Mg-9.95Li合金表面致密铈转化膜制备及耐蚀性研究

在硝酸铈(Ce(NO_3)_3)转化液中同时加入H_2O_2和柠檬酸,利用化学转化法在Mg-9.95Li合金表面获得致密铈转化膜。采用X射线光电子能谱(XPS)和扫描电子显微镜(SEM)表征了致密铈转化膜的成分与形貌,采用电化学阻抗谱、极化曲线和开路电位测试了转化膜的防腐蚀性能。结果表明,转化膜主要由柠檬酸交联的CeO_2和Ce(OH)_4组成,形成的转化膜更加致密均匀,转化膜的阻抗可以达到104?·cm~2;腐蚀电流密度为8.86×10~(-6) A·cm~(-2),较Mg-9.95Li合金降低了2个数量级,转化膜对Mg-9.95Li合金具有良好的耐蚀防护性能。     

AZ31B镁合金表面火焰喷涂Al-Mg_2Si涂层的耐腐蚀性能

为提高AZ31B镁合金表面的耐腐蚀性能,用火焰喷涂方法在镁合金表面制备Al-Mg_2Si复合涂层。采用XRD、SEM和EDS分析涂层的物相组成、微观组织及元素分布;通过电化学试验测试样品在3.5%NaCl溶液中的腐蚀电位、腐蚀电流密度;通过3.5%NaCl溶液浸泡试验测试样品的腐蚀速率;并测试涂层的显微硬度。结果表明:涂层中的主要物相有Mg_2Si、Al,组织比较致密,元素分布均匀。Tafel极化曲线测试表明,Al-Mg_2Si涂层样品与AZ31B镁合金样品相比腐蚀电位从-1.489 V正移到-1.366 V,腐蚀电流密度从2.817×10~(-3) A/cm~2降低到1.198×10~(-3) A/cm~2。浸泡试验结果表明,喷涂Al-Mg_2Si的镁合金的腐蚀速率明显低于没有喷涂的镁合金。显微硬度测试表明,涂层的显微硬度集中分布在259~308 HV0.05之间,镁合金为50~60 HV0.05。因此在AZ31B镁合金表面火焰喷涂Al-Mg_2Si涂层可以提高其耐腐蚀性能,表面硬度显著提高。     

CeN3O9.6H2O对镁空气电池负极性能的影响

通过动电位极化法和电化学阻抗谱法,研究了在8%NaCl电解液中,六水合硝酸铈(CeN_3O_9·6H_2O)对AZ31负极抗腐蚀性能的影响。结果表明:电解液中加入Ce N_3O_9·6H_2O,在AZ31镁合金表面形成Ce(OH)_3保护膜,提高镁合金的耐腐蚀性。随着CeN_3O_9·6H_2O浓度的增大,Ce(OH)_3保护膜逐渐致密,AZ镁合金的腐蚀速率降低。当Ce N_3O_9·6H_2O浓度达到1.0 g/L时,镁合金的腐蚀速率最低,其缓蚀率为70.4%。然而当加入的Ce N_3O_9·6H_2O浓度大于1.0 g/L时,由于Ce(OH)3保护膜被溶解而导致镁合金的腐蚀速率增大。由浸泡50 h AZ合金的SEM图发现CeN_3O_9·6H_2O的添加在镁合金表面形成Ce(OH)_3保护膜,抑制阳极反应。从等效电路图得到Mg~(2+)电荷转移阻力增大了69.5?,改善了镁合金的耐腐蚀性能。通过放电测试得到加入CeN_3O_9·6H_2O提高电池的放电性能,放电时间延长40 min。     

Pr(NO3)3对ZA31镁合金微弧氧化涂层组织与性能的影响

针对生物医用镁合金耐蚀性差的问题,利用微弧氧化技术对ZA31镁合金进行表面改性处理,旨在获得抗腐蚀性优良的陶瓷涂层。在已优化的硅酸盐电解液体系和电化学参数条件下,对ZA31镁合金进行微弧氧化处理,研究电解液中Pr(NO_3)_3含量对微弧氧化涂层的相组成、微观结构、润湿角、表面粗糙度以及电化学性能的影响。研究结果表明:在电解液中添加Pr(NO_3)_3后获得的ZA31镁合金涂层主要由MgO、MgSiO_3和Mg_2SiO_4等晶相组成,未检测到Pr的氧化物相。未添加Pr(NO_3)_3时,涂层具有火山口状的微孔结构。随着Pr(NO_3)_3添加量增加,涂层表面的孔洞和火山状凸起减少,孔洞尺寸也明显减小,伴随出现大量表面平滑的区域,表面粗糙度降低。当Pr(NO_3)_3添加量不同时,涂层表面粗糙度在1. 8～2. 4μm范围内变化。在电解液中添加Pr(NO_3)_3后,涂层的极化曲线向正电位方向移动,涂层腐蚀电位正移,但幅度变化不大,腐蚀电流降低约为1～2个数量级,涂层的耐蚀性提高。     

La(NO3)3与Ce(NO3)3比例对AZ31镁合金微弧氧化涂层显微硬度与耐磨性能的影响

针对镁合金耐磨性偏低的问题,利用微弧氧化技术在AZ31镁合金表面制备陶瓷涂层,探究微弧氧化电解液中添加La(NO_3)_3与Ce(NO_3)_3比例对AZ31镁合金微弧氧化(MAO)涂层显微硬度以及摩擦因数的影响。结果表明:AZ31镁合金微弧氧化涂层主要由MgO、MgSiO_3和MgSiO_4等相组成,未检测到原始添加的La和Ce等氧化物相。La(NO_3)_3与Ce(NO_3)_3添加能够降低镁合金涂层表面的微孔尺寸。随着电解液中La(NO_3)_3与Ce(NO_3)_3的添加比例增加,显微硬度呈现出先增加后降低的趋势。与未添加稀土复合盐相比,电解液添加稀土盐后微弧氧化涂层的显微硬度有所提高。添加La(NO_3)_3与Ce(NO_3)_3不同比例,涂层表面粗糙度在6.1～7.6μm范围内变化,相比未添加稀土盐获得涂层的粗糙度降低约2～3μm。电解液中添加La(NO_3)_3与Ce(NO_3)_3复合盐后,所获得的微弧氧化涂层的摩擦因数降低。     

超疏水涂层的制备及其对Mg-Li合金的防腐蚀性能

以正硅酸乙酯(TEOS)为原料,采用溶胶-凝胶法合成纳米 SiO₂ ,并用乙烯基三甲氧基硅烷(VTMS)进行表面改性,在高化学活性的镁锂(Mg-Li)合金表面制备了超疏水防腐蚀涂层。 利用红外光谱(FTIR)分析 SiO2 和改性 SiO₂ 的化学结构,通过扫描电子显微镜(SEM)观察不同氨水含量下制备的超疏水涂层的表面形貌。 采用接触角(CA) 测试超疏水涂层的疏水性,通过电化学阻抗谱(EIS)和动电位极化曲线分析超疏水涂层的防腐蚀性能,采用 X 射线光电子能谱 (XPS)分析 Mg-Li 合金表面的化学成分变化情况。 结果表明,当所用氨水与 TEOS 的质量比达到 1 ∶1时,制备的超疏水涂层表面表现出良好的粗糙度,接触角达到 151°,滚动角只有 5°。 超疏水纳米 SiO₂ 涂层对 Mg-Li 合金具有良好的防腐蚀性能,阻抗值达到 10⁵ Ω,腐蚀电流密度仅为 6. 19×10^-8 A/ cm² 。     

稀土元素添加对铁基非晶复合材料腐蚀行为的影响

采用工业级原料经包覆剂(CaO-Fe_2O_3-SiO_2)处理制备了Fe-15Mn-5Si-14Cr-0.2C和添加稀土元素Ce、Dy及Ce+Dy的非晶复合材料棒状试样,用XRD和TEM研究不同稀土元素对复合材料微观组织的影响,用电化学工作站三电极体系分析试样在1 mol/L的HCl及1 mol/L的NaOH中的腐蚀行为。结果表明:合金在添加稀土元素后的组织仍为非晶复合材料,晶体相为过冷奥氏体相CFe_(15.1)和铁素体相Fe-Cr。加入质量分数1%Ce的试样在HCl及NaOH中的耐蚀性均为最佳,在HCl中自腐蚀电位为–0.162 05 V,自腐蚀电流密度为7.6999×10~(-8) A·cm~(-2),极化阻值达到9.5774×10~8Ω·cm~2;在NaOH中自腐蚀电位和自腐蚀电流密度分别为–0.1839 V,1.7453×10~(-8) A·cm~(-2),极化阻值为7.1574×10~8Ω·cm~2。耐蚀性远优于AISI304,是潜力巨大的耐蚀材料。     

渗铝铌合金的微弧氧化及热腐蚀性能

为了优化渗铝铌合金的微弧氧化工艺和了解复合涂层的抗热腐蚀性能,利用粉末包埋渗法在铌合金基体上制备渗铝层,再通过调整微弧氧化电参数以及添加剂Y(NO_3)_3的含量获得Al_2O_3陶瓷膜外层,确定最佳工艺参数。以最佳工艺制备复合涂层(MAO-Y/Al/C103),与不含Y(NO_3)_3制备的MAO/Al/C103进行对比,研究其抗热腐蚀性。结果表明:以微弧氧化膜层的硬度和厚度为主要评价指标,获得最佳参数为电压380 V,频率400 Hz,占空比10%,处理时间30 min。添加Y(NO_3)_3可获得均匀规则的多孔形貌;含与不含Y(NO_3)_3制备的试样相结构一致,都由NbAl_3和γ-Al_2O_3相组成。经900℃混合熔融盐中热腐蚀50 h,MAO/Al/C103和MAO-Y/Al/C103试样都生成Al_2O_3和NaNbO_3相,其热腐蚀增重量分别为55.71 mg/cm~2和45.59 mg/cm~2。MAO-Y/Al/C103试样由于在热腐蚀阶段有更多的NaNbO_3生成以及微弧氧化微孔大幅减小,表现出更优异的抗热腐性。     

复合电解液中AZ31B镁合金的放电特性及电压滞后

通过计时电位法和电化学阻抗谱技术研究Mg(NO_3)_2+Mg(ClO_4)_2复合电解液中AZ31B镁合金电极的放电性能和电压滞后,并初步探讨了镁合金电极表面腐蚀膜的结构变化。结果表明:AZ31B合金在Mg(NO_3)_2:Mg(ClO_4)_2溶液体积比为72∶28和74∶26时恒流放电曲线平稳,在2.5和6 m A·cm~(-2)放电时稳定电位均可达到约-1.24 V,电压滞后时间为5~8 s;放电后表面膜的化学基团与放电前相同,放电破坏了镁合金电极表面腐蚀膜,造成连续串珠状点蚀坑,其膜电阻消失,电荷转移电阻减小至375Ω·cm~2。     

AZ31镁合金冷喷涂Al-Al_2O_3复合涂层组织及性能

采用冷喷涂工艺在AZ31镁合金上制备纯Al涂层和Al-50%Al_2O_3复合涂层。通过扫描电镜(SEM)、能谱仪(EDS)、材料分析软件探讨Al_2O_3颗粒的加入对纯Al涂层显微组织的影响。用电化学工作站、显微硬度计和磨耗试验机来对涂层的性能进行表征,分析Al_2O_3颗粒的加入对纯Al涂层耐蚀性、显微硬度和磨损性能的影响。结果表明:与纯Al涂层相比,复合涂层组织更致密,孔隙率更低,硬度从51.2HV0.025提高到94.8HV0.025,滑动磨损率降低80.5%,磨粒磨损率降低40%。复合涂层的自腐蚀电流密度(2.36×10~(-7)A/cm~2)和纯Al涂层的自腐蚀电流密度(1.19×10~(-7) A/cm~2)相近,相对于镁合金的(2.56×10~(-4) A/cm~2)降低3个数量级,可以大大提高镁合金的抗腐蚀性能。     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

Effect of Bi2O3 on structure and wetting studies of Bi2O3-ZnO-B2O3 glasses

Glasses with different Bi₂O₃ contents (37-42 mol%) have been prepared by conventional melt quench technique. The IR and Raman studies indicate that these glasses are made up of [BiO₆], [BiO₃], [BO₃] and [BO₄] basic structural units. The vibrations of [BiO₃] and [BO₃] become stronger as the content of Bi₂O₃ increases, which makes glass structure loosened. Viscosity of the glasses was measured by using a Rheotronic III paralleled plate rheometry, which shows that the viscosity of glass samples decreased when the content of Bi₂O₃ increased at the same temperature (400-460 °C). The temperature range which suits for glasses sealing was calculated by using the approximation of Arrhenian behaviour. The wetting performance of Bi₂O₃-ZnO-B₂O₃ glasses was described by using high-temperature microscope, which also proves that the structure of investigated Bi₂O₃-ZnO-B₂O₃ glasses become loosened due to the increasing of the content of Bi₂O₃.     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

钕的添加对V2O5-MoO3/TiO2平板式脱硝催化剂性能的影响

本研究制备了一系列不同Nd含量的V₂O₅-MoO₃-Nd₂O₃/TiO₂平板式脱硝催化剂。采用XRD、N2-吸附脱附、XPS、H2-TPR、拉曼光谱、NH3-TPD和红外光谱等表征手段对催化剂进行分析。结果表明:适量的Nd2O3(0.25%、0.5%,质量分数)可以增强V₂O₅-MoO₃/TiO₂催化剂的还原性能,增加了催化剂的Oα/(Oα+Oβ)比率,从而提升了催化剂的脱硝活性。然而,过量Nd₂O₃(0.75%、1%)的添加,会导致催化剂酸性性能的显著降低,造成催化剂脱硝性能的下降。此外,过量Nd的添加还会对催化剂的耐磨性能有负面影响。各催化剂中,VMoN d(0.5%)/Ti催化剂显示了最佳的脱硝活性。并且,该催化剂还显示了优良的抗SO₂、H₂O性能。     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.     

国外多孔基体氧化铝/氧化铝复合材料工程应用进展

氧化铝/氧化铝复合材料(Al2O3/Al2O3)是20世纪90年代兴起的一类连续陶瓷纤维增强陶瓷基复合材料,已经发展为与SiC/SiC、C/SiC等非氧化物陶瓷基复合材料并列的一类陶瓷基复合材料。与非氧化物陶瓷基复合材料相比,Al2O3/Al2O3具有长时抗氧化、高温耐腐蚀、低成本等独特优势,已经在航空发动机、地面燃气轮机等军民两用热结构材料领域展现出广阔的应用前景。本文从材料应用的角度出发,系统分析阐述了目前在Al2O3/Al2O3占主导地位的多孔基体Al2O3/Al2O3(P-Al2O3/Al2O3)的增韧机制、成型工艺和性能特点,重点归纳了国外近年来P-Al2O3/Al2O3的工程化应用进展及前景,最后指出了P-Al2O3/Al2O3存在的局限性并展望了未来发展方向,旨在为国内Al2O3/Al2O3体系发展提供借鉴和参考。     

纳米级和微米级稀土氧化物掺杂W-La2O3-Y2O3-ZrO2 阴极尖端的组织和性能

使用粉末冶金法将纳米级(70–80 nm)和微米级(500–600 nm)稀土氧化物(La₂O₃,Y₂O₃)与钨粉混合,随后通过冷等静压、中频感应烧结、旋锻、拉拔等一系列工艺制备了W-1.5La₂O₃-0.1Y₂O₃-0.1ZrO₂(质量分数,%)材料。对含有纳米和微米尺寸稀土氧化物的阴极样品使用相同的焊接电流,分别进行了0.5、1、2 h的氩弧焊。结果表明,具有纳米级稀土氧化物的样品在焊接过程中表现出更高的工作稳定性,烧损同比降低了近85.4%。此外,随着工作时间的延长,阴极尖端不同区域的稀土氧化物聚集度显著增加。结合COMSOL Multiphysics温度模拟发现,第二相的扩散活化能降低了近34%。这是因为更为细小的第二相有效地控制了钨基体组织的演变,保留了大量晶界作为通道,促进了活性物质在电子发射过程中的扩散。     

CVD deposition and characterization of coloured Al2O3/ZrO2 multilayers

Coloured Al₂O₃/ZrO₂ multilayers have been deposited onto WC-Co based inserts by a CVD process. Through physical as well as optical analysis of such multilayers, colour is believed to originate from interference. The coatings are obtained with good process reproducibility. It was found that the ZrO₂ process used in the multilayer, with ZrCl₄ as the only metal chloride precursor, results in a mixture of tetragonal and monoclinic ZrO₂ phases. However by adding a relatively small amount of AlCl₃ during such a process results in ZrO₂ layers being composed of predominantly tetragonal ZrO₂ phase. Corresponding multilayers seem to have a more fine grained and smoother morphology whereas multilayers containing monoclinic ZrO₂ phase seem to be less perfect with existence of larger grains of ZrO₂ which are believed to scatter light and alter the reflectance of such a multilayer. In addition to this, such multilayers were found to be free of or with greatly reduced amount of thermal cracks, normally present in pure CVD grown Al₂O₃ layers.It is believed that, in the studied Al₂O₃/ZrO₂ multilayers, the observed tetragonal ZrO₂ phase is the result of a size effect, where small enough ZrO₂ crystallites energetically favor the tetragonal phase. However as the ZrO₂ crystallite size distribution is shifted to larger sizes it is believed that a mixture of crystallites with both stable and metastable tetragonal phases as well as a stable monoclinic phase is obtained. The proposed metastable tetragonal ZrO₂ phase may in fact explain the absence of thermal cracks in such multilayers through a transformation toughening mechanism, well known in ZrO₂ based ceramics.     

Preparation and properties of sintered molybdenum doped with La2O3/MoSi2

Sintered Mo with the addition of La₂O₃/MoSi₂ was prepared via the process of solid–solid doping + powder metallurgy. X-ray diffraction experiment, hardness test, three-point bending test and high-temperature tensile test were carried out to characterize the samples. The XRD pattern of a typical sample shows that the sintered Mo was mainly composed of Mo, La₂O₃ and Mo₅Si₃. Mo₅Si₃ was probably formed through the reaction between MoSi₂ and the Mo matrix. Densities and fracture toughnesses of both doped Mo and pure Mo were measured and contrasted. Sintered Mo with the addition of 0.2 wt% La₂O₃/MoSi₂ has the highest toughness, while more addition of La₂O₃/MoSi₂ has smaller effect on improving toughness or even embrittles Mo. The results of three-point bending test and high-temperature tensile test show that the bending strength and high-temperature tensile strength of doped Mo are both higher than those of pure Mo. The formation of Mo₅Si₃ improves the high-temperature strength. The La₂O₃/Mo₅Si₃ dispersed in the Mo matrix refined the grains, and thus strengthened the Mo matrix by dispersion strengthening and grain refinement.