CN1174121C - Process for obtaining high-wear-resistant friction-reducing composite function nano-coating - Google Patents
Process for obtaining high-wear-resistant friction-reducing composite function nano-coating Download PDFInfo
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- CN1174121C CN1174121C CNB021334285A CN02133428A CN1174121C CN 1174121 C CN1174121 C CN 1174121C CN B021334285 A CNB021334285 A CN B021334285A CN 02133428 A CN02133428 A CN 02133428A CN 1174121 C CN1174121 C CN 1174121C
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Abstract
The present invention relates to a technology for obtaining nanometer high wear resistance and antifriction composite deposit. The present invention is characterized in that pulp of 100 to 150 g/l is added to Watt nickeling liquor for conventional electroplating or nickeling liquor for ordinary acidic chemical plating, and the pulp is prepared from nanometer particles and uses alpha-Al2O3 or SiC as a main component. Nanometer ions can evenly diffuse in the plating liquor; the content of the nanometer particles diffused in the nanometer composite deposit is from 3 to 10%(wt); the original crystal particle diameter of the nanometer particles is from 1 to 150 nm; the plating liquor is stirred by compressed air at the stirring speed that all particles in the pulp are suspended; and a nanometer composite nickel electroplated layer or a nanometer composite chemical plating layer comprising the metal nickel and the nanometer particles is obtained. The technology reduces the particles in the original composite deposit from a micron level to a nanometer level to obtain a nanometer composite deposit which integrates hardness, wear resistance, friction reduction and toughness; the contradiction of the hardness to the toughness of the composite deposit is harmonized, and the technology provides a reliable technical measure for the surface treatment of easy wear parts and no-oil friction assemblies.
Description
Technical field
This discovery belongs to technical field of surface, relates to a kind ofly utilizing α-Al at metal or nonmetallic surface
2O
3, the mode of nano material such as SiC by composite plating or electroless plating, obtain nickel base nanometer composite galvanized coating or chemical plating.This coating has high abrasion, antifriction performance, can satisfy the surface treatment demand of using goods under friction condition.
Technical background
People since the sixties, with artificial representatives such as the loyal husbands of Japanese woods, have done one's utmost to promote the research and development of compound plating from eighties of last century in order to seek high abrasion coating.After this, compound being plated to is the most active part of research in the modern times plating development history, develops comparatively rapidly, and Application Areas constantly enlarges.At the eighties of last century late nineteen seventies, early eighties has also carried out deep research to compound plating, obtains very gratifying achievement with units such as the University Of Tianjin headed by the Guo Hetong professor, Xiamen University in China.And, play crucial prograding to improving the research and development of cladding wearability.
Conventional composite is electroplated and to be thought, the too little microparticle material disperse of particle diameter is in coating, and is little to the wear resisting property effect that improves coating.Therefore, the galvanized research and development of conventional composite only rests on the micron order particle diameter, and gained coating can not be coordinated the contradiction between hardness and the toughness.Up to now, Shang Weijian collection hardness, wear resistance, antifriction quality and toughness are that the complex function coating of one appears on the market, and also do not see relevant patent and research paper report.
Summary of the invention
The present invention is intended to the particle in the former compound plating is dropped to nano level by micron order, obtaining a kind of hardness, wear-resisting, antifriction, toughness of collecting is the composite function nano-coating of one, coordinated the contradiction between coating hardness and the toughness, for vulnerable part and do not have the oil drag assembly surface reliable technique means that provide are provided.The technical problem to be solved in the present invention is: provide a kind of and can obtain composite function nano-coating, comprise the technology of nano combined nickel electrolytic coating and electroless nanometer composite coating.
Solving the technology of the present invention problem is to realize by following technical scheme:
A kind of technology that obtains high abrasion, friction-reducing composite function nano-coating, it is characterized in that be add in the nickel liquid of watt nickel plating bath in routine is electroplated or common acid chemical plating 100-150g/l with α-Al
2O
3Or SiC is the slurry that main nanoparticle is made, nanoparticle is the energy even dispersion in plating bath, the nano particle content of disperse is 3-10% (wt) in the nano-composite plate, the former crystal grain of nanoparticle directly is 1-150nm, plating bath is stirred with pressurized air, stirring velocity obtains nano combined nickel electrolytic coating or electroless nanometer composite coating that metallic nickel and nanoparticle are formed with all particles suspension degree of being in the slurry.
Above-mentioned technology nano combined nickel electrolytic coating realize the composite function nano electrolytic coating of telotism with following array configuration: flash nickel/semi-bright nickel/nano combined nickel electrolytic coating, the composite function nano electrolytic coating combination of gained are that a kind of hardness, wear resistance, antifriction quality, toughness of collecting is the nano composite galvanized coating of one.
In the wherein nano combined nickel electrolytic coating disperse have 3-10% with α-Al
2O
3Or SiC is main nanoparticle, and the former crystal grain of nanoparticle directly is 1-150nm.
In the above-mentioned coating combination, the flash nickel dam is thick to be 1-2 μ m, and the semi-bright nickel bed thickness is 3-5 μ m, and nano combined nickel dam is thick to be 2-90 μ m (requirement on concrete wear-resisting workpiece is decided).The coating combined overall thickness is 6-100 μ m.
Flash nickel and semi-bright nickel in the combination of composite function nano electrolytic coating adopt conventional electroplating technology, and nano combined nickel electrolytic coating is to add brightening agent 1ml/l, wetting agent 0.5ml/l in conventional watt nickel plating solution, adds α-Al of 100-150g/l again
2O
3The composite Nano slurry, the former grain fineness number of dispersed particle is less than 150nm in the slurry, and it is that a kind of it can be scattered among the coating more equably in electroplating process at acid, equal α-crystalline state particle of stable existence in the alkaline solution, and dispersed granules content is 3-10% (wt).In order to increase the content of dispersed granules in coating, the present invention adds the nano pulp auxiliary agent of 17-20g/l in plating bath.
According to technique scheme, the present invention's employed technical recipe and processing condition in nano combined nickel galvanized coating electroplate liquid are as follows:
Single nickel salt 350-380g/l
Boric acid 40-45g/l
Sodium-chlor 12-15g/l
Nano pulp auxiliary agent 17-20g/l
α-Al
2O
3Composite Nano slurry 100-150g/l
Brightening agent 1ml/l
Wetting agent 0.5ml/l
pH 3.5-4
Dk 4A/dm
2
t℃ 55-65
Time is determined by the technology thickness requirement
In the technology, anode is generally the pure nickel anode, and under the situation of particular requirement, electronickelling is as anode on the available titanium pipe, and plating bath needs pressurized air to stir.Stirring velocity is with all particles suspension degree of being in the plating bath, and new dosing must be stirred the slaking tank liquor 6 hours.The workpiece that particular requirement is arranged, the present invention designs special hanger to adapt to its special requirement.
This coating combination has good abrasion resistance, high temperature oxidation resistance, antifriction performance, oil storage and self-lubricating property, and any surface finish, and hardness is HV450-600, the bonding force height of coating and matrix, and the uniformity coefficient of coating is 0.1-0.5 μ m/cm.
The nanochemistry coating that above-mentioned technology obtained also is that a kind of hardness, wear resistance, antifriction quality, toughness of collecting is the coating of one.Wherein disperse have 3-10% with α-Al
2O
3Or SiC is main nanoparticle, and the former crystal grain of nanoparticle directly is 1-150nm.This coating has good abrasion resistance, particularly can't electroplate or electroplate the comparatively workpiece (deep hole spare, slit spare etc.) of difficulty, and electroless plating then demonstrates its unique advantages.
Electroless nanometer composite coating is to adopt the α-Al that adds 100-150g/l in the common acid chemical nickel-plating liquid
2O
3The composite Nano slurry is realized.Concrete technical recipe and processing condition are as follows:
Single nickel salt 20-25g/1
Sodium hypophosphite 25-30g/l
Sodium-acetate 15-20g/l
Lactic acid 1-3g/l
α-Al
2O
3Composite Nano slurry 100-150g/l
Dodecyl sodium sulfonate is received 0.5-1g/l
pH 3.5-4.5
t℃ 86±1
Time (h) 0.5-1
Pressurized air stirs
Plating bath needs pressurized air to stir, and stirring velocity is with all particles suspension degree of being in the plating bath.Workpiece after the plating needs immersion oil behind baking 30min under 400-450 ℃.
Easily produce low electricity district when electroless nanometer composite coating is applicable to and electroplates, and require attrition resistant part, for example: gear or the workpiece of deep hole, slit pore etc. is arranged.
Superiority of the present invention is conspicuous: at first, will be in coating can even dispersion with α-Al
2O
3Be the slurry that main composite nano particle is made, make an addition in the watt nickel electrolyte that contains a small amount of brightening agent and wetting agent or in the conventional chemical nickel-plating liquid,, obtain the complex function coating of metallic nickel and nanoparticle by electroplating or electroless plating.This kind coating has special construction: nickel is multi-hole state, its aperture＜100nm with the coating of the morphological crystal formation of sodium rice crystalline substance.Nanoparticle evenly is embedded in these holes, forms reticulated structure; And can slide in short distance (15 dust to 20 dust) and move, make coating have very high self-lubricating property and antifriction performance, this has just improved the wear resistance of coating widely, and this is the feature that the compound plating of micron order can't possess; Again because α-Al
2O
3The hardness height, therefore improved the hardness of coating on the whole, the content of nanoparticle in coating only is 1-10%, the main body of coating still is a metallic nickel, so coating has the toughness of metallic nickel.What the present invention obtained is that collection hardness, wear resistance, antifriction quality and toughness are the coating of one, and this kind coating is that conventional coating is incomparable.
Another superiority of the present invention is that it is to transform in the plating bath by watt nickel or the chemical nickel of routine, therefore it very easily is converted into nanometer nickel plating by conventional electronickelling or chemical nickel plating, it only needs negative electrode moved and changes pneumatic blending into, and oil (gas) filling device is very easily promoted no longer in addition.
Embodiment
Embodiment 1: the technology that obtains nickel base nanometer complex function electrolytic coating on the motorcycle engine cylinder body.
1, main technique flow process: Solvent degreasing → electrochemical deoiling → ultrasonic cleaning → pickling → flash nickel → plating semi-bright nickel → nickel base nanometer composite plating → oven dry → immersion oil.
2, the electroplate liquid formulation of the compound nickel of electroplating nano and processing condition.
Single nickel salt 370g/l
Boric acid 45g/l
Sodium-chlor 15g/l
α-Al
2O
3Composite Nano slurry 120g/l
Nano pulp auxiliary agent 17g/l
Brightening agent 1ml/l
Wetting agent 0.5ml/l
D
k 4A/dm
2
t℃ 55-65℃
pH 3.5-4
Because cylinder body is very strict to thickness of coating and uniformity requirement, therefore, the present invention adopts the nickel plating of titanium pipe as picture shape sun plate, and has designed special hanger at cylinder body.Plating bath adopts pressurized air to stir, and electroplating time requires to determine according to cylinder hole dimension size and thickness of coating.
3, measured result.
Cylinder body by after the above-mentioned technology plating carries out endurance test in Chongqing Zongshen Motor Science ﹠ Technology Group Corp. Ltd.Test result is as follows:
| Project | The peak power reference point | Break-in 20h test | Strengthen the 60h test | Strengthen the 100h test | Strengthen the 200h test |
| Peak power kw/r/min (company standard 7.2) | 8.01kw/ 8493r/m in | 8.72 | 9.13 | 8.67 | 8.31 |
| Mean power in the working speed scope | 7.65 | 8.11 | 7.85 | 7.69 | |
| Peak torque NM/r/min (company standard 8.6) | 9.55 | 10.15 | 9.91 | 9.77 | |
| Average torque in the working speed scope | 9.40 | 9.96 | 9.67 | 9.50 | |
| Consumption minimization g/kw.h (company standard 367) | 279.9 | 278.1 | 287.6 | 270.3 | |
| Average fuel consumption in the working speed scope | 286.5 | 287.3 | 296.9 | 289.5 |
Below be Chongqing Zongshen Motor Science ﹠ Technology Group Corp. Ltd to carry out the evaluation (former " technical report " original text is made a copy of) that nickel base nanometer is electroplated the cylinder body that is plated with the present invention:
" from strengthening experiment as can be seen, nanometer is electroplated and is made cylinder body have following characteristics:
1) cylinder body handled of nanometer electroplating technology, skin friction coefficient is little, and engine power, moment of torsion are big, and oil consumption is low.
Test when test 60h, peak power arrives 9.13kw/9064r/min greatly, and peak torque reaches 10.15NM/8000r/min, consumption minimization 278.1g/kw.h.Good like this performance perameter is inaccessiable in common CG125 engine is strengthened.
2) cylinder surface of nanometer electroplating technology processing has self-lubricating property.
The cylinder surface that the nanometer electroplating technology is handled does not have the reticulate pattern of common cylinder body oil storage, the machine oil condition is poor, but the stand by 200h is strengthened experiment, and piston ring scuffing amount very little (a ring bucket face also exists two annular conical surfaces wearing and tearing 1/2nd) cylinder body cross hatch and piston processing lines also exist.
3) nanometer electroplating technology processing cylinder body is lower than gold pottery processing cylinder body cost.”
Embodiment 2: the technology that obtains nickel base nanometer complex function electrolytic coating on chain.
1, main technique flow process: electrochemical deoiling → pickling → plating semi-bright nickel → Ni-based composite plating → oven dry → immersion oil.
2, the electroplate liquid formulation of the compound nickel of electroplating nano and processing condition:
With embodiment 1.
3, test-results.
Through testing in Yangtse River in Chongqing chain company limited with the galvanized chain of the present invention, the said firm makes evaluation to chain that the present invention plates.Now evaluation is made a copy of as follows:
1) after employing whole piece chain nanometer was electroplated, surface-brightening was transparent, can no longer carry out antirust operation fully and handle, and the antirust quality guaranteed period can reach more than 3 years.
2) coating of electroplating chain part through nanometer is in the 0.006-0.012mm scope, and its Vickers' hardness can reach (HV more than 1600
02), exceed 1/3 of metallic cementation composite treatment process level.
3) test of the wear resisting property of this nanometer chain shows that wear resisting property increases substantially.
Embodiment 3: the technology that obtains nickel base nanometer complex function chemical plating on gear.
1, main technique flow process: Solvent degreasing → electrochemical deoiling → ultrasonic cleaning → pickling → electroless nanometer composite coating → dry → immersion oil.
2, the technical recipe of composite function nano electroless plating and processing condition:
Single nickel salt 25g/l
Sodium hypophosphite 30g/l
Sodium-acetate 20g/l
Lactic acid 3g/l
α-Al
2O
3Composite Nano slurry 120g/l
Sodium laurylsulfonate 1g/l
pH 3.7
t℃ 86
Time (h) 1
Pressurized air stirs
3, checking result.
After with the present invention gear being carried out electroless nanometer composite coating, gear company limited carries out quality verification in the autumn fields, Chongqing, and the said firm is to the electroplating quality checking report of gear, will report that now full text makes a copy of as follows:
Gear frock nano coating uses the checking report
My department cooperates since November 18 calendar year 2001 with Apollo company, and Apollo company carries out nano compound electroplating to the frock gear that we produce, and from the single-piece to the batch machining, its technical feature and quality product all are improved.
After the spline stamen axle (m1Z19) of shaving carried out the nanometer plating, durability improved 3 times, and result of use is good in the autumn fields.
Claims (6)
1, a kind of technology that obtains high abrasion, friction-reducing composite function nano-coating, it is characterized in that be add in the nickel liquid of watt nickel plating bath in routine is electroplated or common acid chemical plating 100-150g/l with α-Al
2O
3It is the slurry that main nanoparticle is made, nanoparticle is the energy even dispersion in plating bath, the nano particle content of disperse is 3-10% (wt) in the nano-composite plate, the former crystal grain of nanoparticle directly is 1-150nm, plating bath is stirred with pressurized air, stirring velocity obtains nano combined nickel electrolytic coating or electroless nanometer composite coating that metallic nickel and nanoparticle are formed with all particles suspension degree of being in the slurry.
2, technology according to claim 1, it is characterized in that the compound nickel electrolytic coating that obtains with the flash nickel dam of conventional electroplating technology acquisition, the composite function nano electrolytic coating that the semi-bright nickel layer constitutes telotism jointly, wherein the flash nickel dam is thick is 1-2 μ m, the semi-bright nickel bed thickness is 3-5 μ m, it is 2-90 μ m that nano combined nickel is electroplated bed thickness, and the coating combined overall thickness is 6-100 μ m.
3, technology according to claim 1, it is characterized in that in obtaining the conventional watt nickel plating solution of compound nickel electrolytic coating, being added with brightening agent, wetting agent and 17-20g/l nano pulp auxiliary agent, used galvanic anode is solvable or the insolubility electrode, adopt ultrasonic cleaning before the plating, adopt the bidirectional pulse power supply in the electroplating process.
4, according to claim 1,2 or 3 described technologies, it is as follows to it is characterized in that obtaining technical recipe and the processing condition used in the plating bath of nano combined nickel function electrolytic coating:
Single nickel salt 350-380g/l
Boric acid 40-45g/l
Sodium-chlor 12-15g/l
Nano pulp auxiliary agent 17-20g/l
α-Al
2O
3Composite Nano slurry 100-150g/l
Brightening agent 1ml/l
Wetting agent 0.5ml/l
pH 3.5-4
Dk 4A/dm
2
t℃ 55-65
Time is determined by the technology thickness requirement.
5, technology according to claim 1, the technical recipe and the processing condition that it is characterized in that obtaining nano combined nickel functionalized chemical coating are as follows:
Single nickel salt 20-25g/l
Sodium hypophosphite 25-30g/l
Sodium-acetate 15-20g/l
Lactic acid 1-3g/l
α-Al
2O
3Composite Nano slurry 100-150g/l
Dodecyl sodium sulfonate is received 0.5-1g/l
pH 3.5-4.5
t℃ 86±1
Time (h) 0.5-1
Pressurized air stirs.
6 technologies according to claim 5 is characterized in that the workpiece after obtaining nanochemistry coating needs immersion oil behind baking 30min under 400-450 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021334285A CN1174121C (en) | 2002-07-06 | 2002-07-06 | Process for obtaining high-wear-resistant friction-reducing composite function nano-coating |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021334285A CN1174121C (en) | 2002-07-06 | 2002-07-06 | Process for obtaining high-wear-resistant friction-reducing composite function nano-coating |
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|---|---|
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| CN1174121C true CN1174121C (en) | 2004-11-03 |
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|---|---|---|---|
| CNB021334285A Expired - Fee Related CN1174121C (en) | 2002-07-06 | 2002-07-06 | Process for obtaining high-wear-resistant friction-reducing composite function nano-coating |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390326C (en) * | 2004-01-06 | 2008-05-28 | 上海维安热电材料股份有限公司 | Preparation method of composite cladding material and equipment |
| CN1807702B (en) * | 2005-12-19 | 2010-07-21 | 吉林大学 | Process for preparing gradient nano compound coating on powder metallurgy part surface |
| CN103184457B (en) * | 2011-12-28 | 2015-06-10 | 北京有色金属研究总院 | Surface alloying strengthening method |
| CN103643266A (en) * | 2013-12-18 | 2014-03-19 | 吉林大学 | Nano metal ceramic electrodeposited composite coating at inner hole wall of oil drill pipe and preparation method thereof |
| CN104088002A (en) * | 2014-07-15 | 2014-10-08 | 江西科技师范大学 | Preparation device and method of composite coating |
| CN104213106B (en) * | 2014-09-26 | 2017-01-11 | 国家电网公司 | Ni/Zn/P-particle composite chemical plating layer and preparation method thereof |
| CN107313101B (en) * | 2017-06-08 | 2019-06-18 | 华南理工大学 | A kind of preparation method of environmentally friendly nickel envelope-chromium-free deactivation layer |
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2002
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