柔性ITO衬底电化学沉积制备Cu/Cu2O薄膜

研究了使用电化学沉积法于碱性条件下在柔性ITO衬底上制备Cu/Cu₂O薄膜的方法。循环伏安曲线表明Cu₂O与Cu的阴极峰分别位于-500 mV(vs Ag/AgCl)和-800 mV(vs Ag/AgCl)附近。利用循环伏安法考察了生长温度和电解液pH值等对Cu₂O与Cu阴极峰电位的影响,阴极峰随生长温度的升高以及pH值的降低而略向阳极移动,沉积电流也随之相应增大。与弱酸性条件相比,上述两个阴极峰随pH值升高而移动的程度明显减小,这可能与碱性条件下C₃H₆O电离程度增大以及C₃H₆O根作为配体的过量程度有关。通过X射线衍射光谱和扫描电子显微镜的表征证实,在所研究的生长温度区间和pH值内可利用电化学沉积法在柔性ITO衬底上制备Cu/Cu₂O纳米混晶薄膜。在相同的生长温度和pH条件下,电化学沉积电位对样品表面形貌和晶体性质具有较大影响。     

VHF-PECVD低温制备微晶硅薄膜的拉曼散射光谱和光发射谱研究

采用拉曼散射光谱和PR650光谱光度计对VHF-PECVD制备的微晶硅薄膜进行了结构表征和在线监测研究.结果表明：功率对材料的晶化率（χc）有一定的调节作用，硅烷浓度大，微调作用更明显；SiH*的强度只能在一定的范围内表征材料的沉积速率，功率大相应的速率反而下降；I［Hα*］/I［SiH*］强度比值反映了材料晶化程度，此结果和拉曼散射光谱测试结果显示出一致性；I［Hβ*］/I［Hα*］的强度比表明氢等离子体中的电子温度随功率的增大而逐渐降低. 关键词： 甚高频等离子体增强化学气相沉积 微晶硅 拉曼散射谱 光发射谱     

电沉积制备金属超细Cu粉的研究

探讨了超细铜粉电沉积制备过程中阴极电流密度对粉体粒径的影响机制。结果表明:电流密度的改变对阴极过电位影响显著,电流密度从0.04A/cm2变化到0.1 A/cm2时,过电位从4.08V变化到9.96V;而过电位的变化直接引起粉体粒径的变化,粒径从大约50nm变化到700nm。分析表明,高电流密度可以获得较高的阴极过电位;在高的阴极过电位条件下,新核的生成速率高且稳定存在的晶核临界半径小,使得粉体粒径变细。     

利用交流阻抗谱揭示Ir(111)电极在酸性溶液中的氢吸附动力学（英文）

本文利用阻抗谱研究Ir(111)电极在HClO_4和H_2SO_4中溶液中的氢吸附行为.在HClO_4溶液中,随着施加电位从0.2 V降到0.1 V(vs RHE),Ir(111)电极上氢吸附速率从1.74×10~(-8) mol·cm~(-2)·s~(-1)增大到3.47×10~(-7) mol·cm~(-2)·s~(-1).与相同条件下Pt(111)电极上的氢吸附速率相比,Ir(111)上的氢吸附速率要小1～2个数量级,这是由于Ir(111)电极与H_2O结合能力更强,因此位于水合氢键网络中的氢离子需要克服更高的能垒才能重新定向进而发生欠电位沉积.在H_2SO_4溶液中,氢吸附电位负移了200 mV,吸附速率也下降了一个数量级,这是由于Ir(111)电极表面强吸附的硫酸根/硫酸氢根物种的阻碍作用.结果表明,在电化学环境下,位于电极表面附近的水分子的取代和重新定向在很大程度上影响了氢吸附过程.     

铝酸钠溶液的鲁米诺增强声致发光研究

用荧光光谱分析仪测定了在超声作用下的铝酸钠Luminol溶液的荧光光谱.并对不同超声功率、不同组成的铝酸钠溶液的声致荧光光谱进行了研究,发现在超声空化时,铝酸钠Luminol溶液可以产生声致荧光;在相同功率的超声波作用下,浓度较高,铝酸钠溶液中Na2O/Al2O3摩尔比较低的铝酸钠溶液的声致荧光强度较弱.同时讨论了声致荧光与超声强化铝酸钠溶液结晶过程的关系.     

高速沉积本征微晶硅的优化及其在太阳电池中的应用

采用高压高功率的甚高频等离子体增强化学气相沉积（VHF-PECVD）技术高速（沉积速率约为1.2 nm/s）沉积了一系列不同厚度的本征微晶硅薄膜,并通过Raman谱和XRD谱的测试,研究了高速沉积时本征微晶硅薄膜的微结构演变特性及其对电池性能的影响.针对其微结构特性及高速沉积本身存在的离子轰击作用强的特点,提出了在沉积微晶硅薄膜过程中采用功率梯度的方法,达到有效地控制薄膜微结构变化的目的,并在一定功率梯度范围内降低了电子温度,提高了薄膜质量,从而使电池效率明显提高.最后在沉积速率为1.2 nm/s时,制备 关键词： 高速沉积 微晶硅薄膜 微结构演变 功率梯度     

离子液体存在下铜的电沉积及其表面增强拉曼散射效应研究

离子液体作为一种绿色介质,在电化学领域中的研究正在兴起,引起了研究者的浓厚兴趣。文章运用循环伏安法研究了离子液体(1-丁基-3-甲基咪唑四氟硼酸盐,[bmim]BF4)存在时,酸性硫酸铜溶液中铜在铜电极上的电化学沉积行为。研究表明,[bmim]BF4的加入使铜的沉积峰电位负移,沉积电流增加。采用扫描电镜(SEM)和X射线衍射(XRD)对铜镀层的形貌及结构进行表征,结果显示离子液体的存在可使铜镀层的层状晶粒尺寸减小,镀层出现(220)高择优取向。以甲基橙(MO)为探针分子,研究了所得铜镀层的表面增强拉曼散射(SERS)效应,发现离子液体存在下得到的铜镀层是较好的SERS基底,具有良好的增强效果及稳定性。对MO分子的增强因子可达4.7×105,而且保存了60天后,其检测灵敏度没有显著的降低。     

溅射功率对直流磁控溅射Ti膜结构的影响

 采用直流磁控溅射方法制备了纯Ti膜，研究了不同功率下Ti膜的沉积速率、表面形貌及晶型结构，并对其应力进行了研究。研究表明：薄膜的沉积速率随溅射功率的增加而增加，当溅射功率为20 W时，原子力显微镜(AFM)图像显示Ti膜光洁、致密，均方根粗糙度最小可达0.9 nm。X射线衍射(XRD)分析表明薄膜的晶体结构为六方晶型，Ti膜应力先随溅射功率增大而增大，在60 W时达到最大值（为945.1 MPa），之后随溅射功率的增大有所减小。     

苯并夺氮唑对铜和铁缓蚀作用的拉曼光谱研究

本文利用现场拉曼光谱研究了中性含氯离子溶液中苯并三氮唑在铜和铁电极表面的吸附以及成膜行为，结果表明苯并三氮唑能强烈地化学吸附于铜电极和铁电极表面，形成类似［Ｍｎ（ＢＴＡ）ｐ］的配合物膜，一定程度上阻止了膜内外物质的交换，对金属起缓蚀作用。另一方面两种金属表面配合物膜均具有电位依赖性：在铜电极表面，当外加电位由－０．５Ｖ负移至－０．９时，发生了由［Ｃｕ（Ｉ）（ＢＴＡ）］ｎ向［Ｃｕ（Ｉ）Ｃｌ（ＢＴＡＨ     

氧化镁薄膜的腐蚀速率研究

研究了以氧化镁（MgO）为牺牲层材料制作热成像阵列器件过程中MgO膜层在磷酸溶液中的湿法腐蚀特性，包括横向腐蚀速率和纵向腐蚀速率，获得了MgO膜层的腐蚀速率随磷酸溶液浓度和温度变化的关系曲线，并得到了用于制作图形和制作悬空结构的较好工艺参量.     

Influence of ultrasonic in low thermal expansion Fe-Ni electrodeposition process for micro-electroforming

The electrochemical mechanism of Fe-Ni electrodeposition under ultrasonic was investigated by electrochemistry methods. Linear scanning voltammetry and cyclic voltammetry were used to show that the deposition process changed from the diffusion control under static conditions to an electrochemical control under ultrasonic conditions. Chronoamperometry curves showed that the Fe-Ni deposit occurred by a mechanism that instantaneous nucleation is followed by three-dimensional growth under charge transfer control. Chronopotentiogram indicated that because of the intensity of the ultrasound stripping effect, high ultrasonic power is unsuitable for electroforming Fe-Ni alloy, and a high current density is also not appropriate. Thus, the optimum parameters for Fe-Ni electrodeposition under ultrasonic conditions are ultrasonic power between 80 and 100 W (power density 0.28–0.35 W/cm²), and a current density lower than 10 mA/cm² with temperature 323 K and pH 3. Experiments were performed to verify that the Fe-Ni masks prepared by ultrasonic-assisted electroforming had a good surface quality. The increase in ultrasonic power can obtain a larger grain size, thus got a low thermal expansion coefficient and a high hardness. Therefore, ultrasonic-assisted electrodeposition technology provides an effective and practically feasible manufacturing method for OLED Fe-Ni mask preparation.     

Effects of ultrasound on both electrolytic and electroless nickel depositions

The effects of ultrasound on both electrolytic and electroless nickel depositions were investigated by polarization and a.c. impedance methods. The ultrasound accelerated the charge transfer process at the metal-electrolyte interface in the electrodeposition and the mass transport process in the electroless deposition. In the electrodeposition with Watts bath, the crystal orientations of deposited film largely changed in the presence of ultrasound. The imposition of ultrasound gave rise to decreasing cathodic overpotential and increasing exchange current density, and these effects depended upon the ultrasonic frequency. The values of exchange current density estimated from a.c. impedance were dependent upon the measured electrode potentials. In the electroless deposition with citrate bath, the deposition rates increased in the presence of ultrasound. There were two kinds of Ni(2+)-citrate complex which were reduced at -0.7 V and -1.1 V. The electroless deposition process was controlled by the Ni(2+)-citrate complex that was reduced at -0.7 V. This reduction rate was diffusion controlled and largely increased in the presence of ultrasound. The effects of ultrasonic frequency on both electrodeposition and electroless deposition increased in order of no irradiation < 100 kHz < 28 kHz < or = 45 kHz.     

超声辅助电镀的仿真与实验*

为了提高镀层的表面质量,提出了一种超声辅助电镀的方法。超声的空化与搅拌作用可以影响电镀的电沉积过程。设计了合理的换能器结构,并搭建了超声辅助电镀装置。通过对模型进行压电声学场与电镀场耦合仿真分析,结果表明：在硫酸铜电解液,镀铜时间60s,电压300V条件下,进行超声辅助电镀,镀层厚度分布均匀,镀层中部电流密度分布均匀,边缘最大电流密度是未加超声的2倍左右 。基于仿真结果,进行相同的实验测试,结果表明：超声辅助电镀可以提高镀层的均匀性,减少铜颗粒表面的杂质,提高表面的光洁度。阴极样品距离换能器头部位置在60mm左右,镀层质量良好。     

Intensified removal of copper from waste water using activated watermelon based biosorbent in the presence of ultrasound

Copper is one of the most toxic heavy metals having significant effects on the living organisms and hence effective removal of copper from waste water is crucial. The current work investigates the application of activated watermelon shell based biosorbent for the removal of copper from aqueous solution. The effect of activation using calcium hydroxide and citric acid as well as the effect of operating parameters like contact time, adsorbent dosage, temperature, pH, initial concentration and ultrasonic power on the extent of removal has been investigated. Experiments performed in the presence of ultrasound to investigate the degree of intensification as compared to the conventional agitation based treatment revealed that the adsorption rate significantly increases in the presence of ultrasound and also the time required for reaching the equilibrium reduces from 60 min in conventional approach to only 20 min in the presence of ultrasound. The extent of adsorption of Cu(II) on adsorbents was found to increase with an increase in the operating pH till an optimum value of 5. The extent of adsorption also increased with a decrease in the initial concentration and particle size as well as with an increase in ultrasonic power till an optimum. Kinetics and isotherm study revealed that all the experimental data was found to best fit the pseudo second order kinetics and Langmuir adsorption isotherm model respectively. Maximum adsorption capacity was found to be 31.25 mg/g for watermelon treated with calcium hydroxide and 27.027 mg/g for watermelon treated with citric acid. Overall present study established that activated watermelon is an environmentally friendly, low cost and highly efficient biosorbent that can be successfully applied for the removal of copper from aqueous solution with intensification benefits based on the ultrasound assisted approach.     

Fragmentation of chitosan by ultrasonic irradiation

Kinetics of chitosan fragmentation by ultrasonic irradiation at frequency of 20 kHz, and the effects of experimental variables (power of ultrasound, chitosan concentration and solution temperature) on fragmentation were investigated. The kinetics studies were followed by measuring solution viscosity of the original and its fragments, and determining average number of chain scission of the fragments. The effects of ultrasonic power, chitosan concentration and solution temperature on fragmentation process were followed by viscometry and size exclusion chromatography. The chemical structure of the original chitosan and its fragments were examined by (1)H NMR spectroscopy and elemental analysis. The experimental results showed that the rate of fragmentation increased with an increase in power of ultrasound. Chain scission increased with an increase in power of ultrasound; and solution temperature, but a decrease in chitosan concentration. The chemical structure and polydispersity of the original and the fragments were nearly identical. A model based on experimental data to describe the relationship between chain scission and experimental variables (power of ultrasound; irradiation time; reduced concentration, c[eta]; and solution temperature) was proposed. It was concluded that ultrasonic irradiation is a suitable method to perform partial depolymerization and to obtain moderate macromolecules from large ones.     

The effect of ultrasonic waves on the oxidation current of chlorpromazine in the 38 and 96 kHz-ultrasonic vibrating electrode voltammetry

In the case of 38 and 96 kHz ultrasonic vibrating electrode (USVE) voltammetry of chlorpromazine, the oxidation current increased considerably with ultrasonic power (amplitude). Movement of the first oxidation product, crimson coloured cation radical, and the streaming of liquid in the neighbourhood of the USVE, were visually observed in order to understand the mechanism of the promotive effects of ultrasound on the oxidation reaction. The reaction profile of the oxidation of chlorpromazine in 38 kHz seems to be somewhat different from that in 96 kHz. However, the mechanical agitation of solution in the area nearest the electrode surface, which is essentially the same fundamental mechanism, takes place in both the cases of 38 and 96 kHz. Both micro- and macro-streamings due to the vibration of a small bubble on the electrode surface with a frequency lower than that of the ultrasonic wave were formed in 38 kHz. These streamings seemed to contribute to the agitation and the exchange of the solution near the electrode surface. However, at the same ultrasonic amplitude, the oxidation current at 96 kHz was much greater than that at 38 kHz. Such a promoting effect of ultrasound on the electrode reaction was considered to be due to the increase of the moving speed or to the acceleration of the particle in the solution.     

Crystallization of potash alum: effect of power ultrasound.

The influence of power ultrasound on the crystallization of potash alum was investigated. Experiments have been carried out in a batch stirred vessel. It was found that ultrasonic waves decrease the supersaturation limits and modify the morphology of the crystals produced. The average crystal size decreases with an increase of ultrasonic power. To investigate also the action of ultrasound on already existing crystals, crystals produced in silent conditions were suspended in saturated potash alum solution at various ultrasonic powers. The results show that ultrasound has also an abrasive effect on potash alum crystals for high power inputs.     

Quantification of ultrasonic intensity based on the decomposition reaction of porphyrin

A simple method is proposed for quantification of the effective ultrasonic intensity in the reaction vessel based on the decomposition reaction of 5,10,15,20-tetrakis(4-sulfotophenyl) porphyrin (H₂TPPS⁴⁻). The change of concentration of porphyrin in solution irradiated by the ultrasound wave depends on the irradiation time and the output power of ultrasound generator. The decomposition ratio of porphyrin is defined as the ratio of the concentration of porphyrin after ultrasonic irradiation to that before ultrasonic irradiation. A linear relationship between the decomposition ratio of porphyrin and the concentration Fe³⁺ in the Fricke solution under sonication was obtained. The decomposition ratio was related to the absorption dose in radiation chemistry.     

Sonoelectrochemical and sonochemical effects of cavitation: correlation with interfacial cavitation induced by 20 kHz ultrasound

Sonoelectrochemical measurements at macro-electrodes under extreme conditions with a very short distance between ultrasonic horn tip and electrode and different ultrasound intensity levels are shown to result in violent cavitation detected in form of current peaks superimposed on the average limiting current. Analysis of the current data obtained for the oxidation of ferrocene in dimethylformamide (0.1 M NBu4PF6) at a 4 mm diameter Pt disc electrode and for the reduction of Ru(NH3)6(3+) in aqueous 0.1 M KCl at a 6 mm diameter Pt disc electrode consistently indicate a change of the physicochemical nature of sonoelectrochemical processes under extreme conditions. The sonoelectrochemical measurement of the rate constant for the carbon bromide bond cleavage of a 3-bromobenzophenone radical anion electrogenerated at a glassy carbon electrode in dimethylformamide solution in the presence of power ultrasound is shown to yield evidence for a breakdown of the conventional mass transport model of a planar diffusion layer under extreme conditions. The change can be correlated to the number of current data points deviating more than 10% from the mean of the current due to violent cavitation processes superimposed onto the average limiting current. Further, a study of the sonochemical destruction of aqueous dilute cyanide solution (in 0.1 M NaOH) demonstrates a correlation between the electrochemically detected cavitation violence and the sonochemical activity. Factors that govern the violence of interfacial cavitation appear to be directly proportional to the factors that make cavitation in the bulk solution chemically efficient.     

Ultrasonic effects on electroorganic processes Part 6. Formation of cupric carboxylates at a reactive copper anode in carboxylic acid solutions

Current efficiency for the formation of highly soluble cupric acetate at a reactive (consumable) copper anode in an acetic acid solution was increased almost independently of current density under ultrasonic irradiation. On the other hand, the efficiency for sparingly soluble cupric oxalate depended complicatedly on current density. At a low current density region less than 4 mA cm(-2), ultrasonic irradiation caused an increase in the current efficiency, while at higher current densities no ultrasonic effect was observed because of the formation of a rigid oxalate film on the anode surface. This paper is the first report of ultrasonic effects on an electrochemical reaction at a reactive (consumable) anode which is stoichiometrically involved in the reaction leading to the formation of products derived from anode metal.