CN113201266A - High-performance epoxy bonding type solid self-lubricating coating and preparation and use method thereof - Google Patents
High-performance epoxy bonding type solid self-lubricating coating and preparation and use method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 101
- 239000011248 coating agent Substances 0.000 title claims abstract description 100
- 239000004593 Epoxy Substances 0.000 title claims abstract description 76
- 239000007787 solid Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000011246 composite particle Substances 0.000 claims abstract description 84
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 67
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 48
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- -1 polysiloxane Polymers 0.000 claims description 50
- 229920001296 polysiloxane Polymers 0.000 claims description 50
- 239000002131 composite material Substances 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 23
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- 238000003756 stirring Methods 0.000 claims description 21
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
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- 238000005507 spraying Methods 0.000 claims description 13
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- 238000001291 vacuum drying Methods 0.000 claims description 9
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- 239000003795 chemical substances by application Substances 0.000 claims description 8
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- 230000008569 process Effects 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
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- 238000010992 reflux Methods 0.000 claims description 6
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000853 adhesive Substances 0.000 description 4
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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Abstract
The invention relates to a high-performance epoxy adhesive solid self-lubricating coating and a preparation and use method thereof, which is prepared from HBPSi-PAA and MoS2the/rGO composite particles and epoxy resin are compounded and prepared. The HBPSi-PAA not only can achieve the effects of toughening and strengthening, but also can endow the epoxy coating with good leveling property and film-forming property, and can further improve the flexibility, heat resistance and usability of the epoxy coating under extreme conditions after curing. When the proper amount of MoS is added into the epoxy coating2HBPSi-PAA can be combined with MoS when/rGO composite particles2the/rGO composite particles form the synergistic effect of soft and hard particles, so that the epoxy bonding type solid self-lubricating coating has lower friction coefficient, higher bearing capacity and longer friction life. The invention solves the problems of easy brittle fracture at low temperature, easy shedding at high temperature, short service life and the like of the solid self-lubricating coating for the fields of aviation, aerospace and the like, and the solid self-lubricating coatingThe coating has simple preparation process and great application potential.
Description
Technical Field
The invention belongs to the field of composite coatings, and relates to a high-performance epoxy bonding type solid self-lubricating coating and a preparation and use method thereof.
Background
With the development of aerospace technology, many special tribological problems follow, such as lubrication difficulties under exposure to ultra-high vacuum, radiation, atomic oxygen and extreme high and low temperature conditions. Under such extreme conditions, the grease lubricant is susceptible to evaporation, decomposition, or crosslinking, and it is difficult to achieve a good lubricating effect. The bonding type solid self-lubricating coating is a simple and efficient lubricating technology, can form a film on the surface of a friction part to reduce the friction and wear of the friction part so as to provide effective protection for the friction part, and can provide an effective solution for the lubricating problem under extreme conditions. Epoxy resin is widely applied to various fields because of its excellent characteristics such as high bonding strength, good stability and manufacturability, but pure epoxy resin also has the problems of large brittleness, poor heat resistance, poor friction-reducing and wear-resisting properties and the like, thereby limiting the application in high-tech fields.
Patent CN 110591501 a discloses a bonding solid lubricating material containing hyperbranched polysiloxane epoxy and a preparation method thereof. The amino-terminated hyperbranched polysiloxane is used as a curing agent and a modifier of the epoxy resin, so that the epoxy resin is endowed with excellent performances such as toughness, heat resistance, friction reduction and abrasion resistance and the like, and the amino-terminated hyperbranched polysiloxane is added to MoS2Under the synergistic effect of the/rGO composite particles, the antifriction and abrasion resistance, the bearing capacity and the environmental adaptability of the epoxy coating are further improved. However, the leveling property and film-forming property of the epoxy coating are not greatly improved by introducing the amino-terminated hyperbranched polysiloxane, so that the prepared coating is uneven in thickness and easy to aggregate, and a large amount of amino groups contained in the amino-terminated hyperbranched polysiloxane are easy to react with epoxy groups, so that local excessive crosslinking is easily caused in the preparation process to influence the toughness and other properties of the coating. Furthermore, hyperbranched polysiloxanes and MoS from amino-terminated groups2Epoxy solid lubricating coating prepared from/rGO composite particles has higher friction coefficient and poorer wear resistance and heat resistanceAnd MoS prepared therefrom2The dispersibility of/rGO composite particles is also desired to be improved. Therefore, a new epoxy resin modifier combined with a corresponding high-dispersibility solid lubricant is urgently needed to be searched, so that an epoxy coating with low friction coefficient, high wear resistance, high temperature resistance and long service life is prepared.
Polyimide has incomparably excellent performance compared with other high polymers because of containing quite stable imide aromatic heterocyclic structural units, and especially has outstanding tribological performance under the harsh environment of high temperature, high pressure, high speed and the like. Patent CN 106867395A discloses an oil-wear-resistant and high-temperature-resistant solid lubricating coating material containing POSS polyimide resin and a method thereof. Diamine POSS is introduced into a polyimide molecular chain, and then the diamine POSS and molybdenum disulfide are compounded to prepare the POSS-containing polyimide high-temperature-resistant self-lubricating composite coating. The diamine POSS is a cage structure formed by taking Si-O-Si as a main chain segment, and the structure has the obvious problems of poor compatibility with a resin matrix, complex preparation process, high cost and no contribution to industrial production.
The amino-terminated hyperbranched polysiloxane is a hyperbranched polymer taking Si-O-C as a main chain segment, a large number of active groups and organic chain segments contained in the hyperbranched polymer can effectively improve the compatibility with a resin matrix, and the hyperbranched polymer has the advantages of simple preparation process and low cost. Therefore, the amino-terminated hyperbranched polysiloxane can be introduced into a polyamic acid (PAA) molecular chain to obtain polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA), wherein the bond angle of Si-O-C in the main chain is between Si-O-Si and C-O-C, so that the Si-O-C structure in the main chain has the flexibility of the Si-O-Si structure and the rigidity of the C-O-C, the 'rigid-flexible' chain segment structure can better achieve the toughening and reinforcing modification effects, and the hydroxyl, secondary amine, acid anhydride and a small amount of unreacted primary amine groups contained in the 'rigid-flexible' chain segment structure can react with the epoxy groups of the epoxy resin, so that the HBPSi-PAA can play a role in curing the epoxy resin and can also promote the curing of the epoxy resin, and the interface bonding strength with the epoxy resin matrix is finally enhanced to realize better toughening, toughening and, The effect is enhanced. Meanwhile, the introduction of the polyamic acid can also endow the epoxy coatingThe epoxy resin has good leveling property and film-forming property, and can further improve the flexibility, heat resistance and service performance of the epoxy coating under extreme conditions after curing. In addition, molybdenum disulfide is a layered solid lubricant with larger compressive strength, good wear resistance and adhesion and lower friction coefficient (0.03-0.08), the friction coefficient of the molybdenum disulfide does not change greatly in vacuum and in air even at high temperature of 800 ℃, the molybdenum disulfide is particularly suitable for lubrication in the field of aerospace, and the molybdenum disulfide is an ideal solid lubricant, but the molybdenum disulfide has poor dispersibility and is easy to generate particle aggregation to influence the performance. The graphene has the characteristics of light weight, small size, large specific surface area, good compatibility with a resin matrix and the like, is widely used for modifying the friction property, the mechanical property, the thermal property, the electrical property and the like of a resin-based material, and is a two-dimensional carbon nano material with excellent performance. If molybdenum disulfide and graphene can be compounded, the MoS with high dispersibility is prepared2the/rGO composite particles can enable the epoxy coating to have the characteristics of low friction coefficient, high wear resistance, high temperature resistance and long service life, thereby providing an effective solution for solving the problem of lubrication under extreme conditions.
Therefore, the invention provides a method for preparing MoS with high dispersibility by using a ball-milling intercalation method2The high-performance epoxy bonding type solid self-lubricating coating is prepared by using epoxy resin as a bonding agent and HBPSi-PAA as a modifier for the/rGO composite particles.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a high-performance epoxy bonding type solid self-lubricating coating and a preparation and use method thereof, aiming at the problems of an epoxy coating under extreme conditions. The preparation method of the high-performance epoxy bonding type solid self-lubricating coating can effectively improve the antifriction abrasion resistance, heat resistance, high bearing capacity and friction life of the epoxy coating, and can provide an effective solution for the lubrication problem under extreme conditions.
Firstly, preparing polyamide acid end capping by amidation reaction of amino-terminated hyperbranched polysiloxane and polyamide acidAnd introducing the hyperbranched polysiloxane (HBPSi-PAA) into an epoxy resin matrix to obtain a modified epoxy resin prepolymer. Then, the prepolymer and MoS prepared by a ball milling intercalation method2Compounding the/rGO composite particles to prepare the modified epoxy composite coating. And finally, uniformly spraying the modified epoxy composite coating on the surface of the metal substrate, and curing to obtain the high-performance epoxy bonding type solid self-lubricating coating.
Technical scheme
The high-performance epoxy bonding type solid self-lubricating coating is characterized by comprising, by mass, 1-100 parts of epoxy resin prepolymer and 30-60 parts of MoS2a/rGO composite particle; the epoxy resin prepolymer is prepared by the following steps: 1-100 parts of epoxy resin, 1-20 parts of polyamic acid terminated hyperbranched polysiloxane HBPSi-PAA and 1-60 parts of curing agent.
The curing agents include, but are not limited to: 4,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenylmethane or methyltetrahydrophthalic anhydride.
The hyperbranched polysiloxane HBPSi-PAA has a structural formula as follows:
wherein:
a method for preparing the high-performance epoxy bonding type solid self-lubricating coating is characterized by comprising the following steps:
step 1: 30-60 parts of MoS2Adding the/rGO composite particles into 10-100 parts of organic solvent for ultrasonic dispersion for 30-60 min to obtain MoS2a/rGO composite particle dispersion;
step 2: adding 1-50 parts of amino-terminated hyperbranched polysiloxane into 1-100 parts of polyamic acid by mass, and stirring at normal temperature for reacting for 3-15 hours to obtain a polyamic acid-terminated hyperbranched polysiloxane HBPSi-PAA solution;
and step 3: stirring 1-100 parts of epoxy resin, 1-20 parts of polyamic acid terminated hyperbranched polysiloxane HBPSi-PAA and 1-100 parts of curing agent at 60-130 ℃ for reaction for 10-60 min to obtain a modified epoxy resin prepolymer;
and 4, step 4: mixing modified epoxy resin prepolymer with MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 5-30 min to obtain the modified epoxy composite coating.
The MoS2the/rGO composite particles are obtained by adopting ball milling intercalation, and the method comprises the following steps: firstly, uniformly dispersing molybdenum disulfide and graphene oxide in distilled water according to the mass ratio of 1: 0.1-5, adding hydrazine hydrate which is 10-100% of the mass of the graphene oxide, refluxing for 1-10 h at 90-120 ℃, washing for 2-3 times with distilled water, and performing vacuum drying for 6-12 h to obtain a dry mixture of graphene-loaded molybdenum disulfide; then, treating the dry mixture and sodium chloride in a ball mill with the rotating speed of 300-600 rpm for 2-10 h according to the ball-material mass ratio of 1: 0.1-10, finally washing with distilled water for 2-3 times, and vacuum drying for 6-12 h to obtain the high-dispersity MoS2a/rGO composite particle.
Preparing the amino-terminated hyperbranched polysiloxane: mixing gamma-aminopropyltriethoxysilane and dihydric alcohol according to a molar ratio of 1: 1.6-5, heating to 100-200 ℃ in a stepped manner under the protection of nitrogen, and reacting for 2-10 hours until no distillate exists, thereby obtaining the amino-terminated hyperbranched polysiloxane.
The dihydric alcohol is NPG, MPD, DEG, DEA or NMDEA.
Preparation of the polyamic acid: weighing 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride in a molar ratio of 1: 1-2, dissolving 4,4' -diaminodiphenyl ether in 10-100 parts of organic solvent, slowly adding pyromellitic dianhydride under stirring, and reacting at room temperature for 6-9 hours to obtain polyamic acid.
The organic solvents include, but are not limited to: n, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
A method for obtaining a self-lubricating coating by using the high-performance epoxy bonding type solid self-lubricating coating is characterized by comprising the following steps of: uniformly spraying the high-performance epoxy bonding type solid self-lubricating coating on the polished surface of the tinplate for 2-3 times, curing for 5-10 min at 80 ℃ after each spraying, and then performing segmented curing, wherein the curing process sequentially comprises the following steps: curing at 100-150 ℃ for 60-120 min, curing at 150-170 ℃ for 60-240 min, curing at 170-250 ℃ for 60-120 min, and naturally cooling to room temperature after curing to obtain the high-performance epoxy bonding type solid self-lubricating coating.
Advantageous effects
The invention provides a high-performance epoxy bonding type solid self-lubricating coating and a preparation and use method thereof2the/rGO) composite particles and epoxy resin are compounded and prepared. The HBPSi-PAA molecule contains hydroxyl, secondary amine, acid anhydride and a small amount of unreacted primary amine group, can generate copolymerization reaction with epoxy resin, and a Si-O-C chain segment structure of 'rigid-flexible' is introduced into a resin matrix, so that the effects of strengthening and toughening can be achieved.
Therefore, the HBPSi-PAA not only can play a toughening and reinforcing effect, but also can endow the epoxy coating with good leveling property and film-forming property, and can further improve the flexibility, heat resistance and usability of the epoxy coating under extreme conditions after curing. When the proper amount of MoS is added into the epoxy coating2HBPSi-PAA can be combined with MoS when/rGO composite particles2the/rGO composite particles form the synergistic effect of soft and hard particles, so that the epoxy bonding type solid self-lubricating coating has lower friction coefficient, higher bearing capacity and longer friction life. The high-performance epoxy bonding type solid self-lubricating coating has the characteristics of excellent antifriction and wear resistance, toughness, adhesive force, high temperature resistance, impact resistance, high bearing capacity, long service life and the like, and can solve the problems of easy brittle fracture at low temperature, easy shedding at high temperature, short service life and the like of the solid self-lubricating coating used in the fields of aviation, aerospace and the likeThe coating has simple preparation process and great application potential.
As can be seen from the drawings: FIG. 1 shows HBPSi-NH2Comparative infrared spectra of PAA and HBPSi-PAA. Comparative HBPSi-NH2It can be found that the length of the groove is 3400cm-1A strong and wide peak is nearby, and is a stretching vibration peak of associated-OH, 1130cm-1The vicinity thereof is a stretching vibration peak of an ether bond (C-O-C), 700cm-1The nearby stretching vibration peaks of Si-C correspond to HBPSi-NH2Corresponding characteristic absorption peaks. In addition, 3415cm-1nearby-NH-stretching vibration peak, 1629cm-1Near C ═ O stretching vibration peak and 957cm-1The adjacent carboxyl O-H out-of-plane bending vibration peaks respectively correspond to the corresponding characteristic absorption peaks of PAA. The results of comparative analysis show that HBPSi-PAA is successfully prepared.
FIG. 2 shows MoS2rGO and MoS2And (3) a dispersion diagram of the/rGO composite particles after the/rGO composite particles are subjected to ultrasonic dispersion in DMAc and are kept stand for different times. As can be seen from the figure, the three particles have better dispersibility in DMAc after ultrasonic dispersion; after 24h of standing, MoS was observed2Beginning to settle; after 72h of standing, MoS2Already there is a significant delamination phenomenon, but rGO and MoS2the/rGO composite particles still keep a good dispersion state, which shows that MoS with high dispersibility can be prepared by a ball milling intercalation method2/rGO composite particles, and rGO can effectively improve MoS2Dispersibility in DMAc. Of course, such highly dispersible MoS2the/rGO composite particles also create a prerequisite for preparing a high-performance epoxy bonding type solid self-lubricating coating.
FIG. 3 shows the MoS content in different amounts2The friction coefficient and the loading load of a bonding type solid self-lubricating coating prepared by the/rGO composite particles and an HBPSi-PAA modified epoxy resin matrix are shown in a schematic diagram along with time. It can be seen that each coating sample showed a high coefficient of friction during the run-in period of the first 3min, mainly because the shear pins were in point contact with the epoxy solid lubricating coating during the run-in period, and a large shear stress was generated during the friction process, resulting in a high frictional coefficient of the coatingThe friction coefficient is higher. After the running-in stage, the friction coefficients of all samples gradually decrease and stabilize in a period of time along with the increase of the load, because the epoxy coating forms a layer of self-lubricating transfer film between the coating and the shearing pin after the running-in stage, the contact mode at the moment is surface contact and is changed from the original direct butt-grinding of metal and the coating into the butt-grinding of the transfer film and the coating, and MoS is added2the/rGO composite particle has self-lubricating property and high bearing capacity, so that the friction coefficient of the coating is greatly reduced, and the maximum load can reach about 3500N.
It can be observed from the figure that when MoS2When the addition amount of the/rGO composite particles is small (as shown in samples 1 and 2), the stability of the friction coefficient is poor, which shows that the improvement effect on the friction performance of the coating is not obvious, and a proper amount of MoS is added2The coefficient of friction of the epoxy bonding type solid self-lubricating coating (sample 3) of/rGO composite particles can be stabilized at 0.03 in about 235s, the bearing capacity can reach about 3500N, and the friction life can be about 600s, probably because of adding a proper amount of high-dispersity MoS2the/rGO composite particles can form good bonding effect with an epoxy composite resin matrix, so that HBPSi-PAA and MoS are enabled to be in a friction process2the/rGO composite particles can play a better synergistic effect of soft and hard particles, and the formed self-lubricating transfer film is more continuous and stable, so that the coating has excellent antifriction and wear resistance. When MoS2When the amount of addition of/rGO composite particles is too large (as shown in sample 4), the coefficient of friction of the epoxy coating is very unstable because of MoS2The addition amount of the/rGO composite particles exceeds a proper value, so that the formed self-lubricating transfer membrane is easy to damage, and the friction coefficient is greatly fluctuated.
Drawings
FIG. 1: PAA, HBPSi-NH2And infrared spectrum of HBPSi-PAA
FIG. 2: MoS2rGO and MoS2Dispersion diagram of/rGO composite particles after ultrasonic dispersion in DMAc and standing for different times
FIG. 3: adding MoS with different contents2Epoxy adhesive solid of/rGO composite particleSchematic diagram (1) of change of friction coefficient and loading load of self-lubricating coating with time
FIG. 4: adding MoS with different contents2Schematic diagram (2) of changes of friction coefficient and loading load of epoxy bonding type solid self-lubricating coating of rGO composite particles along with time
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the first step is as follows: a polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) was prepared. Mixing gamma-aminopropyltriethoxysilane and dihydric alcohol (NPG, MPD, DEG, DEA and NMDEA) in a ratio of 1: 1.6-5 by a molar ratio, heating to 100-200 ℃ in a stepped manner under the protection of nitrogen, and reacting for 2-10 h until no distillate exists to obtain amino-terminated hyperbranched polysiloxane; and weighing 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride in the molar ratio of 1: 1-2, dissolving the 4,4' -diaminodiphenyl ether in 10-100 parts of organic solvent, slowly adding the pyromellitic dianhydride under stirring, and reacting at room temperature for 6-9 hours to obtain the polyamic acid. Then, adding 1-50 parts of amino-terminated hyperbranched polysiloxane into 1-100 parts of polyamic acid by mass, and stirring and reacting at normal temperature for 3-15 hours to obtain a light yellow HBPSi-PAA solution. Wherein the organic solvent is N, N-dimethylacetamide, N-dimethylformamide and/or N-methylpyrrolidone.
The second step is that: preparation of MoS2a/rGO composite particle. Firstly, uniformly dispersing molybdenum disulfide and graphene oxide in distilled water according to the mass ratio of 1: 0.1-5, adding hydrazine hydrate which is 10-100% of the mass of the graphene oxide, refluxing for 1-10 h at 90-120 ℃, washing for 2-3 times with distilled water, and vacuum drying for 6-12 h to obtain the dry mixed material of graphene-loaded molybdenum disulfide. Then, treating the dry mixture and sodium chloride in a ball mill with the rotating speed of 300-600 rpm for 2-10 h according to the ball material mass ratio of 1: 0.1-10, finally washing with distilled water for 2-3 times, and vacuum drying for 6-12 h to obtain the high-dispersity MoS2a/rGO composite particle;
the third step: preparing the high-performance epoxy bonding type solid self-lubricating coating.
(1) Firstly, polishing the tinplate by using sand paper, then cleaning most of metal abrasive dust on the surface of the tinplate by using absolute ethyl alcohol, then placing the tinplate in the absolute ethyl alcohol for ultrasonic treatment for 30-60 min, then wiping the polished surface by using acetone, and drying in vacuum for later use;
(2) according to the mass fraction, 30-60 parts of MoS2Adding the/rGO composite particles into 10-100 parts of organic solvent for ultrasonic dispersion for 30-60 min to obtain MoS2a/rGO composite particle dispersion. Wherein the organic solvent is N, N-dimethylacetamide, N-dimethylformamide and/or N-methylpyrrolidone. In addition, stirring 1-100 parts of epoxy resin, 1-20 parts of polyamic acid terminated hyperbranched polysiloxane (HBPSi-PAA) and 1-100 parts of curing agent at 60-130 ℃ for reaction for 10-60 min to obtain the modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2Stirring and mixing the/rGO composite particle dispersion liquid for 5-30 min to obtain a modified epoxy composite coating;
(3) uniformly spraying the prepared modified epoxy composite coating on the polished surface of the tinplate for 2-3 times, curing at 80 ℃ for 5-10 min after each spraying, and then performing segmented curing, wherein the curing process sequentially comprises the following steps: curing at 100-150 ℃ for 60-120 min, curing at 150-170 ℃ for 60-240 min, curing at 170-250 ℃ for 60-120 min, and naturally cooling to room temperature after curing to obtain the high-performance epoxy bonding type solid self-lubricating coating.
Example 1
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA)
Firstly, mixing gamma-aminopropyltriethoxysilane and diethylene glycol according to the molar ratio of 1: 1.6, heating to 170 ℃ in a stepped manner under the protection of nitrogen, and reacting for 8 hours until no distillate exists to obtain amino-terminated hyperbranched polysiloxane; then 1mol of 4,4' -diaminodiphenyl ether is dissolved in 100 parts of N, N-dimethylacetamide, 1.1mol of pyromellitic anhydride is slowly added under stirring, and reaction is carried out for 6h at room temperature to obtain polyamic acid. Then, according to the mass fraction, 10 parts of amino-terminated hyperbranched polysiloxane is added into 100 parts of polyamic acid, and the mixture is stirred and reacts for 8 hours at normal temperature to obtain a light yellow HBPSi-PAA solution.
(2)MoS2Preparation of/rGO composite particles
Firstly, uniformly dispersing molybdenum disulfide and graphene oxide in distilled water according to the mass ratio of 2: 1, adding hydrazine hydrate which is 10% of the mass of the graphene oxide, refluxing for 6 hours at 96 ℃, washing for 2-3 times by using distilled water, and performing vacuum drying for 12 hours to obtain the dry mixture of the graphene-loaded molybdenum disulfide. Then, treating the dry mixture and sodium chloride in a ball mill with the rotation speed of 500rpm for 5 hours according to the ball material mass ratio of 1: 1, finally washing with distilled water for 2-3 times, and drying in vacuum for 12 hours to obtain the MoS with high dispersibility2a/rGO composite particle.
(3) Polishing treatment of tinplate
Firstly, polishing the tinplate by using sand paper, then cleaning most of metal abrasive dust on the surface of the tinplate by using absolute ethyl alcohol, then placing the tinplate in the absolute ethyl alcohol for ultrasonic treatment for 60min, finally wiping the polished surface by using acetone, and drying in vacuum for later use.
(4) Preparation of modified epoxy composite coating
30 parts of MoS2Adding the/rGO composite particles into 20 parts of N, N-dimethylacetamide, and ultrasonically dispersing for 30min to obtain MoS2a/rGO composite particle dispersion. In addition, 100 parts of epoxy resin, 10 parts of polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) and 30 parts of 4,4' -diaminodiphenyl sulfone are stirred and reacted for 20min at 120 ℃ to obtain the modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 10min to obtain the modified epoxy composite coating.
(5) Preparation of epoxy bonding type solid self-lubricating coating
Uniformly spraying the prepared epoxy composite coating on the polished surface of the tinplate for 2-3 times, curing for 10min at 80 ℃ after each spraying, and then performing segmented curing, wherein the curing process sequentially comprises the following steps: curing at 150 ℃ for 120min, curing at 170 ℃ for 240min, curing at 200 ℃ for 60min, and naturally cooling to room temperature after curing to obtain the high-performance epoxy bonding type solid self-lubricating coating.
Example 2
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA)
Firstly, mixing gamma-aminopropyltriethoxysilane and diethylene glycol according to the molar ratio of 1: 1.6, heating to 170 ℃ in a stepped manner under the protection of nitrogen, and reacting for 8 hours until no distillate exists to obtain amino-terminated hyperbranched polysiloxane; then 1mol of 4,4' -diaminodiphenyl ether is dissolved in 100 parts of N, N-dimethylacetamide, 1.1mol of pyromellitic anhydride is slowly added under stirring, and reaction is carried out for 6h at room temperature to obtain polyamic acid. Then, according to the mass fraction, 15 parts of amino-terminated hyperbranched polysiloxane is added into 100 parts of polyamic acid, and the mixture is stirred and reacts for 8 hours at normal temperature to obtain a light yellow HBPSi-PAA solution.
(2)MoS2Preparation of/rGO composite particles as in example 1
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating As in example 1
(5) Preparation of epoxy-bonded solid self-lubricating coating in the same manner as in example 1
Example 3
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles
Firstly, uniformly dispersing molybdenum disulfide and graphene oxide in distilled water according to the mass ratio of 2: 1, adding hydrazine hydrate which is 10% of the mass of the graphene oxide, refluxing for 6 hours at 96 ℃, washing for 2-3 times by using distilled water, and performing vacuum drying for 12 hours to obtain the dry mixture of the graphene-loaded molybdenum disulfide. Then, treating the dry mixture and sodium chloride in a ball mill with the rotation speed of 400rpm for 8 hours according to the mass ratio of 2: 1 of the ball material, finally washing with distilled water for 2-3 times, and drying in vacuum for 12 hours to obtain the MoS with high dispersibility2a/rGO composite particle.
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating As in example 1
(5) Preparation of epoxy-bonded solid self-lubricating coating in the same manner as in example 1
Example 4
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles
Firstly, uniformly dispersing molybdenum disulfide and graphene oxide in distilled water according to the mass ratio of 3: 2, adding hydrazine hydrate which is 10% of the mass of the graphene oxide, refluxing for 6 hours at 96 ℃, washing for 2-3 times by using distilled water, and performing vacuum drying for 12 hours to obtain the dry mixture of the graphene-loaded molybdenum disulfide. Then, treating the dry mixture and sodium chloride in a ball mill with the rotation speed of 500rpm for 5 hours according to the ball material mass ratio of 1: 1, finally washing with distilled water for 2-3 times, and drying in vacuum for 12 hours to obtain the MoS with high dispersibility2a/rGO composite particle.
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating As in example 1
(5) Preparation of epoxy-bonded solid self-lubricating coating in the same manner as in example 1
Example 5
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles as in example 1
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating
30 parts of MoS2Adding the/rGO composite particles into 20 parts of N, N-dimethylacetamide, and ultrasonically dispersing for 30min to obtain MoS2a/rGO composite particle dispersion. In addition, 100 parts of epoxy resin, 10 parts of polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) and 25 parts of 4,4' -diaminodiphenylmethane were stirred at 120 ℃ for 20min to obtain a modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 10min to obtain the modified epoxy composite coating.
(5) Preparation of epoxy bonding type solid self-lubricating coating
Uniformly spraying the prepared epoxy composite coating on the polished surface of the tinplate for 2-3 times, curing for 10min at 80 ℃ after each spraying, and then performing segmented curing, wherein the curing process sequentially comprises the following steps: curing at 150 ℃ for 120min, curing at 170 ℃ for 180min, curing at 200 ℃ for 60min, and naturally cooling to room temperature after curing to obtain the high-performance epoxy bonding type solid self-lubricating coating.
Example 6
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles as in example 1
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating
35 parts of MoS2Adding the/rGO composite particles into 25 parts of N, N-dimethylacetamide, and ultrasonically dispersing for 30min to obtain MoS2a/rGO composite particle dispersion. In addition, 100 parts of epoxy resin, 10 parts of polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) and 80 parts of methyltetrahydrophthalic anhydride are stirred and reacted for 20min at 60 ℃ to obtain the modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 10min to obtain the modified epoxy composite coating.
(5) Preparation of epoxy bonding type solid self-lubricating coating
Uniformly spraying the prepared epoxy composite coating on the polished surface of the tinplate for 2-3 times, curing for 10min at 80 ℃ after each spraying, and then performing segmented curing, wherein the curing process sequentially comprises the following steps: curing at 120 ℃ for 120min, curing at 150 ℃ for 180min, curing at 170 ℃ for 60min, and naturally cooling to room temperature after curing to obtain the high-performance epoxy bonding type solid self-lubricating coating.
Example 7
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles as in example 1
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating
35 portions ofMoS2Adding the/rGO composite particles into 25 parts of N, N-dimethylacetamide, and ultrasonically dispersing for 30min to obtain MoS2a/rGO composite particle dispersion. In addition, 100 parts of epoxy resin, 10 parts of polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) and 30 parts of 4,4' -diaminodiphenyl sulfone are stirred and reacted for 20min at 120 ℃ to obtain the modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 10min to obtain the modified epoxy composite coating.
(5) Preparation of epoxy-bonded solid self-lubricating coating in the same manner as in example 1
Example 8
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles as in example 1
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating
40 parts of MoS2Adding the/rGO composite particles into 30 parts of N, N-dimethylacetamide, and ultrasonically dispersing for 30min to obtain MoS2a/rGO composite particle dispersion. In addition, 100 parts of epoxy resin, 10 parts of polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) and 30 parts of 4,4' -diaminodiphenyl sulfone are stirred and reacted for 20min at 120 ℃ to obtain the modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 10min to obtain the modified epoxy composite coating.
(5) Preparation of epoxy-bonded solid self-lubricating coating in the same manner as in example 1
Example 9
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles as in example 1
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating
45 parts of MoS2adding/rGO composite particles to 35 parts of N, N-dimethylUltrasonically dispersing in acetamide for 30min to obtain MoS2a/rGO composite particle dispersion. In addition, 100 parts of epoxy resin, 10 parts of polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) and 30 parts of 4,4' -diaminodiphenyl sulfone are stirred and reacted for 20min at 120 ℃ to obtain the modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 10min to obtain the modified epoxy composite coating.
(5) Preparation of epoxy-bonded solid self-lubricating coating in the same manner as in example 1
Example 10
(1) Preparation of Polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) As in example 1
(2)MoS2Preparation of/rGO composite particles as in example 1
(3) The tinplate was polished in the same manner as in example 1
(4) Preparation of modified epoxy composite coating
50 parts of MoS2Adding the/rGO composite particles into 40 parts of N, N-dimethylacetamide, and ultrasonically dispersing for 30min to obtain MoS2a/rGO composite particle dispersion. In addition, 100 parts of epoxy resin, 10 parts of polyamic acid-terminated hyperbranched polysiloxane (HBPSi-PAA) and 30 parts of 4,4' -diaminodiphenyl sulfone are stirred and reacted for 20min at 120 ℃ to obtain the modified epoxy resin prepolymer. Then, the prepolymer is mixed with the MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 10min to obtain the modified epoxy composite coating.
(5) Preparation of epoxy-bonded solid self-lubricating coating in the same manner as in example 1
And (3) carrying out performance test analysis on the high-performance epoxy bonding type solid self-lubricating coating correspondingly prepared in the embodiment, and referring to the attached drawings of the specification.
The preparation method of the high-performance epoxy bonding type solid self-lubricating coating provided by the invention can enable the epoxy coating to have better leveling property and film-forming property, and the prepared epoxy bonding type solid self-lubricating coating has better toughness, impact strength and adhesive force. In addition, MoS prepared by ball milling intercalation2the/rGO composite particles obtain better dispersibility and epoxy bondingThe friction coefficient, the bearing capacity and the friction service life of the self-lubricating solid coating are greatly improved.
TABLE 1 addition of different MoS contents2Conventional performance of epoxy bonding type solid self-lubricating coating of/rGO composite particles
Table 1 shows the MoS contents2The thickness, toughness, impact strength and adhesion of the epoxy bonding type solid self-lubricating coating prepared by the/rGO composite particles and the HBPSi-PAA modified epoxy resin matrix are a series of conventional performances. With MoS2The toughness and the impact strength of the epoxy bonding type solid self-lubricating coating are gradually improved due to the increase of the addition amount of/rGO composite particles, the heat resistance is in the trend of increasing firstly and then reducing, but the adhesive force is not changed and is always kept at level 1 because of a proper amount of MoS2the/rGO composite particles and the epoxy composite resin matrix form good bonding effect, and HBPSi-PAA and MoS2The synergistic effect of the soft and hard particles formed by the/rGO composite particles can greatly reduce the external stress to which the coating is subjected.
The foregoing is a more detailed description of the present invention that will be presented in conjunction with specific embodiments, which are not intended to limit the scope of the present invention, but which can be envisioned and determined by those skilled in the art.
Claims (10)
1. The high-performance epoxy bonding type solid self-lubricating coating is characterized by comprising, by mass, 1-100 parts of epoxy resin prepolymer and 30-60 parts of MoS2a/rGO composite particle; the epoxy resin prepolymer is prepared by the following steps: 1-100 parts of epoxy resin, 1-20 parts of polyamic acid terminated hyperbranched polysiloxane HBPSi-PAA and 1-60 parts of curing agent.
2. The high-performance epoxy bonding type solid self-lubricating coating according to claim 1, characterized in that: the curing agents include, but are not limited to: 4,4 '-diaminodiphenyl sulfone, 4' -diaminodiphenylmethane or methyltetrahydrophthalic anhydride.
3. The high-performance epoxy bonding type solid self-lubricating coating according to claim 1, characterized in that: the hyperbranched polysiloxane HBPSi-PAA has a structural formula as follows:
wherein:
4. a method for preparing the high-performance epoxy bonding type solid self-lubricating coating as described in any one of claims 1 to 3, which is characterized by comprising the following steps:
step 1: 30-60 parts of MoS2Adding the/rGO composite particles into 10-100 parts of organic solvent for ultrasonic dispersion for 30-60 min to obtain MoS2a/rGO composite particle dispersion;
step 2: adding 1-50 parts of amino-terminated hyperbranched polysiloxane into 1-100 parts of polyamic acid by mass, and stirring at normal temperature for reacting for 3-15 hours to obtain a polyamic acid-terminated hyperbranched polysiloxane HBPSi-PAA solution;
and step 3: stirring 1-100 parts of epoxy resin, 1-20 parts of polyamic acid terminated hyperbranched polysiloxane HBPSi-PAA and 1-100 parts of curing agent at 60-130 ℃ for reaction for 10-60 min to obtain a modified epoxy resin prepolymer;
and 4, step 4: mixing modified epoxy resin prepolymer with MoS2And stirring and mixing the/rGO composite particle dispersion liquid for 5-30 min to obtain the modified epoxy composite coating.
5. The method of claim 4, wherein: the MoS2the/rGO composite particles are obtained by adopting ball milling intercalation, and the method comprises the following steps: firstly, uniformly dispersing molybdenum disulfide and graphene oxide in distilled water according to the mass ratio of 1: 0.1-5, adding hydrazine hydrate which is 10-100% of the mass of the graphene oxide, refluxing for 1-10 h at 90-120 ℃, washing for 2-3 times with distilled water, and performing vacuum drying for 6-12 h to obtain a dry mixture of graphene-loaded molybdenum disulfide; then, treating the dry mixture and sodium chloride in a ball mill with the rotating speed of 300-600 rpm for 2-10 h according to the ball-material mass ratio of 1: 0.1-10, finally washing with distilled water for 2-3 times, and vacuum drying for 6-12 h to obtain the high-dispersity MoS2a/rGO composite particle.
6. The method of claim 4, wherein: preparing the amino-terminated hyperbranched polysiloxane: mixing gamma-aminopropyltriethoxysilane and dihydric alcohol according to a molar ratio of 1: 1.6-5, heating to 100-200 ℃ in a stepped manner under the protection of nitrogen, and reacting for 2-10 hours until no distillate exists, thereby obtaining the amino-terminated hyperbranched polysiloxane.
7. The method of claim 6, wherein: the dihydric alcohol is NPG, MPD, DEG, DEA or NMDEA.
8. The method of claim 4, wherein: preparation of the polyamic acid: weighing 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride in a molar ratio of 1: 1-2, dissolving 4,4' -diaminodiphenyl ether in 10-100 parts of organic solvent, slowly adding pyromellitic dianhydride under stirring, and reacting at room temperature for 6-9 hours to obtain polyamic acid.
9. The method according to claim 4 or 8, characterized in that: the organic solvents include, but are not limited to: n, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
10. A method for obtaining a self-lubricating coating by using the high-performance epoxy bonding type solid self-lubricating coating as described in any one of claims 1 to 3, wherein: uniformly spraying the high-performance epoxy bonding type solid self-lubricating coating on the polished surface of the tinplate for 2-3 times, curing for 5-10 min at 80 ℃ after each spraying, and then performing segmented curing, wherein the curing process sequentially comprises the following steps: curing at 100-150 ℃ for 60-120 min, curing at 150-170 ℃ for 60-240 min, curing at 170-250 ℃ for 60-120 min, and naturally cooling to room temperature after curing to obtain the high-performance epoxy bonding type solid self-lubricating coating.
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| CN115466459A (en) * | 2022-09-06 | 2022-12-13 | 成都航空职业技术学院 | Modified polypropylene fused deposition molding granule and preparation method thereof |
| CN116285572A (en) * | 2023-02-24 | 2023-06-23 | 上海骋润高分子材料有限公司 | High-lubrication coating and preparation method thereof |
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| CN115466459A (en) * | 2022-09-06 | 2022-12-13 | 成都航空职业技术学院 | Modified polypropylene fused deposition molding granule and preparation method thereof |
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| CN116285572A (en) * | 2023-02-24 | 2023-06-23 | 上海骋润高分子材料有限公司 | High-lubrication coating and preparation method thereof |
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| CN116333557A (en) * | 2023-02-26 | 2023-06-27 | 西北工业大学 | High-temperature-resistant oil-resistant organic-inorganic hybrid epoxy composite wear-resistant lubricating coating and preparation method thereof |
| CN116333557B (en) * | 2023-02-26 | 2024-01-30 | 西北工业大学 | High-temperature-resistant oil-resistant organic-inorganic hybrid epoxy composite wear-resistant lubricating coating and preparation method thereof |
| CN117757341A (en) * | 2023-12-29 | 2024-03-26 | 深圳市安信达存储技术有限公司 | Anti-radiation processing method for embedded memory chip in space environment satellite |
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