CN109096837A - A kind of preparation method of the high-antiwear self-lubricating coating of PMMA modified ptfe - Google Patents
A kind of preparation method of the high-antiwear self-lubricating coating of PMMA modified ptfe Download PDFInfo
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- CN109096837A CN109096837A CN201810736783.8A CN201810736783A CN109096837A CN 109096837 A CN109096837 A CN 109096837A CN 201810736783 A CN201810736783 A CN 201810736783A CN 109096837 A CN109096837 A CN 109096837A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of preparation methods of the high-antiwear self-lubricating coating of PMMA modified ptfe.The preparation method comprises the following steps: b, MMA monomer and potassium persulfate solution is added dropwise in a, preparation PTFE nano dispersion fluid；C, polymerization reaction obtains PMMA modified PTFE powders；D, solvent is prepared: e, preparation PMMA modified ptfe composite coated liquid: f, preparation PMMA modified ptfe coating.The preparation method moulding process is easy, and application property is strong, and preparation cost is cheap；The PMMA modified ptfe high-antiwear self-lubricating coating of preparation has excellent self-lubricating property, wear-resisting property, stability and corrosion resistance, can apply under the particular surroundings such as high temperature, air or vacuum, burn into radiation, top load.
Description
Technical field
The invention belongs to the paintings of the high-antiwear self-lubricating of the technical field of composite coating more particularly to PMMA modified ptfe
The preparation method of layer.
Background technique
Polytetrafluoroethylene (PTFE) (PTFE) is one of most promising material as the engineering material application of structure and lubrication, it is
A kind of self-lubricating material with ultralow friction coefficient.However, due to poor mechanical property (including the severe creep deformation row of pure PTFE
For), linear expansion coefficient is high, thermal coefficient difference and wears no resistance, and poor with the coating compatibility of metal material, therefore its
Using being limited by very large.For a long time, the self-lubrication and wear-resisting property for improving material have become people be concerned about and again
Depending on project.In general, improving tribological property there are mainly two types of the technological means of material.First, in a polymer matrix
The lubricant particles with low shear strength and self-lubrication, such as addition molybdenum disulfide, boron nitride, graphite are added, to reduce material
The coefficient of friction of material.Second, hard particles or fiber enhancer are added, in a polymer matrix to improve the wearability of material.
However the coefficient of friction of the PTFE after being filled through will also tend to increase to some extent, and the PTFE coated film after being filled through needs
Will by priming paint, middle layer, finishing coat be secondary or even multiple sintering, cause the binding performance of final film and substrate to substantially reduce,
And then influence coating service life and substantially reduce coating can application property.Patent of invention CN 103628058A discloses " a kind of
The preparation method of high-wearing feature metal-based self-lubricating coating ", coating described in this method need coated, dry, electronics acceleration
Device irradiation, and irradiation needs inert gas shielding leads to production technology complexity, low efficiency, at high cost.
Summary of the invention
For defect existing for above-mentioned current material and technology, the present invention provide one kind can application property is strong, strong operability,
The preparation method of the high-antiwear self-lubricating coating of the low PMMA modified ptfe of high abrasion, long service life, preparation cost.The present invention
PMMA modified PTFE powders (PTFE&PMMA) is prepared first, later by itself and polyphenylene sulfide (PPS), polyimides (PI)
Resin uniformly mixes, and a kind of high-antiwear self-lubricating coating of PMMA modified ptfe is made in coated and once sintered process.
It is of the invention the preparation method is as follows:
(1) preparation process of PMMA modified ptfe composite coating:
1. the preparation of PMMA modified PTFE powders:
A, composition and ratio is pressed, a certain amount of PTFE nano dispersion fluid is weighed, 500ml deionized water, 200~600rmp is added
10~30min of stirring obtains dispersion liquid A；
B, under argon atmosphere, temperature is 79~90 DEG C, and revolving speed is 300~800rmp, and MMA is slowly added dropwise into dispersion liquid A
Monomer, stablizes 10~30min, and addition 10ml concentration is 40~80mol/L potassium persulfate solution；
C, 2-48h is reacted under argon atmosphere, is filtered for multiple times, is washed after reaction, dry 2~12h at 70~90 DEG C,
Obtain PMMA modified PTFE powders.
2. the preparation of PMMA modified ptfe composite coating:
A, the preparation of the mixed solvent of composite coating: solvent forms following mass ratio relationship, dehydrated alcohol: dimethyl second
Amide: distilled water: neopelex=35~40:15~20:48~50:2~3 are uniformly mixed.
B, the preparation of PMMA modified ptfe composite coated liquid: selecting ultra-fine toughening PPS resin, and molecular weight is 8000~
10000 PI resin, levelling agent 410 help film that above-mentioned in the mixed solvent is added, wherein each raw material dosage has following mass ratio
Relationship, PPS:PI:PTFE&PMMA: levelling agent=20~30:5~20:75~80:
0.3~0.5:0.3~0.5 is added the in the mixed solvent of step a, stirs evenly, wherein the raw material and solvent
Mass ratio=2~4:10~15.
(2) preparation process of PMMA modified ptfe coating:
1. the finish of sample is handled: carrying out finish processing to sample, specimen surface finish is made to reach the μ of Ra2~10
M, and it is cleaned by ultrasonic specimen surface with absolute alcohol；
2. utilizing sol evenning machine or electrostatic coating method prepares coating, step (1) solution that 2. prepared by middle b is uniformly coated into examination
Sample surface；80~120 DEG C of 10~30min of heat preservation solidifications are warming up to 5~10 DEG C/min, are warming up to later with 10~20 DEG C/min
160~270 DEG C of 10~60min of heat preservation sintering, are finally cooled to room temperature with 5~20 DEG C/min cooling rate.
Preferably, the step (1) is 1. in a, and the mass fraction of PTFE is 50~99wt.%, it is highly preferred that the matter of PTFE
Amount score is 60~75wt.%, and mixing speed is 300~400rmp, and mixing time is 10~15min；
Preferably, for step (1) 1. in b, reaction temperature is 79~85 DEG C, and mixing speed is 400~600rmp, stablizes the time
For 10~20min, potassium persulfate solution concentration is 60~80mol/L；
Preferably, step (1) is 1. in c, and the reaction time is 6~for 24 hours, and drying temperature is 70~85 DEG C, and drying time is 4~
10h, more electedly, reaction time are 8~12h, and drying temperature is 80~85 DEG C, and drying time is 4~6h.
Preferably, the step (1) 2. solvent quality described in a, dehydrated alcohol: dimethyl acetamide: distilled water: dodecane
Base benzene sulfonic acid sodium salt=35~38:15~18:48~50:2~2.5.
Preferably, 2. PI resin molecular weight is 9000~10000 to the step (1) in b, and each raw material dosage mass ratio closes
System, PPS:PI:PTFE&PMMA: stream agent :=25~30:5~15:75~78:0.4~0.5:0.4~0.5；The raw material with it is molten
Mass ratio=3 of agent~4:10~12.
Preferably, the step (2) 1. in specimen surface roughness Ra3~4 μm.
Preferably, the step (2) is 2. warming up to 80~100 DEG C of 5~10min of heat preservation solidifications with 5~7 DEG C/min, later
160~240 DEG C of 15~30min of heat preservation sintering are warming up to 10~15 DEG C/min, room is finally cooled to 5~8 DEG C/min cooling rate
Temperature.
The present invention has the following advantages that compared with prior art
(1) moulding process is easy, application property is strong, and preparation cost is cheap；
(2) PMMA modified ptfe is high with metal base bond strength, and the mechanical strength of made composite material is big, uses the longevity
Life length；
(3) the high-antiwear self-lubricating coating of PMMA modified ptfe has excellent self-lubricating property (coefficient of friction position 0.04
~0.07), wear-resisting property, stability and high temperature oxidation resistance.
Detailed description of the invention
Fig. 1 is coating photo prepared by the embodiment of the present invention 1,2,3.
Fig. 2 is coating friction posterior surface pattern photo prepared by the embodiment of the present invention 1,2,3.
Fig. 3 is coating friction coefficient curve figure prepared by the embodiment of the present invention 1,2,3.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.It should be pointed out that following embodiment is only applicable in
In the present invention is further described, it should not be understood as limiting the scope of the invention, ordinary person relevant to the field,
Some nonessential adjustment and improvement that the present invention carries out, including addition soft metal or oxide, hard particles or fiber are increased
Strong agent, self-lubrication lubricant particles still fall within protection scope of the present invention.
Embodiment 1
(1) preparation process of PMMA modified ptfe composite coating:
1. the preparation of PMMA modified PTFE powders:
20mlPTFE nano dispersion fluid is added in flask, then in flask be added 500ml deionized water and
15min is stirred under 300rmp, the PTFE nano dispersion fluid after being diluted；Dispersion liquid after dilution is heated to 79 DEG C, slowly
20mlMMA monomer is added dropwise, stirs 15min under 400rmp, the persulfate aqueous solution that 10mL concentration is 60mol/L is added later,
12h is reacted under argon atmosphere, product is collected in repeated filtration, washing, and dry 5h obtains PMMA modified PTFE powders at 80 DEG C.
2. the preparation of PMMA modified ptfe composite coating:
A, the preparation of the mixed solvent of composite coating: solvent forms following mass ratio relationship, dehydrated alcohol: dimethyl second
Amide: distilled water: neopelex=38:15:49:2 is uniformly mixed.
B, ultra-fine toughening PPS resin, the PI that molecular weight is 10000 preparation of PMMA modified ptfe composite coated liquid: are selected
Resin, levelling agent 410 help film that above-mentioned in the mixed solvent is added, wherein each raw material dosage has following mass ratio relationship, PPS:
PI:PTFE&PMMA: levelling agent :=25:5:75:0.4:0.4；Mass ratio=3:10 of the raw material and solvent.
(2) preparation process of PMMA modified ptfe coating:
1. the finish of sample is handled: finish processing is carried out to sample, specimen surface finish is made to reach Ra4 μm, and
It is cleaned by ultrasonic specimen surface with absolute alcohol；
2. utilizing sol evenning machine coating method prepares coating, step (1) solution that 2. prepared by middle b is uniformly coated into sample table
Face；80 DEG C of heat preservation 10min solidifications are warming up to 5 DEG C/min, 160 DEG C of heat preservation 30min sintering are warming up to 10 DEG C/min later, most
It is cooled to room temperature afterwards with 20 DEG C/min cooling rate.
Embodiment 2
(1) preparation process of PMMA modified ptfe composite coating:
1. the preparation of PMMA modified PTFE powders:
30mlPTFE nano dispersion fluid is added in flask, then in flask be added 500ml deionized water and
20min is stirred under 400rmp, the PTFE nano dispersion fluid after being diluted；Dispersion liquid after dilution is heated to 85 DEG C, slowly
20mlMMA monomer is added dropwise, stirs 20min under 600rmp, the persulfate aqueous solution that 10mL concentration is 74mol/L is added later,
8h is reacted under argon atmosphere, product is collected in repeated filtration, washing, and dry 4h obtains PMMA modified PTFE powders at 85 DEG C.
2. the preparation of PMMA modified ptfe composite coating:
A, the preparation of the mixed solvent of composite coating: solvent forms following mass ratio relationship, dehydrated alcohol: dimethyl second
Amide: distilled water: neopelex=38:18:50:2.5 is uniformly mixed.
B, ultra-fine toughening PPS resin, the PI tree that molecular weight is 9000 preparation of PMMA modified ptfe composite coated liquid: are selected
Rouge, levelling agent 410 help film that above-mentioned in the mixed solvent is added, wherein each raw material dosage has following mass ratio relationship, PPS:
PI:PTFE&PMMA: levelling agent :=30:15:78:0.5:0.5；Mass ratio=4:12 of the raw material and solvent.
(2) preparation process of PMMA modified ptfe coating:
1. the finish of sample is handled: finish processing is carried out to sample, specimen surface finish is made to reach Ra4 μm, and
It is cleaned by ultrasonic specimen surface with absolute alcohol；
2. utilizing sol evenning machine coating method prepares coating, step (1) solution that 2. prepared by middle b is uniformly coated into sample table
Face；100 DEG C of heat preservation 10min solidifications are warming up to 5 DEG C/min, 200 DEG C of heat preservation 30min sintering are warming up to 10 DEG C/min later,
Finally it is cooled to room temperature with 20 DEG C/min cooling rate.
Embodiment 3
(1) preparation process of PMMA modified ptfe composite coating:
1. the preparation of PMMA modified PTFE powders:
40mlPTFE nano dispersion fluid is added in flask, then in flask be added 500ml deionized water and
15min is stirred under 400rmp, the PTFE nano dispersion fluid after being diluted；Dispersion liquid after dilution is heated to 90 DEG C, slowly
20mlMMA monomer is added dropwise, stirs 20min under 600rmp, the persulfate aqueous solution that 10mL concentration is 80mol/L is added later,
6h is reacted under argon atmosphere, product is collected in repeated filtration, washing, and dry 3h obtains PMMA modified PTFE powders at 90 DEG C.
2. the preparation of PMMA modified ptfe composite coating:
A, the preparation of the mixed solvent of composite coating: solvent forms following mass ratio relationship, dehydrated alcohol: dimethyl second
Amide: distilled water: neopelex=35:18:50:2 is uniformly mixed.
B, ultra-fine toughening PPS resin, the PI that molecular weight is 10000 preparation of PMMA modified ptfe composite coated liquid: are selected
Resin, levelling agent 410 help film that above-mentioned in the mixed solvent is added, wherein each raw material dosage has following mass ratio relationship, PPS:
PI:PTFE&PMMA: levelling agent :=25:10:78:0.4:0.4 is added the in the mixed solvent of step a, stirs evenly, wherein institute
State mass ratio=3:11 of raw material and solvent.
(2) preparation process of PMMA modified ptfe coating:
1. the finish of sample is handled: finish processing is carried out to sample, specimen surface finish is made to reach Ra4 μm, and
It is cleaned by ultrasonic specimen surface with absolute alcohol；
2. utilizing electrostatic coating method prepares coating, step (1) solution that 2. prepared by middle b is uniformly coated into specimen surface；
120 DEG C of heat preservation 10min solidifications are warming up to 5 DEG C/min, 240 DEG C of heat preservation 30min sintering are warming up to 10 DEG C/min later, finally
It is cooled to room temperature with 20 DEG C/min cooling rate.
Claims (10)
1. a kind of preparation method of the high-antiwear self-lubricating coating of PMMA modified ptfe, which comprises the steps of:
A, PTFE nano dispersion fluid is weighed, deionized water is added, stirs to get dispersion liquid A；
B, under argon atmosphere, MMA monomer and potassium persulfate solution is added dropwise in dispersion liquid A obtained by heating stepses a；
C, polymerization reaction is carried out under argon atmosphere, is then filtered, washed, and PMMA modified PTFE powders are dried to obtain；
D, prepare solvent: the solvent contains following quality proportioning component: dehydrated alcohol: dimethyl acetamide: distilled water: 12
Sodium alkyl benzene sulfonate=35~40:15~20:48~50:2~3；
E, it prepares PMMA modified ptfe composite coated liquid: following each component, polyphenylene sulfide being added in the solvent obtained by step d
(PPS), polyimides (PI) resin, step c gained PMMA modified PTFE powders and levelling agent, wherein each component quality proportioning
For PPS:PI:PTFE&PMMA: levelling agent=20~30:5~20:75~80:0.3~0.5:0.3~0.5；
F, prepare PMMA modified ptfe coating: the solution coating surface for step e being prepared after specimen surface processing；Heating, solidification,
Sintering.
2. the method according to claim 1, wherein in PTFE nano dispersion fluid described in step a PTFE matter
Measuring score is 50~99%；Mixing speed is 200~600rmp.
3. going forward side by side the method according to claim 1, wherein the temperature of heating described in step b is 79~90 DEG C
Row stirring, speed are 300~800rmp, and the potassium persulfate solution concentration is 40~80mol/L.
4. the method according to claim 1, wherein the reaction time described in step c is 2~48h, drying temperature
It is 70~90 DEG C, drying time is 2~12h.
5. the method according to claim 1, wherein levelling agent described in step e is levelling agent 410.
6. the method according to claim 1, wherein the molecular weight 9000 of polyimides described in step e~
10000, mass ratio=2~4:10~15 of each component and solvent.
7. the method according to claim 1, wherein specimen surface is thick after the processing of specimen surface described in step f
Rugosity Ra2~10 μm.
8. the method according to claim 1, wherein being coated in step f using sol evenning machine or electrostatic coating method
Surface is warming up to 80~120 DEG C with 5~10 DEG C/min, heat preservation 5~20min solidification, 160 are warming up to 10~20 DEG C/min~
270 DEG C of 10~60min of heat preservation sintering, are finally cooled to room temperature with 5~20 DEG C/min cooling rate.
9. the method according to claim 1, wherein be warming up to 80~100 DEG C in step f with 5~8 DEG C/min,
5~10min solidification is kept the temperature, 160~240 DEG C of 15~30min of heat preservation sintering are warming up to 10~15 DEG C/min, finally with 5~8
DEG C/min cooling rate is cooled to room temperature.
10. the high-antiwear self-lubricating coating of the PMMA modified ptfe of the claims 1-9 either method preparation.
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| CN116200110A (en) * | 2023-04-27 | 2023-06-02 | 季华实验室 | Organic-inorganic modified m-benzene polyester self-lubricating composite coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN110922827A (en) * | 2019-12-13 | 2020-03-27 | 绍兴佳卓新材料科技有限公司 | Polytetrafluoroethylene composite coating for preventing scale of electric heating steam generating element and preparation method thereof |
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| CN116200110B (en) * | 2023-04-27 | 2023-08-15 | 季华实验室 | Organic-inorganic modified m-benzene polyester self-lubricating composite coating and preparation method thereof |
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Application publication date: 20181228 |