CN108864636B - A kind of nickel phosphide/fluorinated graphene-ptfe composite and its preparation method and application - Google Patents
A kind of nickel phosphide/fluorinated graphene-ptfe composite and its preparation method and application Download PDFInfo
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- CN108864636B CN108864636B CN201810897250.8A CN201810897250A CN108864636B CN 108864636 B CN108864636 B CN 108864636B CN 201810897250 A CN201810897250 A CN 201810897250A CN 108864636 B CN108864636 B CN 108864636B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
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Abstract
It include the fluorinated graphene that polyvinylpyrrolidone, the polytetrafluoroethylene (PTFE) for being grafted 4- aminostyryl and area load have nickel phosphide on composition the present invention provides a kind of nickel phosphide/fluorinated graphene-ptfe composite.The composite material has excellent anticorrosive, wear-resistant, anti-oxidant and waterproof performance and good mechanical performance；The present invention also provides the nickel phosphide/fluorinated graphene-ptfe composite preparation method, the preparation method is easy, implementation process is easily controllable, and composite material preparation cost is cheap, is applicable to produce in enormous quantities.
Description
Technical field
The present invention relates to technical field of composite materials more particularly to a kind of nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) are multiple
Condensation material and its preparation method and application.
Background technique
Polytetrafluoroethylene (PTFE) has excellent corrosion resistance, insulating properties and non-ignitable as a kind of widely used engineering plastics
Property, it is widely used in industries such as chemical industry, material, medicine, food.Meanwhile polytetrafluoroethylene (PTFE) molecule has in lower
Poly- power and adhesion strength, coefficient of friction is extremely low, has good self-lubricating property, is a kind of self-lubricating material that antifriction performance is excellent
Material, fretting wear, lubrication sealing and aerospace field in using increasingly extensive.But polytetrafluoroethylene (PTFE) molecule
Between the lesser characteristic of active force also result in that its wearability is poor, its application for being individually unable to satisfy friction duty under usual situation
It is required that.Therefore, modified or surface being filled to polytetrafluoroethylene material to be modified, enhancing its antiwear characteristic, oneself, which becomes, is promoted
The important measure of its tribological property.
Currently, domestic and foreign scholars have carried out many work, to promote the abrasion resistance of polytetrafluoroethylene (PTFE), such as Nanowire
Doping is blended in dimension, function carbon material, inorganic nano-particle, and doping, polymer blocks modification etc. is blended in polymer.Publication number
A kind of α-manganese dioxide-graphene-PTFE anti-wear Antifriction Composites are disclosed for the patent of CN105542372A
Preparation method is mainly prepared for nano-graphene first, and carries out amination processing to it, then by polytetrafluoroethylene powder
End is prepared for a nanometer α-manganese dioxide-graphene using hydrothermal synthesis technology later by being grafted acrylic acid after plasma treatment
A kind of nanometer of α-manganese dioxide-graphene-PTFE anti-wear Antifriction Composites, the material is finally made in composite material
Have many advantages, such as that coefficient of friction is small, wear rate is low, mechanical strength is big, but the made ptfe composite of the technology is wear-resisting
It is still necessary to further increase for performance.
Summary of the invention
The purpose of the present invention is to provide a kind of nickel phosphide/fluorinated graphene-ptfe composite and its preparations
Methods and applications, the composite material also have the characteristics that wear-resisting property is good while big with mechanical strength.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
It include polyethylene on composition the present invention provides a kind of nickel phosphide/fluorinated graphene-ptfe composite
Pyrrolidones, the polytetrafluoroethylene (PTFE) for being grafted 4- aminostyryl and area load have the fluorinated graphene of nickel phosphide.
Preferably, the area load has the fluorinated graphene of nickel phosphide, is grafted the polytetrafluoroethylene (PTFE) of 4- aminostyryl
Mass ratio with polyvinylpyrrolidone is (0.4~0.6): (9.34~9.56): (0.04~0.06).
The present invention also provides the nickel phosphide/fluorinated graphene-ptfe composite preparation methods, including
Following steps:
Graphite oxide powder, water and hydrofluoric acid are mixed, hydro-thermal reaction I is carried out, obtains fluorinated graphene powder；
The fluorinated graphene powder, nickel chloride, red phosphorus and water are mixed, hydro-thermal reaction II is carried out, obtains area load
There is the fluorinated graphene of nickel phosphide；
Polytetrafluorethylepowder powder is subjected to graft reaction with 4- aminostyryl after radiation treatment in dehydrated alcohol,
Obtain the polytetrafluoroethylene (PTFE) of grafting 4- aminostyryl；
The area load there are into the fluorinated graphene of nickel phosphide, the polytetrafluoroethylene (PTFE) for being grafted 4- aminostyryl, poly- second
Alkene pyrrolidone and dehydrated alcohol mixing, it is dry, obtain mixed-powder；
The mixed-powder is successively subjected to cold pressing treatment and heat treatment, obtains nickel phosphide/fluorinated graphene-polytetrafluoroethyl-ne
Alkene composite material.
Preferably, the temperature of the hydro-thermal reaction I is 170~190 DEG C, and the time of hydro-thermal reaction I is 15~20h.
Preferably, the temperature of the hydro-thermal reaction II is 170~190 DEG C, time of hydro-thermal reaction II is 18~for 24 hours.
Preferably, the temperature of the graft reaction is 60~80 DEG C, and the time of graft reaction is 5~10h.
Preferably, the pressure of the cold pressing treatment is 38~42MPa, and the time of the cold pressing treatment is 15~25min, institute
The temperature for stating cold pressing treatment is 20~40 DEG C.
Preferably, the temperature of the heat treatment is 370~380 DEG C, and the heating of the temperature of the heat treatment is risen to by room temperature
Rate is 0.8~1.5 DEG C/min, and the soaking time of the heat treatment is 90~120min.
The present invention also provides the nickel phosphide/fluorinated graphene-ptfe composite or by the preparation side
Nickel phosphide/fluorinated graphene-ptfe composite that method is prepared fretting wear field, lubrication field of sealing technology and
Application in aerospace field.
It include polyethylene on composition the present invention provides a kind of nickel phosphide/fluorinated graphene-ptfe composite
Pyrrolidones, the polytetrafluoroethylene (PTFE) for being grafted 4- aminostyryl and area load have the fluorinated graphene of nickel phosphide.In the present invention
In, fluorine atom is introduced in graphene, new C-F key is formed on graphene sheet layer, the hybrid form of carbon atom is by sp2Transformation
For sp3, the electric conductivity of lamella is greatly reduced, or even show insulation performance, the repulsion of fluorinated graphene piece interlayer is strong, easily
It is slided in lamella, improves the greasy property of composite material；Its lamellar structure improves the mechanical property of composite material；Nickel phosphide
Make composite material that there is excellent anticorrosive, wear-resistant, anti-oxidant and waterproof performance；In fluorinated graphene surface uniform load phosphorus
The reunion of nickel phosphide itself can effectively be inhibited by changing nickel particle, make anti-friction wear-resistant synergy constituent element fluorinated graphene and nickel phosphide poly-
It is uniformly dispersed in tetrafluoroethene, the wear-resisting and antifriction performance of significant increase polytetrafluoroethylene (PTFE)；4- is grafted in ptfe surface
Aminostyryl can improve its dispersion stabilization in a solvent, improve its bond properties, guarantee polytetrafluoroethylene (PTFE) and nickel phosphide/
Uniform mixing and adhesive strength of the fluorinated graphene in anhydrous ethanol solvent.
It is described the present invention also provides the nickel phosphide/fluorinated graphene-ptfe composite preparation method
Preparation method is easy, implementation process is easily controllable, and composite material preparation cost is cheap, is applicable to produce in enormous quantities.
Specific embodiment
It include polyethylene on composition the present invention provides a kind of nickel phosphide/fluorinated graphene-ptfe composite
Pyrrolidones, the polytetrafluoroethylene (PTFE) for being grafted 4- aminostyryl and area load have the fluorinated graphene of nickel phosphide.
In the present invention, the area load has the fluorinated graphene of nickel phosphide, is grafted the polytetrafluoro of 4- aminostyryl
The mass ratio of ethylene and polyvinylpyrrolidone is preferably (0.4~0.6): (9.34~9.56): (0.04~0.06), more preferably
For (0.45~0.55): (9.4~9.5): (0.045~0.055), most preferably (0.48~0.52): (9.43~9.46):
(0.048~0.052).
The present invention also provides the nickel phosphide/fluorinated graphene-ptfe composite preparation methods, including
Following steps:
Graphite oxide powder, water and hydrofluoric acid are mixed, hydro-thermal reaction I is carried out, obtains fluorinated graphene powder；
The fluorinated graphene powder, nickel chloride, red phosphorus and water are mixed, hydro-thermal reaction II is carried out, obtains area load
There is the fluorinated graphene of nickel phosphide；
Polytetrafluorethylepowder powder is carried out in dehydrated alcohol after radiation treatment with 4- aminostyryl, is grafted
Reaction obtains the polytetrafluoroethylene (PTFE) of grafting 4- aminostyryl；
The area load there are into the fluorinated graphene of nickel phosphide, the polytetrafluoroethylene (PTFE) for being grafted 4- aminostyryl, poly- second
Alkene pyrrolidone and dehydrated alcohol mixing, it is dry, obtain mixed-powder；
The mixed-powder is successively subjected to cold pressing treatment and heat treatment, obtains nickel phosphide/fluorinated graphene-polytetrafluoroethyl-ne
Alkene composite material.
In the present invention, if without specified otherwise, the component of all raw materials is well known to the skilled person commercially available
Product.
The present invention mixes the graphite oxide powder, water and hydrofluoric acid, carries out hydro-thermal reaction I, obtains fluorinated graphene
Powder.
In the present invention, the preparation method of the graphite oxide powder preferably includes following steps:
Natural flake graphite, potassium permanganate and perchloric acid are mixed, successively carry out first insert layer, at a microwave bulking
Reason, obtains an expanded graphite；
Expanded graphite, potassium permanganate and perchloric acid are mixed, secondary intercalation, secondary microwave extruding are successively carried out
Processing, obtains graphite oxide powder.
The present invention mixes natural flake graphite, potassium permanganate and perchloric acid, and it is swollen successively to carry out first insert layer, a microwave
Change processing, obtains an expanded graphite.In the present invention, the mass ratio of the natural flake graphite, potassium permanganate and perchloric acid
Preferably 1:(0.38~0.42): (9.5~10.5), more preferably 1:(0.39~0.41): (9.8~10.2).In the present invention
In, the mass concentration of the perchloric acid is preferably 65%~75%, and more preferably 68%~72%.
It is any special that the order by merging that the present invention mixes the natural flake graphite, potassium permanganate and perchloric acid does not have
It limits, any order by merging can be used and mixed；In the present invention, can be selected specifically to first will be natural for the order by merging
Crystalline flake graphite and potassium permanganate mixing after obtaining the mixture of natural scale and potassium permanganate, then perchloric acid are added described mixed
It closes in object.
In the present invention, the temperature of the first insert layer is preferably 40~50 DEG C, and more preferably 42~48 DEG C, most preferably
44~46 DEG C；The time of the first insert layer is preferably 50~60min, more preferably 52~58min, most preferably 54~
56min。
In the present invention, after the completion of the first insert layer, after the present invention preferably post-processes obtained product system
Microwave bulking processing is carried out again, and the post-processing preferably includes following steps:
The product system is separated by solid-liquid separation, obtained solid material is successively washed, is dried, is once inserted
The expansible graphite of layer processing.
In the present invention, the mode of the separation of solid and liquid preferably filters；The present invention is no any special to the filtering
Restriction, carried out using filtering well known to those skilled in the art and collect solid；Mode of the present invention to the washing
There is no any special restriction, the pH value of collected solid material is made extremely using water-washing method well known to those skilled in the art
Neutrality.
In the present invention, the drying is preferably freeze-dried；The temperature of the freeze-drying is preferably -35~-45 DEG C,
More preferably -38~-42 DEG C；The time of the freeze-drying is preferably 12~18h, more preferably 13~16h, and most preferably 14
~15h.
In the present invention, the power of the microwave bulking processing is preferably 800~1000W, more preferably 850~
950W, most preferably 880~920W；The time of the microwave bulking processing is preferably 20~25s, more preferably 21~
24s, most preferably 22~23s.
In the present invention, the average expansion rate of an expanded graphite is preferably 250mL/g.
After obtaining an expanded graphite, the present invention mixes an expanded graphite, potassium permanganate and perchloric acid, successively
Secondary intercalation, secondary microwave expanding treatment are carried out, graphite oxide powder is obtained.In the present invention, expanded graphite, a height
The mass ratio of potassium manganate and perchloric acid is preferably 1:(0.38~0.42): (9.5~10.5), more preferably 1:(0.39~
0.41): (9.8~10.2).In the present invention, the mass concentration of the perchloric acid is preferably 65%~75%, more preferably
68%~72%.
It is any special that the order by merging that the present invention mixes an expanded graphite, potassium permanganate and perchloric acid does not have
It limits, any order by merging can be used and mixed；In the present invention, can be selected specifically to now will be primary for the order by merging
Expanded graphite and potassium permanganate mixing, after obtaining the mixture of an expanded graphite and potassium permanganate, then by perchloric acid are added institute
It states in mixture.
In the present invention, the temperature of the secondary intercalation is preferably 40~50 DEG C, and more preferably 42~48 DEG C, most preferably
44~46 DEG C；The time of the secondary intercalation is preferably 50~60min, more preferably 52~58min, most preferably 54~
56min。
In the present invention, after the completion of the secondary intercalation, after the present invention preferably post-processes obtained product system
Microwave bulking processing is carried out again, and the post-processing preferably includes following steps:
The product system is separated by solid-liquid separation, obtained solid material is successively washed, is dried, secondary-plug is obtained
The expansible graphite of layer processing.
In the present invention, the mode of the separation of solid and liquid preferably filters；The present invention is no any special to the filtering
Restriction, carried out using filtering well known to those skilled in the art and collect solid；Mode of the present invention to the washing
There is no any special restriction, the pH value of collected solid material is made extremely using water-washing method well known to those skilled in the art
Neutrality.
In the present invention, the drying is preferably freeze-dried；The temperature of the freeze-drying is preferably -35~-45 DEG C,
More preferably -38~-42 DEG C；The time of the freeze-drying is preferably 12~18h, more preferably 13~16h, and most preferably 14
~15h.
In the present invention, the power of the secondary microwave expanding treatment is preferably 800~1000W, more preferably 850~
950W, most preferably 880~920W；The time of the secondary microwave expanding treatment is preferably 15~20s, more preferably 16~
19s, most preferably 17~18s.
In the present invention, the average expansion rate of the graphite oxide powder is preferably 150mL/g.
In the present invention, the mass concentration of the hydrofluoric acid is preferably 35%~45%, and more preferably 38%~42%.?
In the present invention, the water is preferably deionized water.In the present invention, the mass ratio of the graphite oxide powder, water and hydrofluoric acid
Preferably (0.04~0.06): (20~40): (3.6~4.6), more preferably (0.045~0.055): (25~35): (3.8~
4.3), most preferably (0.048~0.052): (28~32): (3.9~4.1).
In the present invention, the order by merging of the graphite oxide powder, water and hydrofluoric acid preferably includes following steps:
Graphite oxide powder and water are mixed, graphene oxide dispersion is obtained；
The graphene oxide dispersion and hydrofluoric acid are mixed.
In the present invention, the mixing of the graphene oxide and water preferably carries out under conditions of ultrasound.In the present invention,
The frequency of the ultrasound is preferably 30~50kHz, more preferably 35~45kHz, most preferably 38~42kHz；The ultrasound
Temperature is preferably 20~30 DEG C, more preferably 22~28 DEG C, most preferably 24~26 DEG C；The time of the ultrasound is preferably 30~
60min, more preferably 35~55min, most preferably 40~50min.
The mode that the present invention mixes the graphene oxide dispersion and hydrofluoric acid does not have any special restriction, uses
Hybrid mode well known to those skilled in the art is mixed.
In the present invention, the temperature of the hydro-thermal reaction I is preferably 170~190 DEG C, and more preferably 175~180 DEG C；Institute
The time for stating hydro-thermal reaction I is preferably 15~20h, more preferably 16~19h, most preferably 17~18h.
In the present invention, the reaction unit of the hydro-thermal reaction I is preferably hydrothermal reaction kettle.
In the present invention, the granularity of the fluorinated graphene powder is preferably 2~10um, and more preferably 3~8um is optimal
It is selected as 4~6um.
After the completion of hydro-thermal reaction I, the present invention preferably post-processes products therefrom system, obtains fluorinated graphene powder
End.In the present invention, the post-processing preferably includes following steps:
The product system is filtered, obtained solid material is successively washed, is dried, obtains fluorinated graphene powder
End.
The present invention carried out the no any special restriction of filtering using filtering well known to those skilled in the art
Filter, and achieve the purpose that collect solid material；The present invention is to the no any special restriction of washing, using this field
Washing known to technical staff carries out, and achievees the purpose that clean collected solid material.
In the present invention, the drying is preferably freeze-dried；In the present invention, the temperature of the freeze-drying is preferred
It is -35 DEG C~-45 DEG C, more preferably -38 DEG C~-42 DEG C.The time of the freeze-drying is preferably 12~18h, more preferably
13~16h, most preferably 14~15h.
After obtaining fluorinated graphene powder, the present invention mixes the fluorinated graphene powder, nickel chloride, red phosphorus and water,
Hydro-thermal reaction II is carried out, the fluorinated graphene that area load has nickel phosphide is obtained.In the present invention, the water is preferably deionization
Water.In the present invention, the mass ratio of the fluorinated graphene powder, nickel chloride, red phosphorus and water is preferably (0.12~0.24):
(0.8~1.2): (1.1~1.5): (35~45), more preferably (0.15~0.2): (0.9~1.1): (1.2~1.4): (36
~43), most preferably (0.16~0.18): (0.95~1.05): (1.25~1.35): (38~42).
In the present invention, the mixing of the fluorinated graphene powder, nickel chloride, red phosphorus and water, preferably includes following steps:
Nickel chloride, red phosphorus and water are mixed, mixture is obtained；
The mixture is mixed with fluorinated graphene powder.
In the present invention, the mixing of the nickel chloride, red phosphorus and water preferably carries out under stirring conditions；The present invention is to institute
The no any special restriction of stirring is stated, carries out and reach nickel chloride to be completely dissolved using stirring well known to those skilled in the art
Purpose；
In the present invention, the mixing of the mixture and fluorinated graphene powder preferably carries out under conditions of ultrasound；?
In the present invention, the frequency of the ultrasound is preferably 35~45kHz, more preferably 38~42kHz；The temperature of the ultrasound is preferably
20~30 DEG C, more preferably 22~28 DEG C, most preferably 24~26 DEG C；The time of the ultrasound is preferably 20~40min, more excellent
It is selected as 25~35min, most preferably 28~32min.
In the present invention, the temperature of the hydro-thermal reaction II is preferably 170~190 DEG C, and more preferably 175~185 DEG C, most
Preferably 178~182 DEG C；The time of the hydro-thermal reaction II is preferably 18~for 24 hours, more preferably 19~23h, most preferably 20
~22h.
In the present invention, the device of the hydro-thermal reaction II is preferably hydrothermal reaction kettle.
After the completion of hydro-thermal reaction, the present invention preferably post-processes obtained product system；The preferred packet of post-processing
Include following steps:
The product system is separated by solid-liquid separation, obtained solid material is successively washed and dried, nickel phosphide/fluorine is obtained
Graphite alkene composite material.
In the present invention, the separation of solid and liquid is preferably centrifugated；In the present invention, the revolving speed of the centrifuge separation is excellent
It is selected as 2500~3500rpm, more preferably 2800~3200rpm；The time of the centrifuge separation is preferably 8~12min, more excellent
It is selected as 9~11min.In the present invention, the purpose of the separation of solid and liquid is to collect solid product.
In the present invention, the washing reagent of the washing is preferably followed successively by dehydrated alcohol and water；In the present invention, the water
Preferably deionized water；In the present invention, the number of the washing is preferably 2~4 times；In the present invention, the mesh of the washing
Be to remove remaining red phosphorus and nickel chloride.
In the present invention, the drying is preferably freeze-dried；In the present invention, the temperature of the freeze-drying is preferred
It is -35 DEG C~-45 DEG C, more preferably -38 DEG C~-42 DEG C.The time of the freeze-drying is preferably 12~18h, more preferably
13~16h, most preferably 14~15h.
The present invention connects polytetrafluorethylepowder powder after radiation treatment with 4- aminostyryl in dehydrated alcohol
Branch reaction, obtains the polytetrafluoroethylene (PTFE) of grafting 4- aminostyryl.In the present invention, the irradiation dose of the radiation treatment is preferred
For 45~55kGy, more preferably 48~52kGy；The radiation treatment preferably uses the gamma-rays using Co-60 as radioactive source；?
In the present invention, the radiation treatment is preferably carried out under conditions of air atmosphere and room temperature.
In the present invention, the purpose of the radiation treatment is that the fracture of polytetrafluoroethylene (PTFE) chemistry key is made to generate living radical,
Graft reaction is carried out by the free radical and 4- aminostyryl that generate again, so as to improve the performances such as its hydrophily, non-stick.
In the present invention, the mass ratio of the polytetrafluorethylepowder powder, dehydrated alcohol and 4- aminostyryl is preferably (8
~10): (90~110): (90~110), more preferably (8.5~9.5): (95~105): (95~105), most preferably (8.8
~9.2): (98~102): (98~102).
In the present invention, the order by merging of the polytetrafluorethylepowder powder, dehydrated alcohol and 4- aminostyryl is preferably
By after radiation treatment polytetrafluorethylepowder powder and dehydrated alcohol mix after mixed again with 4- aminostyryl；The present invention couple
The mixed mode does not have any special restriction, is carried out using mixing well known to those skilled in the art.
In the present invention, the temperature of the graft reaction is preferably 60~80 DEG C, and more preferably 65~75 DEG C, most preferably
68~72 DEG C；The time of the graft reaction is preferably 5~10h, more preferably 6~9h, most preferably 7~8h.
In the present invention, the graft reaction preferably carries out under conditions of being passed through nitrogen；The intake of the nitrogen is excellent
It is selected as 18~22mL/min, more preferably 19~21mL/min.
In the present invention, the graft reaction preferably carries out under stirring conditions；The present invention is to the stirring without appointing
What special restriction, is carried out using condition well known to those skilled in the art.
After the completion of graft reaction, the present invention preferably post-processes obtained product system；In the present invention, after described
Processing preferably includes following steps:
The product system is centrifuged, obtained solid material is successively washed, is dried.
In the present invention, the revolving speed of the centrifugation is preferably 2500~3500rpm, more preferably 2800~3200rpm；Institute
The time for stating centrifugation is preferably 8~12min, more preferably 9~11min.
In the present invention, the washing reagent of the washing is preferably followed successively by dehydrated alcohol and water；In the present invention, the water
Preferably deionized water；In the present invention, the number of the washing is preferably 2~4 times.
In the present invention, the temperature of the drying is preferably 70 DEG C~90 DEG C, more preferably 75 DEG C~85 DEG C.The drying
Time be preferably 12~18h, more preferably 13~16h, most preferably 14~15h.
After obtaining the polytetrafluoroethylene (PTFE) of grafting 4- aminostyryl, the area load is had the fluorination of nickel phosphide by the present invention
Graphene, the polytetrafluoroethylene (PTFE) for being grafted 4- aminostyryl, polyvinylpyrrolidone and dehydrated alcohol mixing, it is dry, it is mixed
Close powder.In the present invention, the area load has the fluorinated graphene of nickel phosphide, is grafted the polytetrafluoroethyl-ne of 4- aminostyryl
The mass ratio of alkene, polyvinylpyrrolidone and dehydrated alcohol is preferably (0.4~0.6): (9.34~9.56): (0.04~
0.06): (45~55), more preferably (0.45~0.55): (0.48~0.52): (9.4~9.5): (0.045~0.055):
(49~51).
In the present invention, the area load has the fluorinated graphene of nickel phosphide, is grafted the polytetrafluoro of 4- aminostyryl
The order by merging of ethylene, polyvinylpyrrolidone and dehydrated alcohol preferably includes following steps:
There are the fluorinated graphene, polyvinylpyrrolidone and dehydrated alcohol of nickel phosphide to mix area load, is mixed
Object；
The mixture is mixed with the polytetrafluoroethylene (PTFE) of grafting 4- aminostyryl.
In the present invention, the area load has the fluorinated graphene, polyvinylpyrrolidone and dehydrated alcohol of nickel phosphide
Mixing preferably carried out under conditions of ultrasound, in the present invention, the frequency of the ultrasound is preferably 35~45kHz, more preferably
For 38~42kHz；The temperature of the ultrasound is preferably 20~30 DEG C, more preferably 22~28 DEG C, most preferably 24~26 DEG C；Institute
The time for stating ultrasound is preferably 20~40min, more preferably 25~35min, most preferably 28~32min.
In the present invention, the mixing of the polytetrafluoroethylene (PTFE) of the mixture and grafting 4- aminostyryl is preferably in stirring
Under the conditions of carry out；In the present invention, the rate of the stirring is preferably 700~900r/min, more preferably 750~850r/
Min, most preferably 780~820r/min；The time of the stirring is preferably 60~90min, more preferably 65~85min, most
Preferably 70~80min.
In the present invention, the temperature of the drying is preferably 70~90 DEG C, and more preferably 75~85 DEG C, most preferably 78~
82℃；The time of the drying is preferably 12~18h, more preferably 14~16h；In the present invention, the purpose of the drying is
In order to remove the anhydrous ethanol solvent in mixed solution.
After obtaining mixed-powder, the mixed-powder is successively carried out cold pressing treatment, heat treatment by the present invention, obtains phosphatization
Nickel/fluorinated graphene-ptfe composite.In the present invention, the pressure of the cold pressing treatment be preferably 38~
42MPa, more preferably 39~41MPa；The time of the cold pressing treatment is preferably 15~25min, more preferably 18~22min；
The temperature of the cold pressing treatment is preferably 20~40 DEG C, more preferably 25~35 DEG C, most preferably 28~32 DEG C.
In the present invention, the temperature of the heat treatment is preferably 370~380 DEG C, and more preferably 372~378 DEG C, most preferably
It is 374~376 DEG C；The time of the heat treatment is preferably 90~120min, more preferably 95~115min, and most preferably 100
~110min.
In the present invention, the heating rate of the heat treatment is preferably 0.8~1.5 DEG C/min, more preferably 1~1.2 DEG C/
min。
After the completion of heat treatment, after the preferred first rate of temperature fall with 0.5~1.2 DEG C/min of the present invention is down to 140~160 DEG C,
Cooled to room temperature again；After being more preferably down to 145~155 DEG C with the rate of temperature fall of 0.8~1 DEG C/min, then naturally cool to
Room temperature.
In the present invention, first cooled down with above-mentioned rate of temperature fall, the purpose of rear Temperature fall is to avoid Muffle furnace by 370
It DEG C is naturally cooling at about 150 DEG C that rate of temperature fall is fast, is easy to cause sample internal and external temperature different and is deformed.
The present invention also provides the nickel phosphide/fluorinated graphene-ptfe composite or above-mentioned preparation methods
Nickel phosphide/fluorinated graphene-the ptfe composite being prepared is in fretting wear field, lubrication field of sealing technology and boat
Application in empty space industry.
Below with reference to embodiment to nickel phosphate/fluorinated graphene-ptfe composite provided by the invention and its
Preparation method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) prepared by fluorinated graphene powder
1g natural flake graphite, 0.38g potassium permanganate are placed in a beaker, 9.5g perchloric acid is then added to beaker again
In；First insert layer reaction, reaction time 50min are carried out under conditions of 40 DEG C；First insert layer after reaction, is filtered and is received
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of condition
Under, it is freeze-dried 15h, obtains the expansible graphite of first insert layer processing；
The expansible graphite that 4g first insert layer is handled carries out microwave bulking under conditions of power is 900W and handles 20s,
Obtain the expanded graphite that average expansion ratio is 250mL/g；
By expanded graphite of 1g, 0.38g potassium permanganate is placed in a beaker, and 9.5g perchloric acid is then added to beaker again
In, secondary intercalation reaction, reaction time 50min are carried out under conditions of 40 DEG C；Secondary intercalation after reaction, is filtered and is received
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of condition
Under, it is freeze-dried 15h, obtains the expansible graphite of secondary intercalation processing；
The expansible graphite that 3g secondary intercalation is handled carries out microwave bulking under conditions of power is 900W and handles 15s,
Obtain the graphite oxide powder that average expansion ratio is 150mL/g；
50mg graphite oxide powder is mixed under conditions of ultrasound with 30mL deionized water, supersonic frequency 40kHz, is surpassed
Sound temperature is 20 DEG C, ultrasonic time is 30min to get graphene oxide ultrasonic disperse liquid；Later by graphene oxide and 3.6g
The hydrofluoric acid that mass concentration is 40% is mixed and added in reaction kettle, reacts 15h under the conditions of 180 DEG C；Naturally cool to room
Temperature is collected by filtration solid, and is cleaned collected solid with deionized water；It finally is freeze-dried 15h under the conditions of -40 DEG C,
Up to fluorinated graphene powder；
(2) area load has the preparation of the fluorinated graphene powder of nickel phosphide
2.5g nickel chloride, 3.26g red phosphorus and 40mL deionized water are added in beaker, stirred complete to nickel chloride solid
After dissolution, the fluorinated graphene powder of 0.3g is added in mixed solution, in the condition that frequency is 40kHz, temperature is 20 DEG C
Lower ultrasound 20min；Then under conditions of 180 DEG C, hydro-thermal reaction 18h；Cooled to room temperature；Solid is collected in centrifuge separation
Grain, centrifuge speed 3000rpm, centrifugation time 10min, and respectively with dehydrated alcohol and deionized water to solid particle from
The heart washs 3 times to remove remaining red phosphorus and nickel chloride；The solid particle being collected by centrifugation is washed with dehydrated alcohol and deionized water
Afterwards, 15h is freeze-dried under conditions of -40 DEG C, with agate mortar grinding solid particle to get to average after freeze-drying process
The area load that partial size is 5 μm has the fluorinated graphene powder of nickel phosphide；
(3) modification of the radiation grafting 4- aminostyryl of polytetrafluorethylepowder powder
In air atmosphere, under room temperature, 8g polytetrafluorethylepowder powder is placed in using Co-60 as the gamma-rays in radioactive source
Gamma-ray irradiation processing, irradiation dose 50kGy are carried out to powder in irradiation reaction device；By the polytetrafluoroethyl-ne after 8g radiation treatment
Alkene powder is mixed with 100mL anhydrous ethanol solvent, and stirring makes polytetrafluorethylepowder powder even suspension in dehydrated alcohol；Exist later
It is passed through under conditions of nitrogen amount is 20mL/min, 100g 4- aminostyryl is added to polytetrafluoroethylene (PTFE) and dehydrated alcohol
In mixed liquor, 5h is reacted under conditions of stirring, 60 DEG C；Centrifuge separation collection solid particle, centrifuge speed 3000rpm,
Centrifugation time is 10min, and respectively with dehydrated alcohol and deionized water to solid particle centrifuge washing 3 times to remove remaining 4-
Aminostyryl；Finally the solid particle after centrifuge washing is placed in convection oven, at 80 DEG C be dried 15h to get
To the polytetrafluorethylepowder powder of grafting 4- aminostyryl；
(4) nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material preparation
0.4g nickel phosphide/fluorinated graphene powder, 0.04g polyvinylpyrrolidone are added to 50g anhydrous ethanol solvent
In, it is 40kHz, the condition ultrasound 20min that temperature is 20 DEG C with frequency；Again by the poly- of 9.56g 4- aminostyryl grafting processing
Tetrafluoroethene powder is added in mixed solution, mixing time 60min under conditions of 800r/min, and it is molten that mixing is prepared
Liquid；Mixed solution is dried into 15h under the conditions of 80 DEG C, obtains mixed-powder；
The mixed-powder is poured into cold forming mold, powder is cold-pressed with the pressure of 40MPa at room temperature
15min；Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is made；Resulting phosphatization will be cold-pressed
Nickel/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is in Muffle furnace with the heating rate liter of 1.2 DEG C/min
Temperature is to 375 DEG C, heat preservation heat treatment 90min；Muffle furnace hearth temperature is dropped with the cooling rate of 1 DEG C/min from 375 DEG C again later
Closing power supply to 150 DEG C, when muffle furnace hearths temperature being waited to be down to 150 DEG C makes its cooled to room temperature, obtains nickel phosphide/fluorination
Graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material.
Using pure polytetrafluoroethylene material as control sample, to the nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) composite wood
Material has carried out tribological property experimental evaluation；Frictional experiment condition are as follows: friction type is the contact of ball disk, linear reciprocating friction mill
Damage, testing machine model CETR UMT-3, rub the secondary GCr15 steel ball for selecting diameter as 9.525mm, and experiment load is 25N, sliding
Dynamic speed is 0.08m/s, sliding distance 500m.Experimental result is as follows: the coefficient of friction of pure polytetrafluoroethylene material is
0.1951, nickel phosphide/fluorinated graphene-ptfe composite coefficient of friction is 0.1867, is lower than pure polytetrafluoroethyl-ne
The coefficient of friction of alkene material；In addition, the wear rate of pure polytetrafluoroethylene material is 6.37 × 10-13m3/ Nm, and nickel phosphide/fluorination
Graphene-ptfe composite wear rate is 2.65 × 10-15m3/ Nm, than the wear rate of pure polytetrafluoroethylene material
Reduce 240 times.It therefore deduces that, nickel phosphide/fluorinated graphene-ptfe composite has excellent antifriction resistance to
Grind performance.
Nickel phosphide/fluorinated graphene-ptfe composite tensile strength be 31.6MPa, purer poly- four
The 26.6MPa of the tensile strength of vinyl fluoride improves 18.8%；Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) the composite wood
The shore hardness of material is 64HD, and the 55HD of the tensile strength of purer polytetrafluoroethylene (PTFE) improves 16.4%.
Embodiment 2
(1) prepared by fluorinated graphene powder
1g natural flake graphite, 0.39g potassium permanganate are placed in a beaker, 9.75g perchloric acid is then added to burning again
In cup；First insert layer reaction, reaction time 55min are carried out under conditions of 45 DEG C；After reaction, filtering is simultaneously for first insert layer
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of item
Under part, it is freeze-dried 15h, obtains the expansible graphite of first insert layer processing；
The expansible graphite that 4.8g first insert layer is handled carries out microwave bulking processing under conditions of power is 900W
23s obtains the expanded graphite that average expansion ratio is 250mL/g；
By expanded graphite of 1g, 0.39g potassium permanganate is placed in a beaker, and 9.75g perchloric acid is then added to burning again
In cup, secondary intercalation reaction, reaction time 55min are carried out under conditions of 45 DEG C；After reaction, filtering is simultaneously for secondary intercalation
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of item
Under part, it is freeze-dried 15h, obtains the expansible graphite of secondary intercalation processing；
The expansible graphite that 3.8g secondary intercalation is handled carries out microwave bulking processing under conditions of power is 900W
18s obtains the graphite oxide powder that average expansion ratio is 150mL/g；
50mg graphite oxide powder is mixed under conditions of ultrasound with 30mL deionized water, supersonic frequency 40kHz, is surpassed
Sound temperature is 25 DEG C, ultrasonic time is 40min to get graphene oxide ultrasonic disperse liquid；Later by graphene oxide and 3.8g
The hydrofluoric acid that mass concentration is 40% is mixed and added in reaction kettle, reacts 18h under the conditions of 180 DEG C；Naturally cool to room
Temperature is collected by filtration solid, and is cleaned collected solid with deionized water；It finally is freeze-dried 15h under the conditions of -40 DEG C,
Up to fluorinated graphene powder；
(2) area load has the preparation of the fluorinated graphene powder of nickel phosphide
2.5g nickel chloride, 3.26g red phosphorus and 40mL deionized water are added in beaker, stirred complete to nickel chloride solid
After dissolution, the fluorinated graphene powder of 0.4g is added in mixed solution, in the condition that frequency is 40kHz, temperature is 25 DEG C
Lower ultrasound 30min；Then under conditions of 180 DEG C, hydro-thermal reaction 20h；Cooled to room temperature；Solid is collected in centrifuge separation
Grain, centrifuge speed 3000rpm, centrifugation time 10min, and respectively with dehydrated alcohol and deionized water to solid particle from
The heart washs 3 times to remove remaining red phosphorus and nickel chloride；The solid particle being collected by centrifugation is washed with dehydrated alcohol and deionized water
Afterwards, 15h is freeze-dried under conditions of -40 DEG C, with agate mortar grinding solid particle to get to average after freeze-drying process
The area load that partial size is 5 μm has the fluorinated graphene powder of nickel phosphide；
(3) modification of the radiation grafting 4- aminostyryl of polytetrafluorethylepowder powder
In air atmosphere, at room temperature under the conditions of, 8.8g polytetrafluorethylepowder powder is placed in using Co-60 as the γ in radioactive source
Gamma-ray irradiation processing, irradiation dose 50kGy are carried out to powder in x ray irradiation x reactor；It will be poly- after 8.8g radiation treatment
Tetrafluoroethene powder is mixed with 100mL anhydrous ethanol solvent, and stirring makes polytetrafluorethylepowder powder even suspension in dehydrated alcohol；
Later under conditions of being passed through nitrogen amount is 20mL/min, 100g4- aminostyryl is added to polytetrafluoroethylene (PTFE) and anhydrous second
In the mixed liquor of alcohol, 7h is reacted under conditions of stirring, 70 DEG C；Solid particle is collected in centrifuge separation, and centrifuge speed is
3000rpm, centrifugation time 10min, and use dehydrated alcohol and deionized water to solid particle centrifuge washing 3 times to remove respectively
Remaining 4- aminostyryl；Finally the solid particle after centrifuge washing is placed in convection oven, is dried at 80 DEG C
15h is to get the polytetrafluorethylepowder powder for arriving grafting 4- aminostyryl；
(4) nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material preparation
By 0.48g nickel phosphide/fluorinated graphene powder, that 0.048g polyvinylpyrrolidone is added to 50g dehydrated alcohol is molten
It is 40kHz, the condition ultrasound 30min that temperature is 25 DEG C with frequency in agent；9.472g 4- aminostyryl grafting is handled again
Polytetrafluorethylepowder powder be added in mixed solution, mixing is prepared in mixing time 75min under conditions of 800r/min
Solution；Mixed solution is dried into 15h under the conditions of 80 DEG C, obtains nickel phosphide/fluorinated graphene-ptfe composite system
Standby mixed-powder used；
Mixed-powder is poured into cold forming mold, 18min is cold-pressed to powder with the pressure of 40MPa at room temperature；
Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is made；Resulting nickel phosphide/fluorination will be cold-pressed
Graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is warming up to 375 in Muffle furnace with the heating rate of 1.1 DEG C/min
DEG C, heat preservation heat treatment 110min；Muffle furnace hearth temperature is down to 150 from 375 DEG C with the cooling rate of 0.9 DEG C/min again later
DEG C, power supply is closed when muffle furnace hearths temperature being waited to be down to 150 DEG C makes its cooled to room temperature, obtains nickel phosphide/fluorographite
Alkene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material.
Using pure polytetrafluoroethylene material as control sample, to the nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) composite wood
Material has carried out tribological property experimental evaluation；Frictional experiment condition are as follows: friction type is the contact of ball disk, linear reciprocating friction mill
Damage, testing machine model CETRUMT-3, rub the secondary GCr15 steel ball for selecting diameter as 9.525mm, and experiment load is 25N, sliding
Dynamic speed is 0.08m/s, sliding distance 500m.Experimental result is as follows: the coefficient of friction of pure polytetrafluoroethylene material is
0.1951, nickel phosphide/fluorinated graphene-ptfe composite coefficient of friction is 0.1862, is lower than pure polytetrafluoroethyl-ne
The coefficient of friction of alkene material；In addition, the wear rate of pure polytetrafluoroethylene material is 6.37 × 10-13m3/ Nm, and nickel phosphide/fluorination
Graphene-ptfe composite wear rate is 1.68 × 10-15m3/ Nm, than the wear rate of pure polytetrafluoroethylene material
Reduce 379 times.It therefore deduces that, nickel phosphide/fluorinated graphene-ptfe composite has excellent antifriction resistance to
Grind performance.
Nickel phosphide/fluorinated graphene-ptfe composite tensile strength be 32.8MPa, purer poly- four
The 26.6MPa of the tensile strength of vinyl fluoride improves 23.3%；Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) the composite wood
The shore hardness of material is 66HD, and the 55HD of the tensile strength of purer polytetrafluoroethylene (PTFE) improves 20%.
Embodiment 3
(1) prepared by fluorinated graphene powder
1g natural flake graphite, 0.4g potassium permanganate are placed in a beaker, 10g perchloric acid is then added to beaker again
In；First insert layer reaction, reaction time 60min are carried out under conditions of 48 DEG C；First insert layer after reaction, is filtered and is received
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of condition
Under, it is freeze-dried 15h, obtains the expansible graphite of first insert layer processing；
The expansible graphite that 5.5g first insert layer is handled carries out microwave bulking processing under conditions of power is 900W
25s obtains the expanded graphite that average expansion ratio is 250mL/g；
By expanded graphite of 1g, 0.4g potassium permanganate is placed in a beaker, and 10g perchloric acid is then added to beaker again
In, secondary intercalation reaction, reaction time 60min are carried out under conditions of 48 DEG C；Secondary intercalation after reaction, is filtered and is received
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of condition
Under, it is freeze-dried 15h, obtains the expansible graphite of secondary intercalation processing；
The expansible graphite that 4.5g secondary intercalation is handled carries out microwave bulking processing under conditions of power is 900W
20s obtains the graphite oxide powder that average expansion ratio is 150mL/g；
50mg graphite oxide powder is mixed under conditions of ultrasound with 30mL deionized water, supersonic frequency 40kHz, is surpassed
Sound temperature is 28 DEG C, ultrasonic time is 50min to get graphene oxide ultrasonic disperse liquid；Later by graphene oxide and 4.2g
The hydrofluoric acid that mass concentration is 40% is mixed and added in reaction kettle, reacts 20h under the conditions of 180 DEG C；Naturally cool to room
Temperature is collected by filtration solid, and is cleaned collected solid with deionized water；It finally is freeze-dried 15h under the conditions of -40 DEG C,
Up to fluorinated graphene powder；
(2) area load has the preparation of the fluorinated graphene powder of nickel phosphide
2.5g nickel chloride, 3.26g red phosphorus and 40mL deionized water are added in beaker, stirred complete to nickel chloride solid
After dissolution, the fluorinated graphene powder of 0.4g is added in mixed solution, in the condition that frequency is 40kHz, temperature is 28 DEG C
Lower ultrasound 30min；Then under conditions of 180 DEG C, hydro-thermal reaction 22h；Cooled to room temperature；Solid is collected in centrifuge separation
Grain, centrifuge speed 3000rpm, centrifugation time 10min, and respectively with dehydrated alcohol and deionized water to solid particle from
The heart washs 3 times to remove remaining red phosphorus and nickel chloride；The solid particle being collected by centrifugation is washed with dehydrated alcohol and deionized water
Afterwards, 15h is freeze-dried under conditions of -40 DEG C, with agate mortar grinding solid particle to get to average after freeze-drying process
The area load that partial size is 5 μm has the fluorinated graphene powder of nickel phosphide；
(3) modification of the radiation grafting 4- aminostyryl of polytetrafluorethylepowder powder
In air atmosphere, at room temperature under the conditions of, 9.5g polytetrafluorethylepowder powder is placed in using Co-60 as the γ in radioactive source
Gamma-ray irradiation processing, irradiation dose 50kGy are carried out to powder in x ray irradiation x reactor；It will be poly- after 9.5g radiation treatment
Tetrafluoroethene powder is mixed with 100mL anhydrous ethanol solvent, and stirring makes polytetrafluorethylepowder powder even suspension in dehydrated alcohol；
Later under conditions of being passed through nitrogen amount is 20mL/min, 100g4- aminostyryl is added to polytetrafluoroethylene (PTFE) and anhydrous second
In the mixed liquor of alcohol, 9h is reacted under conditions of stirring, 75 DEG C；Solid particle is collected in centrifuge separation, and centrifuge speed is
3000rpm, centrifugation time 10min, and use dehydrated alcohol and deionized water to solid particle centrifuge washing 3 times to remove respectively
Remaining 4- aminostyryl；Finally the solid particle after centrifuge washing is placed in convection oven, is dried at 80 DEG C
15h is to get the polytetrafluorethylepowder powder for arriving grafting 4- aminostyryl；
(4) nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material preparation
By 0.55g nickel phosphide/fluorinated graphene powder, that 0.055g polyvinylpyrrolidone is added to 50g dehydrated alcohol is molten
It is 40kHz, the condition ultrasound 30min that temperature is 28 DEG C with frequency in agent；9.395g 4- aminostyryl grafting is handled again
Polytetrafluorethylepowder powder be added in mixed solution, mixing is prepared in mixing time 90min under conditions of 800r/min
Solution；Mixed solution is dried into 15h under the conditions of 80 DEG C, obtains nickel phosphide/fluorinated graphene-ptfe composite system
Standby mixed-powder used；
Mixed-powder is poured into cold forming mold, 20min is cold-pressed to powder with the pressure of 40MPa at room temperature；
Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is made；Resulting nickel phosphide/fluorination will be cold-pressed
Graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is warming up to 375 in Muffle furnace with the heating rate of 1 DEG C/min
DEG C, heat preservation heat treatment 110min；Muffle furnace hearth temperature is down to 150 from 375 DEG C with the cooling rate of 0.8 DEG C/min again later
DEG C, power supply is closed when muffle furnace hearths temperature being waited to be down to 150 DEG C makes its cooled to room temperature, obtains nickel phosphide/fluorographite
Alkene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material.
Using pure polytetrafluoroethylene material as control sample, to the nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) composite wood
Material has carried out tribological property experimental evaluation；Frictional experiment condition are as follows: friction type is the contact of ball disk, linear reciprocating friction mill
Damage, testing machine model CETRUMT-3, rub the secondary GCr15 steel ball for selecting diameter as 9.525mm, and experiment load is 25N, sliding
Dynamic speed is 0.08m/s, sliding distance 500m.Experimental result is as follows: the coefficient of friction of pure polytetrafluoroethylene material is
0.1951, nickel phosphide/fluorinated graphene-ptfe composite coefficient of friction is 0.1886, is lower than pure polytetrafluoroethyl-ne
The coefficient of friction of alkene material；In addition, the wear rate of pure polytetrafluoroethylene material is 6.37 × 10-13m3/ Nm, and nickel phosphide/fluorination
Graphene-ptfe composite wear rate is 1.49 × 10-15m3/ Nm, than the wear rate of pure polytetrafluoroethylene material
Reduce 428 times.It therefore deduces that, nickel phosphide/fluorinated graphene-ptfe composite has excellent antifriction resistance to
Grind performance.
Nickel phosphide/fluorinated graphene-ptfe composite tensile strength be 33.1MPa, purer poly- four
The 26.6MPa of the tensile strength of vinyl fluoride improves 24.4%；Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) the composite wood
The shore hardness of material is 68HD, and the 55HD of the tensile strength of purer polytetrafluoroethylene (PTFE) improves 23.6%.
Embodiment 4
(1) prepared by fluorinated graphene powder
1g natural flake graphite, 0.42g potassium permanganate are placed in a beaker, 10.5g perchloric acid is then added to burning again
In cup；First insert layer reaction, reaction time 60min are carried out under conditions of 50 DEG C；After reaction, filtering is simultaneously for first insert layer
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of item
Under part, it is freeze-dried 15h, obtains the expansible graphite of first insert layer processing；
The expansible graphite that 6g first insert layer is handled carries out microwave bulking under conditions of power is 900W and handles 25s,
Obtain the expanded graphite that average expansion ratio is 250mL/g；
By expanded graphite of 1g, 0.42g potassium permanganate is placed in a beaker, and 10.5g perchloric acid is then added to burning again
In cup, secondary intercalation reaction, reaction time 60min are carried out under conditions of 50 DEG C；After reaction, filtering is simultaneously for secondary intercalation
The solid for collecting retention repeatedly washs collected solid with deionized water until the pH of washing water is neutral；In -40 DEG C of item
Under part, it is freeze-dried 15h, obtains the expansible graphite of secondary intercalation processing；
The expansible graphite that 5g secondary intercalation is handled carries out microwave bulking under conditions of power is 900W and handles 20s,
Obtain the graphite oxide powder that average expansion ratio is 150mL/g；
50mg graphite oxide powder is mixed under conditions of ultrasound with 30mL deionized water, supersonic frequency 40kHz, is surpassed
Sound temperature is 30 DEG C, ultrasonic time is 60min to get graphene oxide ultrasonic disperse liquid；Later by graphene oxide and 4.6g
The hydrofluoric acid that mass concentration is 40% is mixed and added in reaction kettle, reacts 20h under the conditions of 180 DEG C；Naturally cool to room
Temperature is collected by filtration solid, and is cleaned collected solid with deionized water；It finally is freeze-dried 15h under the conditions of -40 DEG C,
Up to fluorinated graphene powder；
(2) area load has the preparation of the fluorinated graphene powder of nickel phosphide
2.5g nickel chloride, 3.26g red phosphorus and 40mL deionized water are added in beaker, stirred complete to nickel chloride solid
After dissolution, the fluorinated graphene powder of 0.4g is added in mixed solution, in the condition that frequency is 40kHz, temperature is 30 DEG C
Lower ultrasound 40min；Then under conditions of 180 DEG C, hydro-thermal reaction is for 24 hours；Cooled to room temperature；Solid is collected in centrifuge separation
Grain, centrifuge speed 3000rpm, centrifugation time 10min, and respectively with dehydrated alcohol and deionized water to solid particle from
The heart washs 3 times to remove remaining red phosphorus and nickel chloride；The solid particle being collected by centrifugation is washed with dehydrated alcohol and deionized water
Afterwards, 15h is freeze-dried under conditions of -40 DEG C, with agate mortar grinding solid particle to get to average after freeze-drying process
The area load that partial size is 5 μm has the fluorinated graphene powder of nickel phosphide；
(3) modification of the radiation grafting 4- aminostyryl of polytetrafluorethylepowder powder
In air atmosphere, at room temperature under the conditions of, 10g polytetrafluorethylepowder powder is placed in using Co-60 as the γ in radioactive source
Gamma-ray irradiation processing, irradiation dose 50kGy are carried out to powder in x ray irradiation x reactor；It will be poly- after 10g radiation treatment
Tetrafluoroethene powder is mixed with 100mL anhydrous ethanol solvent, and stirring makes polytetrafluorethylepowder powder even suspension in dehydrated alcohol；
Later under conditions of being passed through nitrogen amount is 20mL/min, 100g 4- aminostyryl is added to polytetrafluoroethylene (PTFE) and anhydrous
In the mixed liquor of ethyl alcohol, 10h is reacted under conditions of stirring, 80 DEG C；Solid particle is collected in centrifuge separation, and centrifuge speed is
3000rpm, centrifugation time 10min, and use dehydrated alcohol and deionized water to solid particle centrifuge washing 3 times to remove respectively
Remaining 4- aminostyryl；Finally the solid particle after centrifuge washing is placed in convection oven, is dried at 80 DEG C
15h is to get the polytetrafluorethylepowder powder for arriving grafting 4- aminostyryl；
(4) nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material preparation
0.6g nickel phosphide/fluorinated graphene powder, 0.06g polyvinylpyrrolidone are added to 50g anhydrous ethanol solvent
In, it is 40kHz, the condition ultrasound 40min that temperature is 30 DEG C with frequency；Again by the poly- of 9.34g4- aminostyryl grafting processing
Tetrafluoroethene powder is added in mixed solution, mixing time 90min under conditions of 800r/min, and it is molten that mixing is prepared
Liquid；Mixed solution is dried into 15h under the conditions of 80 DEG C, obtains nickel phosphide/fluorinated graphene-ptfe composite preparation
Mixed-powder used；
Mixed-powder is poured into cold forming mold, 23min is cold-pressed to powder with the pressure of 40MPa at room temperature；
Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is made；Resulting nickel phosphide/fluorination will be cold-pressed
Graphene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material thin slice is warming up to 375 in Muffle furnace with the heating rate of 1 DEG C/min
DEG C, heat preservation heat treatment 110min；Muffle furnace hearth temperature is down to 150 from 375 DEG C with the cooling rate of 1 DEG C/min again later
DEG C, power supply is closed when muffle furnace hearths temperature being waited to be down to 150 DEG C makes its cooled to room temperature, obtains nickel phosphide/fluorographite
Alkene-polytetrafluoroethylene (PTFE) anti-friction wear-resistant composite material.
Using pure polytetrafluoroethylene material as control sample, to the nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) composite wood
Material has carried out tribological property experimental evaluation；Frictional experiment condition are as follows: friction type is the contact of ball disk, linear reciprocating friction mill
Damage, testing machine model CETRUMT-3, rub the secondary GCr15 steel ball for selecting diameter as 9.525mm, and experiment load is 25N, sliding
Dynamic speed is 0.08m/s, sliding distance 500m.Experimental result is as follows: the coefficient of friction of pure polytetrafluoroethylene material is
0.1951, nickel phosphide/fluorinated graphene-ptfe composite coefficient of friction is 0.1890, is lower than pure polytetrafluoroethyl-ne
The coefficient of friction of alkene material；In addition, the wear rate of pure polytetrafluoroethylene material is 6.37 × 10-13m3/ Nm, and nickel phosphide/fluorination
Graphene-ptfe composite wear rate is 1.52 × 10-15m3/ Nm, than the wear rate of pure polytetrafluoroethylene material
Reduce 419 times.It therefore deduces that, nickel phosphide/fluorinated graphene-ptfe composite has excellent antifriction resistance to
Grind performance.
Nickel phosphide/fluorinated graphene-ptfe composite tensile strength be 33.0MPa, purer poly- four
The 26.6MPa of the tensile strength of vinyl fluoride improves 24.1%；Nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) the composite wood
The shore hardness of material is 69HD, and the 55HD of the tensile strength of purer polytetrafluoroethylene (PTFE) improves 25.5%.
As seen from the above embodiment, the present invention preparation nickel phosphide/fluorinated graphene-ptfe composite
With good mechanical performance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
- It include polyvinylpyrrolidone, grafting on composition 1. a kind of nickel phosphide/fluorinated graphene-ptfe composite The polytetrafluoroethylene (PTFE) and area load of 4- aminostyryl have the fluorinated graphene of nickel phosphide；The nickel phosphide/fluorinated graphene-ptfe composite preparation method, comprising the following steps:Graphite oxide powder, water and hydrofluoric acid are mixed, hydro-thermal reaction I is carried out, obtains fluorinated graphene powder；The fluorinated graphene powder, nickel chloride, red phosphorus and water are mixed, carry out hydro-thermal reaction II, obtaining area load has phosphorus Change the fluorinated graphene of nickel；Polytetrafluorethylepowder powder is subjected to graft reaction with 4- aminostyryl after radiation treatment in dehydrated alcohol, is obtained It is grafted the polytetrafluoroethylene (PTFE) of 4- aminostyryl；The area load there is into the fluorinated graphene of nickel phosphide, is grafted polytetrafluoroethylene (PTFE), the polyethylene pyrrole of 4- aminostyryl Pyrrolidone and dehydrated alcohol mixing, it is dry, obtain mixed-powder；The mixed-powder is successively subjected to cold pressing treatment and heat treatment, it is multiple to obtain nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) Condensation material.
- 2. nickel phosphide/fluorinated graphene-ptfe composite as described in claim 1, which is characterized in that the table Face load has the fluorinated graphene of nickel phosphide, is grafted the polytetrafluoroethylene (PTFE) of 4- aminostyryl and the quality of polyvinylpyrrolidone Than for (0.4~0.6): (9.34~9.56): (0.04~0.06).
- 3. the described in any item nickel phosphides of claim 1~2/fluorinated graphene-ptfe composite preparation method, The following steps are included:Graphite oxide powder, water and hydrofluoric acid are mixed, hydro-thermal reaction I is carried out, obtains fluorinated graphene powder；The fluorinated graphene powder, nickel chloride, red phosphorus and water are mixed, carry out hydro-thermal reaction II, obtaining area load has phosphorus Change the fluorinated graphene of nickel；Polytetrafluorethylepowder powder is subjected to graft reaction with 4- aminostyryl after radiation treatment in dehydrated alcohol, is obtained It is grafted the polytetrafluoroethylene (PTFE) of 4- aminostyryl；The area load there is into the fluorinated graphene of nickel phosphide, is grafted polytetrafluoroethylene (PTFE), the polyethylene pyrrole of 4- aminostyryl Pyrrolidone and dehydrated alcohol mixing, it is dry, obtain mixed-powder；The mixed-powder is successively subjected to cold pressing treatment and heat treatment, it is multiple to obtain nickel phosphide/fluorinated graphene-polytetrafluoroethylene (PTFE) Condensation material.
- 4. preparation method as claimed in claim 3, which is characterized in that the temperature of the hydro-thermal reaction I is 170~190 DEG C, water The time of thermal response I is 15~20h.
- 5. preparation method as claimed in claim 3, which is characterized in that the temperature of the hydro-thermal reaction II is 170~190 DEG C, The time of hydro-thermal reaction II be 18~for 24 hours.
- 6. preparation method as claimed in claim 3, which is characterized in that the temperature of the graft reaction is 60~80 DEG C, grafting The time of reaction is 5~10h.
- 7. preparation method as claimed in claim 3, which is characterized in that the pressure of the cold pressing treatment is 38~42MPa, described The time of cold pressing treatment is 15~25min, and the temperature of the cold pressing treatment is 20~40 DEG C.
- 8. the preparation method as described in claim 3 or 7, which is characterized in that the temperature of the heat treatment is 370~380 DEG C, by The heating rate that room temperature rises to the temperature of the heat treatment is 0.8~1.5 DEG C/min, the soaking time of the heat treatment is 90~ 120min。
- 9. the described in any item nickel phosphide/fluorinated graphene-ptfe composites of claim 1~2 or claim 3 Nickel phosphide/fluorinated graphene-ptfe composite that~8 described in any item preparation methods are prepared is ground in friction Application in damage field, lubrication field of sealing technology and aerospace field.
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| CN104772156A (en) * | 2015-03-23 | 2015-07-15 | 陕西科技大学 | Preparation method for graphene loaded cobalt nickel phosphide composite material |
| CN104810165A (en) * | 2015-04-29 | 2015-07-29 | 华东理工大学 | Nickel phosphide / graphene composite film preparing method |
| CN105694309A (en) * | 2016-01-27 | 2016-06-22 | 燕山大学 | Preparation method of nano beta-manganese dioxide-graphite oxide-polytetrafluoroethylene wear-resistant anti-friction composite material |
| CN107043508A (en) * | 2017-06-05 | 2017-08-15 | 巨轮智能装备股份有限公司 | A kind of preparation method of nitrogen-doped graphene/ptfe composite |
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| CN104772156A (en) * | 2015-03-23 | 2015-07-15 | 陕西科技大学 | Preparation method for graphene loaded cobalt nickel phosphide composite material |
| CN104810165A (en) * | 2015-04-29 | 2015-07-29 | 华东理工大学 | Nickel phosphide / graphene composite film preparing method |
| CN105694309A (en) * | 2016-01-27 | 2016-06-22 | 燕山大学 | Preparation method of nano beta-manganese dioxide-graphite oxide-polytetrafluoroethylene wear-resistant anti-friction composite material |
| CN107043508A (en) * | 2017-06-05 | 2017-08-15 | 巨轮智能装备股份有限公司 | A kind of preparation method of nitrogen-doped graphene/ptfe composite |
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