CN113881174B - Binary and ternary hydroxide synergistically modified self-lubricating fabric composite material and preparation method and application thereof - Google Patents
Binary and ternary hydroxide synergistically modified self-lubricating fabric composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a binary and ternary hydroxide synergistically modified self-lubricating fabric composite material and a preparation method and application thereof, and belongs to the technical field of self-lubricating materials. The self-lubricating fabric composite material provided by the invention comprises a polytetrafluoroethylene aramid fiber blended fabric and a solid lubricant loaded on the polytetrafluoroethylene aramid fiber blended fabric, wherein NiAl-LDH has extremely high mechanical bearing capacity and wear resistance, so that the friction performance under a heavy load environment can be improved, ZnNiAl-LDH has a layered crystal structure similar to graphite, molybdenum disulfide and the like, interlayer slippage is easy to occur, and the friction coefficient is reduced.
Description
Technical Field
The invention relates to the technical field of self-lubricating materials, in particular to a binary and ternary hydroxide synergistically modified self-lubricating fabric composite material and a preparation method and application thereof.
Background
Fiber fabric composites are the most attractive materials due to their outstanding advantages of low cost, easy processing, chemical stability, and light weight, and are widely used in the aircraft, automobile, railroad equipment, aerospace equipment, and defense industries. However, with the increasing use requirements, the conventional fabric composite material cannot meet the use of heavy-duty low-temperature conditions.
Hydrotalcite compounds are anionic layered compounds with wide application prospect, including hydrotalcite and hydrotalcite-like compounds, and the main layered plate of the hydrotalcite compounds is generally composed of two or more than two metal hydroxides, so the hydrotalcite compounds are also called layered double-hydroxyl composite metal hydroxides. Wherein, ZnNiAl-LDH and NiAl-LDH are hydroxides with layered structures, and are widely applied to the fields of photocatalysis, electrochemistry and the like.
Disclosure of Invention
The invention aims to provide a binary and ternary hydroxide synergistically modified self-lubricating fabric composite material and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a binary and ternary hydroxide synergistically modified self-lubricating fabric composite material, which comprises a polytetrafluoroethylene aramid fiber blended fabric and a solid lubricant loaded on the polytetrafluoroethylene aramid fiber blended fabric, wherein the solid lubricant comprises two-dimensional layered ZnNiAl-LDH and two-dimensional layered NiAl-LDH; the polytetrafluoroethylene aramid fiber blended fiber fabric and the solid lubricant are bonded through polyetherimide; the mass ratio of the polyetherimide to the two-dimensional layered ZnNiAl-LDH to the two-dimensional layered NiAl-LDH is (10-30): (0.2-0.4): (0.2-0.4).
Preferably, the mass of the polytetrafluoroethylene aramid fiber blended fiber fabric is 60-90% of that of the self-lubricating fabric composite material.
Preferably, the sheet diameter of the two-dimensional layered ZnNiAl-LDH is 1-2 μm, and the thickness is 50-100 nm.
Preferably, the sheet diameter of the two-dimensional layered NiAl-LDH is 10-40 nm.
Preferably, the thickness of the polytetrafluoroethylene aramid fiber blended fabric is 0.2-0.3 mm.
The invention provides a preparation method of the self-lubricating fabric composite material, which comprises the following steps:
according to the mass ratio of polyetherimide to two-dimensional layered ZnNiAl-LDH to two-dimensional layered NiAl-LDH in the self-lubricating composite fabric composite material, dispersing the polyetherimide, the two-dimensional layered ZnNiAl-LDH and the two-dimensional layered NiAl-LDH into N, N-dimethylformamide to obtain an impregnation solution;
and (3) soaking the polytetrafluoroethylene aramid fiber blended fiber fabric into the soaking solution, and drying to obtain the self-lubricating fabric composite material.
Preferably, the dipping and the drying are repeated until the mass of the polytetrafluoroethylene aramid fiber blended fiber fabric reaches 60-90% of that of the self-lubricating fabric composite material.
Preferably, the mass ratio of the polyetherimide to the N, N-dimethylformamide is (10-30): (75-80).
Preferably, the method further comprises the step of pretreating the polytetrafluoroethylene aramid blended fiber fabric before impregnation, wherein the pretreatment comprises the following steps: putting the polytetrafluoroethylene aramid fiber blended fabric into petroleum ether for first ultrasonic cleaning, after first drying, putting the polytetrafluoroethylene aramid fiber blended fabric into a mixed solution of acetone and ethanol for second ultrasonic cleaning, and after taking out, carrying out second drying.
The invention provides an application of the self-lubricating fabric composite material or the self-lubricating fabric composite material prepared by the preparation method in the scheme as a friction material in a heavy-load low-temperature environment; the temperature of the heavy-load low-temperature environment is below-100 ℃, and the load of the heavy-load low-temperature environment is above 20 MPa.
The invention provides a binary and ternary hydroxide synergistically modified self-lubricating fabric composite material, which comprises a polytetrafluoroethylene aramid fiber blended fabric and a solid lubricant loaded on the polytetrafluoroethylene aramid fiber blended fabric, wherein the solid lubricant comprises two-dimensional layered ZnNiAl-LDH and two-dimensional layered NiAl-LDH; the polytetrafluoroethylene aramid fiber blended fiber fabric and the solid lubricant are bonded through polyetherimide; the mass ratio of the polyetherimide to the two-dimensional layered ZnNiAl-LDH to the two-dimensional layered NiAl-LDH is (10-30): (0.2-0.4): (0.2-0.4).
The NiAl-LDH has extremely high mechanical bearing capacity and wear resistance, so that the friction performance under a heavy-load environment can be improved, the ZnNiAl-LDH has a layered crystal structure similar to graphite, molybdenum disulfide and the like, interlayer slippage is easy to occur, and the friction coefficient is reduced.
Drawings
FIG. 1 is an SEM image of a polytetrafluoroethylene aramid blended fiber fabric;
FIG. 2 is an SEM image of ZnNiAl-LDH;
FIG. 3 is an SEM image of NiAl-LDH.
Detailed Description
The invention provides a binary and ternary hydroxide synergistically modified self-lubricating fabric composite material, which comprises a polytetrafluoroethylene aramid fiber blended fabric and a solid lubricant loaded on the polytetrafluoroethylene aramid fiber blended fabric, wherein the solid lubricant comprises two-dimensional layered ZnNiAl-LDH and two-dimensional layered NiAl-LDH; the polytetrafluoroethylene aramid fiber blended fiber fabric and the solid lubricant are bonded through polyetherimide; the mass ratio of the polyetherimide to the two-dimensional layered ZnNiAl-LDH to the two-dimensional layered NiAl-LDH is (10-30): (0.2-0.4): (0.2-0.4).
The self-lubricating fabric composite material provided by the invention comprises a polytetrafluoroethylene aramid fiber blended fabric. In the invention, the thickness of the polytetrafluoroethylene aramid fiber blended fabric is preferably 0.2-0.3 mm. In the invention, the mass of the polytetrafluoroethylene aramid fiber blended fabric is preferably 60-90% of that of the self-lubricating fabric composite material, more preferably 65-85%, and further preferably 70-80%.
The self-lubricating fabric composite material provided by the invention comprises a solid lubricant loaded on the polytetrafluoroethylene aramid fiber blended fabric, wherein the solid lubricant comprises two-dimensional layered ZnNiAl-LDH and two-dimensional layered NiAl-LDH.
In the invention, the polytetrafluoroethylene aramid fiber blended fiber fabric and the solid lubricant are bonded through polyetherimide. In the invention, the mass ratio of the polyetherimide to the two-dimensional layered ZnNiAl-LDH to the two-dimensional layered NiAl-LDH is (10-30): (0.2-0.4): (0.2 to 0.4), preferably 20:0.3:0.3 or 10: 0.2: 0.2. in the invention, the sheet diameter of the two-dimensional layered ZnNiAl-LDH is preferably 1-2 μm, and the thickness is preferably 50-100 nm; the sheet diameter of the two-dimensional layered NiAl-LDH is preferably 10-40 nm.
The composite material has the advantages that the NiAl-LDH has extremely high mechanical bearing capacity and wear resistance, so that the friction performance under a heavy-load environment can be improved, the ZnNiAl-LDH has a layered crystal structure similar to graphite, molybdenum disulfide and the like, interlayer slippage is easy to occur, and the friction coefficient is reduced.
The invention provides a preparation method of the self-lubricating fabric composite material, which comprises the following steps:
according to the mass ratio of polyetherimide to two-dimensional layered ZnNiAl-LDH to two-dimensional layered NiAl-LDH in the self-lubricating composite fabric composite material, dispersing the polyetherimide, the two-dimensional layered ZnNiAl-LDH and the two-dimensional layered NiAl-LDH into N, N-dimethylformamide to obtain an impregnation solution;
and (3) soaking the polytetrafluoroethylene aramid fiber blended fiber fabric into the soaking solution, and drying to obtain the self-lubricating fabric composite material.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
According to the mass ratio of polyetherimide to two-dimensional layered ZnNiAl-LDH to two-dimensional layered NiAl-LDH in the self-lubricating composite fabric composite material, the polyetherimide, the two-dimensional layered ZnNiAl-LDH and the two-dimensional layered NiAl-LDH are dispersed into N, N-dimethylformamide to obtain an impregnation solution.
In the invention, the mass ratio of the polyetherimide to the N, N-dimethylformamide is preferably (10-30): (75-80), more preferably (10-20): (75-77).
In the present invention, the dispersion is preferably performed under a stirring condition, and the rotation speed of the stirring is preferably 1000 to 1500rpm, and more preferably 1100 to 1500 rpm. In the invention, the dispersing time is preferably 2-3 h.
After the impregnation liquid is obtained, the polytetrafluoroethylene aramid fiber blended fiber fabric is impregnated into the impregnation liquid, and the self-lubricating fabric composite material is obtained after drying.
Before impregnation, the invention preferably further comprises pretreatment of the polytetrafluoroethylene aramid blended fiber fabric, wherein the pretreatment preferably comprises the following steps: putting the polytetrafluoroethylene aramid fiber blended fabric into petroleum ether for first ultrasonic cleaning, after first drying, putting the polytetrafluoroethylene aramid fiber blended fabric into a mixed solution of acetone and ethanol for second ultrasonic cleaning, and after taking out, carrying out second drying. In the invention, the time of the first ultrasonic cleaning and the second ultrasonic cleaning is preferably 25-35 min independently. The power of the first ultrasonic cleaning and the second ultrasonic cleaning is not particularly required, and the ultrasonic power well known in the field can be adopted. The present invention has no particular requirement on the conditions of the first drying and the second drying. In the embodiment of the invention, the temperature of the second drying is preferably 80-90 ℃, and the time is preferably 1-2 h. In the invention, the volume ratio of the acetone to the ethanol in the mixed solution of the acetone and the ethanol is preferably (1-3) to (1-2). The invention utilizes pretreatment to remove sizing material and oil agent which are stuck on the fiber in the textile process of the fabric.
The invention has no special requirement on the dosage of the impregnation liquid, and can completely immerse the polytetrafluoroethylene aramid fiber blended fiber fabric. In the invention, the drying temperature is preferably 90-110 ℃, and more preferably 100 ℃. The invention has no special requirement on the drying time, and the drying is complete. In the present invention, the drying is preferably performed in a vacuum drying oven.
The dipping and drying are preferably repeated until the mass of the polytetrafluoroethylene aramid fiber blended fiber fabric reaches 60-90% of the mass of the self-lubricating fabric composite material.
The invention provides an application of the self-lubricating fabric composite material prepared by the preparation method in the scheme or the self-lubricating fabric composite material prepared by the preparation method in the scheme as a friction material in a heavy-load low-temperature environment; the temperature of the heavy-load low-temperature environment is below-100 ℃, and the load of the heavy-load low-temperature environment is above 20 MPa.
The binary and ternary hydroxide synergistically modified self-lubricating fabric composite material and the preparation method thereof provided by the present invention are described in detail in the following examples, which should not be construed as limiting the scope of the present invention.
The following examples and comparative examples used the starting materials:
the adopted polytetrafluoroethylene aramid fiber blended fabric is formed by blending polytetrafluoroethylene fibers and aramid fibers, the thickness of the fabric is 0.2-0.3 mm, the specification is 40s/5 multiplied by 800D, and the appearance is shown in figure 1;
polyetherimide (PEI) of the institute for synthetic resins of Shanghai is adopted;
the two-dimensional layered ZnNiAl-LDH of Jiangsu Xiancheng nano material science and technology limited company is adopted, the appearance is shown in figure 2, and as can be seen from figure 2, the ZnNiAl-LDH is of a two-dimensional layered structure, the sheet diameter is 1-2 mu m, and the thickness is 50-100 nm;
the two-dimensional layered NiAl-LDH of Jiangsu Xiancheng nano material science and technology limited company is adopted, the appearance is shown in figure 3, the two-dimensional layered structure is shown, and the sheet diameter of the NiAl-LDH is 10-40 nm;
n, N-Dimethylformamide (DMF) and petroleum ether of Rianlong Bohua (Tianjin) pharmaceutical chemistry, Inc. are adopted;
the phenolic resin adhesive of the iron anchor plate 204 produced by Shanghai New photo-chemical company Limited is adopted.
Example 1
Putting the polytetrafluoroethylene aramid fiber blended fiber fabric into petroleum ether for ultrasonic cleaning for 35min, and after drying, putting acetone: ultrasonically cleaning the mixture in a mixed solution with the volume ratio of ethanol being 3:2 for 35min, taking out the mixture, and drying the mixture for 2h at the temperature of 80 ℃;
mixing PEI, DMF, ZnNiAl-LDH and NiAl-LDH according to the mass ratio of 30:80:0.4:0.4, magnetically stirring for 3h at the speed of 1500rpm, then putting the pretreated fiber fabric into an impregnation solution for impregnation, drying in a vacuum oven at the temperature of 110 ℃, and repeating the operations of impregnation and drying until the content of the fabric accounts for 60 percent of the total content of the composite material.
Example 2
Putting the polytetrafluoroethylene aramid fiber blended fiber fabric into petroleum ether for ultrasonic cleaning for 30min, and after drying, putting acetone: ultrasonically cleaning in a mixed solution with the volume ratio of ethanol being 3:1 for 33min, taking out and drying at 90 ℃ for 1.5 h;
PEI, DMF, ZnNiAl-LDH and NiAl-LDH are mixed according to the mass ratio of 20:77:0.3:0.3, magnetic stirring is carried out for 2.5h at the speed of 1400rpm, then the pretreated fiber fabric is put into the impregnation liquid for impregnation, the impregnation liquid is dried in a vacuum oven at the temperature of 100 ℃, and the operations of impregnation and drying are repeated until the content of the fabric accounts for 70 percent of the total content of the composite material.
Example 3
Putting the polytetrafluoroethylene aramid fiber blended fiber fabric into petroleum ether for ultrasonic cleaning for 25min, and after drying, putting acetone: ultrasonically cleaning the mixture solution with the volume ratio of ethanol being 1:1 for 25min, taking out the mixture solution, and drying the mixture solution for 1h at 88 ℃.
Mixing PEI, DMF, ZnNiAl-LDH and NiAl-LDH according to the mass ratio of 10:75:0.2:0.2, magnetically stirring for 2h at the speed of 1000rpm, then putting the pretreated fiber fabric into an impregnation solution for impregnation, drying in a vacuum oven at the temperature of 90 ℃, and repeating the operations of impregnation and drying until the content of the fabric accounts for 80 percent of the total content of the composite material.
Example 4
Putting the polytetrafluoroethylene aramid fiber blended fiber fabric into petroleum ether for ultrasonic cleaning for 30min, and after drying, putting acetone: ultrasonically cleaning the mixture solution of ethanol with the volume ratio of 1:2 for 25min, taking out the mixture solution, and drying the mixture solution for 1.5h at 82 ℃.
Mixing PEI, DMF, ZnNiAl-LDH and NiAl-LDH according to the mass ratio of 25:80:0.2:0.4, magnetically stirring for 2h at the speed of 1000rpm, then putting the pretreated fiber fabric into an impregnation solution for impregnation, drying in a vacuum oven at the temperature of 100 ℃, and repeating the operations of impregnation and drying until the content of the fabric accounts for 90 percent of the total content of the composite material.
Comparative example 1
PEI, DMF and ZnNiAl-LDH were mixed in a mass ratio of 10:75:0.4, and the rest of the process was completely the same as in example 3.
Comparative example 2
PEI, DMF and NiAl-LDH were mixed in a mass ratio of 10:75:0.4, and the rest of the process was completely the same as in example 3.
Comparative example 3
PEI and DMF were mixed at a mass ratio of 10:75, and the rest of the process was exactly the same as in example 3.
And (3) performance testing:
1. the self-lubricating fiber fabric composite materials prepared in each example and comparative example are adhered to a pair for a friction test by using phenolic resin, and after being cured, the self-lubricating fiber fabric composite materials are subjected to a friction and wear test under the conditions of heavy load and low temperature, wherein the friction and wear test conditions are as follows: the friction and wear test adopts a high-vacuum low-temperature friction and wear testing machine, the self-lubricating fabric composite material and the GCr15 steel ring are oppositely ground, the test load is 26MPa (1000N), the rotating speed is 3cm/s, the running time is 2h, the friction coefficient and the wear rate are average values of 3-5 tests, and the test temperature is-150 ℃. The test results of each example and comparative example are shown in table 1.
TABLE 1 test results of examples and comparative examples
| Item | Coefficient of friction | Wear rate/10-14m3·N-1·m-1 |
| Example 1 | 0.124 | 9.6 |
| Example 2 | 0.111 | 7.1 |
| Example 3 | 0.103 | 5.2 |
| Example 4 | 0.132 | 10.3 |
| Comparative example 1 | 0.137 | 12.3 |
| Comparative example 2 | 0.142 | 14.5 |
| Comparative example 3 | 0.189 | 18.1 |
As can be seen from comparative examples 1-3 and example 3 in Table 1, ZnNiAl-LDH and NiAl-LDH have the effects of reducing the coefficient and the wear rate when used independently, but the tribological properties of both of the ZnNiAl-LDH and the NiAl-LDH are improved more after the both of the ZnNiAl-LDH and the NiAl-LDH are used simultaneously, which shows that the ZnNiAl-LDH and the NiAl-LDH have synergistic effect.
The results of the examples 1 to 4 show that the friction coefficient can be further improved under the appropriate content of ZnNiAl-LDH and NiAl-LDH, and when the mass ratio of the polyetherimide to the two-dimensional layered ZnNiAl-LDH to the two-dimensional layered NiAl-LDH is 10: 0.2:0.2, the tribological performance of the fiber fabric composite material under the heavy-load low-temperature condition can be improved to the maximum extent.
2. The self-lubricating fabric composite material prepared in example 3 was tested for tribological properties in different environments, and the test results are shown in table 2.
Table 2 tribological properties of the self-lubricating fabric composite prepared in example 3 under different circumstances
| Test temperature | Test pressure | Coefficient of friction | Wear rate/10-14m3·N-1·m-1 |
| -150℃ | 26MPa | 0.103 | 5.2 |
| At room temperature | 26MPa | 0.115 | 7.8 |
| -150℃ | 4MPa | 0.129 | 9.9 |
As can be seen from table 2, the self-lubricating fabric composite material provided by the present application has a low friction coefficient and wear resistance under different environments, especially under heavy-load low-temperature environments.
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 (10)
1. A binary hydroxide and ternary hydroxide synergistically modified self-lubricating fabric composite material comprises a polytetrafluoroethylene aramid fiber blended fabric and a solid lubricant loaded on the polytetrafluoroethylene aramid fiber blended fabric, wherein the solid lubricant comprises two-dimensional layered ZnNiAl-LDH and two-dimensional layered NiAl-LDH; the polytetrafluoroethylene aramid fiber blended fiber fabric and the solid lubricant are bonded through polyetherimide; the mass ratio of the polyetherimide to the two-dimensional layered ZnNiAl-LDH to the two-dimensional layered NiAl-LDH is (10-30): (0.2-0.4): (0.2-0.4).
2. The self-lubricating fabric composite material of claim 1, wherein the mass of the polytetrafluoroethylene aramid blended fiber fabric is 60-90% of the mass of the self-lubricating fabric composite material.
3. The self-lubricating fabric composite material of claim 1, wherein the two-dimensional layered ZnNiAl-LDH has a sheet diameter of 1-2 μm and a thickness of 50-100 nm.
4. The self-lubricating fabric composite material of claim 1, wherein the two-dimensional layered NiAl-LDH has a sheet diameter of 10-40 nm.
5. The self-lubricating fabric composite material of claim 1, wherein the polytetrafluoroethylene aramid blended fiber fabric has a thickness of 0.2-0.3 mm.
6. A method of preparing a self-lubricating fabric composite material according to any one of claims 1 to 5, comprising the steps of:
according to the mass ratio of polyetherimide to two-dimensional layered ZnNiAl-LDH to two-dimensional layered NiAl-LDH in the self-lubricating composite fabric composite material, dispersing the polyetherimide, the two-dimensional layered ZnNiAl-LDH and the two-dimensional layered NiAl-LDH into N, N-dimethylformamide to obtain an impregnation solution;
and (3) soaking the polytetrafluoroethylene aramid fiber blended fiber fabric into the soaking solution, and drying to obtain the self-lubricating fabric composite material.
7. The preparation method of claim 6, wherein the dipping and the drying are repeated until the mass of the polytetrafluoroethylene aramid fiber blended fabric reaches 60-90% of the mass of the self-lubricating fabric composite material.
8. The preparation method according to claim 6, wherein the mass ratio of the polyetherimide to the N, N-dimethylformamide is (10-30): (75-80).
9. The preparation method of claim 6, wherein the impregnation step further comprises a step of pretreating the polytetrafluoroethylene aramid blended fiber fabric, and the pretreatment comprises the following steps: putting the polytetrafluoroethylene aramid fiber blended fabric into petroleum ether for first ultrasonic cleaning, after first drying, putting the polytetrafluoroethylene aramid fiber blended fabric into a mixed solution of acetone and ethanol for second ultrasonic cleaning, and after taking out, carrying out second drying.
10. Use of the self-lubricating fabric composite material according to any one of claims 1 to 5 or the self-lubricating fabric composite material prepared by the preparation method according to any one of claims 6 to 9 as a friction material in a heavy-duty low-temperature environment; the temperature of the heavy-load low-temperature environment is below-100 ℃, and the load of the heavy-load low-temperature environment is above 20 MPa.
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