CN115807330B - Self-lubricating fiber fabric and self-lubricating liner fabric composite material and preparation method thereof - Google Patents
Self-lubricating fiber fabric and self-lubricating liner fabric composite material and preparation method thereof Download PDFInfo
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- CN115807330B CN115807330B CN202210018996.3A CN202210018996A CN115807330B CN 115807330 B CN115807330 B CN 115807330B CN 202210018996 A CN202210018996 A CN 202210018996A CN 115807330 B CN115807330 B CN 115807330B
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- 239000004744 fabric Substances 0.000 title claims abstract description 215
- 239000000835 fiber Substances 0.000 title claims abstract description 188
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 34
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 34
- 238000005530 etching Methods 0.000 claims abstract description 30
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 229960003638 dopamine Drugs 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 67
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 150000003839 salts Chemical class 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000012621 metal-organic framework Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000009832 plasma treatment Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 230000008878 coupling Effects 0.000 claims description 15
- 238000010168 coupling process Methods 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- 125000006850 spacer group Chemical group 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 238000003541 multi-stage reaction Methods 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- HOEJXJMZXGNCBJ-UHFFFAOYSA-N ethene 4-ethenylbenzoic acid Chemical group C=CC1=CC=C(C=C1)C(=O)O.C=C HOEJXJMZXGNCBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 230000001050 lubricating effect Effects 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000011664 nicotinic acid Substances 0.000 description 31
- 239000000805 composite resin Substances 0.000 description 20
- 238000001035 drying Methods 0.000 description 12
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- -1 transition metal salt Chemical class 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- 229920000784 Nomex Polymers 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000004763 nomex Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000678 plasma activation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention belongs to the technical field of composite materials and lubricating materials, and provides a self-lubricating fiber fabric and a preparation method thereof, and a self-lubricating liner fabric composite material and a preparation method thereof. The preparation method provided by the invention constructs lamellar metal hydroxide which is distributed perpendicular to the axial direction of the fiber on the surface of the fiber through an interface growth reaction and etching treatment process and is used as an enhancement component in an interface phase; and then modifying the copolymer between metal hydroxide sheets through polymerization reaction of dopamine, polyethylenimine and a silane coupling agent in the composite solution, and interacting with the metal hydroxide through hydrogen bonds and van der Waals acting force, wherein the polymer is used as a toughening component in an interface phase. When the self-lubricating fiber fabric and resin obtained by the preparation method are compounded to prepare the self-lubricating liner fabric composite material, a strong-toughness integrated interface phase can be constructed in the self-lubricating liner fabric composite material, and the service life of the self-lubricating liner fabric composite material is prolonged.
Description
Technical Field
The invention relates to the technical field of composite materials and lubricating materials, in particular to a self-lubricating fiber fabric and a preparation method thereof, a self-lubricating liner fabric composite material and a preparation method thereof.
Background
The bearing is used as a key device in the industrial field, and has the main functions of supporting a mechanical rotating body, reducing friction coefficient in the motion process and ensuring rotation precision. The self-lubricating knuckle bearing is used as an important functional component with high bearing capacity, wear resistance, self-aligning performance, rotation and the like, is widely applied to aviation, aerospace, advanced weapon systems and high-end civil fields, and is an indispensable component for aero-engines, landing gears, rudders, horizontal tails, flaps and the like. The self-lubricating pad is an important component in the self-lubricating joint bearing, and can play roles in antifriction and antiwear, isolating metal, resisting impact, prolonging the service life of the bearing and the like. The self-lubricating liner also has the advantages of high strength, no maintenance and the like, and has excellent self-lubricating performance and wear resistance in severe service environments such as high temperature, heavy load, high frequency and the like. With the increasing requirements of bearing performance in the high and new technical fields, the comprehensive performance of the self-lubricating liner is also put forward higher and higher requirements.
For self-lubricating spacer fabric composites, the reinforcement is a two-dimensional fabric obtained by blending reinforcing fibers and lubricating fibers (PTFE), and the interface between the fibers and the resin has a decisive influence on the performance of the composite throughout the composite. The interface between the fiber and the resin shows very good bonding strength, and the internal stress of the material can only be released through the continuous generation and expansion of microcracks at the interface between the fiber and the resin; the interfacial bonding strength is too poor, and the mechanical strength and tribological performance of the composite material can be greatly reduced. Therefore, an interface modification layer with matched strength and toughness is required to be constructed between fiber resins, so that the mechanical property and tribological property of the self-lubricating liner fabric composite material are improved to the maximum extent.
At present, the self-lubricating lining fabric composite material prepared by modifying the self-lubricating lining fabric composite material by mainly adopting methods of chemical etching, surface coating, grafting high molecular polymer and the like can achieve the aim of improving the bonding strength of a fiber-resin interface, and the interface toughness of the fiber-resin is not considered.
Disclosure of Invention
In view of the above, the present invention aims to provide a self-lubricating fiber fabric and a preparation method thereof, a self-lubricating liner fabric composite material and a preparation method thereof. The self-lubricating fiber fabric obtained by the preparation method provided by the invention not only can strengthen the bonding strength of fiber-resin, but also can improve the interface toughness of the fiber-resin.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a self-lubricating fiber fabric, which comprises the following steps:
carrying out plasma treatment on the fiber fabric to obtain an activated fiber fabric;
growing a metal organic framework compound on the surface of the activated fiber fabric to obtain a fiber fabric modified by the metal organic framework compound;
immersing the fiber fabric decorated by the metal organic framework compound into etching solution for etching treatment to obtain fiber fabric loaded by metal hydroxide; the etching solution is a metal salt ethanol solution; the metal salt in the metal salt ethanol solution is consistent with the metal salt in the metal organic framework compound precursor solution;
immersing the fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite solution for polymerization and crosslinking reaction to obtain the self-lubricating fiber fabric.
Preferably, the power of the plasma treatment is 30-200W, and the time is 1-40 min.
Preferably, the growing metal-organic framework compound comprises: immersing the activated fiber fabric into a metal salt aqueous solution for loading, and then adding an organic compound aqueous solution for a composite reaction; the concentration of the metal salt aqueous solution is 0.005 mol/L-0.5 mol/L; the concentration of the organic compound aqueous solution is 0.05 mol/L-1.2 mol/L; the volume ratio of the metal salt aqueous solution to the organic compound aqueous solution is 1: (1-3).
Preferably, the metal salt in the aqueous metal salt solution comprises a transition metal salt; the transition metal salt includes a cobalt ion salt or a zinc ion salt.
Preferably, the concentration of the metal salt in the metal salt ethanol solution is 0.005mol/L to 0.5mol/L.
Preferably, in the dopamine-silane coupling agent-polyethyleneimine composite solution, the concentration of dopamine is 0.1 mg/mL-20 mg/mL, the concentration of silane coupling agent is 0.1 mg/mL-1 g/mL, and the concentration of polyethyleneimine is 0.1 mg/mL-40 mg/mL.
The invention also provides the self-lubricating fiber fabric obtained by the preparation method.
The invention also provides a self-lubricating lining fabric composite material, which comprises the self-lubricating fiber fabric and resin according to the technical scheme; the resin includes phenolic resin, polyimide resin or epoxy resin.
Preferably, the mass fraction of self-lubricating fibrous fabric in the self-lubricating spacer fabric composite is 15-35%.
The invention also provides a preparation method of the self-lubricating lining fabric composite material, which comprises the following steps:
dipping the self-lubricating fiber fabric into resin, and curing to obtain the self-lubricating liner fabric composite material;
the curing temperature is 120-300 ℃, the pressure is 0.1-1 MPa, and the curing time is 30 min-6 h.
The invention provides a preparation method of a self-lubricating fiber fabric, which comprises the following steps: carrying out plasma treatment on the fiber fabric to obtain an activated fiber fabric; growing a metal organic framework compound on the surface of the activated fiber fabric to obtain a fiber fabric modified by the metal organic framework compound; immersing the fiber fabric decorated by the metal organic framework compound into etching solution for etching treatment to obtain fiber fabric loaded by metal hydroxide; the etching solution is a metal salt ethanol solution; the metal salt in the metal salt ethanol solution is consistent with the metal salt in the metal organic framework compound precursor solution; immersing the fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite solution to perform polymerization crosslinking reaction, so as to obtain the self-lubricating fiber fabric. The invention carries out plasma treatment on the fiber fabric, increases the surface-OH, -NH of the fiber fabric 2 The content of the equal functional groups improves the activity of the surface of the fiber fabric and is beneficial to the grafting and polymerization of subsequent substances. Growing a metal organic framework compound on the surface of the activated fiber fabric, and further loading a lamellar metal organic framework compound on the surface of the fiber fabric; immersing the fiber fabric loaded with the metal organic framework compound into an etching solution, and carrying out in-situ etching on the metal organic framework compound by utilizing metal salt which is consistent with the metal organic framework in the etching solution, wherein lamellar metal hydroxide which is distributed perpendicular to the axial direction of the fiber is constructed on the surface of the fiber, and the metal hydroxide is used as a reinforcing component in an interface phase, so that the interface strength between the fiber fabric and the resin is improved; immersing the fiber fabric loaded with metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite solution for polymerization crosslinking reaction, modifying the copolymer of dopamine, polyethyleneimine and silane coupling agent between metal hydroxide sheets by polymerization reaction of dopamine, polyethyleneimine and silane coupling agent in the composite solution, and taking the polymer as a toughening component in an interface phase through interaction of hydrogen bond and Van der Waals acting force and metal hydroxide to extractThe interfacial toughness between the fiber fabric and the resin is improved. The self-lubricating fiber fabric provided by the invention has the advantages that the self-lubricating fiber fabric is simultaneously provided with the interface reinforcing component (metal hydroxide) and the interface toughening component (dopamine-silane coupling agent-polyethyleneimine polymerization layer), when the self-lubricating fiber fabric is subjected to external and internal stress, the interface reinforcing component can reduce crack generation, and the interface toughening component can inhibit the expansion of microcracks, so that the service life of the self-lubricating fiber fabric is prolonged.
The invention provides the self-lubricating fiber fabric obtained by the preparation method. The self-lubricating fiber fabric provided by the invention can improve the interface toughness while constructing a strong-tough integrated interface phase at a fiber-resin interface, namely improving the interface bonding strength. When the self-lubricating fiber fabric is subjected to external and internal stress, the reinforcing component in the tough interface phase can reduce crack generation, and the toughening component can inhibit the expansion of microcracks, so that the service life of the self-lubricating fiber fabric is prolonged.
The invention provides a self-lubricating lining fabric composite material, which comprises the self-lubricating fiber fabric and resin according to the technical scheme; the resin includes phenolic resin, polyimide resin or epoxy resin. The self-lubricating lining fabric composite material has excellent self-lubricating performance and service life.
Drawings
FIG. 1 is a graph showing the change of friction coefficient of the bionic interfacial phase modified self-lubricating fiber fabric composite material obtained in example 1 with time;
FIG. 2 is a graph of the coefficient of friction of the respective lubricating spacer fabric composites of example 2 as a function of time;
FIG. 3 is a graph of the average coefficient of friction for each of the lubricating spacer fabric composites of example 2;
FIG. 4 is a graph of the average wear rate of the respective lubricating spacer fabric composites of example 2;
FIG. 5 is a graph showing the relationship between the friction coefficient of the bionic interfacial phase modified self-lubricating fiber fabric resin composite material obtained in example 3 and time;
FIG. 6 is a graph showing the change of the friction coefficient of the bionic interfacial phase modified self-lubricating fiber fabric resin composite material obtained in example 4 with time.
Detailed Description
The invention provides a preparation method of a self-lubricating fiber fabric, which comprises the following steps:
carrying out plasma treatment on the fiber fabric to obtain an activated fiber fabric;
growing a metal organic framework compound on the surface of the activated fiber fabric to obtain a fiber fabric modified by the metal organic framework compound;
immersing the fiber fabric decorated by the metal organic framework compound into etching solution for etching treatment to obtain fiber fabric loaded by metal hydroxide; the etching solution is a metal salt ethanol solution; the metal salt in the metal salt ethanol solution is consistent with the metal salt in the metal organic framework compound precursor solution;
immersing the fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite solution to perform polymerization crosslinking reaction, so as to obtain the self-lubricating fiber fabric.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention carries out plasma treatment on the fiber fabric to obtain the activated fiber fabric.
In the present invention, the fiber fabric preferably includes an aramid fiber/polytetrafluoroethylene fiber blend fabric, a polyimide fiber/polytetrafluoroethylene fiber blend fabric, a glass fiber/polytetrafluoroethylene fiber blend fabric, or a polyether ether ketone fiber/polytetrafluoroethylene fiber blend fabric. In the present invention, the fiber fabric is preferably washed before being subjected to plasma treatment; the present invention does not particularly limit the washing reagent and the number of times, as long as the oxide and the like on the surface of the fiber fabric can be washed cleanly.
In the present invention, the power of the plasma treatment is preferably 30W to 200W, more preferably 100W; the time is preferably 1min to 40min.
In the present inventionIn the method, the plasma treatment can increase the surface-OH and-NH of the fiber fabric 2 The content of the equal functional groups is favorable for grafting and compounding of subsequent substances.
After the activated fiber fabric is obtained, a metal organic framework compound grows on the surface of the activated fiber fabric to obtain the fiber fabric modified by the metal organic framework compound.
In the present invention, the growing metal-organic framework compound preferably includes: immersing the activated fiber fabric into a metal salt aqueous solution for loading, and then adding an organic compound aqueous solution for carrying out a composite reaction. In the present invention, the metal salt in the metal salt aqueous solution preferably includes a transition metal salt; the transition metal salt preferably comprises a cobalt ion salt or a zinc ion salt. In the present invention, the organic compound in the aqueous solution of the organic compound preferably includes 2-methylimidazole, terephthalic acid, trimesic acid or 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene, and further preferably includes 2-methylimidazole.
In the present invention, the concentration of the aqueous metal salt solution is preferably 0.005mol/L to 0.5mol/L, more preferably 0.01 mol/L to 0.1mol/L, and the concentration of the aqueous organic compound solution is preferably 0.05mol/L to 1.2mol/L, more preferably 0.1mol/L to 1.0mol/L. In the present invention, the volume ratio of the aqueous metal salt solution to the aqueous organic compound solution is preferably 1: (1 to 3), more preferably 1:1.
in the present invention, the time of the loading is preferably 10 to 30 minutes, more preferably 15 minutes; the loading is preferably carried out under ultrasound conditions.
In the present invention, the temperature of the complex reaction is preferably room temperature, i.e., neither additional heating nor additional cooling is required. In the present invention, the time for the complexing reaction is preferably 2 to 24 hours, more preferably 8 to 16 hours. In the present invention, the mode of the complex reaction is preferably standing.
After the composite reaction, the fiber fabric is taken out, washed and dried in sequence, and the fiber fabric modified by the metal organic framework compound is obtained. In the present invention, the washed reagent preferably comprises water, which preferably comprises deionized water. In the present invention, the drying temperature is preferably 80 ℃, and the drying time is not particularly limited as long as it is dried to a constant weight.
After obtaining a fiber fabric decorated by a metal organic framework compound, immersing the fiber fabric decorated by the metal organic framework compound into etching solution for etching treatment to obtain a fiber fabric loaded by metal hydroxide; the etching solution is a metal salt ethanol solution; the metal salt in the metal salt ethanol solution is consistent with the metal salt in the metal organic framework compound precursor solution.
In the invention, the etching solution is a metal salt ethanol solution; the metal salt in the metal salt ethanol solution is consistent with the metal salt in the metal organic framework compound precursor solution. In the present invention, the concentration of the metal salt in the metal salt ethanol solution is preferably 0.005mol/L to 0.5mol/L.
In the invention, the temperature of the etching treatment is preferably room temperature, namely, no additional heating or no additional cooling is needed; the etching treatment time is preferably 3min to 2h, and more preferably 30min to 60min. In the present invention, the etching treatment is preferably performed by standing.
After the etching treatment, the invention further comprises the steps of taking out the fiber fabric, and washing and drying the fiber fabric in sequence to obtain the fiber fabric loaded by the metal hydroxide. In the present invention, the washed reagent preferably comprises water, which preferably comprises deionized water. In the present invention, the drying temperature is preferably 80 ℃, and the drying time is not particularly limited as long as it is dried to a constant weight.
In the invention, the etching treatment can carry out in-situ etching on the metal organic framework compound to obtain the strength-enhancing component metal hydroxide.
After obtaining a fiber fabric loaded by metal hydroxide, immersing the fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite solution for polymerization and crosslinking reaction to obtain the self-lubricating fiber fabric.
In the invention, the concentration of dopamine in the dopamine-silane coupling agent-polyethyleneimine composite solution is preferably 0.1 mg/mL-20 mg/mL, and more preferably 1 mg/mL-10 mg/mL; the concentration of the silane coupling agent is preferably 0.1mg/mL to 1g/mL, more preferably 0.5mg/mL to 100mg/mL, still more preferably 1mg/mL to 10mg/mL, and the concentration of the polyethyleneimine is preferably 0.1mg/mL to 40mg/mL, still more preferably 0.5mg/mL to 30mg/mL, and still more preferably 1mg/mL to 10mg/mL. In the present invention, the silane coupling agent preferably includes one or more of 3-aminopropyl triethoxysilane, 1, 2-epoxypropyl triethoxysilane, and 3-mercaptopropyl trimethoxysilane.
In the invention, the temperature of the polymerization crosslinking reaction is preferably room temperature, namely, no additional heating or no additional cooling is needed; the polymerization crosslinking reaction time is preferably 2 to 72 hours. In the present invention, the mode of the polymerization crosslinking reaction is preferably standing.
After the polymerization crosslinking reaction, the invention preferably further comprises the step of taking out the fiber fabric, and sequentially washing and drying to obtain the self-lubricating fiber fabric. In the present invention, the washed reagent preferably comprises water, which preferably comprises deionized water. In the present invention, the drying temperature is preferably 80 ℃, and the drying time is not particularly limited as long as it is dried to a constant weight.
In the invention, the polymerization crosslinking reaction can form a hybrid layer of the toughening component dopamine-silane coupling agent-polyethyleneimine polymer on the surface of the metal hydroxide.
The invention also provides the self-lubricating fiber fabric obtained by the preparation method. The self-lubricating fiber fabric provided by the invention can improve the interface toughness while constructing a strong-tough integrated interface phase at a fiber-resin interface, namely improving the interface bonding strength. When the self-lubricating fiber fabric is subjected to external and internal stress, the reinforcing component in the tough interface phase can reduce crack generation, and the toughening component can inhibit the expansion of microcracks, so that the service life of the self-lubricating fiber fabric is prolonged.
The invention also provides a self-lubricating lining fabric composite material, which comprises the self-lubricating fiber fabric and resin according to the technical scheme; the resin includes phenolic resin, polyimide resin or epoxy resin.
In the present invention, the mass fraction of the self-lubricating fibrous fabric in the self-lubricating spacer fabric composite is preferably 15 to 35%.
The invention also provides a preparation method of the self-lubricating lining fabric composite material, which comprises the following steps:
and (3) soaking the self-lubricating fiber fabric in resin, and curing to obtain the self-lubricating liner fabric composite material.
The number of times of the impregnation is not particularly limited in the present invention, so long as the mass fraction of the self-lubricating fiber fabric in the self-lubricating spacer fabric composite material can be made to meet the requirement.
In the present invention, the curing temperature is preferably 120 to 300 ℃; the pressure is preferably 0.1-1 MPa; the curing time is preferably 30min to 6h.
The self-lubricating fiber fabric and the preparation method thereof, the self-lubricating spacer fabric composite material and the preparation method thereof provided by the invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
(1) And carrying out plasma treatment on the washed Nomex/PTFE self-lubricating fiber fabric in an air atmosphere to increase the content of active functional groups on the fiber surface, wherein the plasma treatment power is 100W, the time is 5min on a bonding surface and 5min on a lubricating surface.
(2) Immersing the self-lubricating fiber fabric subjected to air plasma activation treatment into 50mL of cobalt chloride hexahydrate solution (the concentration is 0.05 mol/L), carrying out ultrasonic treatment for 15min, then adding 50mL of 2-methylimidazole solution into the solution (the concentration is 0.4 mol/L), standing for reaction for 8h, taking out deionized water for washing, and drying at 80 ℃ to obtain the Co-MOFs loaded self-lubricating fiber fabric. The solvent used in the reaction system is deionized water, and the concentration is the concentration before mixing.
(3) Immersing the Co-MOFs loaded self-lubricating fiber fabric into a 6mg/mL cobalt chloride hexahydrate ethanol solution, and carrying out etching treatment for 35min to obtain a metal hydroxide loaded self-lubricating fiber fabric;
(4) Immersing the self-lubricating fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite system to prepare a toughening component in a bionic interface phase, wherein the concentration of dopamine is 2mg/mL, the concentration of 3-aminopropyl triethoxysilane is 1mg/mL, and the concentration of polyethyleneimine is 1mg/mL, and reacting for 24 hours at room temperature to obtain the bionic interface phase modified self-lubricating fiber fabric.
Immersing the obtained bionic interface phase modified self-lubricating fiber fabric into a phenolic resin solution, repeatedly immersing until the mass fraction of the fiber fabric reaches 75+/-2%, adhering the immersed wet composite material on the surface of a metal substrate, and curing at the temperature of 184 ℃ under the pressure of 0.2MPa for 140min to obtain the bionic interface phase modified self-lubricating fiber fabric composite material.
Under the room temperature environment, the dynamic load of 80MPa, the rotating speed of 280 revolutions per minute and the rotating friction test of 2 hours, the friction coefficient of the obtained self-lubricating lining fabric composite material is as follows: 0.040, wear rate: 0.729×10 -14 m 3 /N·m。
FIG. 1 is a graph showing the change of friction coefficient of the obtained bionic interfacial phase modified self-lubricating fiber fabric composite material with time. As can be seen from fig. 1: the friction coefficient of the bionic interface phase modified self-lubricating fiber fabric composite material obtained by the embodiment is smaller, but the friction running-in period is longer.
Example 2
(1) And carrying out plasma treatment on the washed Nomex/PTFE self-lubricating fiber fabric in an air atmosphere to increase the content of active functional groups on the fiber surface, wherein the plasma treatment power is 100W, the time is 10min on a bonding surface and 10min on a lubricating surface.
(2) Immersing the self-lubricating fiber fabric subjected to air plasma activation treatment into 50mL of cobalt chloride hexahydrate solution (the concentration is 0.05 mol/L), carrying out ultrasonic treatment for 15min, then adding 50mL of 2-methylimidazole solution into the solution (the concentration is 0.4 mol/L), standing for reaction for 8h, taking out deionized water for washing, and drying at 80 ℃ to obtain the Co-MOFs loaded self-lubricating fiber fabric.
(3) Immersing the Co-MOFs loaded self-lubricating fiber fabric into a 6mg/mL ethanol solution of cobalt chloride hexahydrate, and carrying out etching treatment for 35min to obtain the metal hydroxide loaded self-lubricating fiber fabric.
(4) Immersing the self-lubricating fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite system to prepare a toughening component in a bionic interface phase, wherein the concentration of dopamine is 2mg/mL, the concentration of 3-aminopropyl triethoxysilane is 1mg/mL, and the concentration of polyethyleneimine is 1mg/mL, and reacting for 24 hours at room temperature to obtain the bionic interface phase modified self-lubricating fiber fabric.
Immersing the washed Nomex/PTFE self-lubricating fiber fabric, the Co-MOFs loaded self-lubricating fiber fabric obtained in the step (2), the metal hydroxide loaded self-lubricating fiber fabric obtained in the step (3) and the bionic interface phase modified self-lubricating fiber fabric obtained in the step (4) into phenolic resin solution respectively, repeatedly immersing until the mass fraction of the fabric reaches 75+/-2%, bonding the immersed wet composite material on the surface of a metal substrate, and curing for 140min at the temperature of 0.2MPa and 184 ℃ to obtain the composite material of the fabric with the respective lubricating liner.
Under the room temperature environment, the dynamic load of 80MPa and the rotating speed of 280 revolutions per minute are adopted, and the friction coefficient of the bionic interface phase modified self-lubricating fiber fabric composite material is obtained by a rotating friction test for 2 hours and is as follows: 0.046, wear rate: 0.704×10 -14 m 3 /N·m。
FIG. 2 is a graph of the coefficient of friction of the respective lubricating mat fabric composites over time, wherein (a) is a graph of the coefficient of friction of the untreated self-lubricating fiber fabric resin composite over time, (b) is a graph of the coefficient of friction of the Co-MOFs-loaded self-lubricating fiber fabric resin composite over time, (c) is a graph of the coefficient of friction of the metal hydroxide-loaded self-lubricating fiber fabric resin composite over time, and (d) is a graph of the coefficient of friction of the bionic interfacial phase modified self-lubricating fiber fabric resin composite over time. As can be seen from fig. 2: untreated self-lubricating fiber fabric resin composite material, co-MOFs loaded self-lubricating fiber fabric resin composite material and metal hydroxide loaded self-lubricating fiber fabric resin composite material have larger fluctuation of friction coefficient and longer running-in period. However, for the bionic interface phase modified self-lubricating fiber fabric resin composite material, the running-in period is 25min, and the fluctuation of friction coefficient in the stationary phase is very small.
Fig. 3 is a graph of average coefficient of friction for the respective lubricating liner fabric composites, and fig. 4 is a graph of average wear rate for the respective lubricating liner fabric composites, as can be seen from fig. 3 and 4: the friction coefficient of the Co-MOFs loaded self-lubricating fiber fabric resin composite material is increased after MOFs loading, but the lining wear rate is greatly reduced; for Co (OH) 2 The friction coefficient of the self-lubricating liner modified by the modified self-lubricating fiber fabric and the self-lubricating liner modified by the bionic interface phase are both reduced, and the self-lubricating fiber fabric resin composite modified by the bionic interface phase shows the minimum wear rate.
Example 3
(1) And carrying out plasma treatment on the washed Nomex/PTFE self-lubricating fiber fabric in an air atmosphere to increase the content of active functional groups on the fiber surface, wherein the plasma treatment power is 100W, the time is 5min on a bonding surface and 5min on a lubricating surface.
(2) The self-lubricating fiber fabric subjected to air plasma activation treatment is immersed in 50mL of cobalt chloride hexahydrate solution (the concentration is 0.05 mol/L), ultrasonic treatment is carried out for 15min, then 50mL of 2-methylimidazole solution is added into the solution (the concentration is 0.4 mol/L), standing reaction is carried out for 16h, deionized water is taken out for washing, and drying is carried out at 80 ℃ to obtain the Co-MOFs loaded self-lubricating fiber fabric.
(3) Immersing the Co-MOFs loaded self-lubricating fiber fabric into a 6mg/mL cobalt chloride hexahydrate ethanol solution, and carrying out etching treatment for 35min to obtain a metal hydroxide loaded self-lubricating fiber fabric;
(4) Immersing the self-lubricating fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite system to prepare a toughening component in a bionic interface phase, wherein the concentration of dopamine is 2mg/mL, the concentration of 3-aminopropyl triethoxysilane is 1mg/mL, and the concentration of polyethyleneimine is 1mg/mL, and reacting for 24 hours at room temperature to obtain the bionic interface phase modified self-lubricating fiber fabric.
Immersing the bionic interface phase modified self-lubricating fiber fabric in a phenolic resin solution, repeatedly immersing until the mass fraction of the fabric reaches 75+/-2%, adhering the immersed and wetted composite material on the surface of a metal substrate, and curing at the temperature of 184 ℃ under the pressure of 0.2MPa for 140min to obtain the bionic interface phase modified self-lubricating fiber fabric resin composite material.
Under the room temperature environment, the friction coefficient of the bionic interface phase modified self-lubricating fiber fabric resin composite material obtained by a rotational friction test for 2h under the dynamic load of 80MPa and the rotational speed of 280 r/min is as follows: 0.059, wear rate: 0.808×10 -14 m 3 /N·m。
FIG. 5 is a graph showing the change of friction coefficient of the obtained bionic interfacial phase modified self-lubricating fiber fabric resin composite material with time. As can be seen from fig. 5: the friction coefficient of the bionic interface phase modified self-lubricating fiber fabric resin composite material obtained by the embodiment has larger fluctuation and is unstable.
Example 4
(1) And carrying out plasma treatment on the washed Nomex/PTFE self-lubricating fiber fabric in an air atmosphere to increase the content of active functional groups on the fiber surface, wherein the plasma treatment power is 100W, the time is 5min on a bonding surface and 5min on a lubricating surface.
(2) The self-lubricating fiber fabric subjected to air plasma activation treatment is immersed in 50mL of cobalt chloride hexahydrate solution (the concentration is 0.05 mol/L), ultrasonic treatment is carried out for 15min, then 50mL of 2-methylimidazole solution is added into the solution (the concentration is 0.4 mol/L), standing reaction is carried out for 16h, deionized water is taken out for washing, and drying is carried out at 80 ℃ to obtain the Co-MOFs loaded self-lubricating fiber fabric.
(3) Immersing the Co-MOFs loaded self-lubricating fiber fabric into a 6mg/mL ethanol solution of cobalt chloride hexahydrate, and carrying out etching treatment for 35min to obtain the metal hydroxide loaded self-lubricating fiber fabric.
(4) Immersing the self-lubricating fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite system to prepare a toughening component in a bionic interface phase, wherein the concentration of dopamine is 2mg/mL, the concentration of 3-aminopropyl triethoxysilane is 2mg/mL, the concentration of polyethyleneimine is 1mg/mL, and reacting for 24 hours at room temperature to obtain the bionic interface phase modified self-lubricating fiber fabric.
Immersing the bionic interface phase modified self-lubricating fiber fabric in a phenolic resin solution, repeatedly immersing until the mass fraction of the fabric reaches 75+/-2%, adhering the immersed and wetted composite material on the surface of a metal substrate, and curing at the temperature of 184 ℃ under the pressure of 0.2MPa for 140min to obtain the bionic interface phase modified self-lubricating fiber fabric resin composite material.
Under the room temperature environment, the friction coefficient of the bionic interface phase modified self-lubricating fiber fabric resin composite material obtained by a rotational friction test for 2h under the dynamic load of 80MPa and the rotational speed of 280 r/min is as follows: 0.055, wear rate: 0.755X10 -14 m 3 /N·m。
FIG. 6 is a graph showing the change of the friction coefficient of the obtained bionic interfacial phase modified self-lubricating fiber fabric resin composite material with time. As can be seen from fig. 6: the friction coefficient of the bionic interface phase modified self-lubricating fiber fabric resin composite material obtained by the embodiment has larger fluctuation and is unstable.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the self-lubricating fiber fabric is characterized by comprising the following steps of:
carrying out plasma treatment on the fiber fabric to obtain an activated fiber fabric;
growing a metal organic framework compound on the surface of the activated fiber fabric to obtain a fiber fabric modified by the metal organic framework compound;
immersing the fiber fabric decorated by the metal organic framework compound into etching solution for etching treatment to obtain fiber fabric loaded by metal hydroxide; the etching solution is a metal salt ethanol solution;
immersing the fiber fabric loaded by the metal hydroxide into a dopamine-silane coupling agent-polyethyleneimine composite solution for polymerization and crosslinking reaction to obtain the self-lubricating fiber fabric;
the fiber fabric comprises aramid fiber/polytetrafluoroethylene fiber blended fabric, polyimide fiber/polytetrafluoroethylene fiber blended fabric, glass fiber/polytetrafluoroethylene fiber blended fabric or polyether-ether-ketone fiber/polytetrafluoroethylene fiber blended fabric;
the growing metal-organic framework compound comprises:
immersing the activated fiber fabric into a metal salt aqueous solution for loading, and then adding an organic compound aqueous solution for a composite reaction;
the metal salt in the metal salt aqueous solution comprises cobalt ion salt or zinc ion salt;
the organic compound in the organic compound aqueous solution comprises 2-methylimidazole, terephthalic acid, trimesic acid or 1, 2-diphenyl-1, 2-bis (4-carboxystyrene) ethylene;
the metal salt in the metal salt ethanol solution is consistent with the metal salt in the metal salt water solution.
2. The method according to claim 1, wherein the plasma treatment is performed at a power of 30w to 200w for 1min to 40min.
3. The method according to claim 1, wherein the concentration of the aqueous metal salt solution is 0.005mol/L to 0.5mol/L; the concentration of the organic compound aqueous solution is 0.05 mol/L-1.2 mol/L; the volume ratio of the metal salt aqueous solution to the organic compound aqueous solution is 1: (1-3).
4. The preparation method according to claim 1, wherein the concentration of the metal salt in the metal salt ethanol solution is 0.005mol/L to 0.5mol/L.
5. The preparation method of claim 1, wherein in the dopamine-silane coupling agent-polyethyleneimine composite solution, the concentration of dopamine is 0.1 mg/mL-20 mg/mL, the concentration of silane coupling agent is 0.1 mg/mL-1 g/mL, and the concentration of polyethyleneimine is 0.1 mg/mL-40 mg/mL.
6. The self-lubricating fiber fabric obtained by the preparation method according to any one of claims 1 to 5.
7. A self-lubricating spacer fabric composite comprising the self-lubricating fibrous fabric of claim 6 and a resin; the resin includes phenolic resin, polyimide resin or epoxy resin.
8. The self-lubricating spacer fabric composite of claim 7, wherein the mass fraction of self-lubricating fiber fabric in the self-lubricating spacer fabric composite is 15-35%.
9. The method for preparing the self-lubricating spacer fabric composite material according to any one of claims 7 to 8, comprising the steps of:
dipping the self-lubricating fiber fabric into resin, and curing to obtain the self-lubricating liner fabric composite material;
the curing temperature is 120-300 ℃, the pressure is 0.1-1 MPa, and the curing time is 30 min-6 h.
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| KR20210060207A (en) * | 2019-11-18 | 2021-05-26 | 주식회사 엘지화학 | Metal organic framework-nanofiber composite and preparation method thereof |
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