CN1303259C - Molybdenum disulfide and nickel phosphorus composite deposition liquid and its electrodeposition method - Google Patents
Molybdenum disulfide and nickel phosphorus composite deposition liquid and its electrodeposition method Download PDFInfo
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- CN1303259C CN1303259C CNB2004100418201A CN200410041820A CN1303259C CN 1303259 C CN1303259 C CN 1303259C CN B2004100418201 A CNB2004100418201 A CN B2004100418201A CN 200410041820 A CN200410041820 A CN 200410041820A CN 1303259 C CN1303259 C CN 1303259C
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Abstract
The present invention discloses molybdenum disulfide and nickel phosphorus compounding deposition liquid used for processing micro-mechanical friction surfaces. The deposition liquid comprises soluble molybdate tetrasulfide, soluble nickel salts, phosphoric soluble oxysalts and water, wherein the molar ratio of the soluble molybdate tetrasulfide to the soluble nickel salts is 0.01 to 0.5:1, the molar ratio of the phosphoric soluble oxysalts to the soluble nickel salts is 0.01 to 30:1, and the molar ratio of the soluble nickel salts to the water is 1 to 100:5000. The present invention also discloses an electrodeposition method for treating the surfaces of mechanical members with the compounding deposition liquid. The method comprises: a surface is cleaned and is put in an electrolytic tank filled with the compounding deposition liquid, a mechanical member is connected with a cathode of a power supply, the power supply is switched on for electrodeposition for 1 to 120 minutes with the current density of 0.1 to 100 mA per square centimeter of areas to be treated at room temperature, and finally, the mechanical member is taken out, washed, dried and is in heat preservation in a protective atmosphere.
Description
Technical field
The present invention relates to a kind of surface treatment liquid and treatment process thereof of mechanical component, relate in particular to a kind of molybdenumdisulphide and nickel phosphorus composite deposition liquid and electro-deposition method thereof that is used to handle the micromechanics friction surface.
Background technology
Molybdenumdisulphide has laminate structure, the layer with layer between for Van der Waals force combines, molecular energy is along the slippage easily of these planes, shearing force is little.Because have lattice imperfection in the real crystal, shearing force further reduces, have excellent antifriction performance, therefore be widely used at friction field.
Nickel-phosphorus coating can be used for strengthening friction surface owing to have very high hardness can improve the wear resistance of friction surface after the thermal treatment.
Molybdenumdisulphide adopts original molybdenumdisulphide particle directly to add method in the solution in general molybdenumdisulphide and the nickel phosphorus composite membrane, and its size is subjected to the restriction of primary particle size, and particle size commonly used at present is a micron order; And this process using electrochemical method generates molybdenumdisulphide particle MoS in the composite membrane of other prepared
2Particle size, and be more evenly distributed, thereby the properties of antifriction and wear resistance on the surface of mechanical component improved.
Other molybdenumdisulphide and nickel phosphorus composite membrane generally only are applicable to macroscopic friction workpiece surface, and this composite membrane not only is applied to macroscopic friction workpiece surface, also can be applicable to micromechanics friction member surface.
Microelectromechanical systems is the new branch of science of the multidisciplinary intersection that grows up on the microelectronics basis, it is a support with microelectronics and Machining Technology, and scope relates to various engineering technology and subjects such as microtronics, mechanics, mechanics, autonetics, Materials science.But because homogeneity friction produces intensive adhesive wear between the micromechanics friction pair, and movable micromechanics stability is to the extreme sensitivity of mild wear, and micromechanics is often in very short time internal cause wearing and tearing and lost efficacy.The surface microscopic friction problem has become the bottleneck on the micromechanics road for development.Molybdenumdisulphide and nickel phosphorus composite membrane combine the advantage of two kinds of compositions, have further improved its properties of antifriction and wear resistance.
Utilize novel electrodip process deposition molybdenumdisulphide and nickel phosphorus composite membrane, closely combine with the micromechanics manufacturing process.Making molybdenumdisulphide and nickel phosphorus composite membrane be easy to be deposited on the micromechanics friction surface, is the effective way that the friction problem of micromechanics obtains the breakthrough on the just sincere justice.This composite deposition molybdenumdisulphide and nickel phosphorus composite membrane process application are not seen open report both at home and abroad as yet in the micromechanics friction surface.
Summary of the invention
The invention provides a kind of molybdenumdisulphide and the nickel phosphorus composite deposition liquid and electro-deposition method that can improve the properties of antifriction and wear resistance of machinery part surface, the present invention especially can be adapted at the micromechanics friction surface and use.
The present invention adopts following technical scheme:
Molybdenumdisulphide of the present invention and nickel phosphorus composite deposition liquid, the solvable oxysalt and the water that comprise solubility tetrathiomolybdate, soluble nickel salt, phosphorus, the mol ratio of solubility tetrathiomolybdate and soluble nickel salt is 0.01～0.5: 1, the solvable oxysalt of phosphorus and the mol ratio of soluble nickel salt are 0.01～30: 1, and the mol ratio of soluble nickel salt and water is 1～100: 5000.
Composite deposition liquid of the present invention carries out the surface-treated electro-deposition method to mechanical component: earlier cleaning is carried out on the pending surface of mechanical component and handled; pending surface with mechanical component places the electrolyzer that contains above-mentioned composite deposition liquid again; and pending mechanical component are connected with power cathode; at room temperature; current density with 0.1 milliampere-100 milliamperes of every square centimeter of pending areas; connect power supply galvanic deposit 1-120 minute; electrochemical reaction takes place; make molybdenumdisulphide and nickel phosphorus composite membrane be deposited on the surface of pending mechanical component; at last; take out pending mechanical component; and to its cleaning; drying is incubated 0.5～4 hour under 100 ℃ of-900 ℃ of conditions in protective atmosphere, promptly obtain the homogeneous molybdenumdisulphide and the nickel phosphorus composite membrane of 10 nanometers-500 micron thickness.
Compared with prior art, the present invention has following advantage:
(1) because nickel ion and Hypophosporous Acid, 50 root are reduced into nickel phosphorus layer at negative electrode, and the tetrathio molybdate is reduced into molybdenumdisulphide and nickel phosphorus is deposited upon together at negative electrode, make composite deposition liquid of the present invention form molybdenumdisulphide and nickel phosphorus composite membrane at piece surface, and molybdenumdisulphide has laminate structure, layer with layer between combine for Van der Waals force, molecular energy is along the slippage easily of these planes, and shearing force is little.Owing to have lattice imperfection in the real crystal, shearing force further reduces, has excellent antifriction performance, nickel-phosphorus coating is owing to have very high hardness can improve the wear resistance of friction surface after the thermal treatment, the present invention is combined with each other molybdenumdisulphide and nickel phosphorus, form composite membrane, thereby improve the properties of antifriction and wear resistance of machinery part surface; Especially provided by the present inventionly can form nano level molybdenumdisulphide and nickel phosphorus composite membrane, the present invention can be combined with the MEMS manufacturing process, be fit to micromechanics and use at piece surface.
(2) electro-deposition method of the present invention not only is applied to the micromechanics surface, also can be applied to macroscopical mechanical friction surface, and the molybdenumdisulphide particle that the present invention adopts electrochemical method to generate is a nano level, has improved the properties of antifriction and wear resistance of composite membrane.
(3) galvanic deposit molybdenumdisulphide and nickel phosphorus composite membrane thickness can change at nanometer one micron order, and the molybdenumdisulphide particle is tiny, the film smooth surface.The dimensional requirement that helps the micromechanics surface reforming layer.
(4) method of employing molybdenumdisulphide and nickel phosphorus composite deposition, the advantage of two kinds of materials of performance can significantly improve the workpiece surface properties of antifriction and wear resistance.
(5) existence of additive makes solution-stabilizedly, changes sedimentation velocity and improves the quality of molybdenumdisulphide and nickel phosphorus composite membrane.
Embodiment
Embodiment 1
A kind of molybdenumdisulphide and nickel phosphorus composite deposition liquid that is used for the machinery part surface processing, the solvable oxysalt and the water that comprise solubility tetrathiomolybdate, soluble nickel salt, phosphorus, the solvable oxysalt of phosphorus can be a trisodium phosphate, simultaneously, trisodium phosphate has also played the effect of complexing agent, the mol ratio of above-mentioned solubility tetrathiomolybdate and soluble nickel salt is 0.01～0.5: 1, and present embodiment can be selected: 0.03: 1,0.1: 1,0.21: 1 and 0.3: 1; The mol ratio of trisodium phosphate and soluble nickel salt is 0.01～10: 1, and present embodiment can be selected: 0.2: 1,0.5: 1,4: 1 and 7: 1; Present embodiment also can comprise additive, this additive comprises a kind of organic acid or salt at least, this additive and soluble nickel salt mol ratio are 1～6: 1, its effect is the effect that keeps solution-stabilized, improve the effect of sedimentation velocity and settled layer performance, present embodiment can be selected: 1.3: 1,1.9: 1,2: 1,3.5: 1,4.4: 1 and 5.8: 1, above-mentioned additive can be in trisodium citrate, ammonium chloride, disodium ethylene diamine tetraacetate, the lactic acid etc. one or more combination and the proportioning of its component can be any proportioning; The mol ratio of soluble nickel salt and water is 1～100: 5000, and present embodiment can be selected: 20: 5000,37: 5000,55: 5000,67: 5000,79: 5000 and 90: 5000.For providing the phosphoric effect in the nickel phosphorus layer deposition process, the solvable oxysalt of part phosphorus prevents that again solution from producing turbidity sediment, keeps the stability of solution to the solvable oxysalt of above-mentioned phosphorus in solution.
Embodiment 2
A kind of molybdenumdisulphide and nickel phosphorus composite deposition liquid that is used for the machinery part surface processing, form by solubility tetrathiomolybdate, soluble nickel salt, trisodium phosphate and additive, the molar percentage of its effective constituent (not comprising water) is a solubility tetrathiomolybdate 1%～20%, and present embodiment can select 2%, 7%, 11%, 16% and 19%; Soluble nickel salt 25%～50%, present embodiment can be selected: 27%, 29%, 33%, 40% and 47%; Sodium hypophosphite 25%～60%, present embodiment can select 28%, 31%, 35%, 36% and 55%; Trisodium phosphate 25%～60%, present embodiment can be selected: 26%, 31%, 34%, 37% and 55%; Disodium ethylene diamine tetraacetate 1%～20%, present embodiment can be selected: 3%, 9%, 14%, 17% and 19%; Trisodium citrate 1～30%, present embodiment can be selected: 3%, 7%, 17%, 25%, 28%.The molar percentage that water accounts for electrodeposit liquid is 99%～30%, and present embodiment can be selected: 35%, 45%, 52%, 60%, 71% and 80%.
Embodiment 3
A kind ofly utilize above-mentioned composite deposition liquid that mechanical component are carried out the surface-treated electro-deposition method to be: earlier cleaning processing is carried out on the pending surface of mechanical component; this cleaning processing comprises carries out degreasing; oil removing; ash disposal and remove insulation layer etc.; pending surface with mechanical component places the electrolyzer that contains above-mentioned composite deposition liquid again; and pending mechanical component are connected with power cathode; at room temperature; current density with 0.1 milliampere-100 milliamperes of every square centimeter of pending areas; connect power supply galvanic deposit 1-120 minute; electrochemical reaction takes place; for example: the time of connecting the power supply galvanic deposit can be: 1; 120; 111; 74; 32; 56 or 15 minutes; make molybdenumdisulphide and the galvanic deposit of nickel phosphorus composite membrane in the surface of pending mechanical component; at last; take out pending mechanical component; and to its cleaning; dry; in protective atmosphere, be incubated 0.5～4 hour under 100 ℃ of-900 ℃ of conditions; for example: at room temperature; current density with every square centimeter of pending area 50mA; connect power supply galvanic deposit 30 minutes; electrochemical reaction takes place; at last; take out pending mechanical component; and to its cleaning; dry; in protective atmosphere, be incubated 1 hour under 400 ℃ of conditions, promptly obtain the homogeneous molybdenumdisulphide and the nickel phosphorus composite membrane of 5 micron thickness.
Embodiment 4
Handle micromechanics single-sided polishing monocrystalline silicon piece with molybdenumdisulphide of the present invention and nickel phosphorus composite deposition liquid formula.The diameter of this disk is 3 inches, crystal orientation＜110 〉, doping As, resistivity 0.002 ohmcm.The composition of molybdenumdisulphide and low temperature electrodeposition technology are as follows:
The composition of molybdenumdisulphide and nickel phosphorus electrodeposit liquid is, the mol ratio of solubility tetrathiomolybdate and soluble nickel salt is 0.05, the mol ratio of sodium hypophosphite and soluble nickel salt is 2, the mol ratio of trisodium phosphate and soluble nickel salt 1.5: 1, the mol ratio of soluble nickel salt and water are 1～100: 5000.
Composite electrodeposition technology
1. configure molybdenumdisulphide and nickel phosphorus composite electrodeposition liquid in proportion, be placed in the electrolyzer;
2. silicon chip surface is carried out pre-treatments such as degreasing, oil removing, ash disposal and deoxygenation;
With silicon chip as for the galvanic deposit liquid bath, be connected with power cathode, platinum electrode is connected with power anode and puts into electrolyzer; Electrolytic solution is in the normal temperature state.
4. set the electric current area according to silicon area, connect power supply galvanic deposit 10 minutes.
5. the taking-up substrate cleans, and drying is at N
2Be incubated 1 hour under 100 ℃ of-900 ℃ of conditions in the atmosphere.Promptly obtain the homogeneous molybdenumdisulphide and the composite lubricated film of nickel phosphorus of 300 nano thickness.
Embodiment 5
Handle Cr12 die steel with molybdenumdisulphide of the present invention and nickel phosphorus composite deposition liquid formula.The composition and the low temperature electrodeposition technology of molybdenumdisulphide and nickel phosphorus composite deposition liquid are as follows:
The composition of molybdenumdisulphide and the galvanic deposit of nickel phosphorus is, the composition of molybdenumdisulphide and nickel phosphorus electrodeposit liquid is, the mol ratio of solubility tetrathiomolybdate and soluble nickel salt is 0.05: 1, the mol ratio of trisodium phosphate and soluble nickel salt 1: 1, the mol ratio of trisodium citrate and soluble nickel salt is 1: 1, and the mol ratio of soluble nickel salt and water is 1～100: 5000.
Electrodeposition technology
1. configure molybdenumdisulphide and nickel phosphorus composite electrodeposition liquid in proportion, be placed in the electrolyzer;
2. pre-treatments such as degreasing, oil removing, rust cleaning are carried out on Cr12 die steel surface;
With Cr12 die steel as for the galvanic deposit liquid bath, be connected with power cathode, platinum electrode is connected with power anode and puts into electrolyzer; Electrolytic solution is in the normal temperature state;
4. set the electric current area according to Cr12 die steel area, connect power supply galvanic deposit 30 minutes.
5. the taking-up substrate cleans, and drying is at N
2Be incubated 1 hour under 100 ℃ of-900 ℃ of conditions in the atmosphere.Promptly obtain the homogeneous molybdenumdisulphide and the nickel phosphorus lubricant film of 18 micron thickness.
Claims (3)
1, a kind of molybdenumdisulphide and nickel phosphorus composite deposition liquid that is used for the machinery part surface processing, it is characterized in that comprising the solvable oxysalt and the water of solubility tetrathiomolybdate, soluble nickel salt, phosphorus, the mol ratio of solubility tetrathiomolybdate and soluble nickel salt is 0.01～0.5: 1, the solvable oxysalt of phosphorus and the mol ratio of soluble nickel salt are 0.01～30: 1, and the mol ratio of soluble nickel salt and water is 1～100: 5000.
2, molybdenumdisulphide according to claim 1 and nickel phosphorus composite deposition liquid is characterized in that comprising additive, and this additive comprises a kind of organic acid or salt at least, and the mol ratio of this additive and soluble nickel salt is 1～6.
3; a kind of described composite deposition liquid of claim 1 that utilizes carries out the surface-treated electro-deposition method to mechanical component; it is characterized in that earlier cleaning being carried out on the pending surface of mechanical component handles; pending surface with mechanical component places the electrolyzer that contains above-mentioned composite deposition liquid again; and pending mechanical component are connected with power cathode; at room temperature; current density with 0.1 milliampere-100 milliamperes of every square centimeter of pending areas; connect power supply galvanic deposit 1-120 minute; electrochemical reaction takes place; make molybdenumdisulphide and the galvanic deposit of nickel phosphorus composite membrane in the surface of pending mechanical component; at last; take out pending mechanical component, and to its cleaning, drying; in protective atmosphere, be incubated 0.5～4 hour under 100 degree-900 degree conditions, promptly obtain the homogeneous molybdenumdisulphide and the nickel phosphorus composite membrane of 10 nanometers-500 micron thickness.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100418201A CN1303259C (en) | 2004-08-31 | 2004-08-31 | Molybdenum disulfide and nickel phosphorus composite deposition liquid and its electrodeposition method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100418201A CN1303259C (en) | 2004-08-31 | 2004-08-31 | Molybdenum disulfide and nickel phosphorus composite deposition liquid and its electrodeposition method |
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| Publication Number | Publication Date |
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| CN1605658A CN1605658A (en) | 2005-04-13 |
| CN1303259C true CN1303259C (en) | 2007-03-07 |
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| CNB2004100418201A Expired - Fee Related CN1303259C (en) | 2004-08-31 | 2004-08-31 | Molybdenum disulfide and nickel phosphorus composite deposition liquid and its electrodeposition method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9498410B2 (en) | 2002-12-30 | 2016-11-22 | Colgate-Palmolive Company | Oral and personal care compositions and methods |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301254B (en) * | 2018-11-12 | 2020-07-07 | 中南大学 | Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5565395A (en) * | 1978-11-07 | 1980-05-16 | Fujikura Ltd | Surface treating method of anodic oxide film |
| JPS63170546A (en) * | 1987-01-05 | 1988-07-14 | Fujikura Ltd | Piston of internal combustion engine |
| JPS6431984A (en) * | 1987-07-28 | 1989-02-02 | Mazda Motor | Sliding structure of iron-based sliding member and al-based sliding member |
| JPH02180993A (en) * | 1989-01-06 | 1990-07-13 | Fujikura Ltd | Lubrication-treated iron part and production thereof |
-
2004
- 2004-08-31 CN CNB2004100418201A patent/CN1303259C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5565395A (en) * | 1978-11-07 | 1980-05-16 | Fujikura Ltd | Surface treating method of anodic oxide film |
| JPS63170546A (en) * | 1987-01-05 | 1988-07-14 | Fujikura Ltd | Piston of internal combustion engine |
| JPS6431984A (en) * | 1987-07-28 | 1989-02-02 | Mazda Motor | Sliding structure of iron-based sliding member and al-based sliding member |
| JPH02180993A (en) * | 1989-01-06 | 1990-07-13 | Fujikura Ltd | Lubrication-treated iron part and production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9498410B2 (en) | 2002-12-30 | 2016-11-22 | Colgate-Palmolive Company | Oral and personal care compositions and methods |
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| CN1605658A (en) | 2005-04-13 |
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