去合金化制备纳米多孔铜

 以Mn-Cu合金为前驱体合金,在0.1 mol/L HCl 溶液中自由腐蚀去合金化成功制备出纳米多孔铜,采用扫描电镜和X射线能谱仪对去合金腐蚀前后样品的形貌和成分进行了分析,结果表明,Mn-Cu合金在0.1 mol/L HCl 溶液中发生锰的选择性溶解,制备出的纳米多孔铜呈3维网络状均匀结构,平均系带尺寸53 nm,平均孔径尺寸为140 nm。     

Mn-Cu合金成分对去合金化法制备纳米多孔铜的影响

 采用电弧熔炼制备出前驱体Mn-Cu合金,在稀盐酸溶液中自由腐蚀去合金化,制备出具有双连续结构的纳米多孔铜。研究了前驱体合金的成分对纳米多孔铜微观结构及Mn的选择性腐蚀程度的影响。结果表明：前驱体Mn-Cu合金的Cu原子分数为43%时,其去合金化受到抑制,存在明显的未完全去合金化的岛状结构;前驱体Mn-Cu合金的Cu原子分数为32%～23%时,可完全去合金化,形成平均孔径尺寸为20～100 nm,平均系带尺寸为30～80 nm,具有双连续结构的纳米多孔铜;前驱体Mn-Cu合金的Cu原子分数低至20%时,去合金化后存在大量裂纹,形成纳米颗粒聚集体。纳米多孔铜中存在少量的残余Mn,残余Mn的原子分数随着前驱体合金Mn原子分数的增高而降低。实验表明腐蚀液浓度对纳米多孔铜形貌也存在影响。     

去合金化工艺对纳米多孔铜纯度的影响

采用腐蚀去合金化方法制备纳米多孔铜材料。研究了固溶时间、腐蚀时间及腐蚀温度对纳米多孔铜表面形貌及残余Mn含量的影响。研究表明:由于固溶时间的延长，合金成分越来越均匀化，去合金化后所得纳米多孔铜的残余Mn原子分数降低。固溶95 h的前驱体合金，随着腐蚀时间的延长，其残余Mn含量降低不明显；随着温度的升高，其残余Mn原子分数由25 ℃的3.54%降至60℃的1.14%，但是60 ℃腐蚀后的孔隙与丝径尺寸明显粗化，样品易碎。通过调整去合金化参数，实验所制备的纳米多孔铜呈现均匀的海绵状纳米多孔结构，残余Mn原子分数1.23%, 平均丝径尺寸40 nm。     

镍基非晶复合涂层激光制备及其纳米压痕测试

采用大功率半导体激光熔覆和重熔的工艺在低碳钢表面制备Ni-Fe-B-Si-Nb合金非晶复合涂层,并对所得涂层进行了纳米压痕性能测试。研究结果表明,当激光熔覆时激光功率为0.8kW,熔覆速度为0.36m/min,送粉速度为12g/min,重熔时激光功率为3.5kW,熔覆速度为8m/min,在低碳钢表面成功制备了Ni40.8Fe27.2B18Si10Nb4非晶复合涂层,涂层主要由非晶相和NbC颗粒相组成。纳米压痕测试结果表明经激光重熔后所得非晶复合涂层的显微硬度和弹性模量远远大于未重熔的熔覆层,并且也大于同成分大块非晶。     

Si,Al对激光熔覆MoFeCrTiW高熵合金涂层组织性能的影响

为了提高材料表面的耐磨性和高温抗氧化性,利用激光熔覆技术在Q235钢表面制备了MoFeCrTiW高熵合金涂层,并采用X射线衍射仪(XRD)、扫描电镜(SEM)和磨损试验机等研究了Si,Al添加对高熵合金涂层组织、相结构、耐磨性和高温抗氧化性能的影响。结果表明:激光熔覆MoFeCrTiW高熵合金涂层组织为等轴晶,单独添加等物质的量的Si或Al时,涂层分别为共晶组织或树枝晶,同时添加等物质的量的Si和Al时,涂层组织为细小的等轴晶。各高熵合金涂层的主体相均为BCC相,随着Si,Al的添加,BCC相的晶格常数减小。添加等物质的量的Al有助于抑制涂层中金属间化合物的形成,使涂层耐磨性降低;添加等物质的量的Si则会形成含Si的金属间化合物和一些未知相,提高涂层耐磨性。激光熔覆MoFeCrTiW高熵合金涂层在800℃的抗氧化性较高,Si、Al的添加可使涂层的高温抗氧化性进一步提高。     

铜钴合金纳米有序阵列的光学特性

用电化学法制备了高度有序的多孔阳极氧化铝模板, 选用CoSO4和CuSO4的混合溶液为电解液,用交流电化学沉积法在多孔阳极氧化铝的柱形微孔内制备铜钴合金纳米线有序阵列.分别用扫描电镜(SEM),X 射线衍射仪(XRD)对多孔氧化铝模板和纳米线阵列的微观形貌和结构进行分析.结果显示,制备的合金纳米线表面光滑、均匀,纳米线中的晶粒在长过程中有(111) 晶面的择优取向.用UV3101分光光度计测试了铜钴合金多孔铝复合结构的透射光谱及偏振光谱表明,合金纳米复合结构在可见及近红外波段具有良好的透射比和消光比;铜钴合金纳米复合结构的确能够改善单一金属的特性,比如在近红外光区,其消光比(30 dB)优于铜纳米复合结构(17 dB).     

激光烧结石墨烯-铜纳米复合材料性能研究

石墨烯拥有许多优异的性能,这些性能使石墨烯有望成为金属基复合材料的理想增强相。采用激光烧结的方法制备了石墨烯-铜纳米复合材料。X射线衍射(XRD)和Raman光谱测试结果表明,石墨烯存在于激光烧结所制备的纳米复合材料中。显微硬度测试结果显示,石墨烯的添加使得石墨烯-铜纳米复合材料的硬度比激光烧结纯铜的硬度提高了约22%。用电化学极化法研究了激光烧结的石墨烯-铜纳米复合材料和纯铜在3.5%(质量分数)NaCl溶液中的腐蚀行为,石墨烯-铜纳米复合材料的腐蚀电位比激光烧结纯铜的腐蚀电位略有降低,腐蚀电流也有所降低,说明其耐腐蚀性能较激光烧结纯铜略好。     

碳化钨对激光熔覆高熵合金的影响

为了获得高性能的涂层材料,采用激光熔覆的方法,在Q235钢基体上制备了FeSiCrCoMo高熵合金涂层,并研究了WC对高熵合金涂层的组织和性能的影响。通过金相、X射线衍射、扫描电镜、硬度计、磨损试验机分别研究了添加WC前后涂层的微观形貌、相结构、硬度及磨损性能。结果表明:高熵合金FeSiCrCoMo涂层组织为粗大枝状晶,主要由BCC相和金属间化合物构成,添加WC后,涂层中形成了致密细小的胞状晶,同时BCC相增多,金属间化合物明显减少;添加WC后涂层的硬度明显增强,平均硬度提升了23%,涂层表面平均硬度达到了687HV0.2;WC的添加使得涂层的摩擦系数减小,磨损率减小,耐磨性能提高。     

激光熔覆FeCrNiMnMoxB0.5高熵合金涂层组织与耐蚀性能

为了获得性能优异的涂层材料,采用激光熔覆的方法在Q235钢基体上制备了不同Mo含量的FeCrNiMnMoB0.5系高熵合金涂层,着重探究Mo对高熵合金组织与性能的影响。通过金相、X射线衍射、扫描电镜、硬度计、电化学工作站分别研究了高熵合金涂层的显微组织、相结构、显微硬度及耐蚀性能。结果表明:FeCrNiMnMoB0.5系高熵合金组织为树枝晶,主要由fcc相和少量金属间化合物构成。当添加少量Mo时,涂层的硬度较低,为290 HV,随着Mo的增加,晶格畸变加剧,出现少量金属化合物,涂层硬度最大增加到658 HV。在模拟饱和盐水泥浆溶液中FeCrNiMnMo0.4B0.5表现出较好的耐腐蚀性。     

纳米Pt-Au合金修饰电极对鲁米诺电化学发光的增敏研究

用化学还原法制备了不同比例及不同粒径的纳米Au-Pt合金,并用UV-Vis、TEM、激光粒径、XRD等方法进行了表征,确认所合成物质确系双金属合金纳米粒子而非两种金属纳米粒子的混合物,通过改变合成方法和条件,可以得到一系列不同含量比和粒径,粒径范围在4.025～92.33 nm之间。采用电化学沉积法可将所制备合金修饰到铂盘电极上,在碱性介质(pH 12)中,随着合金比例的改变和合金粒径的减小,鲁米诺的电化学发光强度显著增强,当合金中Pt∶Au=6∶1,粒子粒径为最小时,所获得修饰电极上鲁米诺的电化学发光强度较裸电极增强近1个数量级。     

The effect of laser remelting in the formation of tunable nanoporous Mn structures on mild steel substrates

Nanoporous manganese was fabricated by a three-step process involving high power laser cladding of a homogeneous Cu₄₀Mn₆₀ alloy coatings onto a mild steel substrate, laser remelting for tuning the grain size and the composition homogeneity followed by selectively electrochemical de-alloying for removal of Cu element and formation of nanoporous Mn. The microstructure and homogeneity of the precursor Cu₄₀Mn₆₀ alloys have a significant influence on the evolution of nanopores during selectively electrochemical de-alloying. Laser remelting can significantly refine the microstructure. The second dendrite arm spacing decreases with increasing of laser remelting scanning speed. A SDAS of 1.17 μm was obtained at the laser scanning speed of 133 mm/s. When the remelting scanning speed reaches 100 mm/s, a nanoporous structure with average pore size less than 100 nm was achieved under optimized dealloying electrode current density about 2 mA/cm². Nanoporous Mn with nanopore sizes ranging from 80 to 130 nm was fabricated by this method. Surface-enhanced Raman scattering characteristics of the nanoporous materials have been investigated. It is found that smaller nanoporosity leads to significant improvements in surface-enhanced Raman scattering.     

Fabrication of nanoporous manganese by laser cladding and selective electrochemical de-alloying

Fabrication of nanoporous Cu-Mn alloy coatings was investigated by a two-step process involving high power laser cladding of a homogeneous Cu40Mn60 alloy coatings followed by selectively electrochemical de-alloying. Auger mapping results indicate that nanoporous manganese was obtained by selective electrochemical etching of the less active Cu component owing to the passivation of the more active manganese in potassium nitrate solution. The surface morphology of the porous Mn was a ribbon-like structure, different from interconnected bicontinuous nanopores that are usually obtained by de-alloying. The influence of de-alloying time, electric potential and temperature on the formation of nanoprosity is systematically investigated. Nanopore sizes can be tailored to be less than 100 nm. Under optimal etching conditions the nanopore size was below 25 nm. The surface area of the nanoporous manganese layer was enhanced by up to 990 times compared with that of a polished sample.     

Fabrication,Microstructure, and Properties of Nanoporous Pd,Ni, and Their Alloys by Dealloying

Nanoporous metals can be fabricated by dealloying, which is one of the reactions that occur during the corrosion of alloys. Nanoporous gold has been widely investigated for several decades, and it has recently been found that other metals, such as platinum, palladium, nickel, and copper, can form nanoporous structures through the dealloying of binary alloys. This article mainly shows fabrication and properties of nanoporous palladium and nickel after introduction of nanoporous metals by referring to nanoporous gold as an example. It is necessary to select binary alloys with suitable elements, in which the dissolution of the less noble element and the aggregation of the nobler element at the solid/electrolyte interface are simultaneously allowed. Postprocessing by thermal or acid treatment alters the nanoporous structure. Various properties of nanoporous metals (including mechanical, catalytic, piezoelectric, hydrogenation, and magnetic ones) are different from those of bulk and nanocrystalline materials and nanoparticles because of their specific three-dimensional network structures consisting of nanosized pores and ligaments. Hydrogenation and magnetic properties are reviewed in terms of lattice strain at curved surfaces. These new metallic nanomaterials are now being investigated from the viewpoint of functional applications, and provide much room for study in various fields.     

Surface effects on saturation magnetization in nanoporous Ni

Nanoporous Ni specimens with ligament lengths of 10–210 nm and specific surface areas of 0.03–0.58 nm^?1 were fabricated by the dealloying of Ni_0.25Mn_0.75 alloy and annealing at 473–873 K, and saturation magnetization investigated in terms of their size dependence. Saturation magnetization decreased with decreasing ligament length or increasing specific surface area. This trend is the same as that for nanoparticle Ni. However, the saturation magnetization of nanoporous Ni tends to be lower than that of the nanoparticle Ni when their specific surface areas are the same. It is suggested, therefore, that the surface effect due to a noncollinear arrangement is enhanced by the surface defects in the nanoporous Ni.     

Based on Cu as framework constructed nanoporous CuO/Cu composites by a dealloy method for sodium-ion battery anode

Nanoporous CuO/Cu composites with a continuous channel structure were fabricated through a corroding Cu-Al alloy process. The width of the continuous channels was about 20~50 nm. Nanoporous structure could effectively sustain the volume expansion during the Na⁺ insertion/extraction process and shorten the Na⁺ diffusion length as well, which thus helps improve the Na⁺ storage performance. Moreover, the nanoporous structure can improve the contact area between the electrolyte and the electrode, leading to an increment in the number of Na⁺ insertion/extraction sites. When used as the anode for sodium-ion batteries, the CuO/Cu exhibited an initial capacity of ~?580 mAh g^?1, and the capacity is maintained at ~?200 mAh g^?1 after 200 cycles at a current density of 500 mA g^?1.     

Preparation and electrochemical performances of nanoporous/cracked cobalt oxide layer for supercapacitors

Nanoporous/cracked structures of cobalt oxide (Co₃O₄) electrodes were successfully fabricated by electroplating of zinc–cobalt onto previously formed TiO₂ nanotubes by anodizing of titanium, leaching of zinc in a concentrated alkaline solution and followed by drying and annealing at 400 °C. The structure and morphology of the obtained Co₃O₄ electrodes were characterized by X-ray diffraction, EDX analysis and scanning electron microscopy. The results showed that the obtained Co₃O₄ electrodes were composed of the nanoporous/cracked structures with an average pore size of about 100 nm. The electrochemical capacitive behaviors of the nanoporous Co₃O₄ electrodes were investigated by cyclic voltammetry, galvanostatic charge–discharge studies and electrochemical impedance spectroscopy in 1 M NaOH solution. The electrochemical data demonstrated that the electrodes display good capacitive behavior with a specific capacitance of 430 F g^?1 at a current density of 1.0 A g^?1 and specific capacitance retention of ca. 80 % after 10 days of being used in electrochemical experiments, indicating to be promising electroactive materials for supercapacitors. Furthermore, in comparison with electrodes prepared by simple cathodic deposition of cobalt onto TiO₂ nanotubes(without dealloying procedure), the impedance studies showed improved performances likely due to nanoporous/cracked structures of electrodes fabricated by dealloying of zinc, which provide fast ion and electron transfer routes and large reaction surface area with the ensued fast reaction kinetics.     

Fabrication of nanoporous AuPt nanoparticles modified indium tin oxide electrode and their electrocatalytic effect

This paper describes the synthesis of nanoporous AuPt nanoparticles (np-AuPt NPs) by galvanic replacement reactions that involve large-sized silver nanoparticles (Ag NPs) electrodeposited upon an indium tin oxide (ITO) film glass as a sacrificial template. Compared to a previous synthetic route based on the formation and dealloying of Ag/Au alloy nanoparticles, this method can easily fabricate nanoporous Au nanoparticles (np-Au NPs), as well as nanoporous AuPt nanoparticles. Structural characterization indicated that the products had a particle size of ～170 nm with a ligament size of tens of nanometers. The fabricated np-Au NPs/ITO and np-AuPt NPs/ITO electrode were also tested and compared for the oxidation of hydrogen peroxide in a phosphate buffer solution (pH 7.0). The np-AuPt NPs/ITO electrode showed a much higher electrocatalytic efficiency and detection sensitivity to hydrogen peroxide than the np-Au NPs/ITO electrode.     

自支撑纳米多孔金薄膜制备研究

采用磁控溅射镀金银膜,长时间热处理合金化制备前驱体合金,以渐进浓度的硝酸自由腐蚀去合金化成功制备出具有自支撑结构的纳米多孔金薄膜。采用扫描电镜和X射线能谱仪对去合金腐蚀前后样品的形貌和成分进行了分析,结果表明:400℃,36h的热处理使得薄膜样品完全合金化,获得了结晶致密的Au42Ag58合金膜;渐进浓度的自由腐蚀避免了薄膜的完全开裂,获得了样品尺寸大于15mm×15mm、厚度400~500nm、孔隙率约56%、具有自支撑结构的纳米多孔金薄膜,其微观结构为连续的三维多孔结构,系带尺寸40~140nm,80~100nm的系带达58%。