CN102127793A - Composite electroplating method of chrome-nano silicon dioxide of steel - Google Patents
Composite electroplating method of chrome-nano silicon dioxide of steel Download PDFInfo
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- CN102127793A CN102127793A CN 201110075256 CN201110075256A CN102127793A CN 102127793 A CN102127793 A CN 102127793A CN 201110075256 CN201110075256 CN 201110075256 CN 201110075256 A CN201110075256 A CN 201110075256A CN 102127793 A CN102127793 A CN 102127793A
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Abstract
The invention relates to a composite electroplating method of chrome-nano silicon dioxide of steel. The method mainly comprises the following step of: preparing nano silicon dioxide into nano powder and adding the nano powder to chromium-plating liquid. The chromium-plating liquid provided by the invention is stable and has strong dispersion capability, the cathode current efficiency is improved; and the plated chromium-plating layer has enhanced microhardness. Through Tafei curve test and Mott-Schottky analysis, the corrosion current density and the surface carrier density of the chromium-plating layer are far lower than those of a chromium-plating layer without the nano silicon dioxide, and a coated layer subjected to composite plating has better corrosion resistance.
Description
Technical field
The present invention relates to the chromium-silicon-dioxide composite electric plating method of a kind of metal or steel, belong to metallic surface electroplating technology technical field.
Background technology
Electroplate on the workpiece such as being widely used in anticorrosion, corrosion protection, wear-resisting, surface decoration, and developed into a plurality of kinds such as common plating, alloy plating, composite plating, plastic electroplating, precious metal electroplating, brush plating.Chromium plating is one of most widely used plating in the electroplating technology, chromium layer excellent property, have intensive passivation ability, good chemical stability, high rigidity and reflection potential and low frictional coefficient, be widely used in decorative and protective and the scuff-resistant coating, and the chromium ratio is easier to come out from aqueous solution deposition, technology is fairly simple, is easy to control.
Electrodeposited chromium remains in many problems in the big industrial production of reality, mainly is: (1) chromic acid has higher toxicity, and is very big to people's healthy harm, and waste gas and spent acid must pass through and handle, thereby expensive more; (2) because current efficiency is very low, and bath voltage is high, so power consumption is bigger; (3) owing to use high current density,, power unit increases so investing; (4) owing to adopt insoluble anode, the chromium metal of consumption will often replenish chromic acid, could keep the relatively stable of each composition in the electroplate liquid; (5) because a large amount of liberations of hydrogen of negative electrode cause chromium coating and matrix metal to produce hydrogen embrittlement.
Though some Electroplate Factory is in the big problem of above existence, a certain overcomes, and for example the light problem of coating has solved, but erosion resistance requires not reach, some use trivalent chromium plating replacement sexavalence chromium plating has reduced the pollution to environment, but bonding strength or thickness of coating thoroughly do not solve.People are seeking a kind of chromium substitute or are studying new chrome-plated process at present.The lifting conventional industries technology content that develops into of nanosecond science and technology provides new opportunity.
Nanoparticle is owing to have special effectses such as surface effects, small-size effect, quantum size effect, macro quanta tunnel effect.Can be used on performances such as the light that improves material, magnetic, electricity, mechanics and be improved or give its new function, can improve its quality product in Application Areas greatly, have good theoretical investigation value and application prospect.In addition, along with technical progress, the preparation cost of nano-powder and rete also descends significantly, for the nanotechnology large-scale application has been established sturdy basic substance.
The Nanosurface technology develops rapidly, and wherein studying and use many is the nano compound electroplating technology.Composite deposite is the method by metal electrodeposition or codeposition, and a kind of or several insoluble solid particulates, fiber evenly are mingled with formed special coating in the metal plating.As discrete particles, the composite deposite that forms with metal is called the superhard material composite deposite with superhard material.Nano-composite plate has become one of focus of nano surface work research field.USSR (Union of Soviet Socialist Republics) scientist adds Nano diamond in chromium plating liquid, make the hardness and the wear resistance of chromium coating significantly improve, this technology has obtained patent, and in member country of the Commonwealth of Independent States's widespread use, China has also carried out relevant work, as the patent No. 200610117075.3 nano ceramic materials and metal alloy in metallic surface compound chemical plating method, the electroplating preparation method of patent No. 200310107939.X nanometer multilayer zinc film.
Summary of the invention
The purpose of this invention is to provide a kind of method at metal or steel surface electrodeposited chromium-silicon-dioxide composite deposite.
The present invention is a kind of chromium-silicon-dioxide composite plating method of steel, and it is characterized in that having has following process and step:
A. prepare composite plating solution, promptly contain the composite plating solution of cadmium and nano silicon;
At first prepare the nano silicon aqueous dispersion: highly purified SiO 2 powder through grinding-dissolving-grinding-oven dry, and is repeated preceding step three times; Then air-dry powder is put into the ball mill ball milling and become nano-powder, handle through ultrasonic activation more at last, obtain the nano silicon aqueous dispersion; In the water-soluble process, the powder dissolution deionized water; Bake out temperature is 80 ~ 95 ℃; Drum's speed of rotation 100 ~ 350r/min; The ball milling time is 8-15 hour; Raw material is 1:(10 ~ 18 with the ratio of zirconium pearl); Ultrasonic activation is at 2A level ultrasound intensity;
Preparation chromium-silicon-dioxide composite plating solution, its composition and consumption thereof are:
Chromic anhydride 240 ~ 260g/L
Sulfuric acid 2.4 ~ 2.6g/L
Nano silicon 1 ~ 5g/L
B. will desire metal or steel that plating handles and be positioned in the plating tank that fills above-mentioned composite plating solution, and with metal or steel electroplating parts as negative electrode, be anode with the lead antimony alloy, negative pole and the positive pole respectively at direct supply is connected by lead simultaneously; It is as follows to electroplate the processing parameter that adopts:
45 ~ 55 ℃ of temperature
Current density 45 ~ 60A/dm
2
Stirred solution circulation 80 ~ 120r/min
The negative electrode annode area is than 1.0 ~ 2.5
Finally obtain chromium-nano silicon composite deposite at steel surface.
The advantage of the inventive method
The present invention compares with the high density chrome-plated process of prior art, has the following advantages:
1) the nano silica powder preparation is simple, stable performance, ability strong acid;
2) nano silicon adding of the present invention is simple to operate, electroplates later coating qualification rate more than 95%; And the cathode efficiency height, save energy.
3) solution dispersibility is better, can electroplate complicated shape, and coating hardness height, wear resistance, corrosion resisting property are superior.
Can not contain fluorochemical in the plating bath of the inventive method and other have the additive of corrodibility composition, otherwise anode can produce a large amount of lead chromate particulates, influences the mechanical property of coating.Solution adopts the magnetic drive pump stirring that circulates.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment
1, in the present embodiment, at first prepare nano silica powder, its process is as described below:
Grinding-dissolving-grinding-oven drying powdered-repetition preceding step 3 times-powder is put into the ball mill ball milling becomes nano-powder-ultrasonic activation to handle.
Powder dissolution deionized water wherein; Oven temperature is 80 ℃; Drum's speed of rotation 300r/min, ball milling time are 12 hours, big zirconium pearl: little zirconium pearl: ball milling raw material=120g:240g:20g, ultrasonic activation handle under 2A level ultrasound intensity, the nano silicon aqueous dispersion is done ultrasonic activation handle.
2, the setting of configuration chromium plating liquid and chrome-plated process parameter
Chromic anhydride 250g
Sulfuric acid 2.5g
Deionized water configuration plating bath, the deionized water volume is 1L; Plating bath was divided into 3 fens, and first part of chromium plating liquid do not add nano silicon, second part of chromium plating liquid adding nano silicon 2g, the 3rd part of chromium plating liquid adding nano silicon 4g.
50 ℃ of temperature
Current density 50A/dm
2
Stirred solution circulation 100r/min
The negative electrode annode area is than 2
Plating substrate is the H13 steel, electroplates the back sample and carries out microhardness, cathode efficiency, corrosion electric current density and carrier density test, and the performance test value that draws sees the following form:
Performance index
As can be seen from the above table, along with the increase of the add-on of silicon-dioxide, the microhardness of chromium coating, cathode efficiency increases gradually; Corrosion electric current density and carrier density descend, and corrosion resisting property increases.
The method of galvanization coating being carried out electro-chemical test is as described below:
Chromium coating is carried out electro-chemical test, and electrochemistry experiment adopts three-electrode system, and reference electrode is a saturated calomel electrode, and supporting electrode is a platinized platinum.Test is adopted analytical reagent with medicine, uses the deionized water obtain solution.After the oven dry, electrode is at the 5%Na of room temperature
2SO
4Soak in the solution (electrode face does not contact with supporting electrode or reference electrode); Carry out the measurement of current potential ~ time, impedance ~ current potential and polarization curve then.The computer-controlled CHI660 type of PC electrochemical workstation (Shanghai occasion China instrument company) is adopted in the measurement of electrode system.Survey frequency is 1000Hz, then impedance ~ potential data is carried out the Mott-Schotty analysis and calculates the surperficial carrier density of electrode, polarization curve analysis is calculated corrosion electric current density.
Claims (1)
1. the chromium of steel-silicon-dioxide composite plating method is characterized in that having following process and step:
A. prepare composite plating solution, promptly contain the composite plating solution of cadmium and nano silicon;
At first prepare the nano silicon aqueous dispersion: highly purified SiO 2 powder through grinding-dissolving-grinding-oven dry, and is repeated preceding step three times; Then air-dry powder is put into the ball mill ball milling and become nano-powder, handle through ultrasonic activation more at last, obtain the nano silicon aqueous dispersion; In the water-soluble process, the powder dissolution deionized water; Bake out temperature is 80 ~ 95 ℃; Drum's speed of rotation 100 ~ 350r/min; The ball milling time is 8-15 hour; Raw material is 1:(10 ~ 18 with the ratio of zirconium pearl); Ultrasonic activation is at 2A level ultrasound intensity;
Preparation chromium-silicon-dioxide composite plating solution, its composition and consumption thereof are:
Chromic anhydride 240 ~ 260g/L
Sulfuric acid 2.4 ~ 2.6g/L
Nano silicon 1 ~ 5g/L
B. will desire metal or steel that plating handles and be positioned in the plating tank that fills above-mentioned composite plating solution, and with metal or steel electroplating parts as negative electrode, be anode with the lead antimony alloy, negative pole and the positive pole respectively at direct supply is connected by lead simultaneously; It is as follows to electroplate the processing parameter that adopts:
45 ~ 55 ℃ of temperature
Current density 45 ~ 60A/dm
2
Stirred solution circulation 80 ~ 120r/min
The negative electrode annode area is than 1.0 ~ 2.5
Finally obtain chromium-nano silicon composite deposite at steel surface.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110075256 CN102127793A (en) | 2011-03-28 | 2011-03-28 | Composite electroplating method of chrome-nano silicon dioxide of steel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110075256 CN102127793A (en) | 2011-03-28 | 2011-03-28 | Composite electroplating method of chrome-nano silicon dioxide of steel |
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| CN102127793A true CN102127793A (en) | 2011-07-20 |
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| CN 201110075256 Pending CN102127793A (en) | 2011-03-28 | 2011-03-28 | Composite electroplating method of chrome-nano silicon dioxide of steel |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383150A (en) * | 2011-11-09 | 2012-03-21 | 广东达志环保科技股份有限公司 | High-corrosion-resistance environmentally-friendly trivalent chromium electroplating solution and electroplating method thereof |
| CN112626572A (en) * | 2020-11-30 | 2021-04-09 | 新疆德丰亿升石油防腐工程有限公司 | Method for corrosion prevention treatment of inner wall of drill rod |
| CN115012008A (en) * | 2022-03-31 | 2022-09-06 | 九牧厨卫股份有限公司 | Environment-friendly composite coating layer capable of improving adhesive force and preparation method thereof |
| CN115058746A (en) * | 2022-07-07 | 2022-09-16 | 中国人民解放军陆军装甲兵学院 | Metal coating, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676674A (en) * | 2005-01-17 | 2005-10-05 | 上海大学 | Method for preparing nickel-phosphor alloy base composite cladding containing nano particle |
| KR20080052115A (en) * | 2006-12-06 | 2008-06-11 | 양경준 | The chromium plating methods using functional fine grains |
-
2011
- 2011-03-28 CN CN 201110075256 patent/CN102127793A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676674A (en) * | 2005-01-17 | 2005-10-05 | 上海大学 | Method for preparing nickel-phosphor alloy base composite cladding containing nano particle |
| KR20080052115A (en) * | 2006-12-06 | 2008-06-11 | 양경준 | The chromium plating methods using functional fine grains |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383150A (en) * | 2011-11-09 | 2012-03-21 | 广东达志环保科技股份有限公司 | High-corrosion-resistance environmentally-friendly trivalent chromium electroplating solution and electroplating method thereof |
| CN102383150B (en) * | 2011-11-09 | 2014-08-20 | 广东达志环保科技股份有限公司 | High-corrosion-resistance environmentally-friendly trivalent chromium electroplating solution and electroplating method thereof |
| CN112626572A (en) * | 2020-11-30 | 2021-04-09 | 新疆德丰亿升石油防腐工程有限公司 | Method for corrosion prevention treatment of inner wall of drill rod |
| CN115012008A (en) * | 2022-03-31 | 2022-09-06 | 九牧厨卫股份有限公司 | Environment-friendly composite coating layer capable of improving adhesive force and preparation method thereof |
| CN115012008B (en) * | 2022-03-31 | 2023-09-19 | 九牧厨卫股份有限公司 | Environment-friendly composite coating layer capable of improving adhesive force and preparation method thereof |
| CN115058746A (en) * | 2022-07-07 | 2022-09-16 | 中国人民解放军陆军装甲兵学院 | Metal coating, preparation method and application thereof |
| CN115058746B (en) * | 2022-07-07 | 2024-04-12 | 中国人民解放军陆军装甲兵学院 | Metal coating, preparation method and application thereof |
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Application publication date: 20110720 |