CN1304644C - Molybdenum disulfide electrodepositing method and liquid for micromachinery surface - Google Patents
Molybdenum disulfide electrodepositing method and liquid for micromachinery surface Download PDFInfo
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- CN1304644C CN1304644C CNB2004100648025A CN200410064802A CN1304644C CN 1304644 C CN1304644 C CN 1304644C CN B2004100648025 A CNB2004100648025 A CN B2004100648025A CN 200410064802 A CN200410064802 A CN 200410064802A CN 1304644 C CN1304644 C CN 1304644C
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- molybdenum disulfide
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- electrodepositing
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- hydrochlorate
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Abstract
The present invention discloses a molybdenum disulfide electrodeposition method and electrodeposition liquid thereof used for micro-mechanical surfaces. The method comprises: a cleaned substrate of micro-mechanical materials is put in an electrolytic tank filled with compounding deposition liquid, a mechanical member to be treated is connected with a cathode of a power supply, the power supply is switched on for electrodeposition for 0.5 to 120 minutes with the current density of 0.1 to 500 mA per square centimeter of areas to be treated at room temperature, and molybdenum disulfide is electrodeposited on the surface of the mechanical member to be treated. Finally, the mechanical member to be treated is taken out, washed, dried and heated to 100 DEG C to 900 DGE C in a protective atmosphere, heat is preserved for 0.5 to 4 hours, homogeneous molybdenum disulfide films with the thickness of 10 nanometers to 500 micrometers can be obtained. The deposition liquid comprises soluble molybdate, soluble sulfide and pH regulating agents, wherein the molar ratio of the soluble sulfide to the soluble molybdate is 4 to 30:1, the molar ratio of the pH regulating agents to the soluble molybdate is 2 to 30:1, and the molar ratio of water to the soluble molybdate is 55 to 5500:1.
Description
Technical field
The present invention relates to a kind of micromechanics working-surface friction that is used to reduce, improve safe, the quick type MoS2 electrodeposit liquid and the low temperature MoS2 lubricant film deposition technique thereof of lubricity.The technical field that belongs to the Nanotribology Surface Engineering.
Background technology
Microelectromechanical systems (MEMS) 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 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 macroscopical friction field.
Molybdenum disulfide film coating means are a lot, and as directly smearing, water-bath applies, magnetron sputtering, electrophoresis etc.Wherein directly coating and water-bath coating generally is used for the macroscopic view friction, size and specification of quality to film are not high: magnetron sputtering generally is used for accurate instrument component, the size of may command film, film quality is good, but magnetron sputtering has directivity, bad around the plating performance, only suitable plane plated film or parts simple in structure, the micromechanics deposition difficulty small in size, that mechanism is complicated.Electrophoretic method is to utilize charged molybdenumdisulphide suspended particle under electric field action, moves and be deposited on piece surface.Particle identical (about 1 μ m) in the sedimentary film particles of this method and the original solution, the micromechanics size is bigger relatively, and film is not fine and close, so generally be applied to macroscopical friction field.
Utilize novel electrodip process can not only be used for modification silicon face Micro Lub and learn performance at micromechanics surface deposition molybdenum disulfide film, can also closely combine with the microelectromechanical systems manufacturing process, be the effective way that the friction problem of micromechanics obtains the breakthrough on the just sincere justice.Molybdenumdisulphide is few in the research in Micro Lub field, particularly acts on the low temperature depositing molybdenumdisulphide technology on micromechanics surface, does not see open report both at home and abroad as yet.
Summary of the invention
The invention provides a kind of coating evenly, coating and matrix bond is firm, oilness is good molybdenum disulfide electrodepositing liquid and electro-deposition method.
The present invention adopts following technical scheme:
The method of the invention:
A kind of being used for carried out the molybdenum disulfide electrodepositing method that surface-treated is used for the micromechanics surface to mechanical component; be that the micromechanics material matrix after the cleaning processing is placed the electrolyzer that contains composite deposition liquid; and pending mechanical component are connected with power cathode; at room temperature; current density with 0.1 milliampere-500 milliamperes of every square centimeter of pending areas; connect power supply galvanic deposit 0.5-120 minute; electrochemical reaction takes place; make molybdenum disulfide electrodepositing in pending machinery part surface; at last; take out pending mechanical component; and to its cleaning; drying is heated to 100 ℃-900 ℃ and be incubated 0.5～4 hour in protective atmosphere, promptly obtain the homogeneous molybdenumdisulphide film of 10 nanometers-500 micron thickness.
Product of the present invention:
1, a kind of molybdenumdisulphide deposit fluid that is used for the machinery part surface processing is characterized in that comprising soluble molybdenum hydrochlorate, solvable sulfide, pH regulator agent; The mol ratio of solvable sulfide and soluble molybdenum hydrochlorate is 4～30: 1, and pH regulator agent and soluble molybdenum hydrochlorate mol ratio are 2～30: 1, and the mol ratio of water and soluble molybdenum hydrochlorate is 55～5500: 1.
Yet there are no about controlled electrodip process molybdenumdisulphide in the application aspect the micromechanics anti-attrition.The present invention has following advantage:
(1) with general sufacing comparison, the photoetching technique that technology of the present invention adopts in making in conjunction with MEMS (micro electro mechanical system) can selectively deposit coating, has realized the controllable operating of coating deposition position; Simultaneously, have superior profiling because many technology such as galvanic deposit and magnetron sputtering deposition are compared, can use on complex-shaped micromechanics, electrodeposition apparatus is simple.
(2) the invention provides a kind of molybdenumdisulphide electroplate liquid formulation safely and fast and sedimentary technology of controlledization thereof that is applicable to the micromechanics material surface, this settled layer has outstanding lubricity, low adhesion energy and stable unreactiveness, can significantly improve the tribological property of silicon, delay its fracture.
(3) chemical nickel phosphorus plating coating is even, and smooth surface, roughness are nano level.
(4) additive of the present invention is one or more of acidic substance HmRn or RnHm for the pH regulator agent, wherein, R is haloid element, phosphate radical, sulfate radical, nitrate radical or alkyl, and H is hydrogen ion or carboxyl, n＜7, m＜4, this pH regulator agent comprises a kind of organic acid or salt at least, it act as regulator solution acidity, improve the galvanic deposit content of effective, improve the speed of thin film deposition, make thin film layer more even, increase surface smoothness.
(5) the present invention utilizes the way of gluing photoetching, has realized coating position-controllable characteristics.
Embodiment
Embodiment 1
A kind of molybdenumdisulphide deposit fluid that is used for the machinery part surface processing, it is characterized in that comprising soluble molybdenum hydrochlorate, solvable sulfide, pH regulator agent, wherein can be chosen as Sodium orthomolybdate, ammonium molybdate in the soluble molybdenum hydrochlorate present embodiment, can be chosen as in the dissolvable sulfide present embodiment in sodium sulphite, ammonium sulfide, the acidity regulator present embodiment and can be chosen as hydrochloric acid, phosphoric acid, acetic acid; The mol ratio of solvable sulfide and soluble molybdenum hydrochlorate is 4～30: 1,5: 1,7: 1,20: 1,27: 1; Acidity regulator and soluble molybdenum hydrochlorate mol ratio are 2～30: 1, can be chosen as 3: 1 in the present embodiment, 7: 1,14: 1,24: 1, the mol ratio of water and soluble molybdenum hydrochlorate is 55～5500: 1, can be chosen as 70: 1 in the present embodiment, 300: 1,2000: 1,3890: 1,5100: 1.
Embodiment 2
A kind of micromechanics surface-treated molybdenum disulfide electrodepositing liquid that is used for, disposing the required composition of this solution is soluble molybdenum hydrochlorate, solvable sulfide, pH regulator agent and water, wherein can be chosen as Sodium orthomolybdate, ammonium molybdate in the soluble molybdenum hydrochlorate present embodiment, can be chosen as in the present embodiment in sodium sulphite, ammonium sulfide, the acidity regulator present embodiment and can be chosen as hydrochloric acid, phosphoric acid; Remove and anhydrate, the shared molar percentage of soluble molybdenum hydrochlorate is 1-30%, can be chosen for 5% in the present embodiment, 20%, 27%, it is 10-50% that dissolvable sulfide accounts for molar percentage, can be chosen as 14% in the present embodiment, 25%, 40%, 45%, the shared molar percentage of acidity regulator is 10-50%, can be chosen as 14% in the present embodiment, 25%, 40%, 45%, above-mentioned additive can be one or more the combination in hydrochloric acid, phosphoric acid, acetic acid, lactic acid, propionic acid, oxysuccinic acid, the Succinic Acid etc., and the proportioning of its component can be any proportioning.
Embodiment 3
Handle micromechanics N type single-sided polishing monocrystalline silicon piece with molybdenumdisulphide deposit fluid prescription of the present invention.The diameter of this disk is 3 inches, crystal orientation 110 directions, arsenic doped, resistivity 0.002 ohmcm.The composition of molybdenumdisulphide and low temperature electrodeposition technology are as follows:
The composition of molybdenum disulfide electrodepositing liquid
Constituent concentration (Mol/L)
Sodium orthomolybdate 0.01 ~ 0.1
Sodium sulphite 0.04 ~ 0.9
Hydrochloric acid 0.04 ~ 0.5
Matrix put into 80 ℃ hydrochloric acid; soaked 20 minutes in the hydrogen peroxide solution; clean second step of back: the micromechanics material matrix is stored in the electrolyzer of above-mentioned composite deposition liquid; and pending mechanical component are connected with power cathode; at room temperature; current density with 0.1 milliampere-500 milliamperes of every square centimeter of pending areas; can be chosen as 0.2 milliampere in the present embodiment; 3 milliamperes; 43 milliamperes; 60 milliamperes; connect power supply galvanic deposit 0.5-120 minute for 80 milliamperes; can be chosen as 2 minutes in the present embodiment; 10 minutes; 23 minutes; 44 minutes; 60 minutes; 90 minutes; electrochemical reaction took place in 111 minutes; make the surface of molybdenum disulfide electrodepositing in pending mechanical component; at last; take out pending mechanical component; and to its cleaning; dry; in nitrogen (or argon gas) protective atmosphere, be incubated 0.5～4 hour under 100 degree-900 degree conditions, can be chosen as 120 ℃ in the present embodiment; 300 ℃; 450 ℃; 600 ℃; 888 ℃; 1.6 hour; 2 hours; 3.5 hour; 3.7 hour promptly obtain the homogeneous molybdenumdisulphide film of 10 nanometers-500 micron thickness.
Embodiment 4
A kind ofly utilize above-mentioned deposit fluid that micromechanics is carried out the surface-treated method to be: earlier cleaning processing is carried out on the pending surface of micromechanical parts, this cleaning processing comprises carries out sodium hydroxide solution degreasing, oil removing, the ash disposal of ethanol sonic oscillation, hydrochloric acid, hydrogen peroxide solution that matrix is put into 80 ℃ soaked 20 minutes, gluing photoetching then, the main technologic parameters of gluing photoetching is: rotating speed 2500-4500 rev/min, the preceding 10-50 minute baking time, 80 ℃-100 ℃ of temperature, time shutter 20-60 second.Place the electrolyzer that contains above-mentioned composite deposition liquid at last; and pending mechanical component are connected with power cathode; at room temperature; current density with 0.1 milliampere-500 milliamperes of every square centimeter of pending areas; can be chosen as 0.2 milliampere in the present embodiment; 3 milliamperes; 43 milliamperes; 60 milliamperes; connect power supply galvanic deposit 0.5-120 minute for 80 milliamperes; can be chosen as 2 minutes in the present embodiment; 10 minutes; 23 minutes; 44 minutes; 60 minutes; 90 minutes; electrochemical reaction took place in 111 minutes; make the surface of molybdenum disulfide electrodepositing in pending mechanical component; at last; take out pending mechanical component; and to its cleaning; dry; in nitrogen (or argon gas) protective atmosphere, be incubated 0.5～4 hour under 100 ℃-900 degree conditions; can be chosen as 120 ℃ in the present embodiment; 300 ℃; 450 ℃; 600 ℃; 888 ℃; 1.6 hour; 2 hours; 3.5 hour; 3.7 hour; put into 80～100 ℃ the sulfuric acid and the solution of hydrogen peroxide after the washed with de-ionized water and remove glue; again to its cleaning, drying.Promptly obtain the homogeneous molybdenumdisulphide film of 10 nanometers-500 micron thickness at selection area.
Claims (4)
1, a kind of micromechanical parts surface-treated molybdenum disulfide electrodepositing method that is used for, it is characterized in that the micromechanics material matrix after the cleaning processing is placed the electrolyzer that contains composite deposition liquid, and pending mechanical component are connected with power cathode, at room temperature, current density with 0.1 milliampere-500 milliamperes of every square centimeter of pending areas, connect power supply galvanic deposit 0.5-120 minute, electrochemical reaction takes place, make molybdenum disulfide electrodepositing in pending machinery part surface, at last, take out pending mechanical component, and to its cleaning, drying is heated to 100 ℃-900 ℃ and be incubated 0.5～4 hour in protective atmosphere, promptly obtain the homogeneous molybdenumdisulphide film of 10 nanometers-500 micron thickness; Above-mentioned composite deposition liquid is molybdenum disulfide electrodepositing liquid, comprise soluble molybdenum hydrochlorate, solvable sulfide, pH regulator agent, the mol ratio of solvable sulfide and soluble molybdenum hydrochlorate is 4～30: 1, pH regulator agent and soluble molybdenum hydrochlorate mol ratio are 2～30: 1, and the mol ratio of water and soluble molybdenum hydrochlorate is 55～5500: 1.
2, the molybdenum disulfide electrodepositing method that is used for the micromechanics surface according to claim 1, it is characterized in that making and treat that deposition surface exposes by the gluing photoetching, after having deposited the molybdenumdisulphide film, the micromechanics material matrix is put into 70 ℃～90 ℃ sulfuric acid and hydrogen peroxide remove glue and remove and remove photoresist.
3, a kind of molybdenum disulfide electrodepositing liquid that is used to implement the described method of claim 1, it is characterized in that comprising soluble molybdenum hydrochlorate, solvable sulfide, pH regulator agent, the mol ratio of solvable sulfide and soluble molybdenum hydrochlorate is 4～30: 1, pH regulator agent and soluble molybdenum hydrochlorate mol ratio are 2～30: 1, and the mol ratio of water and soluble molybdenum hydrochlorate is 55～5500: 1.
4, molybdenum disulfide electrodepositing liquid according to claim 3 is characterized in that the pH regulator agent is acidic substance H
mR
nOr R
nH
mOne or more, wherein, R is haloid element, phosphate radical, sulfate radical, nitrate radical or alkyl, H is hydrogen ion or carboxyl, n＜7, m＜4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100648025A CN1304644C (en) | 2004-09-30 | 2004-09-30 | Molybdenum disulfide electrodepositing method and liquid for micromachinery surface |
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| CNB2004100648025A CN1304644C (en) | 2004-09-30 | 2004-09-30 | Molybdenum disulfide electrodepositing method and liquid for micromachinery surface |
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| CN1614101A CN1614101A (en) | 2005-05-11 |
| CN1304644C true CN1304644C (en) | 2007-03-14 |
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| CNB2004100648025A Expired - Fee Related CN1304644C (en) | 2004-09-30 | 2004-09-30 | Molybdenum disulfide electrodepositing method and liquid for micromachinery surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965707A (en) * | 2012-07-23 | 2013-03-13 | 贵州航天精工制造有限公司 | Method for electrodeposition of solid lubricating film by molybdenum disulfide liquid lubricant |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624756B (en) * | 2015-12-29 | 2018-01-19 | 中国石油大学(华东) | A kind of high activity molybdenum sulfide film elctro-catalyst and preparation method thereof |
| CN111101180B (en) * | 2020-01-14 | 2022-03-11 | 山西大同大学 | Preparation of MoS through electrodeposition in eutectic ionic liquid2Method for producing thin film material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230539A (en) * | 1979-07-09 | 1980-10-28 | Fujikura Cable Works, Ltd. | Method for surface treatment of anodic oxide film |
| JPS575893A (en) * | 1980-06-16 | 1982-01-12 | Fujikura Ltd | Surface treating method for porous metallic article |
| JP2002206198A (en) * | 2000-12-28 | 2002-07-26 | Honda Motor Co Ltd | Ni-Cu ALLOY COMPOSITE PLATING SOLUTION |
-
2004
- 2004-09-30 CN CNB2004100648025A patent/CN1304644C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230539A (en) * | 1979-07-09 | 1980-10-28 | Fujikura Cable Works, Ltd. | Method for surface treatment of anodic oxide film |
| JPS575893A (en) * | 1980-06-16 | 1982-01-12 | Fujikura Ltd | Surface treating method for porous metallic article |
| JP2002206198A (en) * | 2000-12-28 | 2002-07-26 | Honda Motor Co Ltd | Ni-Cu ALLOY COMPOSITE PLATING SOLUTION |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965707A (en) * | 2012-07-23 | 2013-03-13 | 贵州航天精工制造有限公司 | Method for electrodeposition of solid lubricating film by molybdenum disulfide liquid lubricant |
| CN102965707B (en) * | 2012-07-23 | 2016-05-18 | 贵州航天精工制造有限公司 | A kind of method of solid lubricant film with molybdenum bisuphide fluid lubricant electricity |
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| CN1614101A (en) | 2005-05-11 |
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