不同电解条件下制备铜粉的形貌及结晶学比较分析（英文）
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摘要
研究不同析氢条件下恒电位电解法制备铜粉的过程。采用扫描电镜(SEM)、X射线衍射(XRD)、粒度分布(PSD)和比表面积测定(SSA)对铜粉进行表征。根据电解过程析氢量的大小,形成树枝状和菜花状两种类型的颗粒。当析氢量大到足以对近电极层中的流体动力学条件产生强烈影响时,形成菜花状颗粒,否则形成树枝状颗粒。虽然颗粒的宏观结构差异很大,但他们的微观结构却相似,也就是说,这两种颗粒在微观层面上都是由近似球形的Cu颗粒小团聚体组成;球状形貌的存在是造成两种颗粒中Cu晶粒随机取向的原因。菜花样颗粒的比表面积是树枝状颗粒的3倍以上,其粒径则比树枝状颗粒的小很多。由此可见,强析氢条件对于铜粉制备是有益的。
Production of copper powders by the potentiostatic electrolysis under different hydrogen evolution conditions was investigated. Copper powders were characterized by the scanning electron microscope(SEM),X-ray diffraction(XRD),particle size distribution(PSD), and by the determination of the specific surface area(SSA) of the formed powders. Depending on quantity of hydrogen generated during electrolysis, the two types of particles were formed: dendrites and cauliflower-like particles. The dendrites were formed without, while cauliflower-like particles with the quantity of evolved hydrogen enough to achieve strong effect on hydrodynamic conditions in the near-electrode layer. Although macro structure of the particles was very different, they showed similar micro structure. Namely, both types of the particles consisted of smalal agglomerates of approximately spherical Cu grains at the micro level. The existence of the spherical morphology was just responsible for random orientation of Cu crystallites in both types of particles. The SSA of cauliflower-like particles was more than two times larger than that of the dendrites, while their size was considerably smaller than that of the dendritic particles. In this way, the useful benefit of Cu powder formation in the conditions of vigorous hydrogen evolution is shown.
Production of copper powders by the potentiostatic electrolysis under different hydrogen evolution conditions was investigated. Copper powders were characterized by the scanning electron microscope(SEM),X-ray diffraction(XRD),particle size distribution(PSD), and by the determination of the specific surface area(SSA) of the formed powders. Depending on quantity of hydrogen generated during electrolysis, the two types of particles were formed: dendrites and cauliflower-like particles. The dendrites were formed without, while cauliflower-like particles with the quantity of evolved hydrogen enough to achieve strong effect on hydrodynamic conditions in the near-electrode layer. Although macro structure of the particles was very different, they showed similar micro structure. Namely, both types of the particles consisted of smalal agglomerates of approximately spherical Cu grains at the micro level. The existence of the spherical morphology was just responsible for random orientation of Cu crystallites in both types of particles. The SSA of cauliflower-like particles was more than two times larger than that of the dendrites, while their size was considerably smaller than that of the dendritic particles. In this way, the useful benefit of Cu powder formation in the conditions of vigorous hydrogen evolution is shown.
引文
[1]POPOV K I,DJOKI?S S,NIKOLI?N D,JOVI?V D.Morphology of electrochemically and chemically deposited metals[M].New York:Springer,2016.
[2]NIKOLI?N D,STEVANOVI?S I,BRANKOVI?G.Nucleation and the early stages of growth of lead onto copper electrodes from the dilute electrolytes[J].Transactions of Nonferrous Metals Society of China,2016,26:3274-3282.
[3]ZHOU Hai-hui,LIAO Zuo-wei,FANG Chen-xu,LI Huan-xin,FENG Bin,XU Song,CAO Guo-fei,KUANG Ya-fei.Pulse electroplating of Ni-W-P coating and its anti-corrosion performance[J].Transactions of Nonferrous Metals Society of China,2018,28:88-95.
[4]MAHDAVI S,ALLAHKARAM S R.Effect of bath composition and pulse electrodeposition condition on characteristics and microhardness of cobalt coatings[J].Transactions of Nonferrous Metals Society of China,2018,28:2017-2027.
[5]KARTAL L,TIMUR S.Electrolytic production of Cu-Ni alloys in Ca Cl2-Cu2S-NiS molten salt[J].Transactions of Nonferrous Metals Society of China,2018,28:2143-2150.
[6]SEKAR R.Synergistic effect of additives on electrodeposition of copper from cyanide-free electrolytes and its structural and morphological characteristics[J].Transactions of Nonferrous Metals Society of China,2017,27:1665-1676.
[7]YUAN Liang,DING Zhi-ying,LIU Shi-jun,SHU Wei-fa,HEYa-ning.Effects of additives on zinc electrodeposition from alkaline zincate solution[J].Transactions of Nonferrous Metals Society of China,2017,27:1656-1664.
[8]SEAKR R.Microstructure and crystallographic characteristics of nanocrystalline copper prepared from acetate solutions by electrodeposition technique[J].Transactions of Nonferrous Metals Society of China,2017,27:1423-1430.
[9]WINAND R.Electrodeposition of metals and alloys-New results and perspectives[J].Electrochimica Acta,1994,39:1091-1105.
[10]NIKOLI?N D,RAKO?EVI?Z,POPOV K I.Structural characteristics of bright copper surfaces[J].Journal of Electroanalytical Chemistry,2001,514:56-66.
[11]OSTANINA T N,RUDOI V M,PATRUSHEV A V,DARINTSEVAA B,FARLENKOV A S.Modelling the dynamic growth of copper and zinc dendritic deposits under the galvanostatic electrolysis conditions[J].Journal of Electroanalytical Chemistry,2015,750:9-18.
[12]NIKOLI?N D,PAVLOVI?Lj J,PAVLOVI?M G,POPOV K I.Morphologies of electrochemically formed copper powder particles and their dependence on the quantity of evolved hydrogen[J].Powder Technology,2008,185:195-201.
[13]ORHAN G,HAPCI G.Effect of electrolysis parameters on the morphologies of copper powder obtained in a rotating cylinder electrode cell[J].Powder Technology,2010,201:57-63.
[14]ORHAN G,GEZGIN G G.Effect of electrolysis parameters on the morphologies of copper powder obtained at high current densities[J].Journal of the Serbian Chemical Society,2012,77:651-665.
[15]NIKOLI?N D,BRANKOVI?G,PAVLOVI?M G.Correlate between morphology of powder particles obtained by the different regimes of electrolysis and the quantity of evolved hydrogen[J].Powder Technology,2012,221:271-277.
[16]NEKOUEI R K,RASHCHI F,JODA N N.Effect of organic additives on synthesis of copper nano powders by pulsing electrolysis[J].Powder Technology,2013,237:554-561.
[17]NEKOUEI R K,RASHCHI F,RAVANBAKHSH A.Copper nanopowder synthesis by electrolysis method in nitrate and sulfate solutions[J].Powder Technology,2013,250:91-96.
[18]NEKOUEI R K,RASHCHI F,AMADEH A A.Using design of experiments in synthesis of ultra-fine copper particles by electrolysis[J].Powder Technology,2013,237:165-171.
[19]WANG Ming-yong,WANG Zhi,GUO Zhan-cheng.Preparation of electrolytic copper powders with high current efficiency enhanced by super gravity field and its mechanism[J].Transactions of Nonferrous Metals Society of China,2010,20:1154-1160.
[20]GERMAN R M.Powder metallurgy science[M].New Jersey:Metal Powder Industries Federation,1994.
[21]AVRAMOVI?Lj,PAVLOVI?M M,MAKSIMOVI?V M,VUKOVI?M,STEVANOVI?J S,BUGARIN M,NIKOLI?N D.Comparative morphological and crystallographic analysis of electrochemically and chemically-produced silver powder particles[J].Metals,2017,7:160.
[22]AVRAMOVI?Lj,IVANOVI?E R,MAKSIMOVI?V M,PAVLOVI?M M,VUKOVI?M,STEVANOVI?J S,NIKOLI?ND.Correlation between crystal structure and morphology of potentiostatically electrodeposited silver dendritic nanostructures[J].Transactions of Nonferrous Metals Society of China,2018,28:1903-1912.
[23]NIKOLI?N D,POPOV K I,PAVLOVI?Lj J,PAVLOVI?M G.The effect of hydrogen codeposition on the morphology of copper electrodeposits.I:The concept of effective overpotential[J].Journal of Electroanalytical Chemistry,2006,588:88-98.
[24]BERUBE L P H,ESPERANCE G L.A quantitative method of determining the degree of texture of zinc electrodeposits[J].Journal of the Electrochemical Society,1989,136:2314-2315.
[25]SURYANARAYANA C,NORTON M G.X-ray diffraction,a practical approach[M].New York:Springer,1998.
[26]KAROLUS M,LAGIEWKA E.Crystallite size and lattice strain in nanocrystalline Ni-Mo alloys studied by rietveld refinement[J].Journal of Alloys and Compounds,2004,367:235-238.
[27]SIVASUBRAMANIAN R,SANGARANARAYANAN M V.Electrodeposition of silver nanostructures:From polygons to dendrites[J].CrystEngComm,2013,15:2052-2056.
[28]XIA Y,XIONG Y,LIM B,SKRABALAK S E.Shape-controlled synthesis of metal nanocrystals:Simple chemistry meets complex physics?[J].Angewandte Chemie International Edition,2009,48:60-103.
[29]HAMILTON D R,SEIDENSTICKER R G.Propagation mechanism of germanium dendrites[J].Journal of Applied Physics,1960,31:1165-1168.
[30]WAGNER R S.On the growth of germanium dendrites[J].Acta Metallurgica,1960,8:57-60.
[31]NIKOLI?N D,?IVKOVI?P M,JOKI?B,PAVLOVI?M G,STEVANOVI?J S.Comparative analysis of the polarisation and morphological characteristics of electrochemically produced powder forms of the intermediate metals[J].Macedonian Journal of Chemistry and Chemical Engineering,2014,33:169-180.
[32]NIKOLI?N D,PAVLOVI?Lj J,PAVLOVI?M G,POPOV K I.Formation of dish-like holes and a channel structure in electrodeposition of copper under hydrogen co-deposition[J].Electrochimica Acta,2007,52:8096-8104.
[33]NIKOLI?N D,MAKSIMOVI?V M,BRANKOVI?G,?IVKOVI?P M,PAVLOVI?M G.Correlation between crystal orientation and morphology of electrolytically produced powder particles:Analysis of the limiting cases[J].Materials Protection,2018,59:256-264.
[2]NIKOLI?N D,STEVANOVI?S I,BRANKOVI?G.Nucleation and the early stages of growth of lead onto copper electrodes from the dilute electrolytes[J].Transactions of Nonferrous Metals Society of China,2016,26:3274-3282.
[3]ZHOU Hai-hui,LIAO Zuo-wei,FANG Chen-xu,LI Huan-xin,FENG Bin,XU Song,CAO Guo-fei,KUANG Ya-fei.Pulse electroplating of Ni-W-P coating and its anti-corrosion performance[J].Transactions of Nonferrous Metals Society of China,2018,28:88-95.
[4]MAHDAVI S,ALLAHKARAM S R.Effect of bath composition and pulse electrodeposition condition on characteristics and microhardness of cobalt coatings[J].Transactions of Nonferrous Metals Society of China,2018,28:2017-2027.
[5]KARTAL L,TIMUR S.Electrolytic production of Cu-Ni alloys in Ca Cl2-Cu2S-NiS molten salt[J].Transactions of Nonferrous Metals Society of China,2018,28:2143-2150.
[6]SEKAR R.Synergistic effect of additives on electrodeposition of copper from cyanide-free electrolytes and its structural and morphological characteristics[J].Transactions of Nonferrous Metals Society of China,2017,27:1665-1676.
[7]YUAN Liang,DING Zhi-ying,LIU Shi-jun,SHU Wei-fa,HEYa-ning.Effects of additives on zinc electrodeposition from alkaline zincate solution[J].Transactions of Nonferrous Metals Society of China,2017,27:1656-1664.
[8]SEAKR R.Microstructure and crystallographic characteristics of nanocrystalline copper prepared from acetate solutions by electrodeposition technique[J].Transactions of Nonferrous Metals Society of China,2017,27:1423-1430.
[9]WINAND R.Electrodeposition of metals and alloys-New results and perspectives[J].Electrochimica Acta,1994,39:1091-1105.
[10]NIKOLI?N D,RAKO?EVI?Z,POPOV K I.Structural characteristics of bright copper surfaces[J].Journal of Electroanalytical Chemistry,2001,514:56-66.
[11]OSTANINA T N,RUDOI V M,PATRUSHEV A V,DARINTSEVAA B,FARLENKOV A S.Modelling the dynamic growth of copper and zinc dendritic deposits under the galvanostatic electrolysis conditions[J].Journal of Electroanalytical Chemistry,2015,750:9-18.
[12]NIKOLI?N D,PAVLOVI?Lj J,PAVLOVI?M G,POPOV K I.Morphologies of electrochemically formed copper powder particles and their dependence on the quantity of evolved hydrogen[J].Powder Technology,2008,185:195-201.
[13]ORHAN G,HAPCI G.Effect of electrolysis parameters on the morphologies of copper powder obtained in a rotating cylinder electrode cell[J].Powder Technology,2010,201:57-63.
[14]ORHAN G,GEZGIN G G.Effect of electrolysis parameters on the morphologies of copper powder obtained at high current densities[J].Journal of the Serbian Chemical Society,2012,77:651-665.
[15]NIKOLI?N D,BRANKOVI?G,PAVLOVI?M G.Correlate between morphology of powder particles obtained by the different regimes of electrolysis and the quantity of evolved hydrogen[J].Powder Technology,2012,221:271-277.
[16]NEKOUEI R K,RASHCHI F,JODA N N.Effect of organic additives on synthesis of copper nano powders by pulsing electrolysis[J].Powder Technology,2013,237:554-561.
[17]NEKOUEI R K,RASHCHI F,RAVANBAKHSH A.Copper nanopowder synthesis by electrolysis method in nitrate and sulfate solutions[J].Powder Technology,2013,250:91-96.
[18]NEKOUEI R K,RASHCHI F,AMADEH A A.Using design of experiments in synthesis of ultra-fine copper particles by electrolysis[J].Powder Technology,2013,237:165-171.
[19]WANG Ming-yong,WANG Zhi,GUO Zhan-cheng.Preparation of electrolytic copper powders with high current efficiency enhanced by super gravity field and its mechanism[J].Transactions of Nonferrous Metals Society of China,2010,20:1154-1160.
[20]GERMAN R M.Powder metallurgy science[M].New Jersey:Metal Powder Industries Federation,1994.
[21]AVRAMOVI?Lj,PAVLOVI?M M,MAKSIMOVI?V M,VUKOVI?M,STEVANOVI?J S,BUGARIN M,NIKOLI?N D.Comparative morphological and crystallographic analysis of electrochemically and chemically-produced silver powder particles[J].Metals,2017,7:160.
[22]AVRAMOVI?Lj,IVANOVI?E R,MAKSIMOVI?V M,PAVLOVI?M M,VUKOVI?M,STEVANOVI?J S,NIKOLI?ND.Correlation between crystal structure and morphology of potentiostatically electrodeposited silver dendritic nanostructures[J].Transactions of Nonferrous Metals Society of China,2018,28:1903-1912.
[23]NIKOLI?N D,POPOV K I,PAVLOVI?Lj J,PAVLOVI?M G.The effect of hydrogen codeposition on the morphology of copper electrodeposits.I:The concept of effective overpotential[J].Journal of Electroanalytical Chemistry,2006,588:88-98.
[24]BERUBE L P H,ESPERANCE G L.A quantitative method of determining the degree of texture of zinc electrodeposits[J].Journal of the Electrochemical Society,1989,136:2314-2315.
[25]SURYANARAYANA C,NORTON M G.X-ray diffraction,a practical approach[M].New York:Springer,1998.
[26]KAROLUS M,LAGIEWKA E.Crystallite size and lattice strain in nanocrystalline Ni-Mo alloys studied by rietveld refinement[J].Journal of Alloys and Compounds,2004,367:235-238.
[27]SIVASUBRAMANIAN R,SANGARANARAYANAN M V.Electrodeposition of silver nanostructures:From polygons to dendrites[J].CrystEngComm,2013,15:2052-2056.
[28]XIA Y,XIONG Y,LIM B,SKRABALAK S E.Shape-controlled synthesis of metal nanocrystals:Simple chemistry meets complex physics?[J].Angewandte Chemie International Edition,2009,48:60-103.
[29]HAMILTON D R,SEIDENSTICKER R G.Propagation mechanism of germanium dendrites[J].Journal of Applied Physics,1960,31:1165-1168.
[30]WAGNER R S.On the growth of germanium dendrites[J].Acta Metallurgica,1960,8:57-60.
[31]NIKOLI?N D,?IVKOVI?P M,JOKI?B,PAVLOVI?M G,STEVANOVI?J S.Comparative analysis of the polarisation and morphological characteristics of electrochemically produced powder forms of the intermediate metals[J].Macedonian Journal of Chemistry and Chemical Engineering,2014,33:169-180.
[32]NIKOLI?N D,PAVLOVI?Lj J,PAVLOVI?M G,POPOV K I.Formation of dish-like holes and a channel structure in electrodeposition of copper under hydrogen co-deposition[J].Electrochimica Acta,2007,52:8096-8104.
[33]NIKOLI?N D,MAKSIMOVI?V M,BRANKOVI?G,?IVKOVI?P M,PAVLOVI?M G.Correlation between crystal orientation and morphology of electrolytically produced powder particles:Analysis of the limiting cases[J].Materials Protection,2018,59:256-264.
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