CN108164925A - A kind of oil stain self-cleaning composite material and preparation method thereof - Google Patents
A kind of oil stain self-cleaning composite material and preparation method thereof Download PDFInfo
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- CN108164925A CN108164925A CN201711297068.0A CN201711297068A CN108164925A CN 108164925 A CN108164925 A CN 108164925A CN 201711297068 A CN201711297068 A CN 201711297068A CN 108164925 A CN108164925 A CN 108164925A
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- composite material
- nano particle
- oleophylic nano
- oil stain
- sintering
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to a kind of oil stain self-cleaning composite material and preparation method thereof, the composite material based on oleophylic nano particle filling phase includes following components：Oleophylic nano particle, polymeric matrix.Compared with existing Metal Substrate and polymer matrix friction materials technology, the present invention uses oleophylic nano particle and polyether-ether-ketone, disperseed mixing according to certain method, a kind of novel oil stain automatically cleaning composite material for being capable of spontaneous oil suction is formed by cold press and sintering or hot-forming or extrusion and injection molding.The oleophylic nano particle of dispersion in the base effectively removes the media such as the lubricating oil of composite material surface, on the one hand pollution of the oil medium to friction surface is prevented, on the other hand ensure the good mechanical performance of composite material and friction and wear behavior, the composite material has good oil stain self-cleaning performance, it can be widely applied to the fields such as aviation, machinery, chemical industry, traffic, it particularly paddles in oily special operation condition environment, therefore the application prospect of the material is boundless.
Description
Technical field
The invention belongs to technical field of composite materials more particularly to a kind of oil stain self-cleaning composite material and its preparation sides
Method.
Background technology
Polyether-ether-ketone is a kind of with wear-resisting, heatproof, hydrolysis and corrosion resistant thermoplastic, polymeric materials, extensively should
For fields such as aerospace, machine-building, communications and transportation.By enhancings such as potassium titanate crystal whisker, carbon fiber, nano particles,
Mechanical property, thermal property are greatly improved.In recent years, polymer matrix friction material, which has, is more and more widely used.So
And there is the risks that adherency easily occurs in oily operating mode of paddling and causes the accident for such material.It is therefore desirable to it is various
Use, the particularly use in the case where relating to oily operating mode can be stablized under complex working condition.Surface treated oleophylic nano particle can be with
It is solid or porous structure, the relatively rich permeability substance of internal pore structure has many unique properties, therefore extensive
Used in fields such as catalysis, absorption, separation.Aluminosilicate nanoparticles can form stephanoporate framework, with excellent heat-resisting quantity
And mechanical performance.Oleophylic nano particle and polyether-ether-ketone is compound, not only can with the mechanical performance and mechanical property of reinforcing material, but also
It can be made to show oil stain self-cleaning performance.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of oil stain self-cleaning is answered
Condensation material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of oil stain self-cleaning composite material, including following component：
5~50wt% of oleophylic nano particle filling phase
50~95wt% of polymeric matrix
Oleophylic nano particle filling is mutually surface through processed solid or with micropore, mesoporous particle, described
Polymeric matrix is polyether-ether-ketone.
Further, oleophylic nano particle filling is mutually 0.1~100 μm of grain size, silica alumina ratio 20~3000, aperture
The particle of 0.55~6nm.
Further, the polymeric matrix grain size is 200~800 mesh.
A kind of preparation method of the composite material based on oleophylic nano particle, includes the following steps：
(1) it is small that the oleophylic nano particle and polyether-ether-ketone powder centainly handled surface process dries 3 at a certain temperature
When, the oleophylic centainly matched nano particle and polyether-ether-ketone powder is taken to be placed in ball grinder, adds in a certain amount of ethanol solution and mill
Ball carries out wet ball grinding mixing under certain rotating speed.
(2) mixed composite powder is dried 6 hours at a certain temperature, 100 mesh of sieving are to get required composite powder
Composite powder is added in mold and is cold-pressed by end, and simultaneously pressurize 5~60 minutes are suppressed under 10~70MPa pressure, obtain block material
Material.
(3) obtained block materials in vacuum tube furnace are sintered or are sintered in plasma vacuum sintering furnace, obtained
Composite material.
Preferably, oleophylic nano particle is added in polymeric matrix 1 ︰ 5 in mass ratio to ball mill in the step (1)
In；Drum's speed of rotation is 200~300 revs/min；Ball-milling Time 2~4 hours.
Preferably, the compacting pressure in the step (2) is 10~30MPa.
Preferably, the sintering described in the sintering in the step (3) carries out in vacuum tube furnace, sintering temperature 320
It~360 DEG C or is carried out in plasma vacuum sintering furnace, pressurize 5~10MPa, 220~280 DEG C of sintering temperature.In sintering process
Vacuumize process is carried out to sintering tube body, ensures that micropore has strong suction-operated after sintering in sintering process.
Preferably, the block materials in the step (3) are wrapped up by carbon paper, it is ensured that the electric conductivity of mold.
Preferably, " exhaling-inhale processing procedure " is carried out in pressure sintering process, to discharge the air in hole.
The present invention also provides the preparation methods of another oil stain self-cleaning composite material, include the following steps：
(1) using ball-milling method mixing oleophylic nano particle and polymeric matrix.Obtain mixture of powders；
(2) mixture of powders obtained by step (1) is placed in the mold of hot-pressed sintering furnace, carries out hot pressed sintering, hot pressing temperature
330~390 DEG C of degree, hot pressing 10~70MPa of pressure, 10~60min of dwell time obtain composite material.
The present invention provides a kind of preparation method of oil stain self-cleaning composite material again, includes the following steps：
(1) using ball-milling method mixing oleophylic nano particle and polymeric matrix.Obtain mixture of powders；
(2) mixture of powders obtained by step (1) in double screw extruder is squeezed out, then injection molding again, squeezes out temperature
360~390 DEG C of degree, 10~40MPa of extrusion pressure obtains composite material.
Above-mentioned technical proposal prepare oil stain self-cleaning composite material be applied to aerospace, mechanical industry component it is all kinds of
Bearing, gear, sound friction plate etc..
Beneficial effects of the present invention：
(1) the method for the present invention is simple for process, can be realized to different liquid using the oleophylic nano particle of different pore size and structure
The cleaning effect of body medium for specific use condition, can prepare corresponding composite material, and the spontaneous oil suction of composite material is made
With achievable targetedly automatically cleaning effect.
(2) composite material prepared by the present invention, can quickly and effectively remove the liquid medium on interface, avoid friction
Adherency between material and mating material, and then friction coefficient and wear rate are reduced, extend the service life of friction material.
(3) composite material prepared by the present invention, dispersion performance is preferable in a polymer matrix for oleophylic nano particle, plays
Good humidification, polymeric matrix binding performance is stronger, can effectively enhance the mechanical performance and heat of polymeric matrix
Learn performance.
(4) composite material prepared by the present invention has preferable mechanical property and abrasion resistance properties, suitable for low temperature, corruption
It loses, have the special operation conditions such as liquid medium pollution, can be widely applied to the fields such as aerospace, machine-building, communications and transportation, especially
It is suitable for gear, bearing, all kinds of sound friction plates of all parts etc. so that performance and service life greatly improve.
Specific embodiment
Example given below is that the present invention is specifically described, it is pointed out that following embodiment is only applicable to pair
The present invention further illustrates, it is impossible to be interpreted as limiting the scope of the invention, and the relevant ordinary person in the field, to this
Invent carry out some nonessential adjustment and improvement, include the use of it is solid or with various apertures oleophylic nano particle and
Other kinds of polymeric matrix still falls within protection scope of the present invention to prepare oil stain self-cleaning composite material.
Embodiment 1
(1) oleophylic nano particle and 7.2g polyether-ether-ketones the powder dry 3h at 120 DEG C of 0.8g surface treatments are weighed, with
It adds in ball grinder afterwards, and adds in 20ml absolute ethyl alcohols and 40g abrading-balls, wet ball grinding mixing 3h, 200 revs/min of rotating speed, is anti-
It only overheats, per ball milling 20min, stops 10min.Gained mixture dry 6h at 80 DEG C, obtains composite granule after ball milling.
(2) composite granule is added in into mold, is cold-pressed under 10MPa, and pressurize 5min, subsequent block materials are in vacuum
It is sintered in tube furnace, 340 DEG C of sintering temperature under vacuum atmosphere, sintering time 2h finally obtains composite material.
(3) self-cleaning performance of the composite material of oleophylic nano-particle reinforcement is tested using base oil PAO-6, is dripped on surface
The PAO-6 of 10 μ L carries out the spontaneous oil-absorbing process of composite material, and after placing for 24 hours at room temperature, composite material surface oil stain is reduced,
The oil on pure polyether-ether-ketone surface still remains；
(4) frictional behaviour of the composite material of oleophylic nano-particle reinforcement is evaluated using micro tribology testing machine (UMT),
It rubs in a manner that silicon nitride ball is to plane.It is used as using the silicon nitride ball of a diameter of 4mm to pair of rubbing, rub reciprocal fortune
Dynamic stroke is 3.2mm, and average slip speed is 8mm/s, fraction time 0.2h, plus load 3N.UMT frictional experiment knots
Fruit show add oleophylic nano particle after composite material stable friction factor than pure polyetheretherketonematerials materials slightly improve.
Embodiment 2
(1) 3.2g oleophylics nano particle and 4.8g polyether-ether-ketones the powder dry 3h at 120 DEG C are weighed, then adds in ball milling
In tank, and 20ml absolute ethyl alcohols and 40g abrading-balls are added in, wet ball grinding mixing 3h, 200 revs/min of rotating speed overheats, often to prevent
Ball milling 20min stops 10min.Gained mixture dry 6h at 80 DEG C, obtains composite granule after ball milling.
(2) composite granule is added in into mold, is cold-pressed under 10MPa, and pressurize 5min, subsequent block materials are in vacuum
It is sintered in tube furnace, 340 DEG C of sintering temperature under vacuum atmosphere, sintering time 2h finally obtains composite material.
(3) self-cleaning performance of the composite material of oleophylic nano-particle reinforcement is tested using base oil PAO-6, is dripped on surface
The PAO-6 of 10 μ L carries out the spontaneous oil-absorbing process of composite material, after placing 5min at room temperature, the base on composite friction material surface
Plinth oil is eliminated, and the oil on pure polyether-ether-ketone surface still remains；
(4) frictional behaviour of the composite material of oleophylic nano-particle reinforcement is evaluated using micro tribology testing machine (UMT),
It rubs in a manner that silicon nitride ball is to plane.It is used as using the silicon nitride ball of a diameter of 4mm to pair of rubbing, rub reciprocal fortune
Dynamic stroke is 3.2mm, and average slip speed is 8mm/s, fraction time 0.2h, plus load 3N.UMT frictional experiment knots
Fruit show add oleophylic nano particle after composite material friction coefficient average value and stability than pure polyetheretherketonematerials materials
It is improved.
Embodiment 3
(1) 3.2g oleophylics nano particle and 4.8g polyether-ether-ketones the powder dry 3h at 120 DEG C are weighed, then adds in ball milling
In tank, and 20ml absolute ethyl alcohols and 40g abrading-balls are added in, wet ball grinding mixing 3h, 200 revs/min of rotating speed overheats, often to prevent
Ball milling 20min stops 10min.Gained mixture dry 6h at 80 DEG C, obtains composite granule after ball milling.
(2) composite granule is added in into mold, is cold-pressed under 10MPa, and pressurize 5min, subsequent block materials are discharging
It is sintered in plasma agglomeration stove, pressurize 10Mpa, and 260 DEG C, sintering time 5min of sintering temperature under vacuum atmosphere finally obtains multiple
Condensation material.
(3) self-cleaning performance of the composite material of oleophylic nano-particle reinforcement is tested using base oil PAO-6, is dripped on surface
The PAO-6 of 10 μ L carries out the spontaneous oil-absorbing process of composite material, after placing 5min at room temperature, the base on composite friction material surface
Plinth oil is eliminated, and the oil on pure polyether-ether-ketone surface still remains；
(4) frictional behaviour of the composite material of oleophylic nano-particle reinforcement is evaluated using micro tribology testing machine (UMT),
It rubs in a manner that silicon nitride ball is to plane.It is used as using the silicon nitride ball of a diameter of 4mm to pair of rubbing, rub reciprocal fortune
Dynamic stroke is 3.2mm, and average slip speed is 8mm/s, fraction time 0.2h, plus load 3N.UMT frictional experiment knots
Fruit show add oleophylic nano particle after composite material friction coefficient average value and stability than pure polyetheretherketonematerials materials
It is improved.
Embodiment 4
(1) 3.2g oleophylics nano particle and 4.8g polyether-ether-ketones the powder dry 3h at 120 DEG C are weighed, then adds in ball milling
In tank, and 20ml absolute ethyl alcohols and 40g abrading-balls are added in, wet ball grinding mixing 3h, 200 revs/min of rotating speed overheats, often to prevent
Ball milling 20min stops 10min.Gained mixture dry 6h at 80 DEG C, obtains composite granule after ball milling.
(2) composite granule is added in into mold, is cold-pressed under 10MPa, and pressurize 5min, subsequent block materials are discharging
It is sintered in plasma agglomeration stove, pressurize 10MPa, and 260 DEG C, sintering time 5min of sintering temperature under vacuum atmosphere finally obtains multiple
Condensation material.
(3) self-cleaning performance of the composite material of oleophylic nano-particle reinforcement is tested using base oil PAO-6, is dripped on surface
The PAO-6 of 10 μ L carries out the spontaneous oil-absorbing process of composite material, after placing 5min at room temperature, the base on composite friction material surface
Plinth oil is eliminated, and the oil on pure polyether-ether-ketone surface still remains；
(4) frictional behaviour of the composite material of oleophylic nano-particle reinforcement is evaluated using micro tribology testing machine (UMT),
It is rubbed by the way of plane-plane contact.It is used as using the polyether-ether-ketone disk of a diameter of 30mm to pair of rubbing, rub reciprocal fortune
Dynamic stroke is 3.2mm, and average slip speed is 8mm/s, fraction time 0.2h, plus load 1N.To rubbing before experiment
Secondary surface drips 5 μ L base oils PAO-6, UMT frictional experiments the result shows that adding the friction system of composite material after oleophylic nano particle
Several average value is lower than pure polyetheretherketonematerials materials, and stability is higher than pure polyetheretherketonematerials materials.After experiment, composite material with to rubbing
Pair is adhered in the case where oil acts on to rubbing in pair without adherency, pure polyetheretherketonematerials materials.
Claims (10)
1. a kind of oil stain self-cleaning composite material, which is characterized in that including following components：
5~50wt% of oleophylic nano particle filling phase
50~95wt% of polymeric matrix
Oleophylic nano particle filling is mutually surface through processed solid or with micropore, mesoporous particle, the polymerization
Object matrix is polyether-ether-ketone.
2. material according to claim 1, which is characterized in that described oleophylic nano particle filling mutually for grain size 0.1~
100 μm, silica alumina ratio 20~3000, the particle of 0.55~6nm of aperture.
3. material according to claim 1, which is characterized in that the polymeric matrix grain size is 200~800 mesh.
4. a kind of preparation method of oil stain self-cleaning composite material, which is characterized in that include the following steps：
(1) using ball-milling method mixing oleophylic nano particle and polymeric matrix.Obtain mixture of powders；
(2) by mixture of powders compression moulding obtained by step (1), 5~60min of dwell time；
(3) material after compression moulding is sintered, 2~6h of sintering time obtains composite material.
5. according to the method described in claim 4, it is characterized in that, oleophylic nano particle and polymer matrix described in step (1)
Body 1 ︰ 5 in mass ratio is added in into ball mill；Drum's speed of rotation is 200~300 revs/min；Ball-milling Time 2~4 hours.
6. according to the method described in claim 4, it is characterized in that, the pressure of compression moulding described in step (2) for 10~
30MPa。
7. according to the method described in claim 4, it is characterized in that, sintering described in step (3) in vacuum tube furnace into
Row, sintering temperature are carried out for 320~360 DEG C or in plasma vacuum sintering furnace, and pressurize 5~10MPa, and sintering temperature 220~
280℃。
8. it according to the method described in claim 4, it is characterized in that, is burnt in plasma vacuum sintering furnace described in step (3)
Knot is to wrap up material with carbon paper, it is ensured that the electric conductivity of mold.
9. a kind of preparation method of oil stain self-cleaning composite material, which is characterized in that include the following steps：
(1) using ball-milling method mixing oleophylic nano particle and polymeric matrix.Obtain mixture of powders；
(2) mixture of powders obtained by step (1) is placed in the mold of hot-pressed sintering furnace, carries out hot pressed sintering, hot pressing temperature 330
~390 DEG C, hot pressing 10~70MPa of pressure, 10~60min of dwell time obtain composite material.
10. a kind of preparation method of oil stain self-cleaning composite material, which is characterized in that include the following steps：
(1) using ball-milling method mixing oleophylic nano particle and polymeric matrix.Obtain mixture of powders；
(2) mixture of powders obtained by step (1) is squeezed out in double screw extruder, then injection molding again, extrusion temperature 360
~390 DEG C, 10~40MPa of extrusion pressure obtains composite material.
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| CN201711297068.0A CN108164925A (en) | 2017-12-08 | 2017-12-08 | A kind of oil stain self-cleaning composite material and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5080970A (en) * | 1988-07-05 | 1992-01-14 | T&N Technology Limited | Poly cyano aryl ether bearing materials |
| CN101580753A (en) * | 2009-06-19 | 2009-11-18 | 大庆石油学院 | Novel polyetheretherketone self-lubricating hard wearing compound material and method for preparing same |
| CN102399413A (en) * | 2010-09-15 | 2012-04-04 | 哈尔滨鑫达高分子材料工程中心有限责任公司 | Microporous zeolite material modified PEEK and its preparation method |
| CN102504478A (en) * | 2011-11-24 | 2012-06-20 | 东北石油大学 | Porous-grade polyether-ether-ketone self-lubricating wear-resistant composite material and preparation method thereof |
| CN107011627A (en) * | 2017-06-08 | 2017-08-04 | 东莞市联洲知识产权运营管理有限公司 | A kind of high intensity polyether-ether-ketone resin composite and preparation method thereof |
-
2017
- 2017-12-08 CN CN201711297068.0A patent/CN108164925A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5080970A (en) * | 1988-07-05 | 1992-01-14 | T&N Technology Limited | Poly cyano aryl ether bearing materials |
| CN101580753A (en) * | 2009-06-19 | 2009-11-18 | 大庆石油学院 | Novel polyetheretherketone self-lubricating hard wearing compound material and method for preparing same |
| CN102399413A (en) * | 2010-09-15 | 2012-04-04 | 哈尔滨鑫达高分子材料工程中心有限责任公司 | Microporous zeolite material modified PEEK and its preparation method |
| CN102504478A (en) * | 2011-11-24 | 2012-06-20 | 东北石油大学 | Porous-grade polyether-ether-ketone self-lubricating wear-resistant composite material and preparation method thereof |
| CN107011627A (en) * | 2017-06-08 | 2017-08-04 | 东莞市联洲知识产权运营管理有限公司 | A kind of high intensity polyether-ether-ketone resin composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 温变英 等: "《高分子材料加工》", 30 June 2016, 中国轻工业出版社 * |
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Application publication date: 20180615 |