CN111154376A - Ag/BNNSs nano material modified epoxy resin composite coating - Google Patents
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- 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
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Abstract
The invention discloses a preparation method of a silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating. The method mainly comprises the following steps: firstly, preparing a hexagonal boron nitride nanosheet by simple hydrothermal stripping under mild reaction conditions, then preparing a silver/hexagonal boron nitride nano hybrid material by a hydrothermal method, adding the silver/hexagonal boron nitride nanosheet hybrid material into epoxy resin, a curing agent and an organic solvent according to a certain proportion, and mechanically stirring and ultrasonically dispersing to obtain a mixed solution. And finally, spraying the mixed solution on a base material, naturally drying, and then placing the base material into a vacuum drying oven for curing and forming to obtain the epoxy resin self-lubricating composite coating. The composite coating prepared by the invention has the advantages of low friction coefficient, high wear resistance, mild reaction conditions, simple preparation method operation, easy preparation of large-area antifriction and wear-resistant surfaces and suitability for large-scale production.
Description
The technical field is as follows:
the invention relates to an epoxy resin self-lubricating composite material, in particular to an epoxy resin self-lubricating composite material filled and modified by a silver/hexagonal boron nitride nano hybrid material lubricant.
Background art:
in recent years, self-lubricating composite materials in the field of tribology are new materials with special purposes developed for solving the problem of friction and wear of materials under specific working conditions, and the development of self-lubricating composite materials with high mechanical strength and good friction performance becomes an important hotspot in the field of tribology. Polymer-based self-lubricating composite materials are also receiving attention from researchers in this field due to their advantages such as light weight and good moldability.
The pure polymer has the performances of corrosion resistance, excellent chemical stability, light weight and excellent damping and shock absorption performance, but the pure polymer often has the defect of poor wear resistance and cannot meet the use under extreme working conditions, so that the design and preparation of the high-performance polymer-based self-lubricating composite coating are very important. Zhang et al synthesized an RGO/ZnS hybrid material by a simple and effective hydrothermal method, so as to improve the tribological performance of the epoxy resin composite coating and effectively improve the problem of easy agglomeration of nanoparticles; when ZnS nanoparticles are added to epoxy coatings, severe agglomeration is exhibited; for the RGO/ZnS hybrid material, ZnS nano particles can be uniformly attached to the RGO nano sheet, so that the agglomeration phenomenon of the ZnS nano particles is reduced, the ZnS nano particles can roll and slide along the direction of the shearing force under the limitation of the RGO nano sheet, and the friction and wear performance of the RGO/ZnS/EP composite coating is improved.
Epoxy resin is an important thermosetting polymer, has excellent properties such as high bonding strength, high chemical stability, excellent mechanical property and corrosion resistance, good insulativity, low toxicity, low cost, high adaptability and the like, is developed into a main matrix material of an advanced composite material, and is widely applied to the fields of mechanical manufacturing, ships, electronic devices, coatings and the like. In order to adapt to the severer use environment, higher requirements are put forward on the tribological performance of the epoxy resin. The high brittleness and poor tribological properties are caused by the three-dimensional network structure and high crosslinking density of the epoxy resin. Therefore, the tribological properties of epoxy resins are improved by the addition of various fillers having good mechanical and self-lubricating properties.
The hexagonal boron nitride (h-BN) nanosheet is used as a graphene-like two-dimensional flaky nanomaterial, also called white graphene, and shows remarkable thermal and chemical stability, good mechanical properties, good adsorption performance, high thermal conductivity coefficient, low expansion coefficient, wide energy band gap, good oxidation resistance and excellent lubricating performance; due to the fact that the hexagonal boron nitride nanosheet is large in surface area, strong in inertia, few in surface functional groups, strong in interaction of van der waals force of the intermediate layer and serious in agglomeration phenomenon in the process of compounding with a polymer, the hexagonal boron nitride nanosheet needs to be stripped and subjected to surface modification (functionalization) chemical modification, and common modification methods include hydroxylation, silanization, amination and compounding of soft metals (such as silver). Silver simple substance is grafted to the surface of the thin-layer hexagonal boron nitride nanosheet through a chemical grafting method, so that a better synergistic effect is achieved when the silver simple substance is combined with matrix epoxy resin, and the effects of wear reduction and wear resistance are effectively achieved.
The invention content is as follows:
the invention aims to provide a silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating and a preparation method thereof.
The invention is realized by the following technical scheme:
an Ag/BNNSs nano material modified epoxy resin composite coating comprises the following steps:
(1) preparing a hexagonal boron nitride nanosheet by hydrothermal stripping: firstly, sequentially adding deionized water, sodium hydroxide, potassium hydroxide and hexagonal boron nitride powder into a polytetrafluoroethylene reaction kettle, ultrasonically dispersing, magnetically stirring and uniformly mixing, sealing and heating, cooling to room temperature after the reaction is finished, centrifuging, cleaning a product, and drying to obtain hexagonal boron nitride nanosheet powder;
(2) preparing a silver/hexagonal boron nitride nanosheet hybrid material by a hydrothermal method: ultrasonically dispersing the hexagonal boron nitride nanosheet prepared in the step (1) in deionized water; stirring a certain amount of silver nitrate to dissolve in deionized water to form a silver nitrate solution, adding polyvinylpyrrolidone K30 into the silver nitrate solution, and dissolving by ultrasonic; sequentially adding the prepared two solutions into a polytetrafluoroethylene reaction kettle, uniformly mixing the two solutions by magnetic stirring, sealing and heating, cooling to room temperature after the reaction is finished, centrifuging, cleaning a product, and freeze-drying to obtain silver/hexagonal boron nitride nano hybrid material powder;
(3) preparing the self-lubricating composite coating of the epoxy resin base modified by the silver/hexagonal boron nitride nanometer hybrid material: adding the prepared silver/hexagonal boron nitride nanosheet hybrid material powder into epoxy resin, adding a curing agent after magnetic stirring, continuing magnetic stirring, performing ultrasonic treatment, spraying the mixture on a prepared substrate by using a spray gun, and curing for several hours at a certain temperature to obtain the self-lubricating composite coating.
In the step (1), the mass ratio of sodium hydroxide to potassium hydroxide is 14: 5-2: 1; the mass ratio of the total mass of the sodium hydroxide and the potassium hydroxide to the mass of the hexagonal boron nitride is 19: 4-9: 2.
In the step (1), deionized water, sodium hydroxide, potassium hydroxide and hexagonal boron nitride powder are added, the ultrasonic dispersion time is 20-30 minutes, and the magnetic stirring time is 15-30 minutes.
In the step (1), the temperature for sealing and heating is 180 ℃, and the temperature is kept for 2 hours.
In the step (1), the three times of distilled water and the three times of ethanol are centrifugally cleaned, and the freeze drying is carried out for 48 hours.
In the step (2), the dosage ratio of the silver nitrate, the polyvinylpyrrolidone K30 and the hexagonal boron nitride nanosheets is 10:20: 1-16: 32: 1.
And (2) adding deionized water, silver nitrate, polyvinylpyrrolidone K30 and hexagonal boron nitride nanosheets, wherein the ultrasonic dispersion time is 20-30 minutes, and the magnetic stirring time is 15-30 minutes.
In the step (2), the temperature for sealing and heating is 180 ℃, and the temperature is kept for 18 hours.
And (2) centrifugally cleaning three times of distilled water and three times of ethanol, and freeze-drying for 48 hours.
In the step (3), the content of the silver/hexagonal boron nitride nanosheet hybrid material powder accounts for 0.5-5% of the total mass of the epoxy resin and the curing agent; the mass ratio of the epoxy resin to the curing agent is 5: 3-5: 5.
In the step (3), uniformly spraying the epoxy resin uniformly stirred by ultrasonic magnetic force on a prepared substrate by using a spray gun in a common nitrogen atmosphere with the pressure of 0.10-0.13 MPa; the curing condition is 100-120 ℃ and 2-6 h.
Has the advantages that:
the epoxy resin is selected as a main material because the epoxy resin has the excellent performances of high bonding strength, high chemical stability, excellent mechanical property and corrosion resistance, good insulativity, low toxicity, low cost, high adaptability and the like; the inorganic lubricating phase hexagonal boron nitride and silver are selected as the filler, so that the strength of the composite material can be effectively improved, and the abrasion and friction coefficient of the composite material are further reduced. The invention has the characteristics that the prepared silver/hexagonal boron nitride nanosheet/epoxy resin-based self-lubricating composite material has high mechanical strength, small friction coefficient, low wear rate and the like, has good lubricating property and mechanical property, can reduce the friction coefficient of the epoxy resin material by a method of generating a transfer film on a contact surface, improves the antifriction and wear-resistant capability of the material, and prolongs the service life of the material.
Description of the drawings:
FIG. 1 is a transmission electron microscope topography of a exfoliated hexagonal boron nitride nanosheet of example 1 of the present invention;
FIG. 2 is a scanning electron microscope topography of the hybrid material of example 1 of the present invention;
the specific implementation mode is as follows:
the invention is further described below with reference to specific examples:
example 1
Firstly, sequentially adding 75mL of deionized water, 2.84g of sodium hydroxide, 1.08g of potassium hydroxide and 1g of hexagonal boron nitride powder (hBN) into a 100mL polytetrafluoroethylene reaction kettle, carrying out ultrasonic dispersion for 30 minutes, carrying out magnetic stirring for 30 minutes, heating for 2 hours at 180 ℃ in a sealed manner, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and carrying out freeze drying for 48 hours to obtain hexagonal boron nitride nanosheet powder (BNNSs); adding 80mL of deionized water, 0.6g of silver nitrate and 1.2g of polyvinylpyrrolidone K30 into a 100mL of polytetrafluoroethylene reaction kettle in sequence, taking 0.05g of prepared hexagonal boron nitride nanosheet powder, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing at 180 ℃, heating for 18 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain silver/hexagonal boron nitride nanosheet hybrid powder (Ag/BNNSs); mixing the prepared silver/hexagonal boron nitride nanosheet hybrid powder with an epoxy resin (EP) curing agent according to the formula (mass percentage) of 1.2: 99.5, stirring and mixing the materials fully and uniformly by ultrasonic magnetic force, spraying the epoxy resin uniformly stirred by the ultrasonic magnetic force on a prepared steel sheet by using a spray gun under the atmosphere of ordinary nitrogen with the pressure of 0.13MPa, drying the sprayed steel sheet for 2-6 hours in a vacuum drying oven at 100-120 ℃, and cooling the steel sheet along with the oven to obtain the prepared coating.
FIG. 1 is a transmission electron microscope topography of a hydrothermal method peeled hexagonal boron nitride nanosheet, from which a hydrothermal method peeled BNNSs nanosheet with curled edges can be seen, which can be distinguished as a transparent sheet layered structure, the peeled BNNSs nanosheet has an average thickness of 0.5-1.0 nm and an average width of 0.2-0.5 μm, and the result shows that the peeled BNNSs nanosheet has a relatively thin thickness and a relatively good overall structure.
FIG. 2 is a scanning electron microscope topography of the Ag/BNNSs hybrid material, from which it can be seen that the silver nanoparticles are well dispersed and grafted on the hexagonal boron nitride nanosheets, and due to the existence of the silver nanoparticles, the agglomeration of the hexagonal boron nitride is effectively improved.
Table 1 shows the friction coefficient and wear rate of the coating with the mass percent of pure epoxy resin, Ag/EP, hBN/EP, BNNSs/EP and Ag/BNNSs/EP hybrid materials being 1.2%, and the friction coefficient and wear rate of the obtained coating are obviously reduced along with the addition of the filler under the condition that the content of the nano filler is the same, and the addition effect of the Ag/BNNSs hybrid materials is more obvious.
Example 2
Firstly, sequentially adding 75mL of deionized water, 2.80g of sodium hydroxide, 1.0g of potassium hydroxide and 0.8g of hexagonal boron nitride powder into a 100mL polytetrafluoroethylene reaction kettle, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing and heating at 180 ℃ for 2 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain hexagonal boron nitride nanosheet powder; adding 80mL of deionized water, 0.5g of silver nitrate and 1.0g of polyvinylpyrrolidone K30 into a 100mL of polytetrafluoroethylene reaction kettle in sequence, taking 0.05g of prepared hexagonal boron nitride nanosheet powder, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing at 180 ℃, heating for 18 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain silver/hexagonal boron nitride nanosheet hybrid powder; mixing the prepared silver/hexagonal boron nitride nanosheet hybrid powder with an epoxy resin curing agent according to the formula (mass percentage) of 1.0: 99, stirring and mixing the materials uniformly by using ultrasonic magnetic force, uniformly spraying the epoxy resin uniformly stirred by using the ultrasonic magnetic force on a prepared steel sheet by using a spray gun in a common nitrogen atmosphere with the pressure of 0.13MPa, drying the sprayed steel sheet in a vacuum drying oven at 100-120 ℃ for 2-6 hours, and cooling the steel sheet along with the oven to obtain the prepared coating.
Example 3
Firstly, sequentially adding 75mL of deionized water, 2.86g of sodium hydroxide, 1.2g of potassium hydroxide and 0.9g of hexagonal boron nitride powder into a 100mL polytetrafluoroethylene reaction kettle, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing and heating at 180 ℃ for 2 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain hexagonal boron nitride nanosheet powder; adding 80mL of deionized water, 0.7g of silver nitrate and 1.4g of polyvinylpyrrolidone K30 into a 100mL of polytetrafluoroethylene reaction kettle in sequence, taking 0.05g of prepared hexagonal boron nitride nanosheet powder, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing at 180 ℃, heating for 18 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain silver/hexagonal boron nitride nanosheet hybrid powder; mixing the prepared silver/hexagonal boron nitride nanosheet hybrid powder with an epoxy resin curing agent according to the formula (mass percentage) of 1.5: and (2) stirring and uniformly mixing the materials by ultrasonic magnetic force, uniformly spraying the epoxy resin uniformly stirred by the ultrasonic magnetic force on a prepared steel sheet by using a spray gun under the general nitrogen atmosphere with the pressure of 0.13MPa, drying the sprayed steel sheet for 2-6 hours in a vacuum drying oven at 100-120 ℃, and cooling the steel sheet along with the oven to obtain the prepared coating.
Example 4
Firstly, sequentially adding 75mL of deionized water, 2.9g of sodium hydroxide, 1.3g of potassium hydroxide and 1g of hexagonal boron nitride powder into a 100mL polytetrafluoroethylene reaction kettle, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing and heating at 180 ℃ for 2 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain hexagonal boron nitride nanosheet powder; adding 80mL of deionized water, 0.8g of silver nitrate and 1.6g of polyvinylpyrrolidone K30 into a 100mL of polytetrafluoroethylene reaction kettle in sequence, taking 0.05g of prepared hexagonal boron nitride nanosheet powder, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing at 180 ℃, heating for 18 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain silver/hexagonal boron nitride nanosheet hybrid powder; taking the prepared silver/hexagonal boron nitride nanosheet hybrid powder and an epoxy resin curing agent according to the formula (mass percentage) 2: 98, uniformly mixing the materials, uniformly spraying the epoxy resin uniformly stirred by the ultrasonic magnetic force on a prepared steel sheet by using a spray gun in a general nitrogen atmosphere with the pressure of 0.13MPa, drying the sprayed steel sheet in a vacuum drying oven at 100-120 ℃ for 2-6 hours, and cooling the steel sheet along with the oven to obtain the prepared coating.
Example 5
Firstly, sequentially adding 75mL of deionized water, 3.0g of sodium hydroxide, 1.5g of potassium hydroxide and 1g of hexagonal boron nitride powder into a 100mL polytetrafluoroethylene reaction kettle, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing and heating at 180 ℃ for 2 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain hexagonal boron nitride nanosheet powder; adding 80mL of deionized water, 0.8g of silver nitrate and 1.6g of polyvinylpyrrolidone K30 into a 100mL of polytetrafluoroethylene reaction kettle in sequence, taking 0.05g of prepared hexagonal boron nitride nanosheet powder, ultrasonically dispersing for 30 minutes, magnetically stirring for 30 minutes, sealing at 180 ℃, heating for 18 hours, cooling to room temperature after the reaction is finished, centrifuging, washing the product with deionized water and ethanol for three times respectively, and freeze-drying for 48 hours to obtain silver/hexagonal boron nitride nanosheet hybrid powder; taking the prepared silver/hexagonal boron nitride nanosheet hybrid powder and an epoxy resin curing agent according to a formula (mass percentage) of 3: 97, uniformly mixing, uniformly spraying the epoxy resin uniformly stirred by the ultrasonic magnetic force on a prepared steel sheet by using a spray gun under the general nitrogen atmosphere with the pressure of 0.13MPa, drying the sprayed steel sheet for 2-6 hours in a vacuum drying oven at 100-120 ℃, and cooling along with the oven to obtain the prepared coating.
TABLE 1 coating coefficient of friction and wear
Claims (10)
1. The Ag/BNNSs nano material modified epoxy resin composite coating is characterized by comprising the following steps:
(1) preparing a hexagonal boron nitride nanosheet by hydrothermal stripping: sequentially adding deionized water, sodium hydroxide, potassium hydroxide and hexagonal boron nitride powder into a polytetrafluoroethylene reaction kettle, ultrasonically dispersing, magnetically stirring and uniformly mixing, sealing and heating, cooling to room temperature after the reaction is finished, centrifuging, cleaning a product, and drying to obtain hexagonal boron nitride nanosheet powder;
(2) preparing a silver/hexagonal boron nitride nano hybrid material by a hydrothermal method: ultrasonically dispersing the hexagonal boron nitride nanosheet prepared in the step (1) in deionized water; stirring and dissolving silver nitrate in deionized water to form a silver nitrate solution, adding polyvinylpyrrolidone K30 into the silver nitrate solution, and dissolving by ultrasonic; sequentially adding the prepared two solutions into a polytetrafluoroethylene reaction kettle, uniformly mixing the two solutions by magnetic stirring, sealing and heating, cooling to room temperature after the reaction is finished, centrifuging, cleaning a product, and freeze-drying to obtain silver/hexagonal boron nitride nano hybrid material powder;
(3) preparing the self-lubricating composite coating of the epoxy resin base modified by the silver/hexagonal boron nitride nanometer hybrid material: adding the prepared silver/hexagonal boron nitride nanosheet hybrid material powder into epoxy resin, adding a curing agent after magnetic stirring, continuing magnetic stirring, performing ultrasonic treatment, spraying the mixture on a prepared substrate by using a spray gun, and curing for several hours at a certain temperature to obtain the self-lubricating composite coating.
2. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, wherein in the step (1), the mass ratio of sodium hydroxide to potassium hydroxide is 14: 5-2: 1; the mass ratio of the total mass of the sodium hydroxide and the potassium hydroxide to the mass of the hexagonal boron nitride is 19: 4-9: 2.
3. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, wherein in the step (1), deionized water, sodium hydroxide, potassium hydroxide and hexagonal boron nitride powder are added, the ultrasonic dispersion time is 20-30 minutes, and the magnetic stirring time is 15-30 minutes.
4. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, wherein in the step (1), the sealing and heating temperature is 180 ℃, the temperature is kept for 2 hours, and the freeze drying is carried out for 48 hours.
5. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, wherein in the step (2), the mass ratio of silver nitrate, polyvinylpyrrolidone K30 and hexagonal boron nitride nanosheets is 10:20: 1-16: 32: 1.
6. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, wherein in the step (2), the ultrasonic dispersion time is 20-30 minutes, and the magnetic stirring time is 15-30 minutes.
7. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, wherein in the step (2), the sealing and heating temperature is 180 ℃, the temperature is kept for 18 hours, and the freeze drying is carried out for 48 hours.
8. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, wherein in the step (3), the content of the silver/hexagonal boron nitride nano sheet hybrid material powder is 0.5% -5% of the total mass of the epoxy resin and the curing agent; the mass ratio of the epoxy resin to the curing agent is 5: 3-5: 5.
9. The preparation method of the silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating according to claim 1, characterized in that in the step (3), the epoxy resin uniformly stirred by ultrasonic magnetic force is uniformly sprayed on a prepared substrate by a spray gun in a common nitrogen atmosphere with the pressure of 0.10 MPa-0.13 MPa; the curing condition is 100-120 ℃ and 2-6 h.
10. The silver/hexagonal boron nitride nano hybrid material modified epoxy resin self-lubricating composite coating prepared by the preparation method according to any one of claims 1 to 9.
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| CN114479774A (en) * | 2022-01-20 | 2022-05-13 | 国网河北省电力有限公司电力科学研究院 | Preparation method and preparation equipment of heat-conducting insulating material GBN |
| CN115058128A (en) * | 2022-06-06 | 2022-09-16 | 江苏大学 | h-BN nano hybrid material and preparation method and application thereof |
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| CN114479774A (en) * | 2022-01-20 | 2022-05-13 | 国网河北省电力有限公司电力科学研究院 | Preparation method and preparation equipment of heat-conducting insulating material GBN |
| CN114479774B (en) * | 2022-01-20 | 2023-09-26 | 国网河北省电力有限公司电力科学研究院 | Preparation method and preparation equipment of heat-conducting insulating material GBN |
| CN115058128A (en) * | 2022-06-06 | 2022-09-16 | 江苏大学 | h-BN nano hybrid material and preparation method and application thereof |
| CN115058128B (en) * | 2022-06-06 | 2023-11-10 | 江苏大学 | h-BN nano hybrid material and preparation method and application thereof |
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