CN111303628B - Polyimide self-lubricating composite material and preparation method thereof - Google Patents
Polyimide self-lubricating composite material and preparation method thereof Download PDFInfo
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- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to the technical field of polyimide films, in particular to a polyimide self-lubricating composite material and a preparation method thereof. The invention relates to a polyimide self-lubricating composite material prepared by combining polyimide molding powder which takes pyromellitic dianhydride as a main monomer with commercialized polyimide. In addition, the traditional graphite solid lubricant is introduced, so that the polyimide composite material has good self-lubricating performance. Moreover, the addition of the silicon dioxide and zirconium dioxide nano-particles meets the requirements of high bearing capacity and strong impact toughness of the polymer self-lubricating composite material on one hand; on the other hand, the composite material is combined with a graphite solid lubricant to construct a unique ball effect, and the polyimide composite material is endowed with excellent lubricating performance.
Description
Technical Field
The invention relates to the technical field of polyimide films, in particular to a polyimide self-lubricating composite material and a preparation method thereof.
Background
The polymer-based composite material has various advantages of light weight, excellent mechanical property, adjustable structural design, easy processing and the like, so that the polymer-based composite material is widely applied to the high and new technical fields of aviation, aerospace, electronics, oceans, high-end equipment and the like, and particularly the polymer self-lubricating composite material is increasingly and widely used for replacing the traditional material in the application directions of lubrication, sealing, bearings and the like. Polyimide is widely used for the design and preparation of polymer self-lubricating composite materials with excellent mechanical properties, outstanding temperature resistance and excellent thermal stability. However, the commercial polyimide has a single molding process and cannot meet the wide application requirements. Particularly, the polyimide prepared from pyromellitic dianhydride as a synthetic monomer has extremely high rigidity, and excellent mechanical properties and heat resistance are provided for the polyimide. However, it presents new challenges to the process of forming because it is difficult to melt. Although there are many reports on polymer self-lubricating composites every year, emphasis is placed on reducing the frictional wear performance of the polymer composite itself, and there are few reports on the equally important damage to the friction couple. The service life of the polymer friction pair is prolonged, energy conservation and emission reduction are realized, and the polymer friction pair is a target constantly pursued by scientific researchers.
Disclosure of Invention
The invention aims to provide a preparation method of polyimide molding powder, a polyimide self-lubricating composite material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyimide self-lubricating composite material which comprises, by weight, 65-85 parts of polyimide blend molding powder, 10-20 parts of reinforcing fibers, 4.9-14.9 parts of graphite solid lubricant and 0.1-1.2 parts of nano oxides;
the polyimide blending molding powder comprises self-made polyimide molding powder and commercialized polyimide molding powder;
the type of the commercial polyimide molding powder is YS-20, SP-1 or SF-1;
the nano oxide is SiO2Nanoparticles and ZrO2A nanoparticle;
the preparation method of the self-made polyimide molding powder comprises the following steps:
mixing 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether and an organic solvent to obtain a mixed solution;
adding pyromellitic dianhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 5-10 times respectively, and carrying out polymerization reaction to obtain a polyamic acid solution;
and mixing toluene with the polyamic acid solution, heating and refluxing, and precipitating to obtain the self-made polyimide molding powder.
Preferably, the mass ratio of the self-made polyimide molding powder to the commercial polyimide molding powder is (1-4): 1.
preferably, the molar ratio of the 3,4 '-diaminodiphenyl ether to the 4,4' -diaminodiphenyl ether is (1-9): 1;
the organic solvent is N-methyl pyrrolidone, N-dimethyl formamide or N, N-dimethyl acetamide.
Preferably, the molar ratio of the pyromellitic dianhydride to the 3,3',4,4' -biphenyltetracarboxylic dianhydride is (4-7): 1;
the ratio of the total molar amount of pyromellitic dianhydride and 3,3',4,4' -biphenyltetracarboxylic dianhydride to the total molar amount of 3,4 '-oxydianiline and 4,4' -oxydianiline was 1: 1.
Preferably, the polymerization reaction is carried out under a nitrogen atmosphere;
the temperature of the polymerization reaction is room temperature, and the time of the polymerization reaction is 12-36 h;
the solid content of the polyamic acid solution is 10-25%.
Preferably, the heating reflux is performed under a nitrogen atmosphere;
the heating reflux temperature is 160-220 ℃, and the heating reflux time is 24-72 hours;
the volume ratio of the toluene to the organic solvent is (6-10): 1.
preferably, the reinforcing fiber is one or more of carbon fiber, aramid fiber and glass fiber.
Preferably, the SiO2Nanoparticles and ZrO2The mass ratio of the nanoparticles is (1-4): 1.
the invention also provides a preparation method of the polyimide self-lubricating composite material, which comprises the following steps:
mixing self-made polyimide molding powder with commercialized polyimide molding powder to obtain polyimide blending molding powder;
mixing the polyimide blending molding powder, reinforcing fibers, nano oxides, a graphite solid lubricant and absolute ethyl alcohol to obtain polyimide composite material molding powder;
carrying out hot-molding on the polyimide composite molding powder to obtain the polyimide self-lubricating composite material;
the self-made polyimide molding powder is prepared by the preparation method in the technical scheme.
Preferably, the hot press molding process comprises: and (3) placing the polyimide composite material molding powder into a mold, raising the temperature to 250-300 ℃ at a speed of 5-10 ℃, preserving heat for 1-5 h, and finally raising the temperature to 350 ℃ and preserving heat for 2-6 h.
The invention provides a polyimide self-lubricating composite material which comprises, by weight, 65-85 parts of polyimide blend molding powder, 10-20 parts of reinforcing fibers, 4.9-14.9 parts of graphite solid lubricant and 0.1-1.2 parts of nano oxides; the polyimide blending molding powder comprises self-made polyimide molding powder and commercialized polyimide molding powder; the type of the commercial polyimide molding powder is YS-20, SP-1 or SF-1; the nano oxide is SiO2Nanoparticles and ZrO2A nanoparticle; the preparation method of the self-made polyimide molding powder comprises the following steps: mixing 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether and an organic solvent to obtain a mixed solution; adding pyromellitic dianhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 5-10 times respectively, and carrying out polymerization reaction to obtain the self-made polyamic acid solution; and mixing toluene with the polyamic acid solution, and heating and refluxing to obtain the polyimide molding powder. The invention combines the polyimide molding powder which takes the pyromellitic dianhydride as the main monomer with the commercialized polyimide, and in addition, introduces the traditional graphite solid lubricant, thereby ensuring that the polyimide composite material has good self-lubricating performance. Moreover, the addition of silicon dioxide and zirconium dioxide meets the requirements of high bearing capacity and strong impact toughness of the polymer self-lubricating composite material; on the other hand, the composite material is combined with a graphite solid lubricant to construct a unique ball effect and endow the polyimide with the special ball effectThe imine composite material has excellent lubricating property.
Drawings
FIG. 1 is a TEM image of a dual surface transfer film prepared using the polyimide self-lubricating composite material of example 5 in a test example;
FIG. 2 is a high resolution TEM image of a dual surface transfer film prepared by using the polyimide self-lubricating composite material of example 5 in the test example;
FIG. 3 is a TEM image of a dual surface transfer film prepared using the polyimide self-lubricating composite material of comparative example 1 in the test example;
fig. 4 is a high resolution TEM image of a dual surface transfer film prepared using the polyimide self-lubricating composite material of comparative example 1 in the test example.
Detailed Description
The invention provides a polyimide self-lubricating composite material which comprises, by weight, 65-85 parts of polyimide blend molding powder, 10-20 parts of reinforcing fibers, 4.9-14.9 parts of graphite solid lubricant and 0.1-1.2 parts of nano oxides;
the polyimide blending molding powder comprises self-made polyimide molding powder and commercialized polyimide molding powder;
the type of the commercial polyimide molding powder is YS-20, SP-1 or SF-1;
the nano oxide is SiO2Nanoparticles and ZrO2A nanoparticle;
the preparation method of the self-made polyimide molding powder comprises the following steps:
mixing 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether and an organic solvent to obtain a mixed solution;
adding pyromellitic dianhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 5-10 times respectively, and carrying out polymerization reaction to obtain a polyamic acid solution;
and mixing toluene with the polyamic acid solution, heating and refluxing, and precipitating to obtain the self-made polyimide molding powder.
The polyimide self-lubricating composite material comprises, by weight, 65-85 parts of polyimide blend molding powder, preferably 70-80 parts, and more preferably 72-78 parts. In the invention, the polyimide blend molding powder comprises polyimide molding powder and commercial polyimide molding powder; the model number of the commercial polyimide molding powder is YS-20, SP-1 or SF-1. In the present invention, the mass ratio of the polyimide molding powder to the commercial polyimide molding powder is preferably (1 to 4): 1, more preferably (2-3): 1.
in the invention, the preparation method of the self-made polyimide molding powder comprises the following steps:
mixing 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether and an organic solvent to obtain a mixed solution;
adding pyromellitic dianhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 5-10 times respectively, and carrying out polymerization reaction to obtain a polyamic acid solution;
and mixing toluene with the polyamic acid solution, and heating and refluxing to obtain the self-made polyimide molding powder.
The invention mixes 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether and organic solvent to obtain mixed solution. In the present invention, the organic solvent is preferably N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide. In the present invention, the molar ratio of the 3,4 '-diaminodiphenyl ether to the 4,4' -diaminodiphenyl ether is preferably (1 to 9): 1, more preferably (2-8): 1, most preferably (4-6): 1. the invention does not have any special limitation on the dosage of the organic solvent, and the dosage well known to a person skilled in the art can ensure that the 3,4 '-diaminodiphenyl ether and the 4,4' -diaminodiphenyl ether in the mixed solution are uniformly dispersed, and the solid content of the polyamide acid solution prepared subsequently can be in the range of 10-25%. In the present invention, the mixing is preferably performed under a dry nitrogen atmosphere; the temperature of the mixing is preferably room temperature; the mixing is preferably carried out under stirring, and the stirring is not particularly limited in the present invention and may be carried out by a procedure well known to those skilled in the art.
After a mixed solution is obtained, pyromellitic dianhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride are respectively added into the mixed solution for 5-10 times to perform polymerization reaction, so that a polyamic acid solution is obtained. In the present invention, the molar ratio of pyromellitic dianhydride to 3,3',4,4' -biphenyltetracarboxylic dianhydride is preferably (4 to 7): 1, more preferably (5-6): 1; the total molar ratio of the pyromellitic dianhydride and the 3,3',4,4' -biphenyltetracarboxylic dianhydride to the total molar ratio of the 3,4 '-oxydianiline and the 4,4' -oxydianiline is preferably 1: 1; the pyromellitic dianhydride and the 3,3',4,4' -biphenyltetracarboxylic dianhydride are added to the mixed solution for 5 to 10 times, preferably 6 to 9 times, and more preferably 7 to 8 times. In the present invention, the polymerization reaction is preferably carried out under a nitrogen atmosphere; the temperature of the polymerization reaction is preferably room temperature, and the time of the polymerization reaction is preferably 12-36 h, more preferably 15-30 h, and most preferably 20-25 h. In the invention, the solid content of the polyamic acid solution is preferably 10-25%, and more preferably 15-20%.
After the polyamic acid solution is obtained, the invention mixes toluene with the polyamic acid solution, and precipitates are separated out after heating and refluxing, so as to obtain the self-made polyimide molding powder. In the invention, the volume ratio of the toluene to the organic solvent is preferably (6-10): 1, more preferably (7-8): 1. in the present invention, the heating reflux is preferably performed under a nitrogen atmosphere; the nitrogen atmosphere is preferably a dry nitrogen atmosphere. The heating reflux temperature is preferably 160-220 ℃, more preferably 170-210 ℃, and most preferably 180-200 ℃; the heating and refluxing time is preferably 24-72 h, more preferably 30-60 h, and most preferably 40-50 h.
In the invention, the process of precipitating the precipitate is preferably to pour the system obtained by heating and refluxing into an industrial ethanol solution to precipitate the precipitate.
After the precipitation, the invention preferably further comprises washing, filtering and drying the precipitate in sequence. The washing and suction filtration are not particularly limited in the present invention, and may be carried out by a procedure well known to those skilled in the art. In the present invention, the temperature of the drying is preferably 150 ℃; the drying time is preferably 24-36 h, and more preferably 28-32 h.
The polyimide self-lubricating composite material further comprises 10-20 parts by weight of reinforcing fibers, preferably 12-18 parts by weight of reinforcing fibers, and more preferably 14-16 parts by weight of polyimide blend molding powder. In the invention, the reinforcing fiber is preferably one or more of carbon fiber, aramid fiber and glass fiber; when the reinforced fibers are more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the reinforced fibers can be prepared according to any proportion. In the invention, the length of the reinforcing fiber is preferably 20-50 μm, and more preferably 25-45 μm; the diameter is preferably 5 to 9 μm, and more preferably 7 μm.
The polyimide self-lubricating composite material also comprises 4.9-14.9 parts of graphite solid lubricant, preferably 6-12 parts, and more preferably 8-10 parts by weight of the polyimide blend molding powder. In the invention, the particle size of the graphite solid lubricant is preferably 5-100 μm, and more preferably 20-50 μm.
The polyimide self-lubricating composite material also comprises 0.1-1.2 parts of nano oxide, preferably 0.4-1.0 part, and more preferably 0.6-0.8 part by weight of the polyimide blend molding powder. In the invention, the nano oxide is SiO2And ZrO2(ii) a The SiO2And ZrO2The mass ratio of (1-4): 1, more preferably (2-3): 1. in the invention, the particle size of the nano oxide is preferably 10-50 nm, and more preferably 20-30 nm.
The invention also provides a preparation method of the polyimide self-lubricating composite material, which comprises the following steps:
mixing the polyimide molding powder prepared by the preparation method in the technical scheme with commercial polyimide molding powder to obtain polyimide blending molding powder;
mixing the polyimide blending molding powder, reinforcing fibers, nano oxides, a graphite solid lubricant and absolute ethyl alcohol to obtain polyimide composite material molding powder;
and carrying out hot die pressing molding on the polyimide composite material molding powder to obtain the polyimide self-lubricating composite material.
The invention mixes the polyimide molding powder prepared by the preparation method in the technical scheme with commercial polyimide molding powder to obtain polyimide blending molding powder. In the present invention, the mixing is preferably performed by ball milling; the rotation speed of the ball milling is preferably 200-600 rpm, and more preferably 300-500 rpm; the time for ball milling is preferably 10-36 h, and more preferably 20-30 h.
After the polyimide blending molding powder is obtained, the polyimide blending molding powder, the reinforcing fiber, the nano oxide, the graphite solid lubricant and the absolute ethyl alcohol are mixed to obtain the polyimide composite material molding powder. The invention has no special limitation on the dosage of the absolute ethyl alcohol, and can be obtained by uniformly mixing the polyimide blend molding powder, the reinforced fiber, the nano oxide and the graphite solid lubricant. In the present invention, the mixing is preferably performed by mechanical stirring; the mechanical stirring process is not particularly limited, and may be performed by a process known to those skilled in the art. After the mixing is complete, the present invention also preferably includes drying; the drying temperature is preferably 100-200 ℃, more preferably 120-180 ℃, and more preferably 140-160 ℃; the drying time is preferably 10-24 h, more preferably 12-20 h, and most preferably 14-16 h.
After the polyimide composite material molding powder is obtained, the polyimide composite material molding powder is subjected to hot molding to obtain the polyimide self-lubricating composite material. In the present invention, the hot press molding process is preferably: putting the polyimide composite material molding powder into a mold, raising the temperature to 250-300 ℃ at a speed of 5-10 ℃, preserving heat for 1-5 h, and finally raising the temperature to 350 ℃ and preserving heat for 2-6 h; more preferably: and (3) putting the polyimide composite material molding powder into a mold, raising the temperature to 260-280 ℃ at a speed of 6-8 ℃, preserving heat for 2-3 h, and finally raising the temperature to 350 ℃ and preserving heat for 4-5 h.
After the hot press molding, the present invention also preferably includes a process of cooling to room temperature and then demolding. The cooling and demolding processes are not particularly limited in the present invention, and commercially available products well known to those skilled in the art are used.
The polyimide self-lubricating composite material and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Mixing 0.1mol (20.02g) of 3,4 '-diaminodiphenyl ether and 0.1mol (20.02g) of 4,4' -diaminodiphenyl ether with 365g of N-methylpyrrolidone, and stirring the mixture at room temperature in a dry nitrogen atmosphere until the mixture is dissolved to obtain a mixed solution;
respectively adding 0.1mol (21.81g) of pyromellitic dianhydride and 0.1mol (29.42g) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution by 10 times, and stirring for 36 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution;
mixing 36.5g of toluene with the polyamic acid solution, heating and refluxing (220 ℃, 4h, dry nitrogen atmosphere), pouring into an industrial ethanol solution to precipitate, washing, performing suction filtration, and drying (150 ℃, 24h) to obtain polyimide molding powder;
mixing commercial YS-20 polyimide molding powder with the polyimide molding powder according to the mass ratio of 1:4 (ball milling, 200rpm, 10 hours) to obtain blended polyimide molding powder;
mixing 65g of blended polyimide molding powder, 20g of carbon fiber, 0.6g of silicon dioxide, 0.6g of zirconium dioxide, 13.8g of graphite solid lubricant and absolute ethyl alcohol, stirring for 2h, drying (200 ℃, 10h), placing the obtained polyimide composite molding powder in a fixed mold, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 1h, finally heating to 350 ℃ and preserving heat for 2h, cooling to room temperature, and demolding to obtain the polyimide self-lubricating composite.
Example 2
Mixing 0.18mol (36.04g) of 3,4 '-diaminodiphenyl ether and 0.02mol (4.00g) of 4,4' -diaminodiphenyl ether with 770g of N, N-dimethylacetamide, and stirring at room temperature under a dry nitrogen atmosphere until the mixture is dissolved to obtain a mixed solution;
respectively adding 0.175mol (38.17g) of pyromellitic dianhydride and 0.025mol (7.35g) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 8 times, and stirring for 36 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution;
mixing 36.5g of toluene with the polyamic acid solution, heating and refluxing (220 ℃, 4h, dry nitrogen atmosphere), pouring into an industrial ethanol solution to precipitate, washing, performing suction filtration, and drying (150 ℃, 36h) to obtain polyimide molding powder;
mixing commercial YS-20 polyimide molding powder with the polyimide molding powder according to the mass ratio of 1:1 (ball milling, 600rpm, 36h) to obtain blended polyimide molding powder;
mixing 85g of blended polyimide molding powder, 10g of aramid fiber, 0.08g of silicon dioxide, 0.02g of zirconium dioxide, 4.9g of graphite solid lubricant and absolute ethyl alcohol, stirring for 10h, drying (100 ℃, 24h), putting the obtained polyimide composite molding powder into a fixed mold, heating to 300 ℃ at the speed of 5 ℃/min, preserving heat for 1h, finally heating to 350 ℃ and preserving heat for 6h, cooling to room temperature, and demolding to obtain the polyimide self-lubricating composite.
Example 3
Mixing 0.15mol (30.03g) of 3,4 '-diaminodiphenyl ether and 0.05mol (10.01g) of 4,4' -diaminodiphenyl ether with 342.2g of N, N-dimethylformamide, and stirring at room temperature under a dry nitrogen atmosphere until the mixture is dissolved to obtain a mixed solution;
respectively adding 0.175mol (38.17g) of pyromellitic dianhydride and 0.025mol (7.35g) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 8 times, and stirring for 24 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution;
mixing 42.8g of toluene with the polyamic acid solution, heating and refluxing (160 ℃, 24h, dry nitrogen atmosphere), pouring into an industrial ethanol solution to precipitate, washing, performing suction filtration, and drying (150 ℃, 24h) to obtain polyimide molding powder;
mixing commercial SF-1 polyimide molding powder with the polyimide molding powder according to the mass ratio of 1:3 (ball milling, 300rpm, 24h) to obtain blended polyimide molding powder;
mixing 70g of blended polyimide molding powder, 15g of aramid fiber, 0.08g of silicon dioxide, 0.02g of zirconium dioxide, 14.9g of graphite solid lubricant and absolute ethyl alcohol, stirring for 10h, drying (100 ℃, 10h), putting the obtained polyimide composite molding powder into a fixed mold, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 1h, finally heating to 350 ℃ and preserving heat for 2h, cooling to room temperature, and demolding to obtain the polyimide self-lubricating composite.
Example 4
Mixing 0.18mol (36.04g) of 3,4 '-diaminodiphenyl ether and 0.02mol (4.00g) of 4,4' -diaminodiphenyl ether with 516g (15%) of N, N-dimethylacetamide, and stirring the mixture at room temperature in a dry nitrogen atmosphere until the mixture is dissolved to obtain a mixed solution;
adding 0.1mol (21.81g) of pyromellitic dianhydride and 0.1mol (29.42g) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution respectively for 6 times, and stirring for 36 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution;
mixing 51.6g of toluene with the polyamic acid solution, heating and refluxing (180 ℃, 72 hours, dry nitrogen atmosphere), pouring into an industrial ethanol solution to precipitate, washing, performing suction filtration, and drying (150 ℃, 24 hours) to obtain polyimide molding powder;
mixing commercial YS-20 polyimide molding powder with the polyimide molding powder according to the mass ratio of 1:4 (ball milling, 300rpm, 24h) to obtain blended polyimide molding powder;
mixing 70g of blended polyimide molding powder, 20g of aramid fiber, 0.6g of silicon dioxide, 0.2g of zirconium dioxide, 9.2g of graphite solid lubricant and absolute ethyl alcohol, stirring for 10h, drying (100 ℃, 10h), putting the obtained polyimide composite molding powder into a fixed mold, heating to 250 ℃ at the speed of 8 ℃/min, preserving heat for 1h, finally heating to 350 ℃ and preserving heat for 2h, cooling to room temperature, and demolding to obtain the polyimide self-lubricating composite.
Example 5
Mixing 0.175mol (35.04g) of 3,4 '-diaminodiphenyl ether and 0.025mol (5.00g) of 4,4' -diaminodiphenyl ether with 262.5g of N, N-dimethylformamide, and stirring the mixture at room temperature in a dry nitrogen atmosphere until the mixture is dissolved to obtain a mixed solution;
respectively adding 0.15mol (32.72g) of pyromellitic dianhydride and 0.05mol (14.71g) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 10 times, and stirring for 24 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution;
mixing 26.2g of toluene with the polyamic acid solution, heating and refluxing (160 ℃, 36h, dry nitrogen atmosphere), pouring into an industrial ethanol solution to precipitate, washing, performing suction filtration, and drying (150 ℃, 24h) to obtain polyimide molding powder;
mixing commercial SP-1 polyimide molding powder with the polyimide molding powder according to the mass ratio of 1:2 (ball milling, 500rpm, 24h) to obtain blended polyimide molding powder;
mixing 65g of blended polyimide molding powder, 20g of aramid fiber, 0.05g of silicon dioxide, 0.05g of zirconium dioxide, 14.9g of graphite solid lubricant and absolute ethyl alcohol, stirring for 10h, drying (100 ℃, 10h), placing the obtained polyimide composite molding powder in a fixed mold, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 1h, finally heating to 350 ℃ and preserving heat for 2h, cooling to room temperature, and demolding to obtain the polyimide self-lubricating composite.
Comparative example 1
Mixing 0.175mol (35.04g) of 3,4 '-diaminodiphenyl ether and 0.025mol (5.00g) of 4,4' -diaminodiphenyl ether with 262.5g of N, N-dimethylformamide, and stirring the mixture at room temperature in a dry nitrogen atmosphere until the mixture is dissolved to obtain a mixed solution;
respectively adding 0.15mol (32.72g) of pyromellitic dianhydride and 0.05mol (14.71g) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 10 times, and stirring for 24 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution;
mixing 26.2g of toluene with the polyamic acid solution, heating and refluxing (160 ℃, 36h, dry nitrogen atmosphere), pouring into an industrial ethanol solution to precipitate, washing, performing suction filtration, and drying (150 ℃, 24h) to obtain polyimide molding powder;
mixing commercial SP-1 polyimide molding powder with the polyimide molding powder according to the mass ratio of 1:2 (ball milling, 500rpm, 24h) to obtain blended polyimide molding powder;
mixing 65g of blended polyimide molding powder, 20g of aramid fiber, 15g of graphite solid lubricant and absolute ethyl alcohol, stirring for 10h, drying (100 ℃ and 10h), placing the obtained polyimide composite molding powder in a fixed mold, heating to 250 ℃ at the speed of 6 ℃/min, preserving heat for 1h, finally heating to 350 ℃ and preserving heat for 2h, cooling to room temperature, and demolding to obtain the polyimide self-lubricating composite.
Comparative example 2
Mixing 0.175mol (35.04g) of 3,4 '-diaminodiphenyl ether and 0.025mol (5.00g) of 4,4' -diaminodiphenyl ether with 262.5g of N, N-dimethylformamide, and stirring the mixture at room temperature in a dry nitrogen atmosphere until the mixture is dissolved to obtain a mixed solution;
respectively adding 0.15mol (32.72g) of pyromellitic dianhydride and 0.05mol (14.71g) of 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 8 times, and stirring for 24 hours at room temperature under a nitrogen atmosphere to obtain a polyamic acid solution;
mixing 26.2g of toluene with the polyamic acid solution, heating and refluxing (160 ℃, 36h, dry nitrogen atmosphere), pouring into an industrial ethanol solution to precipitate, washing, performing suction filtration, and drying (150 ℃, 24h) to obtain polyimide molding powder;
mixing commercial SP-1 polyimide molding powder with the polyimide molding powder according to the mass ratio of 1:2 (ball milling, 500rpm, 24h) to obtain blended polyimide molding powder;
and (3) placing the blended polyimide molding powder in a fixed mold, heating to 250 ℃ at the speed of 10 ℃/min, preserving heat for 1h, finally heating to 350 ℃, preserving heat for 2h, cooling to room temperature, and demolding to obtain the polyimide self-lubricating composite material.
Test example
The materials in example 5 and comparative examples 1-2 are subjected to friction wear testing by adopting a CSEM-THT07-135 high-temperature ball-disk friction wear testing machineRub and wear test. The polyimide composite was processed into a specimen of 18 mm. times.18 mm. times.2 mm. The test conditions were: the dual balls are GCr15 bearing steel, and the initial end surface roughness Ra is approximately equal to 0.3-0.5 mu m; the test environment temperature is 25 ℃, the relative humidity is 45%, the atmosphere is the atmospheric environment, the test loading force is 5N, and the linear velocity is 10 cm/min; comparing the dual surface transfer film nanostructure of example 5 with that of comparative examples 1-2, it can be seen that, after the ceramic nano oxide is added, the dual surface has no oxide layer, and the polyimide self-lubricating composite material with only solid lubricant forms a uniform oxide layer on the dual surface. When the ceramic nano oxide is introduced into the polymer matrix, the ceramic nano oxide plays a role in protecting the dual material and avoids the abrasion and oxidation of the dual material. Simultaneous friction Coefficient (COF) and wear rate (WR, mm)3Nm), the results obtained are shown in Table 1,
TABLE 1 Friction coefficient and wear rate of polyimide self-lubricating composite materials described in example 5 and comparative examples 1 to 2
| Examples | Coefficient of friction | Wear Rate (. times.10)-6) |
| Example 5 | 0.26±0.02 | 4.47±0.40 |
| Comparative example 1 | 0.29±0.08 | 5.59±0.11 |
| Comparative example 2 | 0.41±0.02 | 15.2±0.07 |
As can be seen from Table 1, the graphite solid lubricant with the easily sheared and laminated structure of the polyimide self-lubricating composite material provided by the invention carries the ceramic oxide with high hardness and high modulus, so that the polymer self-lubricating composite material is endowed with excellent lubricating property.
TEM analysis is performed on the dual transfer films corresponding to the example 5 and the comparison document 1, and the analysis results are shown in FIGS. 1-2 (example 5) and FIGS. 3-4 (comparative example 1), and as can be seen from FIGS. 1-4, after the nano oxide is added to the polymer matrix, the surface of the dual material is obviously free from the oxide layer (as shown in FIG. 4, the structure of the dual oxide layer is shown), while the polyimide self-lubricating material which only contains the solid lubricant forms a relatively uniform oxide layer on the surface of the dual material. When the ceramic nano oxide is introduced into the polymer matrix, the ceramic nano oxide plays a role in protecting the coupled material and avoids abrasion and oxidation of the coupled material (as shown in a TEM of figure 2, no oxide layer exists).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A polyimide self-lubricating composite material comprises, by weight, 65-85 parts of polyimide blend molding powder, 10-20 parts of reinforcing fibers, 4.9-14.9 parts of graphite solid lubricant and 0.1-1.2 parts of nano oxides;
the polyimide blending molding powder comprises self-made polyimide molding powder and commercialized polyimide molding powder;
the type of the commercial polyimide molding powder is YS-20 or SP-1;
the nano oxide is SiO2Nanoparticles and ZrO2A nanoparticle;
the preparation method of the self-made polyimide molding powder comprises the following steps:
mixing 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether and an organic solvent to obtain a mixed solution;
adding pyromellitic dianhydride and 3,3',4,4' -biphenyl tetracarboxylic dianhydride into the mixed solution for 5-10 times respectively, and carrying out polymerization reaction to obtain a polyamic acid solution;
mixing toluene with the polyamic acid solution, heating and refluxing, and precipitating to obtain the self-made polyimide molding powder;
the mass ratio of the self-made polyimide molding powder to the commercialized polyimide molding powder is (1-4): 1;
the SiO2Nanoparticles and ZrO2The mass ratio of the nanoparticles is (1-4): 1.
2. the polyimide self-lubricating composite material according to claim 1, wherein the molar ratio of 3,4 '-diaminodiphenyl ether to 4,4' -diaminodiphenyl ether is (1 to 9): 1;
the organic solvent is N-methyl pyrrolidone, N-dimethyl formamide or N, N-dimethyl acetamide.
3. The polyimide self-lubricating composite material according to claim 1, wherein the molar ratio of pyromellitic dianhydride to 3,3',4,4' -biphenyltetracarboxylic dianhydride is (4 to 7): 1;
the ratio of the total molar amount of pyromellitic dianhydride and 3,3',4,4' -biphenyltetracarboxylic dianhydride to the total molar amount of 3,4 '-oxydianiline and 4,4' -oxydianiline was 1: 1.
4. The polyimide self-lubricating composite material of claim 1, wherein the polymerization reaction is carried out under a nitrogen atmosphere;
the temperature of the polymerization reaction is room temperature, and the time of the polymerization reaction is 12-36 h;
the solid content of the polyamic acid solution is 10-25%.
5. The polyimide self-lubricating composite material according to claim 1, wherein the heating reflow is performed under a nitrogen atmosphere;
the heating reflux temperature is 160-220 ℃, and the heating reflux time is 24-72 hours;
the volume ratio of the toluene to the organic solvent is (6-10): 1.
6. the polyimide self-lubricating composite material of claim 1, wherein the reinforcing fibers are one or more of carbon fibers, aramid fibers and glass fibers.
7. The method for preparing the polyimide self-lubricating composite material according to any one of claims 1 to 6, comprising the steps of:
mixing self-made polyimide molding powder with commercialized polyimide molding powder to obtain polyimide blending molding powder;
mixing the polyimide blending molding powder, reinforcing fibers, nano oxides, a graphite solid lubricant and absolute ethyl alcohol to obtain polyimide composite material molding powder;
and carrying out hot die pressing molding on the polyimide composite material molding powder to obtain the polyimide self-lubricating composite material.
8. The manufacturing method according to claim 7, wherein the hot press molding is performed by: and (3) placing the polyimide composite material molding powder into a mold, raising the temperature to 250-300 ℃ at a speed of 5-10 ℃, preserving heat for 1-5 h, and finally raising the temperature to 350 ℃ and preserving heat for 2-6 h.
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