CN105239137A - Electroplating technology - Google Patents
Electroplating technology Download PDFInfo
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- CN105239137A CN105239137A CN201510718912.7A CN201510718912A CN105239137A CN 105239137 A CN105239137 A CN 105239137A CN 201510718912 A CN201510718912 A CN 201510718912A CN 105239137 A CN105239137 A CN 105239137A
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Abstract
The invention discloses an electroplating technology. Proper current density, PH values and other technology parameters are selected, and Al2O3 nano-particles are added in a metal coating so that the performance of the coating can be improved. The electroplating technology includes the steps of degreasing, washing, acid pickling, electrolysis cleaning, passivating, neutralizing, electroplating technology parameter selecting, primary electroplating, secondary electroplating, washing and drying. Degreasing is conducted through ultrasonic cleaning, surfactant active agent emulsion is used as a solution, the temperature of the solution is 80 DEG C, and time is 5 min. A mixed solution prepared from 50 g/L of nitric acid and 40 g/L of HF is adopted for acid pickling, the temperature is 65 DEG C, and time is 10 min. According to the electroplating technology parameters, a Watt plating solution serves as the mother solution; the grain size of Al2O3 is 15 nm, the current density is 6-12 A/dm<2>, PH is 2.5-3.0, the temperature of the plating solution is 40-60 DEG C, primary electroplating time is 1.5-2 h, and the secondary electroplating time is 0.5-1 h. According to the electroplating technology, the coating is uniform, the mechanical properties such as wear resistance, corrosion resistance and oxidation resistance of parts can be effectively improved; and in addition, the electroplating technology parameters are easy to control, and the coating quality is stable.
Description
Technical field
The present invention relates to a kind of electroplating technology.
Background technology
So-called composite plating, adds non-water-soluble solia particle exactly in electroplate liquid, and makes itself and the coating processes of base metal codeposition on base material, and the coating obtained is composite deposite.In order to improve component of machine work-ing life, Chinese scholars conducts extensive research material surface modifying technology, and these technology are summed up and mainly contain two classes: hot-work method (as thermospray, laser, vapour deposition etc.) and wet method (galvanic deposit, electroless plating, Brush Plating etc.).Wherein composite plating technology because its technique is simple, the performance of coating can be improved significantly, save a large amount of valuable starting material and attract attention a mouthful J.
The composite plating history of existing 1 year abroad, domesticly starts late, and nearly two more than ten years are just developed rapidly.At present, composite plating technology is still the focus that countries in the world are competitively studied, especially Japanese, Russian more deep in the research in this field.The coating developed at present has functionally formed multiple series: in multiple platform electroplating technology, from binary to polynary, from common solia particle to nano particle, is plated to graded composite plating, and introduces rare earth compound from general compound in coating.
Composite plating preparation characteristic repeatly
With each matrix material of multiple platform electroplating technology system than infiltration method, hot extrusion method, the hot-work methods such as powder metallurgic method have significant superiority, and its feature is as follows:
Make temperature low; Generally must process under 500 ~ 1000 DEG C or higher temperature with each matrix material of thermal processing method system, unavoidable between matrix metal with solia particle the phenomenon such as phase mutual diffusion and chemical reaction occur, and organism can not be realized be mingled with; Adopt composite plating method, because great majority carry out in aqueous phase, temperature rarely exceeds 90 DEG C, generally carries out at about 50 ~ 60 DEG C, even organism also can stable existence.Matrix metal and each type impurity do not interact substantially, still can keep its characteristic separately.
Material in use often surface be damaged at first, abrasion and corrosion is two kinds of topmost collapse modes.According to estimates, the financial loss that frictional wear causes to the U.S. every year, up to 4,200 hundred million dollars, is equivalent to 6% of its gross national product.People have developed many technique means improving material surface performance to improve the work-ing life of material for this reason, the research of current material surface modifying technology oneself become study hotspot in Materials science.Metal surface properties modification technology roughly can be divided into two classes: a class is hot-work method, as electron beam deposition, coating produced by laser cladding, vapour deposition, ion deposition etc.; Another kind of is wet method, as galvanic deposit (plating), electroless plating, brush plating, anodic oxidation, phosphatization etc.In these methods, just produce with regard to wearing face material, electrodip process
Due to have less investment, simple to operate, be easy to control, the low and less cost of power of production cost and be subject to people's favor.Current electro-deposition techniques there has been tremendous development, from single metal deposition, develops into now as meeting the alloy of specified property requirement, the composite electrodeposition technique of metal/multiple particle.
Composite plating (composite electrodeposition or dispersion plating) is in metal (or alloy) electroplate liquid, add one or several insoluble non-metal solid particles, or in solution, add certain chemical substance produce precipitation to obtain solid particulate, make itself and metal (or alloy) codeposition and obtain a kind of technique of composite deposite.Since American A.Simos in 1949 obtains first composite plating patent, composite plating process handy root canal preparation constantly improves, and metal/ceramic particle (micron order) coating matrix material has appearred in early 1970s.Start research work nano particle being introduced metal plating the beginning of the eighties, but until the mid-90 just study the surface composite plating material obtaining metal/nanometer ceramic particle.
Nanometer material science and technology are the new branch of science occurring for 20 end of the centurys and will show up prominently in 21 century, and its development will produce profound influence to many subjects.Nano-powder material is one of study hotspot of nanosecond science and technology, is also the nano material be most widely used at present.Being introduced by nano-powder material in Composite Plating is significant development to Application of micron, is also the development trend in Composite Plating future.Current people have made respectively multiple nano-composite plate, as high rigidity, wear resistant composite plating, self-lubricating composite coating, has the composite deposite of electrical contact function, the composite deposite etc. of anti-corrosion, decoration functions, wherein high rigidity, wear resistant composite plating are research coating materials that is more and comparatively system.The research and development of nanometer antiwear composite deposite will relate to the multi-subject knowledges such as materialogy, composite electrodeposition, nanomaterial science and Nanotribology.
Nano material refers to any material be made up of nano structured unit, and as metal, pottery, polymkeric substance, semi-conductor, glass and matrix material etc., nano material is mainly made into nano-powder material, crystalline material and thin-film material three kinds.Be in the material under nanoscale, interaction between the ripple of its electronics and atom will be subject to the impact of scale size, such as fusing point, magnetic performance, electric property, optical property, mechanical property and chemically reactive there will be the character far different with traditional material, and the special performance shown cannot be explained by traditional theoretical system.Nano material is made up of nanoparticle, and nanoparticle is the structural unit that preparation nano composite material is commonly used, and is also energy and traditional material phase compound, carries out the most frequently used nanometer Addition ofelements of nano modification to traditional material.
Nanoparticle refers to that particle size is the ultrafine particulate of nanometer scale, and its yardstick is greater than cluster, is less than common micro mist.Nano-particles size, generally between 100nm, is also referred to as ultramicron.From the common viewpoint about both macro and micro, such system is atypical microscopic system also atypical macrosystem both, is a kind of typical Mesoscopic structure.When the size of small-particle enters nanometer scale, itself there is quantum size effect, small-size effect, surface effects and macro quanta tunnel effect, this four large effect causes small-particle and the nano material that is made up of them shows much distinctive character, has broad application prospects in catalysis, optical filtering, photoabsorption, medicine, magneticmedium and novel material etc.
When size of particles drops to a certain value, electronic level near Fermi level is existed discontinuously the highlyest be occupied molecular orbital(MO) and to the molecular orbital energy level be not occupied from the quasi-continuous dispersion phenomenon of energy level and the Nano semiconductor particulate of becoming, and the energy gap phenomenon that broadens is called quantum size effect.When level spacing give greatly heat energy, magnetic energy, magnetostatic energy, electrostatic energy, photon energy, superconducting state cohesion energy time, significantly different by causing the magnetic of nanoparticle, light, sound, heat, electricity, supraconductivity and macroscopic property to exist.Such as, susceptibility, the specific heat capacity of particle are relevant with the odd, even number of electronics contained by it, and the frequency displacement, change in dielectric constant etc. of corresponding generation spectral line, even odd, even several electronics also can affect its catalytic property.Small-size effect (volume effect) refer to the wavelength of nanoparticle size and light wave, the de broglie wavelength of conduction electron, the characteristic dimension such as the coherence length of superconducting state or transmission depth quite or less time, periodic final condition will be destroyed, and all present small-size effect in sound, optical, electrical, the characteristic such as magnetic, thermodynamics.This specific response is that applications to nanostructures has opened up wide frontier, and such as, along with the reduction of nano material particle diameter, its fusing point constantly reduces, and sintering temperature also significantly declines, thus provides novel process for powder metallurgy industry; Utilize the character that plasma resonance frequency displacement changes with grain-size, can control to absorb by changing grain-size the displacement of ripple, thus produce the microwave absorbing material with certain frequency range, for electromagnetic shielding, stealth aircraft etc.When the particle diameter of material is far longer than atomic diameter, surface atom can be ignored; But when particle diameter moves closer in atomic diameter, number and the effect thereof of surface atom just can not be ignored, and at this moment the surface-area of crystal grain, surface energy and Surface binding energy etc. all have a very large change, people are referred to as surface effects all specific responses caused thus.Due to increasing of surface atom number, the surface energy that Atomic coordinate is not enough and high, makes these surface atoms have high activity, extremely unstable, is easy to be combined with other atoms.Such as, the nanoparticle of metal can burn in atmosphere, and inorganic nanoparticle exposes in atmosphere can adsorbed gas, and react with gas.
Microcosmic particle has the effect running through potential barrier ability and is called tunnel effect.It is found that some maroscopic quantities in recent years, as the magnetic flux etc. in the specific magnetising moment of particulate, quantum coherent device also has tunnel effect, they can pass through the potential barrier of meta system and change, therefore are referred to as the quantum tunneling effect of macroscopic view.This effect, together with quantum size effect, will be the basis of future electronic device, and they determine the microelectronic device limit microminiaturized further.
Above 4 kinds of effects are fundamental characteristics of nanoparticle and nano-solid, it makes nanoparticle and solid present many peculiar physical propertiess, chemical property, occur " abnormal phenomena ", if metal is conductor, but nano-metal particles at low temperature because quantum size effect can present electrical insulating property.But increase along with particle diameter reduces specific surface area, nanoparticle respectively and in use procedure will face serious agglomeration traits in system, so want the Application Areas widening nanoparticle, must resolve reunion and the scattering problem of nanoparticle.
The activity of nanoparticle surface makes them be easy to reunite together thus forms the larger-size coacervate with some loosely-boned interface.In order to address this problem, no matter be often adopt dispersion to collect in the solution with physical method or the nanoparticle chemically prepared.The particulate suspended in the solution is generally subject to the effect of model moral gas force and is easy to reunite, and whether the electrostatic double layer with certain potentials gradient formed owing to being adsorbed on small-particle surface has the effect overcoming model moral gas force and stop particle agglomeration, particulate to reunite primarily of these two factors decisions.If reunited once occur, ultrasonic wave is usually adopted to be smashed by the coacervate in dispersion agent (water or organic reagent).Its principle to be vibrated the Coulomb's force or model moral gas force destroyed in coacervate between small particle due to ultrasonic frequency, thus make Granular composite in dispersion agent.Usually adopt for more short grained dispersion and add the way that defloculating agent forms electrostatic double layer and Jia Biao (boundary) surface-active agent parcel particulate, the former is comparatively applicable to the dispersion that nano-oxide particles and the latter are comparatively applicable to magnetic nanoparticle.
Tensio-active agent is added in nano combined plating solution, by the absorption of tensio-active agent at nanoparticle, reduce the surface energy of nanoparticle, effectively can improve the dispersion situation of nanoparticle in plating solution and coating, reduce the reunion of nanoparticle, this solves the method that nanoparticle agglomeration traits generally adopts in current Development of Nano-composite Plating Technoloyg.The dispersiveness impact on nanoparticle in plating solution of the kind of tensio-active agent is very large, and the dispersiveness of adding nanoparticle in the plating solution of non-polar surfactant and coating is best, and when adding cationic active agent, the dispersiveness of nanoparticle is the poorest.The effect of pH value Surfactant also has a significant impact, and should select nonpolar and aniorfic surfactant in an acidic solution, and should select cationic surfactant in basic solution.
Summary of the invention
The object of the invention is to propose a kind of electroplating technology.
For reaching this object, the present invention by the following technical solutions:
A kind of electroplating technology, selects the processing parameters such as suitable current density, pH value to add Al in metal plating
2o
3nano particle, to improve the performance of coating, comprising: oil removing, and---------electrolytic cleaning---------select electroplating technological parameter and---once electroplate---second time electroplating---washing---drying in passivation by neutralization in pickling in washing.Oil removing adopts ultrasonic cleaning to carry out oil removing, and solution uses surfactant emulsifies liquid, and solution temperature is 80 DEG C, time 5min.Pickling adopts the mixing of nitric acid 50g/L and HF40g/L molten, temperature 65 degree, time 10min.It is watt plating solution that electroplating technological parameter comprises mother liquor, Al
2o
3particle diameter is 15nm, current density 6---12A/dm
2, PH is 2.5---3.0, and bath temperature 40---60 degree, an electroplating time 1.5---2h, second time electroplating time 0.5---1h.
Embodiment
Embodiment 1
A kind of electroplating technology, selects the processing parameters such as suitable current density, pH value to add Al in metal plating
2o
3nano particle, to improve the performance of coating, comprising: oil removing, and---------electrolytic cleaning---------select electroplating technological parameter and---once electroplate---second time electroplating---washing---drying in passivation by neutralization in pickling in washing.Oil removing adopts ultrasonic cleaning to carry out oil removing, and solution uses surfactant emulsifies liquid, and solution temperature is 80 DEG C, time 5min.Pickling adopts the mixing of nitric acid 50g/L and HF40g/L molten, temperature 65 degree, time 10min.It is watt plating solution that electroplating technological parameter comprises mother liquor, Al
2o
3particle diameter is 15nm, current density 12A/dm
2, PH is 3.0, bath temperature 60 degree, an electroplating time 1.5h, second time electroplating time 0.5h.
Embodiment 2
A kind of electroplating technology, selects the processing parameters such as suitable current density, pH value to add Al in metal plating
2o
3nano particle, to improve the performance of coating, comprising: oil removing, and---------electrolytic cleaning---------select electroplating technological parameter and---once electroplate---second time electroplating---washing---drying in passivation by neutralization in pickling in washing.Oil removing adopts ultrasonic cleaning to carry out oil removing, and solution uses surfactant emulsifies liquid, and solution temperature is 70 DEG C, time 5min.Pickling adopts nitric acid 50g/L solution, temperature 65 degree, time 10min.It is copper electrolyte that electroplating technological parameter comprises mother liquor, Al
2o
3particle diameter is 20nm, current density 9A/dm
2, PH is 3.0, bath temperature 55 degree, an electroplating time 2h, second time electroplating time 0.7h.
Claims (4)
1. an electroplating technology, is characterized in that selecting the suitable processing parameter such as current density, pH value to add Al in metal plating
2o
3nano particle, to improve the performance of coating, comprising: oil removing, and---------electrolytic cleaning---------select electroplating technological parameter and---once electroplate---second time electroplating---washing---drying in passivation by neutralization in pickling in washing.
2. method according to claim 1, is characterized in that, described oil removing adopts ultrasonic cleaning to carry out oil removing, and solution uses surfactant emulsifies liquid, and solution temperature is 80 DEG C, time 5min.
3. method according to claim 1, is characterized in that, described pickling adopts the mixing of nitric acid 50g/L and HF40g/L molten, temperature 65 degree, time 10min.
4. method according to claim 1, is characterized in that, it is watt plating solution that described electroplating technological parameter comprises mother liquor, Al
2o
3particle diameter is 15nm, current density 6---12A/dm
2, PH is 2.5---3.0, and bath temperature 40---60 degree, an electroplating time 1.5---2h, second time electroplating time 0.5---1h.
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| CN201510718912.7A CN105239137A (en) | 2015-10-29 | 2015-10-29 | Electroplating technology |
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| CN201510718912.7A CN105239137A (en) | 2015-10-29 | 2015-10-29 | Electroplating technology |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1131558A (en) * | 1966-06-02 | 1968-10-23 | Toyoda Chuo Kenkyusho Kk | Method of electroplating nickel on an aluminium article |
| CN1553952A (en) * | 2001-08-13 | 2004-12-08 | ��ѧ�о��� | Materials and methods to promote repair of nerve tissue |
| CN1834307A (en) * | 2006-03-15 | 2006-09-20 | 哈尔滨工业大学 | Zn-Ni-Al2O3 nano composite deposit and its prepn. process |
| CN103243373A (en) * | 2012-02-13 | 2013-08-14 | 南车戚墅堰机车车辆工艺研究所有限公司 | Brush plating solution for Zn-Ni-Al2O3 composite coating and preparation method thereof |
-
2015
- 2015-10-29 CN CN201510718912.7A patent/CN105239137A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1131558A (en) * | 1966-06-02 | 1968-10-23 | Toyoda Chuo Kenkyusho Kk | Method of electroplating nickel on an aluminium article |
| CN1553952A (en) * | 2001-08-13 | 2004-12-08 | ��ѧ�о��� | Materials and methods to promote repair of nerve tissue |
| CN1834307A (en) * | 2006-03-15 | 2006-09-20 | 哈尔滨工业大学 | Zn-Ni-Al2O3 nano composite deposit and its prepn. process |
| CN103243373A (en) * | 2012-02-13 | 2013-08-14 | 南车戚墅堰机车车辆工艺研究所有限公司 | Brush plating solution for Zn-Ni-Al2O3 composite coating and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 张允诚 等: "《电镀手册》", 31 January 2007, 国防工业出版社 * |
| 李雪松 等: "脉冲电沉积Ni-Al2O3纳米复合镀层晶体结构的变化", 《金属热处理》 * |
| 田海燕 等: "两步沉积法制备Ni/Al2O3复合镀层及其耐磨性能研究", 《兵器材料科学与工程》 * |
| 谭澄宇 等: "Ni-Al2O3纳米复合电镀工艺的初步研究", 《材料保护》 * |
| 陈天玉 编著: "《复合镀镍和特种镀镍》", 31 January 2009, 化学工业出版社 * |
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Application publication date: 20160113 |