氧化钆改性铈酸镧热障涂层材料设计 及涂层抗热震性能研究

La2Ce2O7(LC) 由于具有比 YSZ 更低的热导率、 更高的热膨胀系数和良好的高温相稳定性, 是一种极具前 景的热障涂层陶瓷材料。 但该材料热膨胀系数在 200~400℃温度区间存在异常下降现象, 从而引起涂层过早失效 的问题。 目前, 通过掺杂 Gd2O3 可有效解决 LC 低温段热膨胀系数下降的问题, 但是, Gd2O3 改性 La2Ce2O7 热障 涂层最优掺杂浓度及涂层性能还未见报道。 本文采用化学共沉淀法制备了三种不同浓度 Gd2O3 改性 La2Ce2O7 材 料 ((LaxGd1-x)2Ce2O7(x=0,0.1,0.2,0.3)), 研究了掺杂浓度对其热物理性能及相稳定性的影响, 采用等离子喷涂工艺 制备了(La0.8Gd0.2)2Ce2O7 (LGC)涂层, 研究了涂层的抗热震性能和涂层的失效机理。 研究结果表明： (La0.8Gd0.2)2Ce2O7 (LGC) 材料具有较低的热导率, 室温到 1400℃无相变, 并且经 1400℃长时间热处理无相变; 其制备的双陶瓷结 构 LGC/YSZ 热障涂层 1100℃热震次数可达到 109 次, 较未改性 LC/YSZ 热障涂层提升了大约 60%; 两种涂层的 失效模式相似, 均为陶瓷顶层烧结引起的片状剥落失效。     

Al2O3 含量对 YSZ 热障涂层性能的影响

Al_2O_3等氧化物对YSZ热障涂层的高温使用性能有一定的影响。本文用HVOF喷涂Ni Co Cr Al Y合金粘结层,APS喷涂YSZ陶瓷面层,制备了Al_2O_3含量为0.01~0.64wt%的YSZ涂层。比较了不同Al_2O_3含量的YSZ涂层在1100℃下的热震性能和抗烧结性能,并探讨Al_2O_3对涂层的影响机理。结果表明相较于高纯YSZ涂层,随着涂层中Al_2O_3含量升高,涂层的抗热震性能降低,且Al_2O_3促进YSZ涂层的烧结。Al_2O_3含量在小于0.01wt%-0.12wt%区间内时,对涂层抗热震和抗烧结性能有显著影响,含量继续增加至0.64%时,对性能影响减缓。显微组织观察与EDS检测结果表明涂层中Al_2O_3并未在熔融颗粒界面处偏聚,但在颗粒内部有局部偏析。由此推测,含Al_2O_3的YSZ涂层热震失效的原因可能是Al_2O_3在YSZ颗粒内部偏析,并影响涂层的烧结性能,导致裂纹容易萌生和扩展。     

热障涂层的研究现状及其制备技术

热障涂层用于燃气轮机的热端部件,可以显著提高其使用温度,延长热端部件的使用寿命,并增大燃气轮机发动机的效率。介绍了热障涂层的研究现状,以及两种主要制备热障涂层方法,即等离子喷涂法和电子束物理气相沉积法的原理、特点及不足。     

纳米 YSZ 热障涂层高温时效过程中组织演变研究

燃气轮机长期运行过程中,热端部件如燃烧室内壁和前级涡轮叶片长期经受高温火焰冲击,涂层材料会产生时效行为。在时效过程中,热障涂层会发生组织演变,影响涂层性能与寿命。本文对一种高纯纳米YSZ热障涂层进行了不同温度的时效考核,研究材料在高温中组织演变行为,并对涂层孔隙率变化规律进行了热动力学分析。结果表明,在高温过程中,YSZ涂层中残留的纳米界面会进一步融合并逐渐演变为微米晶;受热动力学机制支配,涂层中孔隙闭合消损,造成涂层孔隙率下降。另外,本文还统计分析了涂层的相变行为。     

稀土改性NiCoCrAlY层对YSZ和LZ/YSZ热障涂层高温性能的影响

以纳米结构的La_2O_3、ZrO_2、8YSZ粉体为原材料,利用纳米调控技术制备可用于等离子喷涂的粉体材料;利用等离子喷涂技术在304不锈钢基体上分别喷涂含未改性粘结打底层和改性粘结打底层的YSZ和LZ/YSZ两种结构的热障涂层。研究了热障涂层的结合强度和抗氧化行为,并分析稀土改性的粘结打底层对其组织结构的影响。根据涂层氧化不同时间后涂层的截面形貌图及能谱图分析其氧化后的组织结构,进而研究稀土改性粘结打底层对热生长氧化物(TGO)层的影响。结果表明:含改性粘结打底层的双陶瓷型热障涂层La_2Zr_2O_7+8YSZ+mNiCoCrAlY在800℃和900℃下均具有最低的氧化速率,氧化增重速率常数分别为0.04372mg~2·cm~(-4)·h~(-1)和0.12406mg~2·cm~(-4)·h~(-1),比含未改性粘结打底层的La_2Zr_2O_7+8YSZ+NiCoCrAlY涂层分别降低45%和36%,说明改性粘结打底层提高了热障涂层的抗氧化性能。     

长春应用化学研究所热障涂层的设计和失效机理研究获进展

正檴檴檴檴檴檴檴檴檴檴中国科学院长春应用化学研究所在热障涂层的设计思路、失效机理以及新型热障涂层材料研发等方面取得新进展,设计并成功制备出使用温度≥1250℃的双陶瓷层热障涂层材料,"热障涂层的设计和失效机理研究"成果(主要完成人:曹学强等)荣获2013年吉林省自然科学奖一等奖。热障涂层技术利用陶瓷材料的高隔热性和耐腐蚀性来保护金属基底,在能源、航空、航天等方面都有重大应用价值。常规热障涂层材料8YSZ(8%Y2O3(质量分数)稳定化的ZrO2)因在高温下发生相变、烧结和透氧,不能承受1200℃以上的高温。目前,世界各国都在努力研究能替代8YSZ、在更高温度下使用的热障涂层材料。     

粉体制备工艺对Gd、Yb改性YSZ热障涂层性能影响的研究

随着航空航天技术的快速发展,飞行器热端部件的服役温度越来越高,YSZ热障涂层已经无法满足目前航空发动机热端部件的服役需求,稀土元素钆(Gd)与镱(Yb)对YSZ进行掺杂得到的Gd₂O₃-Yb₂O₃-Y₂O₃共稳定氧化锆(GYYZO)被广泛认为在超高温工况下具有广阔的应用前景。本研究采用固相反应法与化学沉淀法分别制备了两种球形GYYZO粉末,并采用大气等离子喷涂法制备了两种GYYZO陶瓷热障涂层,研究了粉末制备工艺对粉体结构以及涂层结构与性能的影响。     

氧化铈稳定纳米氧化锆高温性能的研究

等离子喷涂热障涂层技术广泛应用于航空发动机热端部件的高温防护。应用大气等离子喷涂法成功制备了纳米氧化铈氧化钇稳定的氧化锆(CYSZ)涂层,并与常规氧化钇稳定氧化锆(YSZ)涂层在1300℃下热处理10小时,研究高温对两种涂层性能的影响,与常规的YSZ涂层相比,CeO2的掺杂使涂层具有更高的稳定性。经过高温处理,CYSZ涂层的相结构没有发生明显变化。显微形貌结果表明,CYSZ涂层没有产生裂纹缺陷,涂层中纳米区域晶粒度随着温度的升高略有增大,这表明了纳米结构的CYSZ涂层具有更优异的高温稳定性。热循环氧化实验结果证明,CYSZ涂层具有更长的热循环寿命以及优异的高温抗氧化性能。     

三菱重工地面燃气轮机热障涂层研究进展

燃气轮机联合循环热效率的提高,要求涡轮进口温度不断增加。目前,三菱重工(MHI)已经积极参与日本国家项目,通过发展1700℃级燃气轮机,以使联合循环热效率实现达到62%指标。在此国家项目中开发的部分组件技术适用于1600℃级燃气轮机M501J,它具有世界上最高的涡轮进口温度。而热障涂层(TBC)是实现此目标的最关键技术之一。在发展先进的热障涂层中,在MHI工厂中建立名为T点的试验电厂是有必要的。在真实热部件中制备的先进TBC可以在工厂中进行验证,并且运行后的效果可以得到反馈。本文讨论了TBC的开发以及在三菱重工实际电厂中的验证。     

稀土氧化物稳定氧化铪热障涂层的制备及热冲击性能研究

采用大气等离子喷涂(APS)技术制备了稀土元素掺杂量为19 mol.%的HfO2涂层,即Hf0.81Y0.19O1.905 (YSH19)/YSZ与Hf0.81Yb0.0475Y0.1425O1.905(YbYSH19)/YSZ双陶瓷层热障涂层,研究了其在1300℃下耐高温燃气热冲击性能。结果表明,两种热障涂层的隔热能力约为200℃,YbYSH19/YSZ体系热障涂层经280次燃气热冲击循环后涂层结构依然较为完整,性能显著优于YSH19/YSZ及YSZ热障涂层体系。涂层的失效模式为因中心区域处较大冲击载荷造成的涂层逐层剥落,以及边缘位置处轴向应力和剪切应力导致的涂层剥落。     

Effects of incorporation of micro and nano Al2O3 layers on thermal shock behaviour of YSZ thermal barrier coatings

In the present paper, thermal shock behaviour of usual YSZ and layered composite TBCs was evaluated. The layered composite TBCs used in this study were YSZ/micro Al₂O₃ and YSZ/nano Al₂O₃ in which Al₂O₃ was as a topcoat on the YSZ layer. In addition, coating microstructures were investigated using scanning electron microscope; EDS and X-ray diffraction techniques before and after thermal shock test. The results showed that incorporation of a nano Al₂O₃ oxygen barrier layer caused better thermal shock resistance, while micro Al₂O₃ layer on the top of YSZ sample resulted in sooner coating failure, compared to the usual TBC coating. Also, the thermal shock behaviour and failure mechanism of mentioned coatings were investigated.     

Investigation on pumping oxygen characteristics of （Bi2O3）0.73（Y2O3）0.27 solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.     

Thermal expansion anomaly and spontaneous magnetostriction of Gd2Fe17 compound

Materials with negative thermal expansion have many practical applications. However, these materials are known in only several oxide systems, and when the negative thermal expansion occurs, the contraction is usually small and limited to a narrow temperature range beyond room temperature. For obtaining a compound with negative thermal expansion in broad temperature range, the structural and magnetic properties of Gd2Fe17 compound were investigated by means of X-ray diffraction and magnetization measurements. The Gd2Fe17 compound annealed at 1050 oC had a Th2Zn17-type structure. There existed an anisotropic strong spontaneous magnetostriction and a negative thermal expansion in Gd2Fe17 compound. The average thermal expansion coefficients was =-7.40×10-6/K in the temperature range of 294-453 K and =-1.80×10-5/K in 453-534 K, respectively. The spontaneous magnetostrictive deformation ωS decreased from 4.34×10-3 to near zero with temperature increasing from 294 to 572 K. The spontaneous linear deformation λc was much larger than λa at the same temperature below about 500 K.     

Gas release from the ZrO<Subscript>2</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics used in the seeded growth of diamond single crystals

Gas release from the ZrO₂-Y₂O₃ ceramics used for the seeded growth of diamond single crystals in a temperature range from 100 to 700°C and a pressure of 10^?4 Pa is investigated. It is experimentally found that the air content in the pores of ceramic elements of the container is 0.086 sccm³/g. The coefficient of the gas release and diffusivity are determined; this allows one to determine the degassing time for which the gas fraction from the sample attains a definite value from the starting amount. It is revealed that vacuum annealing at a temperature no lower than 700°C and P = 10^?4 Pa provides a decrease in the content of the adsorbed gas on the parts of the reaction cell by an order of magnitude.     

Luminescent properties of β-Lu2Si2O7:RE(RE=Ce, Tb) nanoparticles by sol-gel method

Nanoscale RE³⁺ (RE=Ce, Tb) doped and codoped lutetium pyrosilicate Lu₂Si₂O₇ (LPS) phosphors were prepared by using the sol-gel method. Heat treatment was performed in the temperature range from 900 to 1100 °C. The crystal structure was analyzed by X-ray diffraction (XRD). The results showed that the β-type structure of LPS was obtained at 1100 °C. The excitation spectra in the UV and VUV ranges and the emission spectra of the samples were measured at room temperature, and their luminescent properties were studied. The energy transfer from Ce³⁺ to Tb³⁺ in the codoped samples were observed and discussed.     

Study on Sulfation of CeO2/γ-Al2O3 Sorbent in Simulated Flue Gas

It is well known that sulfur dioxide(SO2) , morethan50%of which arise fromcombustion of fossil fu-els ,are precursors of acidrain andtheir emission pos-es a global threat tothe atmosphere .Environmental a-gencies have ,therefore ,regulated emissions of SO…     

Up-conversion luminescence of Er~（3＋）-doped and Yb~（3＋）/Er~（3＋） co-doped 12CaO·7Al_2O_3 poly-crystals

The optical properties of Er3+-doped and Yb3+/Er3+ co-doped 12CaO·7Al2O3 (C12A7) poly-crystals, synthesized by high temperature solid state method, were investigated in detail. For Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals, two main emission bands centered around 530/550 nm (green) and 660 nm (red) were observed under 980 nm diode laser excitation via an up-conversion process. The intensity of green up-conversion emission had a strong increase in Er3+ (1.0 mol.%, 1.5 mol.%, 3.0 mol.%), and the intensity ratio of red to green up-conversion emission had an increase in Yb3+ (1.0 mol.%, 2.0 mol.%, 10. 0 mol.%)/Er3+ (fixed at 1.0 mol.%). This detailed study of the up-conversion processes allowed us to identify the dominant up-conversion mechanisms in Er3+-doped and Yb3+/Er3+ co-doped C12A7 poly-crystals.     

Three-photon-excited fluorescence of Tb-doped CaO-Al2O3-SiO2 glass by femtosecond laser irradiation

A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence was attributed to ^5D3→^7F5, ^5D3→^7F4, ^5D3→^7F3, ^5D4→^7F6, ^5D4→^7F5, ^5D4→^7F4, and ^5D4→^7F3 transitions of Tb^3＋. The relationship between upconversion luminescence intensity and the pump power indicated that a three-photon simultaneous absorption process was dominant in this upconversion luminescence. The intense red, green, and blue upconversion luminescence of Tb^3＋-doped CaO-Al2O3-SiO2 glass may be potentially useful in developing three-dimensional display applications.     

基于正交实验设计方法的APS喷涂Al_2O_3涂层性能的研究

采用正交实验方法研究了大气等离子喷涂工艺参数主气流量、喷涂功率和送粉量对Al2O3陶瓷涂层结合强度和显微硬度的影响,通过X射线衍射仪和扫描电子显微镜研究了粉末和涂层的组织结构,采用WDW-50微机控制电子万能试验机、HV-1000维氏硬度计测量了涂层的结合强度、截面硬度,结合涂层组织结构并应用极差和方差分析方法对实验结果进行了分析,得到了优化后的工艺参数。结果表明,涂层由熔融和未熔融区域混合而成,截面形貌凹凸咬合,以机械结合为主。影响大气等离子喷涂Al2O3涂层性能工艺参数的主次顺序依次为:喷涂功率、主气流量、送粉量,随着功率和主气流量的升高,涂层的结合强度和硬度均出现先增加后降低的趋势。大气等离子喷涂Al_2O_3最优工艺参数为喷涂功率44KW,主气流量40L/min,送粉量40g/min,制备的涂层结合强度52MPa,显微硬度1219.4HV0.3,孔隙率值为4.00%。