铝合金防护涂层老化动力学研究

在紫外/盐雾加速综合环境条件下,研究了铝合金试样上聚酰胺清漆老化过程。采用环境扫描电子显微镜观察了防护涂层表面形貌的变化,采用电化学阻抗(EIS)分析了涂层的老化过程,同时还测量了光泽度、颜色、表面电阻和体积电阻在涂层老化过程中的变化。结果表明：在涂层老化过程中,涂层孔隙率增加,而体积电阻、表面电阻则降低, EIS给出了在涂层老化的不同阶段的特征。采用光泽度、颜色、表面电阻和体积电阻以及电化学阻抗数据作为性能参数,建立了涂层老化动力学方程,并给出了涂层失效判据,并对涂层老化动力学的参数进行了讨论,认为采用体积电阻或低频阻抗模值作为性能参数描述涂层老化动力学过程更为合理。     

Phase transformations in face centered cubic (Al0.32Cr0.68)2O3 thin films

Face centered cubic (Al_0.32Cr_0.68)₂O₃ thin films have been annealed in the temperature range of 500–1000 °C during 2–8 h. The fcc structure of the film remains intact when annealed at temperatures up to 700 °C for 8 h. X-ray diffraction and transmission electron microscopy show the onset of phase transformation to corundum phase alloys in the sample annealed at 900 °C for 2 h, where annealing at 1000 °C for 2 h results in complete phase transformation to α-(Al_0.32Cr_0.68)₂O₃. In-plane and out-of-plane line scans performed in EDX TEM and θ/2θ XRD patterns did not show any phase separation into α-Cr₂O₃ and Al₂O₃ prior and after the annealing. The apparent activation energy of this process is 380–480 kJ/mol as determined by the Johnson–Mehl–Avrami model.     

Fe-Ni合金在600 ℃空气中的氧化行为

采用称量法研究了两种Fe-Ni合金（Ni含量分别为5%和9%,质量分数）在600 ℃静态空气中的高温氧化行为,对比分析了两种合金的氧化动力学特征,采用扫描电镜（SEM）、X射线衍射（XRD）和能谱分析（EDS）等手段分析了表面氧化膜的物相组成及显微结构。结果表明：Fe-5%Ni和Fe-9%Ni合金在 600 ℃空气中的氧化行为基本类似,氧化前期Ni-5合金质量增加量较高,16 h后发生逆转,其氧化动力学遵循近似抛物线规律,表明氧化膜内的离子扩散过程受氧化过程控制。两种合金的表面氧化膜均由Fe3O4 和 Fe2O3 组成,同时含有尖晶石相(Ni, Fe)3O4。Ni-9合金氧化膜中尖晶石相含量相对较高,是导致氧化质量增加发生逆转的主要原因。     

Growth morphology and crystallography of precipitate in a new high-temperature structural intermetallic Ti–40Al–10Fe

Based on TiAl alloys bearing high levels of Nb, which are prospective high-temperature intermetallics, a new dual-phase alloy (Ti–40Al–10Fe (at%)) with precipitate growth direction close to the slipping plane normal of the matrix was developed. Transmission electron microscopy revealed that the annealed alloy was composed of equiaxed grains of τ₂-TiAl₂Fe and γ-TiAl phases. Aging treatment at 1000 °C produced polygon-shaped γ-TiAl precipitate from the τ₂-TiAl₂Fe matrix. The precipitation reaction of the face-centered cubic structure of τ₂-TiAl₂Fe into the ordered face-centered tetragonal structure of γ-TiAl phase was systematically investigated in terms of crystallographic features, including mutual orientation relationship, growth direction, habit plane, side facets, and interfacial dislocation structure. The observed growth direction <973> was close to the normal of the slip plane {111}, with a discrepancy angle of ∼20°. Thus, the observed two-phase microstructure might significantly improve strengthening. It could also be quantitatively controlled by selection of precipitate and matrix with phase structures and lattice parameters that meet a certain requirement.     

含铝奥氏体耐热钢的高温氧化性能

以Fe-18Cr-30Ni为基础,添加不同含量的Al设计了4组新型奥氏体耐热钢。利用氧化质量增加法研究了4组新型奥氏体耐热钢在700、800和900 ℃下空气中的氧化行为,绘制了氧化动力学质量增加曲线,并利用XRD、SEM和EDS对氧化膜的表面形貌及结构进行了表征。结果表明,1～3号钢在900 ℃时均形成了较为致密的Al2O3内层氧化膜,合金表面生成的复合氧化膜由内到外依次为 Al2O3、(Al0.9Cr0.1)2O3、尖晶石氧化物Fe(Cr, Al)2O4;1号钢氧化过程中还形成了富（Cr, Fe）的混合氧化物,降低了Al2O3氧化膜的连续性;4号钢900 ℃并没有形成致密的Al2O3内层氧化膜,生成的复合氧化膜由内到外依次为 (Al0.9Cr0.1)2O3、尖晶石氧化物Fe(Cr, Al)2O4。     

Kinetics of Enthalpy Relaxation at the Glass Transition in Ternary Tellurite Glasses

The kinetics of enthalpy relaxation (recovery) at the glass transition in x K₂O·(20− x )MgO·80TeO₂ glasses has been examined from heat capacity measurements using differential scanning calorimetry to clarify the features of the structural relaxation in ternary TeO₂-based glasses. Ternary glasses such as 10K₂O·10MgO·80TeO₂ show high thermal resistance against crystallization compared with binary glasses. The degree of fragility m estimated from the activation energy for viscous flow E _η and the glass transition temperature T _g is m = 55–62, indicating a fragile character in TeO₂-based glasses. Large heat capacity changes of 43.1–48.2 J·mol⁻¹·K⁻¹ are also observed at the glass transition. The activation energy for enthalpy relaxation Δ H is evaluated from the cooling rate dependence of the limiting fictive temperature, and values of Δ H = 897–1268 kJ·mol⁻¹ are obtained. Negative deviation from additivity in Δ H is also observed. Values of the Kovacs–Aklonis–Huchinson–Ramos (KAHR) parameter θ estimated from Δ H and T _g are 0.33–0.42 K⁻¹. It has been proposed that ternary glasses have more homogeneous and constrained glass structure compared with binary glasses.     

Reduction of hexavalent chromium by copper

The galvanic reaction of metallic copper in Cr(VI)-laden aqueous solutions of varying pH was examined by in situ u.v.–visible spectrophotometry, rotating disc electrode chronopotentiometry and cyclic voltammetry. The galvanic reaction in 0.2 M H₂SO₄ solutions was pseudo first order in Cr(VI) concentration. Experiments with both magnetically stirred solutions and a copper mesh or a copper film in a rotating disc electrode configuration revealed the reaction to be diffusion-controlled with respect to Cr(VI) transport to the copper surface. Finally, cyclic voltammetry data in Cr(VI)-laden media of varying pH underline the important role of protons in the galvanic reaction.     

Methane activation by surface oxygen in calcia-stabilized zirconia

Methane activation at 450–700°C by 14 mol% calcia-stabilized zirconia was studied by the transient reaction of pure methane with the oxidized material. Three distinct sequential reaction regimes are observed. Initially, methane oxidation rates are similar to those in cofed methane–oxygen mixtures. After a small amount of oxygen (amount) is removed from the material, the reactivity of the material suddenly increases while a larger amount of oxygen, roughly equivalent to 1 surface layer, is removed. Finally, after this reductive phase, methane continues to react rapidly to deposit a surface layer of carbonaceous material which can be removed by reoxidation. This cycle can be repeated.     

分布活化能模型用于模拟蒸馏的初步研究

对分布活化能模型向二级反应体系中的应用进行了推广,将最新的Miura分析方法应用于煤焦油馏分的模拟蒸馏曲线分析,发现所得活化能数据同非线性动力学回归分析结果非常接近,初步表明了该法应用于二级反应体系的可行性。     

Investigation of crude latex from various Carica papaya varietices for lipid bioconversions

The protein contents in crude latices from various varieties of papaya (Carica papaya) and their catalytic activities in proteolysis, lipolysis, and interesterification reactions were studied with regard to the variety, the geographic location of cultures, and the frequency of fruit tapping. Biocatalytic activities of these raw materials were compared to several commercially available crude and purified preparations of papain. These investigations were carried out in order to have a better physicochemical characterization of these raw materials, to select the adequate papaya latex for protein or lipid bioconversions, and to valorize them on an industrial scale. For the purified preparations of papain, only proteolytic activity was obtained. All crude papaya latices exhibit proteolytic, lipolytic, and interesterification activities, and no relationship between the proteolytic and lipolytic activities was observed. The high multiple correlation coefficient (R) on the order of R=0.93–0.99, obtained from the regression analysis for the lipolytic and interesterification activities for all crude papaya latices investigated suggested that there was a correlation between these enzyme activities. However, for the same lipase preparation, the interesterification activity differed substantially depending on the type of interesterification reaction.