堇青石陶瓷表面Ca0.6Mg0.4Zr4(PO4)6涂层的显微结构及耐碱性

采用溶胶-凝胶法在致密堇青石陶瓷表面制备了Ca0.6Mg0.4Zr4(PO4)6(C0.6M04ZP)涂层,以提高堇青石陶瓷的高温耐碱腐蚀性.研究了溶胶pH值和黏度、浓度及涂覆次数等工艺条件对制备的C0.6M0.4ZP涂层的显微结构和耐碱腐蚀性能的影响.结果表明:工艺条件对涂层的显微结构有着重要影响,采用C0.6M0.4ZP的质量分数为25%～30%,黏度为30mPa·s左右的溶胶,经3次涂覆后可在堇青石陶瓷表面制备连续致密的C0.6M0.4ZP涂层,涂层与堇青石基体间结合良好.涂覆有致密的C0.6M0.4ZP涂层的堇青石陶瓷样品,在1 000℃,96h耐碱腐蚀实验表明其耐碱腐蚀性能得到显著提高.     

C0.6M0．4Zr4（PO4）6涂层的料浆性能的研究

采用料浆法和浸渍涂覆工艺在低膨胀致密碳化硅基体上制备高温耐碱腐蚀低膨胀的C0.6Mg0．4Zr4（PO4）6（C0.6M0．4ZP）涂层,研究了形成稳定C0.6M0．4ZP料浆的工艺参数及影响因素。研究结果表明,通过调整C0.6M0．4ZP的pH值、PVA加入量、固含量后,C0.6M0．4Z料浆具有很好的涂覆性能,涂覆后与基体结合紧密,基体的耐碱腐蚀性能得到改善。     

Ca0.6Mg0.4Zr4P6O24陶瓷的烧结

本文研究了ZnO烧结助剂对Ca0.6Mg0.4Zr4P6O24陶瓷烧结行为的影响.ZnO的引入导致Ca0.6Mg0.4Zr4P6O24陶瓷的液相烧结.引入3wt%ZnO,在1100℃保温1.5小时烧结,Ca0.6Mg0.4Zr4P6O24陶瓷的相对密度可达99.1%.ZnO引入量过多或烧结时间过长,将导致二次再结晶,抑制Ca0.6Mg0.4Zr4P6O24陶瓷的致密化.     

蜂窝堇青石陶瓷负载的CaZr_4P_6O_(24)涂层的制备及表征

采用溶胶-凝胶法制备了化学组成为CaZr4P6O24(CZP)的溶胶态前驱物,用其涂覆薄壁蜂窝堇青石陶瓷,经过700℃焙烧2h转化为具有低热膨胀特性的结晶态CZP涂层。用X射线衍射和BET(Brunauer-Emmett-Teller)氮吸附法表征了涂层的物相和孔结构,用扫描电镜观察了涂层表面及涂层与基体的界面结合处的形貌,用能量色散光谱仪分析了涂层中的元素分布及含量。结果表明:在蜂窝堇青石陶瓷基体上形成的涂层组成为CZP;表面沉积了19.5%(质量分数)CZP的蜂窝堇青石陶瓷的BET比表面积、孔体积和平均孔径分别为16.4m2/g,0.0225mL/g和2.74nm。CZP涂层与蜂窝堇青石基体的界面结合良好。发动机台架性能试验结果表明:"CZP-蜂窝堇青石"复合载体负载的单钯催化剂表现出与"γ-Al2O3-蜂窝堇青石"负载的单钯催化剂相近的三效转化活性。     

ZrSiO4颗粒/Ca0.6Mg0.4Zr4P6O24基复相陶瓷的烧结行为及力学性能

本文对ZrSiO4颗粒/Ca0.6Mg0.4Zr4P6O24基复相陶瓷的烧结行为及力学性能进行了研究.发现引入ZrSiO4相,可促进Ca0.6Mg0.4Zr4P6O24基陶瓷的烧结,并抑制主晶相的晶粒长大.在Ca0.6Mg0.4Zr4P6O24中引入10vol%ZrSiO4,可获得一种具有较高抗弯强度(197MPa)和较低热膨胀系数(1.54×10-6/℃)的NZP基复相陶瓷材料.     

含堇青石涂层碳化硅网状多孔陶瓷的制备及燃烧特性

针对多孔介质高温燃烧用碳化硅多孔陶瓷因高温氧化导致抗热震性能以及辐射效率衰减等问题,首先采用有机泡沫浸渍法制备碳化硅素坯,经低温预烧、真空浸渍含Mg（OH）₂、单质Si和α-Al₂O₃浆料,经过原位反应烧结在碳化硅骨架表面构筑含堇青石红外辐射涂层的碳化硅多孔陶瓷。结果表明：真空浸渍浆料能在碳化硅骨架表面涂覆连续涂层的同时,能完全填充骨架的三角孔洞,经1 350℃烧结成功制备了具有堇青石涂层、碳化硅骨架中间层、堇青石填充层的3层结构碳化硅多孔陶瓷。3层结构的形成显著提高了碳化硅多孔陶瓷力学性能及抗热震性能以及高温抗湿氧化能力,碳化硅多孔陶瓷在1 350℃热处理后耐压强度达到1.18 MPa、残余强度保持率达67%;碳化硅多孔陶瓷中3层结构孔筋表面堇青石红外辐射涂层的形成,强化了碳化硅多孔介质燃烧器辐射换热过程和燃烧效率,将燃烧器表面温度提高约140℃,并显著降低了燃烧器中CO、NO_x等污染物的排放量。     

氧化锆-堇青石复相涂层对氧化铝基体影响的研究

在陶瓷材料表面引入压应力涂层已经被证明可以提高其强度和韧性。用高纯堇青石粉和氧化锆细粉制备了堇青石-氧化锆复相涂层浆料,将加工好的氧化铝样条浸润于浆料中,经过无压烧结制备出复相涂层增强的氧化铝材料。研究了不同氧化锆添加量（质量分数）的涂层对基体的整体性能的影响,结果表明,当复相涂层含质量分数为10%的氧化锆时其表面残余压应力为最大值1.34 GPa,相应地其弯曲强度也为最大值376.55 MPa,相比于未镀层的基体试样其弯曲强度增长了64.6%。此外,对试样还进行了高温弹性模量的试验,并分析了其弹性模量随温度变化的具体原因。镀层试样还进行了导热系数的试验,发现随着低热导率材料的加入,镀层试样的热导率也随之下降。最后由于表面残余压应力的存在,镀层试样相较于基体材料展现出了较好的抗热震性能,在900℃前,镀层试样水淬后的剩余强度均大于未镀层试样。     

Ca0.5Sr0.5Zr4P6O24/堇青石复相陶瓷的抗热震性

采用热压烧结工艺制备了Ca05Sr05Zr4P6O24/堇青石复相陶瓷材料,研究了Ca05Sr05Zr4P6O24/堇青石复相陶瓷材料在900℃时抗热震性能和热震压缩断裂后的断口形貌.研究结果表明,堇青石掺杂量分别为5％、10％、15％的Ca0.5Sr0.5Zr4P6O24/堇青石复相陶瓷在900℃热震时,临界热震次数Tc分别为TCC1=9,TCC2=10,TCC3=7;热震后复相陶瓷的断口为明显的脆性断裂断口,裂纹的扩展和延伸主要是沿着Ca05Sr05Zr4P6O24/堇青石的界面不断发生,属典型的沿结合面发生的断裂.     

堇青石加入方式对堇青石-莫来石窑具材料性能的影响

为满足锂离子电池正极材料烧成的需要,以堇青石、莫来石、高岭土和氧化铝为原料制备堇青石-莫来石窑具材料,研究了堇青石颗粒和细粉加入量对堇青石-莫来石窑具材料的常温性能、高温抗折强度和抗热震性的影响.并用XRD和SEM分析了试样烧后的物相变化与显微结构.结果表明:随着堇青石颗粒或细粉加入量从0到30％(质量分数),试样的线变化率、显气孔率、高温抗折强度增大,体积密度下降;而对常温抗折强度的影响不大,试样的耐压强度分别呈现下降或提高的趋势,试样的抗热震性先增加后降低,当堇青石颗粒含量为20％,细粉含量为20％时,试样的抗热震性最好.     

(Mg1–xCax)2Al4Si5O18陶瓷的相演变与微波介电性能

采用固相烧结反应法制备(Mg1–x,Cax)2Al4Si5O18陶瓷。XRD测试结果表明:0≤x<0.2时,陶瓷以(Mg,Ca)2Al4Si5O18堇青石单一相固溶体形式存在;0.2≤x<0.8时,陶瓷以Mg2Al4Si5O18/CaAl2Si2O8两相复合形式存在;0.8≤x<1.0时,陶瓷以单一相(Ca,Mg)Al2Si2O8固溶体形式存在。SEM结果显示:Ca2+掺杂可以有效地降低堇青石陶瓷的气孔率与微裂纹,并能有效地控制Mg2Al4Si5O18/CaAl2Si2O8复相陶瓷的颗粒分布与晶粒尺寸。微波介电性能测试结果表明:0≤x≤0.4时,(Mg1–xCax)2Al4Si5O18陶瓷介电常数εr为7.0左右;0.6≤x≤1.0时,εr从7.0增加到8.6,然后又降低到6.9。随着x增加,品质因数Qf值从24100GHz降低到4400GHz。但是,在x=0.6时,由于[Si,AlO4]四面体中Al/Si原子排列的有序化,(Mg0.4,Ca0.6)2Al4Si5O18陶瓷Qf值(Qf=5500GHz)比两侧x值成分点Qf值有较大提高。(Mg1–x,Cax)2Al4Si5O18陶瓷谐振频率温度系数在整个x值范围内保持在–20×10–6～–35×10–6℃–1。     

NZP陶瓷增压器蜗壳隔热管的研制

NZP陶瓷具有低膨胀、低导热、高抗热震性，是用于隔热抗热震场合的理想材料，本文采用沉淀法合成CM粉料、等静压成型、分段烧成制度，成功地制备出NZP陶瓷增压器蜗壳隔热管。     

Al diffusion coating on Mg alloy by a surface nanocrystallization enhanced CVD process

Surface nanocrystallization by mechanical attrition was used to enhance the chemical vapor deposition process. An aluminum (Al) diffusion coating was produced on AZ91 Mg alloy surface. This process was conducted at a relatively low temperature (400°C) for a short time of 120 min. The results indicated that a continuous and dense Mg₁₇Al₁₂ intermetallic coating with a thickness of ～8 μm formed on the Mg alloy substrate. Almost no corrosion was observed after the coated samples were immersed in 3 wt % NaCl solution for 6 h, reflecting a relatively good corrosion resistance. The formation mechanism of the Al diffusion coating is discussed based on the experimental results.     

医用镁合金表面磷化处理及生物腐蚀性能

采用回归正交试验,确定了适用于挤压态Mg-Mn-Zn合金的磷酸钙盐化学转化膜的工艺条件。扫描电镜观察及能谱分析结果表明,该转化膜主要由板条状晶体组成,主要含有O、P、Ca和Zn元素。由X-射线衍射分析可知,其相组成为具有良好生物相容性的CaHPO4.2H2O。电化学测试结果表明,转化膜可以提高基体合金在模拟体液中的耐腐蚀性能。     

Preparation and corrosion resistance of cordierite–spodumene composite ceramics using zircon as a modifying agent

To prolong the service life of cordierite–spodumene composite ceramics applied to the solar heat transmission pipeline, the zircon modifier was introduced to improve the corrosion resistance of the ceramics. The effects of zircon on the density, bending strength, crystalline phase, microstructure and chemical stability were studied. The results showed that the sintering temperature range of the composite ceramics was broadened to 40–60?°C with the introduction of 5–15?wt% zircon. Moreover, the mechanical strength and corrosion resistance of the ceramic materials were improved with the zircon introduction. In particular, sample C3 containing 15?wt% of zircon and sintered at 1360?°C exhibited the best performance, which had the 0.03% Wa, 0.07% Pa, 2.34?g?cm^?3 Db and 100.17?MPa bending strength. After acid and alkali corrosion, the water absorption was still less than 0.5% and the strength loss rate decreased to less than 5.3%. The XRD and SEM analyses demonstrated that the ZrSiO₄ grains dispersed at the grain boundaries could enhance the mechanical properties. Furthermore, the existence of the Zr⁴⁺ ions not only reduced the cationic solubility of the glassy phases but also led to a reaction with OH^? to form Zr(OH)₄ on the surfaces. This improved the corrosion resistance of the composite ceramics and endowed it with a high residual strength after the acid and alkali corrosion.     

Fabrication and characterization of hybrid coating on Mg–Zn–Ca Mg alloy for enhanced corrosion and degradation resistance as medical implant

Magnesium (Mg)-based alloys have appealing properties as promising implants for medical applications. However, their clinical applications are hindered due to the rapid corrosion and degradation rate in the physiological environment. In this investigation, we reported a novel interfacial engineering approach for the fabrication of polymer/ceramic hybrid coating on Mg–Zn–Ca Mg alloy. Firstly, hydroxyapatite (HA) coating was fabricated on the Mg–Zn–Ca sample followed by an alkali treatment that was performed in 1 M NaOH solution at 60 °C. Finally, polycaprolactone (PCL) coating was synthesized using a dip-coating approach on the top of the HA-coated Mg–Zn–Ca specimen. Microhardness test and adhesion test revealed that PCL/HA hybrid coating significantly improved mechanical properties and enhanced biointerface property between the substrate and coating. The immersion tests showed that the hybrid coating considerably slowed down the degradation in the simulated body fluid (SBF) solution. In addition, in vitro electrochemical investigations confirmed that PCL/HA coating significantly improved corrosion resistance and greatly reduced corrosion rate by about 10 times compared to HA coating and about 900 times to untreated Mg–Zn–Ca sample. Moreover, cytotoxicity assessment exhibited PCL/HA hybrid coating enhanced biocompatibility and bioactivity due to adopting a suitable interfacial engineering approach.     

经Al掺杂改性的介孔CaZr4（PO4）6的酸催化活性

对溶胶-凝胶法合成的NZP族介孔CaZr4(PO4)6进行Al掺杂改性,获得了一系列含Al的新型酸性催化剂样品Al-CaZr4(PO4)6。利用X射线衍射、X射线荧光、N2吸附-脱附和NH3的程序升温脱附等技术,表征了样品的物相、Al掺杂量、孔结构和表面酸性;以α-蒎烯的异构化为模型反应表征了样品的酸催化活性。结果表明:经适量Al掺杂改性后的CaZr4(PO4)6仍保持了均匀分布的介孔结构特征,与未经掺杂的CaZr4(PO4)6相比,表面酸性有明显提高。当掺杂的Al与CZP中Zr的物质的量的比分别为0.15和0.20时,获得的催化剂样品Al-CaZr4(PO4)6-0.15和Al-CaZr4(PO4)6-0.20在150℃下对α-蒎烯异构化反应的转化率可以达到40%～47%,而未经掺杂改性的介孔CaZr4(PO4)6在相同反应条件下对α-蒎烯异构化反应的转化率仅为3%,因此,Al掺杂改性可以显著提高介孔CaZr4(PO4)6的酸催化活性。     

A novel biomedical TiN-embedded TiO2 nanotubes composite coating with remarkable mechanical properties,corrosion, tribocorrosion resistance,and antibacterial activity

Tribocorrosion is a severe problem in dental implants, artificial joints, and other implants, and it will affect the long-term safety of the implants. To improve the deficiencies of titanium alloys, we combined physical vapor deposition technology and anodic oxidation to prepare TiN to embed TiO₂ nanotube composite coatings (NTNTs-TiN). Results show that the hardness of the NTNTs-TiN composite coatings reaches 33.2 ± 0.6 GPa, and the grains of the composite coatings were further refined. The NTNTs-TiN coating has the smallest average coefficient of friction (0.22) during tribocorrosion. The tribocorrosion resistance of NTNTs-TiN coating in SBF is increased by ∼44 and ∼2 times compared with Ti6Al4V alloy and TiN coating, respectively. The capillarity effect of the lower contact angle of NTNTs-TiN can form a continuous water-lubrication film at the interface between the counter-ball and coating and produce a lubrication film composed of Ca, Mg, and P, which reduces the coefficient of friction significantly. The NTNTs/TiN composite coating exhibits the best synergistic effect of wear and corrosion. In addition, the NTNTs-TiN coating also exhibits excellent antimicrobial and corrosion properties, which provides a new solution for the long-term safe use of implants in the human body.