模板沉积-去合金化法制备块体泡沫金

在聚苯乙烯微球表面直接镀覆具有自支撑金层的基础上,结合去合金化工艺成功制备出双模式孔径分布的块体泡沫金样品,建立模板沉积-去合金化法制备超低密度泡沫金的工艺方法,并对其制备工艺进行研究。研究表明:化学镀金后PS微球表面的金沉积层厚度为70～90nm;在Au/PS表面进行化学镀银后镀覆层厚度增至200～400nm;模板去除后,获得了完全自支撑的Au40Ag60金银合金空心微球结构泡沫;去合金化干燥后,样品由约10μm的空心球壳和平均系带尺寸47nm的双连续结构纳米多孔球壳层的双模式孔隙形貌组成,并且由于去合金化形成的纳米多孔球壳层,样品的密度进一步减小至0.8g/cm3。     

去合金化工艺对纳米多孔铜孔结构的影响

以Mn-Cu合金为前驱体合金,在酸溶液中腐蚀去合金化成功制备出孔径尺寸为纳米量级的纳米多孔铜。 研究了去合金化工艺参数中的酸溶液成分、腐蚀时间及腐蚀温度对最终纳米多孔铜孔结构及Mn的选择性腐蚀程度影响。结果表明：在0.1 mol/L HCl溶液中自由腐蚀去合金化后可得到孔结构均匀的纳米多孔铜;随着腐蚀时间的延长,孔结构有显著变化,腐蚀2 d所得纳米多孔铜样品的孔结构呈蜂窝状,腐蚀5 d所得样品的孔结构呈均匀的三维网络状结构,而后随着腐蚀时间的延长,孔壁逐渐粗化;随着腐蚀温度升高到60 ℃,样品中的残余Mn含量降低明显。通过调整去合金化工艺,实验所制备的纳米多孔铜孔结构呈均匀的三维网络状,孔隙率为57.7%,平均孔径尺寸约140 nm。     

模板法-脱合金制备低密度分级纳米多孔金及其电催化性能（英文）

提出了以模板法-脱合金复合方法制备低密度分级多孔金。以直径为700 nm的二氧化硅(SiO_2)微球作为模板,通过化学镀方法制备了Ag@SiO_2和Au@Ag@SiO_2核壳粒子,并通过冷压-烧结方法制备了Au@Ag@SiO_2合金块材。通过连续改变腐蚀溶液,将SiO_2模板以及Ag元素从Au@Ag@SiO_2合金中完全去除。将SiO_2从Au@Ag@SiO_2微球完全去除从而得到了大尺寸空心球壳(直径约为675nm),将Ag元素脱合金去除从而在球壳表面形成了许多小尺寸的孔结构(直径约为75 nm)。TEM图像表明,块状金样品中的韧带由具有多晶特性的纳米晶粒组成。这种具有低密度1.1 g/cm~3(相对密度为5.7%)和高比表面积4.24 m~2/g的分级纳米多孔金材料在碱性溶液中对甲醇电氧化具有优良的催化活性以及快速的传质速率,表明其在催化领域具有广阔的应用前景。     

模板法-脱合金制备低密度、分级多孔金及其电催化性能

本文提出了以模板法-脱合金复合方法制备低密度分级多孔金。在该方法中,以直径为700 nm的二氧化（SiO2）微球作为模板,通过化学镀的方法依次制备了Ag@SiO2和Au@ Ag@ SiO2核壳粒子,并通过冷压-烧结方法制备了Au@ Ag@ SiO2合金块材。通过连续改变腐蚀溶液,SiO2模板以及Ag元素从Au@ Ag@ SiO2合金中完全去除。将SiO2从Au@ Ag@ SiO2微球完全去除从而得到了大尺寸空心球壳（直径约为675 nm）,将Ag元素脱合金去除从而在球壳表面形成了许多小尺寸的孔结构（直径约为75nm）。TEM图像表明,块状金样品中的韧带由具有多晶特性的纳米晶粒组成。这种具有低密度1.1 g/cm3（相对密度为5.7%）和高表面积4.24 m2/g的分级纳米多孔金材料在碱性溶液中对甲醇电氧化具有优良的催化活性以及快速的传质速率,表明其在催化领域具有广阔的应用前景。     

Cu0.3Mn0.7去合金化制备纳米多孔铜块体材料

采用去合金化法对Cu0.3Mn0.7合金进行自腐蚀制备出厚度为1 mm的纳米多孔铜块体材料。采用XRD、SEM、EDS、AAS等分析了样品的相组成、微观形貌和元素含量。结果表明：样品在室温0.1 mol/L盐酸溶液中自腐蚀10 d,得到成分单一,结构均匀的三维连通纳米多孔铜块体材料,其表面平均孔径尺寸约125 nm,平均骨架尺寸约80 nm,横截面平均孔径尺寸约300 nm。     

纳米多孔镍的多层次结构及其影响因素

采用真空熔炼,快速凝固与去合金化相结合的方法制备纳米多孔镍,用XRD、SEM、EDS分析试样的相组成及形貌,研究多层次纳米孔的形成机制及不同工艺对其结构的影响.结果表明:快速凝固可制备晶粒均匀、细小的理想前驱体Ni30Al70合金,经去合金化可获得由100 ～ 300 nm大骨架及孔径尺寸10 nm的蜂窝状多孔结构共同构成的纳米多孔镍.NiAl3和Ni2Al3两相腐蚀的协同作用对新颖多层次纳米多孔镍结构的形成有重要影响.最佳去合金化温度65℃,最佳溶液浓度25％.     

Al-Cu合金成分对去合金化制备纳米多孔铜的影响

采用快速凝固与去合金化相结合的方法制备纳米多孔铜,用XRD、SEM分析样品的相组成和微观形貌,研究前驱体AlCu合金成分对纳米多孔铜微观结构及Al2Cu、AlCu协同性腐蚀的影响.结果表明:Cu原子分数为33％时,去合金化后形成具有双连续结构的纳米多孔铜;Cu原子分数为38％时,形成比表面积更高、更均匀细小的双连续结构纳米多孔铜,平均孔径尺寸约100 ～ 150 nm,平均系带尺寸约50 ～ 80 nm;Cu原子分数为43％时,形成了双连续结构的纳米多孔铜并在其中分散着纳米颗粒聚集体;Cu原子分数为50％时,形成了纳米颗粒聚集的纳米多孔铜.实验发现,Al2Cu、AlCu腐蚀的协同作用对双连续结构的形貌有重要的影响.     

中国工程物理研究院 激光聚变研究中心，四川 绵阳 621900

以聚苯乙烯微球(PS)为模板,采用"种子-生长"法在聚苯乙烯微球表面直接镀覆具有自支撑性的金壳层,成形热处理去除PS模板,成功制备出空心微球结构圆柱形块体的泡沫金样品,并对其制备工艺进行了研究。研究表明:平均晶粒尺寸为4.6nm的金纳米粒子通过静电作用可成功粘附于交联聚苯乙烯微球(PS-DVB)表面。化学镀时以粘附的金纳米粒子为种子继续生长,沉积的金颗粒细小而致密,粒径主要分布于30～60nm,且微球表面金沉积层的包覆率高,包覆厚度70～90nm,PS模板去除后金沉积层具有良好的自支撑性。采用类似粉浆铸造工艺使gold/PS有孔隙地随机堆积成型,热处理去除聚苯乙烯模板后可成功获得圆柱体形状的泡沫金样品。制备的泡沫金由直径8～9μm的空心球壳组成,圆柱体直径约4mm,密度约1.5g/cm3,孔隙率高达92%。     

种子-生长法制备块体泡沫金

以聚苯乙烯微球(PS)为模板,采用"种子-生长"法在聚苯乙烯微球表面直接镀覆具有自支撑性的金壳层,成形热处理去除PS模板,成功制备出空心微球结构圆柱形块体的泡沫金样品,并对其制备工艺进行了研究。研究表明:平均晶粒尺寸为4.6nm的金纳米粒子通过静电作用可成功粘附于交联聚苯乙烯微球(PS-DVB)表面。化学镀时以粘附的金纳米粒子为种子继续生长,沉积的金颗粒细小而致密,粒径主要分布于30～60nm,且微球表面金沉积层的包覆率高,包覆厚度70～90nm,PS模板去除后金沉积层具有良好的自支撑性。采用类似粉浆铸造工艺使gold/PS有孔隙地随机堆积成型,热处理去除聚苯乙烯模板后可成功获得圆柱体形状的泡沫金样品。制备的泡沫金由直径8～9μm的空心球壳组成,圆柱体直径约4mm,密度约1.5g/cm3,孔隙率高达92%。     

去合金化制备纳米片阵列和纳米球颗粒多孔锡

以Mg₈₉Sn₁₁(二元合金)为前驱体合金,在腐蚀介质中通过去合金化方法成功制备了纳米片阵列和纳米颗粒形貌的多孔锡。通过调整腐蚀介质和腐蚀时间研究了纳米多孔锡的形貌结构以及去合金化程度的影响因素。结果表明,在酸性腐蚀介质中去合金化,能够获得双连续结构的纳米多孔锡结构。其中,在0.1%H₃PO₄溶液中,孔壁由不连续的纳米球颗粒堆积而成,而在0.1mol/L HCl溶液中,孔壁为纳米片结构,形成了纳米片阵列的多孔锡;而在中性的NaCl溶液中,同样成功制备出了均匀的纳米片状阵列多孔锡。在5%的NaCl中,随着去合金化时间的延长,多孔形貌从均匀的纳米片阵列多孔转变为团簇状的纳米多孔形貌。去合金化1h时,表面形成了均匀的纳米片阵列多孔结构,6h后表面开始生成不连续的团簇状多孔形貌,并最终演化为连续起伏的片状纳米锡多孔结构,其孔径平均尺寸保持在50nm。通过对去合金化工艺进行调整,制备了不同形貌的纳米多孔锡结构。     

Hydrothermal synthesis and characterization of mesoporous zinc selenide agglomerates by nitrogen bubble templates

Mesoporous coral-like and litchi-like zinc selenide agglomerates were successfully synthesized with sodium selenite and zinc acetate dihydrate as precursors by adding hydrazine hydrate using the hydrothermal method. The experimental parameters were varied and hard agglomerates of small nanoparticles were observed. Increasing amounts of hydrazine hydrate were added to control the pH values of the reaction system. The effective control of the morphology and size of the ZnSe nanopores agglomerates by varying the pH was also demonstrated. The N₂ bubble templates produced provided the aggregation centers during the reaction, and then result in agglomerates of the small ZnSe nanoparticles with mesopores. The litchi-like zinc selenide has two different morphologies, including hollow spherical agglomerates comprising of 4-8 nm diameter nanoparticles and 15-25 nm diameter nanorods. The coral-like ZnSe mesoporous structure has a very high specific surface area of 129 m²/g and an emission band at 626 nm as measured by a photoluminescence (PL).     

Porous silica aerogel/honeycomb ceramic composites fabricated by an ultrasound stimulation process

The synthesis behavior of nanoporous hydrophobic silica aerogel in honeycomb-type ceramics was observed using TEOS and MTES. Silica aerogel in the honeycomb ceramic structure was synthesized under ultrasound stimulation. The synthesized aerogel/honeycomb ceramic composites were dried under supercritical CO₂ drying conditions. The values for the line shrinkage of the wet gels during supercritical CO₂ drying declined from 19% to 4% with an increase in the H₂O/TEOS molar ratio from 8 to 24. Low shrinkage was a key factor in increasing the interface compatibility with the aerogel/honeycomb ceramic composites. The optimum condition of silica aerogel in the honeycomb-type ceramic structure had a TEOS:MTES: H₂O:glycerol ratio equal to 1:1.2:24:0.05 (mol%).     

Enhanced thermoelectric performance via randomly arranged nanopores: Excellent transport properties of YbZn2Sb2 nanoporous materials

Fabricating nanoporous bulk thermoelectric (TE) materials with periodically arranged nanopores is highly challenging and expensive, although TE materials exhibit high power factors (α²σ) and low thermal conductivities (κ). Enhanced TE performance via randomly arranged nanopores is demonstrated with a YbZn₂Sb₂ nanoporous material (nPM) fabricated by a combination of melt quenching and two stage spark plasma sintering in less than 10 h. Measurement of the electrical conductivity, Hall mobility, Seebeck coefficient, and thermal conductivity show that simultaneously enhancing α²σ and reducing κ can realize in the YbZn₂Sb₂ nPM with randomly arranged nanopores about 50-200 nm in diameter. Compared with YbZn₂Sb₂ dense bulk materials (dBM) fabricated by a conventional method taking more than 180 h, α²σ at 300 K increases by 122%, κ at 300 K decreases by 29%, and the maximum ZT value at 775 K reaches 0.67, increasing by 46% for the nPM725 sample. This work shows that a periodic arrangement of nanopores is not essential for the fabrication of attractive TE materials, which offers a wider approach to nanostructure engineering to improve TE performance.     

Self-Ordered Nanoporous Alumina Templates Formed by Anodization of Aluminum in Oxalic Acid

Anodic aluminum oxide (AAO) membranes with highly ordered nanopores serve as ideal templates for the formation of various nanostructured materials. The procedure of the template preparation is based on a two-step self-organized anodization of aluminum. In the current study, AAO templates were fabricated in 0.3?M oxalic acid under the anodizing potential range of 30?C60?V at an electrolyte temperature of ~5°C. The AAO templates were analyzed using scanning electron microscopy, x-ray diffraction, Fourier-transform infrared spectroscopy, and differential thermal analysis. The as obtained layers are amorphous; the mean pore size is between 40?nm and 75?nm and increases with the increase of the anodization potential. Well-defined pores across the whole aluminum template, a pore density of ~10¹⁰?pores/cm², and a tendency to form a porous structure with hexagonal symmetry were observed.     

Nanostructural Free-Volume Effects in Humidity-Sensitive MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ceramics for Sensor Applications

Technologically modified spinel MgO-Al₂O₃ ceramics were prepared from Al₂O₃ and 4MgCO₃·Mg(OH)₂·5H₂O powders at sintering temperatures of 1200, 1300, and 1400 °C. Free-volume structural effects in MgO-Al₂O₃ ceramics and their electrophysical properties were studied using combined x-ray diffraction, scanning electron microscopy, Hg-porosimetry, and positron annihilation lifetime spectroscopy. It is shown that increasing of sintering temperature from 1200 to 1400 °C results in the transformation of pore size distribution in ceramics from tri- to bi-modal including open macro- and meso(micro)pores with sizes from ten to hundreds nm and nanopores with sizes up to a few nm. Microstructure of these ceramics is improved with the increase of sintering temperature, which results in decreased amount of additional phases located near grain boundaries. These phase extractions serve as specific trapping centers for positrons penetrating the ceramics. The positron trapping and ortho-positronium decaying components are considered in the mathematical treatment of the measured spectra. Classic Tao-Eldrup model is used to draw the correlation between the ortho-positronium lifetime and the size of nanopores, which is complementary to porosimetry data. The studied ceramics with optimal nanoporous structure are highly sensitive to humidity changes in the region of 31-96% with minimal hysteresis in adsorption-desorption cycles.     

Effect of Steam Activation on Development of Light Weight Biomorphic Porous SiC from Pine Wood Precursor

Biomorphic SiC materials with tailor-made microstructure and properties similar to ceramic materials manufactured by conventional method are a new class of materials derived from natural biopolymeric cellulose templates (wood). Porous silicon carbide (SiC) ceramics with wood-like microstructure have been prepared by carbothermal reduction of charcoal/silica composites at 1300-1600 °C in inert Ar atmosphere. The C/SiO₂ composites were fabricated by infiltrating silica sol into porous activated biocarbon template. Silica in the charcoal/silica composite, preferentially in the cellular pores, was found to get transformed in forms of fibers and rods due to shrinkage during drying. The changes in the morphology of resulting porous SiC ceramics after heat treatment to 1600 °C, as well as the conversion mechanism of wood to activated carbon and then to porous SiC ceramic have been investigated using scanning electron microscope, x-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. Activation of carbon prior to silica infiltration has been found to enhance conversion of charcoal to SiC. The pore structure is found to be uniform in these materials than in those made from as-such charcoal/silica composites. This provides a low-cost and eco-friendly route to advanced ceramic materials, with near-net shape potential.     

The role of nanosized gold particles in adsorption and oxidation of carbon monoxide over Au/Fe2O3 Catalyst

The presence of gold is found to promote the development of weakly bonded (CO)_ad species over the surface of Au/Fe₂O₃ catalyst during interaction with carbon monoxide (CO) or a mixture of carbon monoxide and oxygen. The concentration of these species and the nature of the bonding depend on the gold particle size. No such species are formed for gold particles larger than ∼11 nm or over gold-free iron oxide. The bulk carbonate-like species, formed in the process with the involvement of the hydroxy groups of the support, are merely side products not responsible for the low temperature activity of this catalyst.     

On solidification shrinkage of copper–lead and copper–tin–lead alloys

Abstract

Solidification shrinkage is an important concept in achieving sound castings. In the present work solidification shrinkage was studied in copper–lead and copper–lead–tin alloys. A series of solidification experiments was performed under different cooling rates using a dilatometer which was developed for melting and solidification purposes. The volume change was measured during primary solidification and the monotectic reaction. In order to explain the volume-changing results, the sample macrostructures were studied to evaluate gas and shrinkage cavities which were formed during the solidification. Furthermore, the volume fraction of the primary phase during solidification was evaluated in the samples that were quenched from different temperatures below the liquidus temperature. A shrinkage model was used to explain the volume changes during solidification.     

Melt-casting of Y3Al5O12 (YAG) ceramics by combustion synthesis under high gravity with the addition of glass

Bulk YAG-based ceramics have been prepared by melt-casting under high gravity with the addition of glass. The glass helps to reduce the porosity and grain size of the casted ceramics. In the casting process, the glass melt can feed the shrinkage cavities produced during fast solidification of YAG. With the addition of glass, the grain boundary migration of YAG is pinned and thus grain growth is limited. The effect of the glass strongly depends on its chemical composition and crystallization behavior, where a higher SiO₂ content is necessary to avoid devitrification.