CN102604714A - Method for preparing graphene lubrication film - Google Patents
Method for preparing graphene lubrication film Download PDFInfo
- Publication number
- CN102604714A CN102604714A CN2012100439607A CN201210043960A CN102604714A CN 102604714 A CN102604714 A CN 102604714A CN 2012100439607 A CN2012100439607 A CN 2012100439607A CN 201210043960 A CN201210043960 A CN 201210043960A CN 102604714 A CN102604714 A CN 102604714A
- Authority
- CN
- China
- Prior art keywords
- film
- coupling agent
- preparation
- graphene oxide
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a method for preparing a graphene lubrication film, which comprises the following steps: preparing an amino silane coupling agent film on the surface of a hydroxylated monocrystalline silicon substrate by adopting the self-assembling method, preparing a grapheneoxide (GO) film on the surface of the amino silane coupling agent film by adopting the solution dipping method, and subjecting the GO film to thermal reduction to obtain the graphene lubrication film. The method has the characteristics of simple instrument, low cost and easy and operational preparation process. The prepared graphene lubrication film has a thickness of 1-2nm. The friction and wear test results show that the graphene lubrication film disclosed by the invention can be well combined with the monocrystalline silicon substrate, has good friction reducing and wear resisting properties and is expected to be an effective measure to solve the problem on the protection and the lubrication of the material of the micro machinery.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene composite lubricating film.
Background technology
Microelectromechanical systems (the micro electro-mechanical system that the middle and later periods eighties 20th century rises; MEMS) have that volume is little, characteristics such as light weight, energy consumption are low, integrated level and intelligent degree height, represented huge development potentiality in modern technologies fields such as biology, medical science, environment control, aerospace, digital communication, sensing technologies.
But; After the scantlings of the structure microminiaturization; Each parts clearance of MEMS often is in nano level even zero stand-off, in moving process, receives the influence of dimensional effect, and various surface forces such as surface adhesion force, frictional force are for traditional mechanical; Show very outstandingly, become the key factor that influences MEMS performance, stability and work-ing life.Therefore, the effective lubricating film is extremely important to the practical application of MEMS.Yet in this system, conventional lubricant is no longer suitable.In some researchs in the past, various novel lubricating methods such as LB film, self-assembled monolayer etc. have all received extensive concern.
Graphene has just caused investigator's attention rapidly with its particular structure and performance in various fields since 2004 come to light.The bulk material of Graphene---graphite---is owing to weak interlaminar action has outstanding lubricity.Similarly, Nanotribology research shows that the nano thin-film that graphene nanometer sheet is formed also will have good antifriction, abrasion resistance.Yet, up to the present, about the preparation and the also not expansion of application of Graphene composite lubricating film.This mainly is because be difficult on monocrystalline silicon substrate, prepare stable graphene film through simple method.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with graphene nano composite lubricating film of good antifriction, wear-resistant effect.
Preparing method of the present invention is simple, mainly may further comprise the steps:
(1) preparation amino silicane coupling agent dilute solution: choose amino silicane coupling agent, be dissolved in the mixed solvent that volume ratio is acetone: water=95:5, preparation amino silicane coupling agent dilute solution.
(2) monocrystalline silicon surface amino silicane coupling agent self-assembly: it is H that monocrystalline silicon substrate is dipped in volume ratio
2SO
4(massfraction 98 %): H
2O
2In the solution of (massfraction 30 %)=7:3; Handled 0.5 ~ 1 hour down in 90 ℃; With drying up with nitrogen after the ultrapure water ultrasonic cleaning, then it is immersed in the amino silicane coupling agent dilute solution of above-mentioned preparation, leave standstill taking-up in 0.5 ~ 1 hour; In ultrapure water, dry up with nitrogen after the ultrasonic cleaning, obtain the monocrystalline silicon substrate that surface-assembled has the amino silicane coupling agent film.
(3) preparation graphene oxide dilute solution: graphene oxide is dissolved in the ultrapure water ultra-sonic dispersion, preparation graphene oxide dilute solution.
(4) graphene oxide self-assembly: have the monocrystalline silicon substrate of amino silicane coupling agent film to immerse the graphene oxide dilute solution of above-mentioned preparation surface-assembled; Under 80 ℃, leave standstill taking-up in 6 ~ 12 hours; In ultrapure water, dry up with nitrogen after the ultrasonic cleaning, obtain the monocrystalline silicon substrate that surface-assembled has the graphene oxide nanometer sheet.
(5) reduction of graphene oxide: above-mentioned surface-assembled is had the monocrystalline silicon substrate of graphene oxide nanometer sheet under argon gas atmosphere, carry out thermal reduction, reduction temperature is 200 ℃, and temperature rise rate is 1 ℃/minute, and constant temperature time is 2 ~ 4 hours.When waiting to naturally cool to room temperature, take out sample, promptly get the Graphene composite lubricating film.
Amino silicane coupling agent involved in the present invention is 3-aminopropyltriethoxywerene werene (APTES).
The concentration of aminosilane dilute solution is 2 mmol/L ~ 10 mmol/L; Graphene oxide dilute solution concentration is 0.1 ~ 1.0 mg/mL.
Can find out that from above-mentioned technical scheme the invention provides the preparation method of a kind of monocrystalline silicon substrate surface graphene nano composite lubricating film, comprising: amino silane molecules is in the self-assembly of hydroxylation monocrystalline silicon surface; Graphene oxide is in the chemisorption on amino silane molecules surface; The thermal reduction of graphene oxide.The present invention is transition layer with the aminosilane, through reaction amino and graphene oxide epoxide group, carboxylic group, obtains constitutionally stable graphene nano film.Compared with prior art, the introducing of aminosilane self-assembled film has increased the bonding strength of Graphene and substrate greatly, has improved its stability, further uses for it and lays a good foundation.
Description of drawings
Fig. 1 prepares the process synoptic diagram for the Graphene composite lubricating film;
Fig. 2 is C element XPS spectrum figure before and after the silicon base surface oxidation graphene nanometer sheet reduction heat;
Fig. 3 is a silicon base surface Graphene composite lubricating film AFM shape appearance figure;
Fig. 4 is a Graphene composite lubricating film frictional coefficient graphic representation over time under the different experimental conditions.
Embodiment
For a better understanding of the present invention, describe through instance:
(1) the APTES dilute solution of preparation 5 mmol/L, solvent is that volume ratio is water/acetone mixture of 95:5.
(2) monocrystalline silicon piece is carried out pre-treatment,, insert the vitriol oil and 30% H that volume ratio is 7:3 after nitrogen dries up the monocrystalline silicon piece P (100) of single-sided polishing ultrasonic cleaning 10 minutes in acetone solvent
2O
2In the solution, handled 0.5 hour down in 90 ℃.Take out, above-mentioned APTES dilute solution is immersed in ultrasonic cleaning and dry up with nitrogen in ultrapure water, leaves standstill 0.5 hour, takes out back ultrasonic cleaning in ultrapure water, and nitrogen dries up.
(3) preparation graphite oxide aqueous solution, concentration is 0.4mg/mL.
The monocrystalline silicon substrate that (4) will be assembled with APTES immerses in the graphite oxide aqueous solution immediately, leaves standstill after 12 hours under 80 ℃ and takes out sample, and ultrasonic cleaning 5 minutes is to remove the Surface Physical adsorption layer in ultrapure water.
(5) have the monocrystalline silicon substrate of graphene oxide nanometer sheet under argon gas atmosphere, to carry out thermal reduction above-mentioned surface-assembled, reduction temperature is 200 ℃, and temperature rise rate is 1 ℃/minute, and constant temperature time is 2 hours.When waiting to naturally cool to room temperature, take out sample, promptly get the Graphene composite lubricating film.
The letter of preparation process is shown in Fig. 1.
Utilize x-ray photoelectron power spectrum (XPS) that the graphene oxide film C element of preparation is analyzed that (Fig. 2 a); Find that C 1s can simulate four peaks; Correspond respectively to different chemical states: C-C (284.6 eV), C-O (285.8 eV), C=O (287.1 eV), O-C=O (288.9 eV), wherein the C of non-oxide attitude (being C-C) content is 52.5 %.After the thermal reduction, a little moving takes place in the match peak position, C-C (284.8 eV), C-O (286.0 eV), C=O (287.1 eV), O-C=O (289.1 eV), and non-oxide attitude C content is increased to 75.5 % (Fig. 2 b).This explanation, reduction (being deoxidation) process has taken place in graphene oxide under the effect of heat.
In order further to verify the validity of thermal reduction, we measure the water contact angle before and after the graphene oxide film reduction.The result shows that contact angle is about 40.2 ° before the reduction, and reduction back contact angle is 85.5 °.The rising of contact angle is because the minimizing of surface polarity oxygen-containing functional group content.
Adopt the Nanoscope III AFM of DI company to the stannic oxide/graphene nano sheet film of preparation (Fig. 3 a) with reduction after graphene nanometer sheet film (Fig. 3 b, 3 c) pattern characterize.Can find the nanometer sheet not of uniform size that distributing of silicon base surface imperfection.Can know that through analyzing the thickness of nanometer sheet is about 1.1 nm.Approaching with the single-layer graphene nanometer sheet thickness of bibliographical information.
Graphene nano film involved in the present invention has good tribological property under little loading condiction, the boundary lubricant that can be used as antifriction, wear-resistant effect uses.The rub(bing)test method that is adopted is following: select for use the little frictional testing machines of the U.S. CE TR UMT-2MT of company that the frictional coefficient and the wear-out life of film are estimated.The to-and-fro movement stroke is 5 mm, and normal load is 0.1 ~ 0.2 N, and sliding velocity is 10 mm/s.Frictional coefficient when frictional coefficient rises to 0.6, thinks that film lost efficacy by the automatic record of computer, and the sliding time that is experienced this moment is the friction durability of film, can calculate the slip number of times of antithesis on film thus.Antithesis is selected for use
φThe 3GCr15 steel ball.Test result is: load 0.1 N, and sliding velocity is 10 mm/s, friction durability＞10000 time, average friction coefficient 0.24 (Fig. 4); Load 0.2 N, sliding velocity is 10 mm/s, friction durability＞320 time, average friction coefficient 0.26 (Fig. 4).This shows that the graphene nano film has good antifriction, wear-resistant effect, is expected the protection lubricant as MEMS.
Claims (3)
1. the preparation method of a Graphene composite lubricating film is characterized in that mainly may further comprise the steps:
(1) preparation amino silicane coupling agent dilute solution: choose amino silicane coupling agent, be dissolved in the mixed solvent that volume ratio is acetone: water=95:5, preparation amino silicane coupling agent dilute solution;
(2) monocrystalline silicon surface amino silicane coupling agent self-assembly: it is H that monocrystalline silicon substrate is dipped in volume ratio
2SO
4: H
2O
2In the solution of=7:3; Handled 0.5 ~ 1 hour down in 90 ℃; With drying up with nitrogen after the ultrapure water ultrasonic cleaning, then it is immersed in the amino silicane coupling agent dilute solution of above-mentioned preparation, leave standstill taking-up in 0.5 ~ 1 hour; In ultrapure water, dry up with nitrogen after the ultrasonic cleaning, obtain the monocrystalline silicon substrate that surface-assembled has the amino silicane coupling agent film; Said H
2SO
4Be massfraction 98 %), H
2O
2Be massfraction 30 %;
(3) preparation graphene oxide dilute solution: graphene oxide is dissolved in the ultrapure water ultra-sonic dispersion, preparation graphene oxide dilute solution;
(4) graphene oxide self-assembly: have the monocrystalline silicon substrate of amino silicane coupling agent film to immerse the graphene oxide dilute solution of above-mentioned preparation surface-assembled; Under 80 ℃, leave standstill taking-up in 6 ~ 12 hours; In ultrapure water, dry up with nitrogen after the ultrasonic cleaning, obtain the monocrystalline silicon substrate that surface-assembled has the graphene oxide nanometer sheet;
(5) reduction of graphene oxide: above-mentioned surface-assembled is had the monocrystalline silicon substrate of graphene oxide nanometer sheet under argon gas atmosphere, carry out thermal reduction; Reduction temperature is 200 ℃; Temperature rise rate is 1 ℃/minute, and constant temperature time is 2 ~ 4 hours, when waiting to naturally cool to room temperature; Take out sample, promptly get the Graphene composite lubricating film.
2. the preparation method of Graphene composite lubricating film as claimed in claim 1 is characterized in that amino silicane coupling agent is 3-aminopropyltriethoxywerene werene (APTES).
3. the preparation method of Graphene composite lubricating film as claimed in claim 1, the concentration that it is characterized in that the aminosilane dilute solution are 2 mmol/L ~ 10 mmol/L; Graphene oxide dilute solution concentration is 0.1 ~ 1.0 mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100439607A CN102604714A (en) | 2012-02-26 | 2012-02-26 | Method for preparing graphene lubrication film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100439607A CN102604714A (en) | 2012-02-26 | 2012-02-26 | Method for preparing graphene lubrication film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102604714A true CN102604714A (en) | 2012-07-25 |
Family
ID=46522494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100439607A Pending CN102604714A (en) | 2012-02-26 | 2012-02-26 | Method for preparing graphene lubrication film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102604714A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408856A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Graphene oxide-containing wear resistance film |
| CN103441223A (en) * | 2013-09-12 | 2013-12-11 | 中国科学院微电子研究所 | Surface treatment method of carrier concentration of adjustable controlled carbon-based semiconductor device |
| CN103482622A (en) * | 2013-09-18 | 2014-01-01 | 武汉理工大学 | Preparing method for single-layer graphene film with strong stability and high conductivity |
| CN104109405A (en) * | 2014-07-28 | 2014-10-22 | 深圳市沃特新材料股份有限公司 | Surface-modified c-Si as well as preparation method and application thereof |
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN105602298A (en) * | 2015-12-25 | 2016-05-25 | 山东重山光电材料股份有限公司 | Preparation method of ultrathin fluorinated graphene composite lubrication film |
| CN105948526A (en) * | 2016-04-28 | 2016-09-21 | 南京理工大学 | Method for preparing smooth graphene film by pulling method |
| CN107365090A (en) * | 2016-05-13 | 2017-11-21 | 南京理工大学 | A kind of method for preparing patterned Graphene film on electrospinning fibre network with czochralski method |
| CN107973621A (en) * | 2017-11-03 | 2018-05-01 | 东南大学 | A kind of reaction island based on graphene/nanometer gold plating and its preparation method and application |
| CN108075088A (en) * | 2016-11-10 | 2018-05-25 | 苏州高通新材料科技有限公司 | Lithium battery diaphragm, its preparation method and the application of the lithium salts containing sulfonated graphene |
| CN109022339A (en) * | 2017-06-08 | 2018-12-18 | 南京理工大学 | A kind of preparation method of the graphene film of surface modification orientated nano fibers |
| CN109593592A (en) * | 2018-12-25 | 2019-04-09 | 湘潭大学 | A kind of interlayer graphene oxide/binary ionic liquid composite lubricating film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730631A (en) * | 2005-08-10 | 2006-02-08 | 湖南大学 | Preparation method of carbon nanotube compounded lubricating oil |
| CN101935036A (en) * | 2009-05-26 | 2011-01-05 | 巴莱诺斯清洁能源控股公司 | Individual layer and the stabilising dispersions of multi-layer graphene layer in solution |
| US20110046026A1 (en) * | 2009-08-18 | 2011-02-24 | Gm Global Technology Operations, Inc. | Nanographene layers and particles and lubricants incorporating the same |
| CN102350334A (en) * | 2011-08-08 | 2012-02-15 | 江苏大学 | Graphene/mesoporous titanium dioxide visible light catalyst and preparation method |
-
2012
- 2012-02-26 CN CN2012100439607A patent/CN102604714A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730631A (en) * | 2005-08-10 | 2006-02-08 | 湖南大学 | Preparation method of carbon nanotube compounded lubricating oil |
| CN101935036A (en) * | 2009-05-26 | 2011-01-05 | 巴莱诺斯清洁能源控股公司 | Individual layer and the stabilising dispersions of multi-layer graphene layer in solution |
| US20110046026A1 (en) * | 2009-08-18 | 2011-02-24 | Gm Global Technology Operations, Inc. | Nanographene layers and particles and lubricants incorporating the same |
| CN102350334A (en) * | 2011-08-08 | 2012-02-15 | 江苏大学 | Graphene/mesoporous titanium dioxide visible light catalyst and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 《The Journal of Physical Chemistry C》 20110504 Junfei Ou et al. "Self-Assembly of Octadecyltrichlorosilane on Graphene Oxide and the Tribological Performances of the Resultant Film" p10080-10086 1-3 , * |
| JUNFEI OU ET AL.: ""Self-Assembly of Octadecyltrichlorosilane on Graphene Oxide and the Tribological Performances of the Resultant Film"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408856A (en) * | 2013-07-17 | 2013-11-27 | 苏州艾特斯环保材料有限公司 | Graphene oxide-containing wear resistance film |
| CN103441223A (en) * | 2013-09-12 | 2013-12-11 | 中国科学院微电子研究所 | Surface treatment method of carrier concentration of adjustable controlled carbon-based semiconductor device |
| CN103482622A (en) * | 2013-09-18 | 2014-01-01 | 武汉理工大学 | Preparing method for single-layer graphene film with strong stability and high conductivity |
| CN104109405B (en) * | 2014-07-28 | 2016-08-24 | 深圳市沃特新材料股份有限公司 | C-Si of surface modification and preparation method and application |
| CN104109405A (en) * | 2014-07-28 | 2014-10-22 | 深圳市沃特新材料股份有限公司 | Surface-modified c-Si as well as preparation method and application thereof |
| CN104319367A (en) * | 2014-10-09 | 2015-01-28 | 奇瑞汽车股份有限公司 | Silicon/graphite composite anode material and preparation method thereof |
| CN105602298A (en) * | 2015-12-25 | 2016-05-25 | 山东重山光电材料股份有限公司 | Preparation method of ultrathin fluorinated graphene composite lubrication film |
| CN105948526A (en) * | 2016-04-28 | 2016-09-21 | 南京理工大学 | Method for preparing smooth graphene film by pulling method |
| CN107365090A (en) * | 2016-05-13 | 2017-11-21 | 南京理工大学 | A kind of method for preparing patterned Graphene film on electrospinning fibre network with czochralski method |
| CN108075088A (en) * | 2016-11-10 | 2018-05-25 | 苏州高通新材料科技有限公司 | Lithium battery diaphragm, its preparation method and the application of the lithium salts containing sulfonated graphene |
| CN109022339A (en) * | 2017-06-08 | 2018-12-18 | 南京理工大学 | A kind of preparation method of the graphene film of surface modification orientated nano fibers |
| CN109022339B (en) * | 2017-06-08 | 2021-05-07 | 南京理工大学 | Preparation method of graphene film with surface modified oriented nanofibers |
| CN107973621A (en) * | 2017-11-03 | 2018-05-01 | 东南大学 | A kind of reaction island based on graphene/nanometer gold plating and its preparation method and application |
| CN109593592A (en) * | 2018-12-25 | 2019-04-09 | 湘潭大学 | A kind of interlayer graphene oxide/binary ionic liquid composite lubricating film and preparation method thereof |
| CN109593592B (en) * | 2018-12-25 | 2021-06-29 | 湘潭大学 | Interlayer graphene oxide/binary ionic liquid composite lubricating film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604714A (en) | Method for preparing graphene lubrication film | |
| CN102677052A (en) | Preparation method of graphite alkenyl self-assembly multilayer nanometer lubricating film | |
| Beckford et al. | The effects of polydopamine coated Cu nanoparticles on the tribological properties of polydopamine/PTFE coatings | |
| Sun et al. | Facile fabrication of novel multifunctional lubricant-infused surfaces with exceptional tribological and anticorrosive properties | |
| Ou et al. | Fabrication and tribological investigation of a novel hydrophobic polydopamine/graphene oxide multilayer film | |
| CN100479931C (en) | Method for producing compound thin film of phosphoric acid radicle silane-carbon nanotubes on the surface of single crystal silicon wafers | |
| Bai et al. | Self-assembly of ceria/graphene oxide composite films with ultra-long antiwear lifetime under a high applied load | |
| Pu et al. | Micro/nano-tribological behaviors of crown-type phosphate ionic liquid ultrathin films on self-assembled monolayer modified silicon | |
| Huo et al. | Fabrication and tribological properties of self-assembled monolayer of n-alkyltrimethoxysilane on silicon: Effect of SAM alkyl chain length | |
| Ma et al. | Achieving macroscale liquid superlubricity using glycerol aqueous solutions | |
| Dhanola et al. | A critical review on liquid superlubricitive technology for attaining ultra-low friction | |
| CN111471507A (en) | Recyclable carbon quantum dot nano lubricating oil additive and preparation method thereof | |
| Wang et al. | Fabrication and tribological study of graphene oxide/multiply-alkylated cyclopentanes multilayer lubrication films on Si substrates | |
| Songfeng et al. | Tribological properties of self-assembled gold nanoparticles on silicon with polydopamine as the adhesion layer | |
| CN109593592B (en) | Interlayer graphene oxide/binary ionic liquid composite lubricating film and preparation method thereof | |
| CN102464498B (en) | Preparation method of ionic liquid binary composite nano lubricating film | |
| Li et al. | One-pot synthesis and self-assembly of anti-wear octadecyltrichlorosilane/silica nanoparticles composite films on silicon | |
| Zheng et al. | Preparation of PFDTS-kaolin/PU superamphiphobic coatings with antibacterial, antifouling and improved durability property | |
| Zeng et al. | Self-assembled multilayer WS2/GO films on amorphous silicon coating for enhancing the lubricating properties | |
| Wang et al. | Trilayered film with excellent tribological performance: a combination of graphene oxide and perfluoropolyethers | |
| CN102584331A (en) | Method for preparing double-component and double-layer nano lubrication thin film by taking nano-particle array as template | |
| Tao et al. | Investigation of the tribological behavior of 3-mercaptopropyl trimethoxysilane deposited on silicon | |
| Liu et al. | Interlayer graphene oxide/binary ionic liquids composite lubricating films with improved load-carrying and anti-wear properties | |
| Akulova et al. | Formation and tribological properties of octacosanoic acid monomolecular Langmuir–Blodgett films | |
| Wang et al. | Fabrication and tribological behavior of patterned multiply-alkylated cyclopentanes (MACs)–octadecyltrichlorosilane (OTS) dual-component film by a soft lithographic approach |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120725 |
|
| WD01 | Invention patent application deemed withdrawn after publication |