蚀层深度小。 结论 添加适量纳米 Al₂O₃ 颗粒对 NiCoCrAlY 合金激光熔覆层界面区裂纹的形成有一定的抑制作用,可使熔覆层的抗高温热腐蚀性能明显提高。     

溶胶凝胶法制备含铁介孔催化剂用于二苯甲烷的合成

本文采用溶胶凝胶法以柠檬酸铁为铁源合成含Fe纳米介孔材料。室温下凝胶样品60 ℃真空干燥后得到的干凝胶采用热重分析(TG)。最终400 ℃焙烧3 h得到介孔Fe₂O₃/SiO₂纳米粒子。合成材料的结构和性能采用XRD、N₂吸脱附、TEM、FT-IF、及H₂-TPR测试方法表征,结果显示合成了尺寸约50 nm的带有30-45? 介孔孔道的球形的Fe₂O₃/SiO₂纳米粒子,并且成功引入了高分散的Fe₃₊物种。催化性能是通过傅克烷基化法合成二苯甲烷的反应测试的,实验结果表明该催化剂具有优异的催化性能,高达100 % 苄基氯的转化率和相对较高的二苯甲烷的选择性,并且能够重复利用。     

环境障涂层用纳米结构Yb2SiO5粉体喂料的制备与表征

纳米结构稀土硅酸盐涂层被认为是未来新型环境障涂层的发展方向,其中 Yb₂ SiO₅ 由于与中间层莫来石的热物性能匹配良好、优异的抗水氧腐蚀能力成为非常有发展前景的环境障涂层面层候选材料。 从材料制备的角度出发, 探索纳米结构 Yb₂ SiO₅ 喂料制备工艺并对喂料进行物相、组织结构和性能表征。 采用喷雾造粒加固相烧结的方法制备了纳米结构 Yb₂ SiO₅ 喷涂粉体喂料,探索了制备高纯度 Yb₂ SiO₅ 的固相烧结工艺,后续通过等离子处理改善粉体喂料的喷涂性能。 借助 X 射线衍射仪研究了粉体喂料的物相,采用扫描电镜、透射电镜研究了粉体喂料的形貌与微观结构。 结果显示,固相烧结工艺采用在 1500 ℃下保温 4 h,再将得到的粉体喂料等离子处理可得到高纯度的 Yb₂ SiO₅ 喷涂粉体喂料,等离子处理之后的喂料为纳米结构,喂料粒度分布均符合等离子喷涂要求,喂料具有良好的流动性和致密性。     

Effects of sulfur pressure on the sulfidation behavior of 310 stainless steel

High-temperature sulfidation behavior of 310 stainless steel was studied over the temperature range of 700–900°C above a pure sulfur pool with the sulfurvapor range of 10^–4–10^–1 atm. The corrosion kinetics followed the parabolic rate law in all cases. The corrosion rates increased with increasing temperature and sulfur pressure. The scales formed on 310 stainless steel were complex and multilayered. The outer scale consisted of iron sulfide (with dissolved Cr), (Fe, Ni)₉S₈ and chromium sulfides (Cr₂S₃ and Cr₃S₄ with dissolved Fe), while the inner layer was a heterophasic mixture of Cr₂S₃, Cr₃S₄, NiCr₂S₄, and Fe₁–_xS. Platinum markers were found to be located at the interface between the inner and outer scales, suggesting that the outer scale grew by the outward transport of cations (Fe, Ni, and Cr), and the inner scale grew by the inward transport of sulfur. The formation of Cr₂S₃, Cr₃S₄, and NiCr₂S₄ partly blocked the transport of iron through the inner scale, resulting in a reduction of the corrosion rates as compared with the results in the literature.     

Effects of Mo and Al Additions on the Sulfidation Behavior of 310 Stainless Steel

The high-temperature sulfidation behavior of 310stainless steel (310SS) with Mo and Al additions (up to10 at.%) was studied over the temperature range700-900°C in pure-sulfur vapor over the range of 10^-3 to 10^-1 atm. Thecorrosion kinetics followed the parabolic rate law inall cases and the sulfidation rates increased withincreasing temperature and sulfur pressure. Thesulfidation rates decreased with increasing Mo and Al contents and it wasfound that the addition of 10 at.% Mo resulted in themost pronounced reduction among the alloys studied. Thescales formed on 310SS with Mo additions were complex, consisting of an outer layer of ironsulfide (with dissolved Cr), (Fe,Ni)₉S₈, andCr₂S₃/Cr₃S₄(with dissolved Fe), and an inner heterophasic layer ofFe_1-xS,Cr₂S₃/Cr₃S₄,NiCr₂S₄,Fe_1.25Mo₆S_7.7, FeMo₂S₄, andMoS₂. The scales formed on 310SS with Mo andAl additions had a similar mixture as above, except thatAl_0.55Mo₂S₄ was alsoobserved in the inner layer. The formation ofMoS₂ andAl_0.55Mo₂S₄ partly blocked the transport of cations throughthe inner scale, resulting in the reduction of thesulfidation rates compared to 310SS.     

LaSrCuO4粉体微结构对Ag/LSCO电接触材料性能的影响

以硝酸镧、硝酸铜、硝酸锶等为原料,分别采用固相法、溶胶-凝胶法和共沉淀法合成了不规则颗粒状(LSCO_g)、介孔状(LSCOm)和片层状(LSCOl)的LaSrCuO_4(LSCO)粉体。采用高能球磨并结合初压-初烧-热压工艺制备出Ag/LSCO电接触材料。利用X射线衍射(XRD)、扫描电镜(SEM)、金属电导率仪、维氏硬度计和电寿命试验机等对粉体形貌及电接触材料的物理和电学性能进行了表征。结果表明:与Ag/LSCO_(m)、Ag/LSCO_l材料相比,Ag/LSCO_(g)电接触材料表现出更加优异的物理性能,其电阻率为2.37μΩ·cm,硬度为800MPa,密度为9.32g/cm~3;但电学性能差异较小,其在AC220V12A开断状态下的燃弧能量为400 mJ、燃弧时间为23 ms,关合状态下的燃弧能量为1500 mJ,燃弧时间为68ms。Ag/LSCO电接触材料的主要失效形式是液滴喷溅,微裂纹和孔洞。     

不同催化剂对镁合金表面SiO_2-ZrO_2涂层耐蚀性的影响

镁合金表面溶胶凝胶涂层存在易析出氢气、涂层缺陷多及防腐性能提升不明显等问题。为改善这些问题利用Ce(NO_3)_3催化制得SiO_2-ZrO_2溶胶并旋涂3层于AZ91D镁合金表面,并与HCl催化制得的镁合金表面SiO_2-ZrO_2溶胶涂层进行对比分析。采用扫描电镜和傅里叶红外光谱等分析涂层微观形貌和化学成分;通过接触角测试涂层亲疏水性;利用极化曲线和电化学阻抗谱对比研究不同催化剂加入的溶胶凝胶层在3.5%NaCl溶液中的耐腐蚀性能。结果显示:与HCl催化制得的镁合金表面SiO_2-ZrO_2溶胶涂层相比,Ce(NO_3)_3催化制得的涂层表面微观缺陷少;接触角由84.2°增大到93.5°;同镁合金基体自腐蚀电流密度1.480×10~(-4) A/cm~2相比,HCl催化和Ce(NO_3)_3催化涂层的自腐蚀电流密度分别为2.562×10~(-6) A/cm~2和7.821×10~(-7) A/cm~2,其耐蚀性提升明显;HCl和Ce(NO_3)_3催化涂层阻抗极化电阻值由镁合金基材的224.9Ω分别增大至4 401Ω和53 888Ω,HCl催化涂层的失效时间为1 d,Ce(NO_3)_3催化涂层失效时间延长为3 d。可见,两种催化剂制备的涂层,Ce(NO_3)_3催化涂层防护更持久,耐蚀性更好。     

Effect of some ternary additions on the sulfidation of Ni-Mo alloys

Five ternary additions, Cr, Ti, Mn, V, and Al were studied at equi-atomicpercent levels (17 a/o) for their effect on the sulfidation behavior of Ni-19a/o Mo (28–30 w/o) over the range of 600–800°C in 0.01 atm S₂. Al was by far the most effective addition. A linear decrease in log k_p vs. Al content was observed up to 7.5w/o Al, beyond which no further change was observed. All alloys followed the parabolic rate law. Arrhenius plots gave activation energies of 36.9–41.2 Kcal/mol for alloys containing Ti, Cr, Mn, and V, whereas the activation energies for Al-containing alloys were 47.2 Kcal/mol, indicating that a different diffusion process was involved. Complex scales were formed on all alloys, consisting of an outer layer of Nis_1+x and complex inner layers which depended upon alloy composition. Two alloys, those with Cr and Mn, formed intermediate layers of Cr₂S₃ and MnS, respectively, but these layers had little effect on the kinetics. MoS₂ was a constituent of the inner scales except for the alloys with Al. A ternary sulfide, Al_0.55Mo₂S₄ and Al₂S₃ were observed. The presence of the mixed sulfide was always associated with the low sulfidation rates. The formation of MoS₂ on alloys results in a different, less-protective behavior than for MoS₂ formed on pure Mo. This effect is due to the intercalation of Ni into MoS₂ in octahedral positions between the weakly bonded layers of covalently bonded sheets of trigonal prisms. The size of Al⁺³ is too small to be intercalated, and thus MoS₂ is destabilized by Al.     

Effect of Y2O3 additions on the plasticity of sintered Cr2O3

We have carried our constant strain-rate compression tests on polycrystalline Cr₂O₃ and Cr₂O₃ doped with 0.09 wt. % Y₂O₃ to establish whether there exists an effect of Y₂O₃ on the plasticity of Cr₂O₃. This study is motivated by previous work on the oxidation of alloys containing reactive-element additions. In that work, it has been observed that the addition of oxygen-active elements, such as Y to alloys that form Cr₂O₃ or Al₂O₃ oxide layers upon exposure at high temperature, strongly enhances the adhesion of the oxide layer to the base alloy as compared with alloys without reactive-element additions. We have found that at 1200°C (1) chromia exhibits limited plasticity at high temperatures, and (2) the presence of Y in the oxides does not enhance plasticity compared with addition-free oxides.     

The combined effect of refractory coatings containing reactive elements on high temperature oxidation behavior of chromia-forming alloys

The high temperature oxidation behaviors of chromia-forming alloys (F17Ti and Fe-30Cr alloys) have been studied at 1273 K under isothermal conditions and at 1223 K under cyclic conditions, in air under the atmospheric pressure. To extend the oxidation lifetime, coatings have been applied onto the alloy surfaces. Al₂O₃ and Cr₂O₃ films doped with Sm₂O₃ or Nd₂O₃ were prepared via the metal-organic chemical vapor deposition technique. Single Cr₂O₃, Al₂O₃, Nd₂O₃ and codeposited Cr₂O₃-Nd₂O₃, Al₂O₃-Nd₂O₃, Al₂O₃-Sm₂O₃ coatings drastically improved the chromia-forming alloy high temperature oxidation behavior, since they decreased the oxidation rate and enhanced the oxide scale adhesion. Results showed that a critical amount of reactive element (Nd or Sm) in chromia or alumina coatings (11-18 at.%) was needed to observe the most effective effect. The fast precipitation of NdCrO₃ or NdTi₂₁O₃₈ and the segregation of reactive elements at the chromia grain boundaries slowing down outward cation transport and consequently blocking the chromia grain growth, was supposed to be the main reasons of the beneficial effect ascribed to the reactive elements in chromia scales.     

Effect of Nb on the high-temperature sulfidation behavior of cobalt

The sulfidation behavior of Co-Nb alloys containing up to 30wt.% Nb was studied in sulfur vapor at a pressure of 0.01 atm in the temperature range of 600–700°C. Increasing niobium content decreased the sulfidation rate, following the parabolic rate law. An activation energy of 25.6 kcal/mole was obtained for Co-10Nb, Co-20Nb, and Co-25Nb, while a value of 20.5 kcal/mole was found for Co-30Nb. All were two-phase alloys, consisting of solid solution -Co and the intermetallic compound, NbCo₃. The two-phase alloys formed a rather thick outer layer of cobalt sulfides and a heterophasic inner layer that was complex. The inner layer always contained the mixed sulfide CoNb₂S₄ which, depending on the alloy composition, coexisted with cobalt sulfide, NbS₂, and / or NbCo₃ particles. Short-time sulfidations showed that the solid solution initially sulfidized rapidly to form nodules of cobalt sulfide, whereas the NbCo₃ phase formed a thin protective layer of NbS₂. The nodules grew laterally until they coalesced into the continuous, outer thick layer, while the NbS₂ completely or partially reacted with the cobalt sulfide to form CoNb₂S₄. Platinum markers were always found at the interface between the inner and outer scales, the location of the original metal surface.     

改进型镁扩散法制备高临界电流密度MgB2超导体性能研究

本文采用一种改进型镁扩散法成功制备出密度达到1.95g/cm₃的MgB₂超导块材。论文研究了不同的热处理条件对MgB₂块材的超导转变温度(T_c)和临界电流密度(J_c)性能的影响。采用最佳热处理条件制备的MgB₂超导体T_c和J_c分别达到了38.1K和0.53MA/cm₂(10K,自场)。为了改进镁扩散法MgB₂超导体中弱的高场磁通钉扎性能,本文还研究了nano-Pr₆O₁₁和C掺杂对MgB₂超导体的临界电流密度和不可逆场(H_irr)的影响。结果表明C掺杂的MgB₂超导体临界电流密度在10K,6T下达到了10₄A/cm₂,该结果比未掺杂MgB₂超导体在同样条件下性能提高了两个量级,甚至比固态反应法制备的nano-C掺杂MgB₂超导体性能更好。利用该方法制备的nano-Pr₆O₁₁掺杂的MgB₂超导体在10K,2T下也比未掺杂样品J_c提高达9.4倍。根据大量的实验结果和理论分析我们提出基于改进型镁扩散法和化学掺杂,包括纳米粒子和C掺杂,很有可能是一种制备高性能MgB₂超导体非常有效的途径。     

Protective effect in sulfuric acid media of alumina and ceria oxide layers electrodeposited on stainless steel

The influence of thin layers of Al₂O₃ and Ce₂O₃-CeO₂, electrodeposited on stainless steel OC4004, on the corrosion behaviour of the systems Al₂O₃/SS, Ce₂O₃-CeO₂/SS and Al₂O₃-Ce₂O₃-CeO₂/SS has been studied in sulfuric acid medium. A pronounced stabilizing effect on the passive state of steel and enhancement of its corrosion resistance has been established both for the samples as deposited and for the thermally treated Ce₂O₃-CeO₂/SS systems. In comparison to them the layers of Al₂O₃ have a substantial impact on the corrosion resistance of the Al₂O₃/SS system only in the cases when the system is not subjected to thermal treatment. The consecutive deposition of Al₂O₃ and Ce₂O₃-CeO₂ films on SS gives as a result an outstanding corrosion-protective effect, whereupon the corrosion potential of the system Al₂O₃/Ce₂O₃-CeO₂/SS is shifted in positive direction with ∼ 0.3 V for the samples as deposited and with ∼ 1 V—for the thermally treated samples. The so established favourable effect has been explained by the increased concentration of chromium oxides in the surface passive film, caused by the presence of cerium oxides, as well as by their action as cathode, effective with respect to the reduction corrosion reaction, shifting strongly the potential (at which this reaction is occurring) in positive direction.