CN116749562A - Method for preparing flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride - Google Patents
Method for preparing flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride Download PDFInfo
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 97
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 62
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000004528 spin coating Methods 0.000 claims abstract description 20
- 238000007731 hot pressing Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 43
- 238000000498 ball milling Methods 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 25
- 238000005303 weighing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 238000007605 air drying Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002356 single layer Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- 239000000945 filler Substances 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 56
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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Abstract
The invention relates to the technical field of polymer composite material processing, in particular to a method for preparing a flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride. Aiming at the defects of the prior heat-conducting film technology, the first object of the invention is to provide a method for preparing a flexible polyvinyl alcohol heat-conducting film based on low-content boron nitride; the second purpose of the invention is to regulate the phase structure by a spin coating film forming process, and prepare the BNSs/PEI/PVA composite material film with high mechanical strength and continuous heat conduction paths by hot pressing. The invention is based on water phase preparation, has simple process and low addition of the heat conducting filler. The film prepared by the method has a cement-brick-like stacked structure, and a high-efficiency heat conduction path can be obtained by adding a low-content heat conduction filler, so that the composite material film has high heat conduction and excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of polymer composite material processing, in particular to a method for preparing a flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride.
Background
In recent years, under the promotion of 5G commercialization, the fields of electronic communication equipment, new energy automobiles, artificial intelligence and the like are rapidly developed, and accordingly, the development of heat-conducting composite materials is driven. In order to meet the stable and efficient working requirements of new-generation electronic equipment, development of novel high-heat-conductivity composite materials for solving the thermal failure problem of modern electronic equipment has gradually become one of research hotspots. Compared with the traditional metal and ceramic heat conduction materials, the polymer material has the advantages of light weight, easy processing and forming, good mechanical toughness, low price, high stability and the like, and is an ideal choice for preparing the heat conduction composite material. However, most polymers have a generally low thermal conductivity and are greatly limited in the field of materials with heat dissipation requirements. Based on the polymer composite material, the polymer composite material has high heat conduction and good mechanical property, and can be industrially produced, and has great market application prospect.
Polyvinyl alcohol (PVA) has the advantages of good film forming performance, ideal mechanical strength, excellent biocompatibility and the like, but has poor heat conductivity coefficient lambda, and is difficult to meet the heat dissipation requirement of a flexible device for efficient and rapid heat dissipation.
Boron Nitride (BN) is a common heat conducting inorganic filler, has a special structure similar to graphite, has ultrahigh heat conductivity, and can improve other physical properties of the material.
In the invention, hexagonal boron nitride is called as h-BN, boron nitride nano-sheets are called as BNSs, and triammonium phosphate and triatomic water are called as (NH) 3 PO 4 ·3H 2 O ", polyethylenimine is abbreviated as" PEI ", and polyvinyl alcohol is abbreviated as" PVA ".
The conventional blending method is based on that a large amount of heat conductive filler with high heat conductivity is generally added into the heat conductive polymer composite material, but the addition of a large amount of heat conductive filler causes insufficient mechanical properties. According to the invention, aiming at the requirements of the flexible and light-weight composite material on heat conducting performance, a micro continuous phase structure is formed by utilizing the phase separation of the bi-component polymer, a heat conducting path of the film is constructed by directional dispersion of anisotropic two-dimensional BN, and an efficient heat conducting path is formed in a low-content filler system, so that the flexible BNSs/PEI/PVA composite material film with high mechanical strength and continuous heat conducting path is prepared.
Disclosure of Invention
Aiming at the defects of the prior heat-conducting film technology, the first object of the invention is to provide a method for preparing a flexible polyvinyl alcohol heat-conducting film based on low-content boron nitride; the second purpose of the invention is to regulate the phase structure by a spin coating film forming process, and prepare the BNSs/PEI/PVA composite material film with high mechanical strength and continuous heat conduction paths by hot pressing. The invention is based on water phase preparation, has simple process and low addition of the heat conducting filler.
The aim of the invention can be achieved by the following technical scheme, which comprises the following steps:
(1) Weighing a certain amount of h-BN and (NH) 3 PO 4 ·3H 2 O, stripping and functionalizing the h-BN to obtain BNSs;
(2) Placing a proper amount of PVA and deionized water into a container, and heating until PVA particles are completely dissolved in water;
(3) Adding a silane coupling agent into the BNSs dispersion solution prepared in the step (1), and uniformly dispersing by using ultrasonic waves; weighing a certain mass of PEI, adding the PEI, and mechanically stirring to completely dissolve the PEI in BNSS aqueous dispersion containing a silane coupling agent; adding PVA water solution with certain mass into BNSs/PEI water solution prepared in the previous step, heating and stirring to obtain uniformly mixed solution;
(4) Under certain spin coating conditions, placing the uniform mixed solution on a glass sheet to spin-coat the glass sheet into a film by using a spin coater, naturally air-drying the glass sheet in a room temperature environment to obtain a single-layer composite material film, and then superposing the single-layer composite material films together.
(5) And finally, hot-pressing the stacked single-layer composite material film under a certain hot-pressing condition to obtain a finished product.
Further, in the step (1), the specific steps of stripping and functionalizing the h-BN are as follows:
weighing a certain amount of h-BN sum (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank for ball milling; washing the ball milled BNSs with deionized water until the pH is 7 to remove (NH) 3 PO 4 ·3H 2 O; crushing the solution obtained after cleaning, and crushing for 1-2 hours under the power of 500W by using a point-to-point cell crusher; centrifuging to obtain supernatant, removing unpeeled h-BN, wherein the centrifuging time is 10min, and the rotating speed is 1500-2500 rpm;
further, in the specific step of stripping and functionalizing the h-BN, the h-BN and (NH) are weighed 3 PO 4 ·3H 2 The mass ratio of O is 1:25 to 1:100, most preferably, the mass ratio is 1:50; the ball milling condition is 560-720 r/min, the ball milling time is 20h, and most preferably, the ball milling condition is 640r/min.
Further, in the step (2), the ratio of the PVA to the deionized water is 90ml of deionized water corresponding to 10g of PVA.
Further, in the step (3), the silane coupling agent is KH-570 or KH-550; BNSs aqueous dispersion after adding silane coupling agent, the ultrasonic power is 200-400W; preferably, the ultrasonic power is 300W.
Further, in the step (3), the mass of BNSs is 5-20wt% of the total mass of the composite material, and the mass ratio of PEI to PVA is 1:10-3:10.
In step (3), BNNSs interact strongly with PEI in aqueous solution via a silane coupling agent such that BNNSs are fully present in the PEI phase. The BNSs/PEI phase is a continuous phase, providing an efficient thermal conduction path for BNSs.
Further, in the step (4), spin coating conditions are as follows: 3000rpm, 20s.
Further, in the step (4), after a single-layer composite material film is obtained, the composite material film is placed in a room temperature environment and naturally dried for 48 hours.
Further, in the step (5), the hot pressing condition is 80-100 ℃,15MPa and 15min.
The technical scheme principle of the invention is as follows:
(1) Principle of stripping and functionalization of BN using physical ball milling:
the mechanical ball milling stripping method is to strip the h-BN layer by a physical and mechanical action. In the ball milling process, h-BN receives strong shearing force and impact force, and under the action of the shearing force and the impact force, van der Waals force between the sheet layers is destroyed, so that h-BN stripping is realized. Meanwhile, the B atom site is fully exposed due to strong physical action, so that the functionalization of the h-BN is realized. While (NH) 3 PO 4 ·3H 2 O acts as a ball milling aid during ball milling. The ball milling device has the functions of buffering and lubricating in the ball milling process, reduces impact of grinding balls and related abrasion and pollution, avoids generating BNSs with smaller size under strong shearing force, and minimizes damage to the crystal structure in the h-BN plane. And amino groups are introduced to realize the functionalization of BNSs.
(2) Preparation principle of highly oriented BNSs/PEI/PVA high heat conduction film:
1) In the film forming process, BNSs are completely dispersed in a PEI phase under the combined action of quenching and solvent volatilization and a silane coupling agent, so that the viscosity of the BNSs/PEI enrichment phase is increased, the PVA with higher mass fraction is formed into a sea island phase instead, the BNSs/PEI phase becomes a continuous phase structure, and a high-efficiency heat conduction path is provided for the BNSs.
2) Compared with other film forming methods, the spin coating process can not only take away part of low-boiling organic solvent due to high-speed rotation, but also enable the heat conducting filler to be distributed in a layered manner in the matrix.
3) Finally, the hot pressing process firstly enables BNSs/PEI/PVA to form a highly oriented structure in the in-plane direction, and secondly enables the film to form a stacked structure similar to cement-brick, so that interface thermal resistance is reduced, and heat conduction performance and mechanical performance are improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) The film prepared by the method has a cement-brick-like stacked structure, and a high-efficiency heat conduction path can be obtained by adding a low-content heat conduction filler, so that the composite material film has high heat conduction and excellent mechanical properties. According to the heat conduction data, BNSs/20 PEI/PVA has the highest TC, and the continuous phase structure formed in a system with 20wt% PEI is proved to be optimal, so that a high-efficiency continuous heat conduction path is provided, and the heat conduction performance of the material is greatly improved. When BNSs filling amount is 10wt%, TC of the composite material can reach 1.3 W.m -1 K -1 . The tensile strength of the composite material is increased from 13.8MPa to 27.4MPa through a stress-strain curve, so that the mechanical property is improved.
(2) The film prepared by the method still has excellent flexibility and stretchability.
(3) The method has low cost of required materials, is simple to process based on water phase preparation, and can be used in the fields of flexible electronics, biomedical appliances and the like through proper process treatment.
Drawings
Figure 1 is a morphological characterization of BN and BNNSs.
FIG. 2 is a SEM image of a cross section of a 10 BNSs/20 PEI/PVA composite material
FIG. 3 thermal conductivity of BNSs/PEI/PVA composite thermal conductive films of examples 1, 2, 3 and comparative example 1 pure PVA film.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
The embodiment provides a method for preparing a flexible polyvinyl alcohol heat conduction film based on low-content boron nitride, which comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 25 h-BN & lt (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
(2) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(3) Weighing 0.818g of PEI, adding the PEI into the BNSs dispersion solution in the step (1), and mechanically stirring to completely dissolve the PEI in the BNSs aqueous solution; the silane coupling agent is one of KH-570 and KH-550. In this step, the mass of the fixed BNSs is 10% by weight of the total mass of the composite material, and the total mass of the composite material is 10g. (4) Adding PVA water solution with certain mass into BNSs/PEI water solution, heating and stirring for 5min at 100 ℃ to obtain uniformly mixed solution. The PVA mass in this step was 8.182g.
(5) And (3) placing the uniform mixed solution on a glass sheet by using a spin coater, spin-coating the mixed solution to form a film, and placing the film in a room temperature environment for 48h for natural air drying.
(6) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Example 2
The embodiment provides a method for preparing a flexible polyvinyl alcohol heat conduction film based on low-content boron nitride, which comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 O-utilizing articleAnd stripping and functionalizing the h-BN by a ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 50 h-BN and (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
(2) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(3) Weighing 1.500g of PEI, adding the PEI into the BNSs dispersion solution obtained in the step (1), and mechanically stirring to completely dissolve the PEI in the BNSs aqueous solution; the silane coupling agent is one of KH-570 and KH-550. In this step, the mass of BNSs was fixed (10 wt% of the total mass of the composite, 10g of the total mass of the composite).
(4) Adding PVA water solution with certain mass into BNSs/PEI water solution, heating and stirring for 5min at 100 ℃ to obtain uniformly mixed solution. The PVA mass in this step was 7.500g.
(5) And (3) placing the uniform mixed solution on a glass sheet by using a spin coater, spin-coating the mixed solution to form a film, and placing the film in a room temperature environment for 48h for natural air drying.
(6) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Example 3
The embodiment provides a method for preparing a flexible polyvinyl alcohol heat conduction film based on low-content boron nitride, which comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: h-BN with (NH) of 100 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
(2) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(3) Weighing 2.077g of PEI, adding into the BNSs dispersion solution obtained in the step (1), and mechanically stirring to completely dissolve the PEI in the BNSs aqueous solution; the silane coupling agent is one of KH-570 and KH-550. In this step, the mass of BNSs was fixed (10 wt% of the total mass of the composite, 10g of the total mass of the composite).
(4) Adding PVA water solution with certain mass into BNSs/PEI water solution, heating and stirring for 5min at 100 ℃ to obtain uniformly mixed solution. The PVA mass in this step was 6.923g.
(5) And (3) placing the uniform mixed solution on a glass sheet by using a spin coater, spin-coating the mixed solution to form a film, and placing the film in a room temperature environment for 48h for natural air drying.
(6) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Example 4
The embodiment provides a method for preparing a flexible polyvinyl alcohol heat conduction film based on low-content boron nitride, which comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 50 h-BN and (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Ball millingBNSs are dispersed in deionized water and rinsed with deionized water multiple times to remove residual (NH) from the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
(2) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(3) Weighing 1.583g of PEI, adding into the BNSs dispersion solution in the step (1), and mechanically stirring to completely dissolve in the BNSs aqueous solution; the silane coupling agent is one of KH-570 and KH-550. In this step, the mass of BNSs was 0.5g.
(4) Adding PVA water solution with certain mass into BNSs/PEI water solution, heating and stirring for 5min at 100 ℃ to obtain uniformly mixed solution. The PVA mass in this step was 7.917g.
(5) And (3) placing the uniform mixed solution on a glass sheet by using a spin coater, spin-coating the mixed solution to form a film, and placing the film in a room temperature environment for 48h for natural air drying.
(6) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Example 5
The embodiment provides a method for preparing a flexible polyvinyl alcohol heat conduction film based on low-content boron nitride, which comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 50 h-BN and (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
(2) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(3) Weighing 1.500g of PEI, adding the PEI into the BNSs dispersion solution obtained in the step (1), and mechanically stirring to completely dissolve the PEI in the BNSs aqueous solution; the silane coupling agent is one of KH-570 and KH-550. In this step, BNSs mass was 1.0g.
(4) Adding PVA water solution with certain mass into BNSs/PEI water solution, heating and stirring for 5min at 100 ℃ to obtain uniformly mixed solution. The PVA mass in this step was 7.500g.
(5) And (3) placing the uniform mixed solution on a glass sheet by using a spin coater, spin-coating the mixed solution to form a film, and placing the film in a room temperature environment for 48h for natural air drying.
(6) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Example 6
The embodiment provides a method for preparing a flexible polyvinyl alcohol heat conduction film based on low-content boron nitride, which comprises the following steps:
(1) h-BN and (NH) 3 PO 4 ·3H 2 And stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) Weighing the following components in percentage by mass: 50 h-BN and (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank, and ball milling is carried out for 20 hours at the rotating speed of 640 r/min;
2) Dispersing ball-milled BNSs in deionized water, and washing with deionized water for multiple times to remove residual (NH) in the solution 3 PO 4 ·3H 2 O, until the pH value is 7;
3) Crushing the obtained uniformly dispersed solution for 1 hour under the power of 500W by using a point-to-point cytoclasis instrument;
4) Centrifuging at 2000rpm for 10min, collecting supernatant, and removing non-stripped h-BN;
(2) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(3) Weighing 1.333g of PEI, adding into the BNSs dispersion solution in the step (1), and mechanically stirring to completely dissolve in the BNSs aqueous solution; the silane coupling agent is one of KH-570 and KH-550. In this step, BNSs mass was 2.0g.
(4) Adding PVA water solution with certain mass into BNSs/PEI water solution, heating and stirring for 5min at 100 ℃ to obtain uniformly mixed solution. The PVA mass in this step was 6.667g.
(5) And (3) placing the uniform mixed solution on a glass sheet by using a spin coater, spin-coating the mixed solution to form a film, and placing the film in a room temperature environment for 48h for natural air drying.
(6) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Comparative example 1
The comparative example provides a method for preparing a PVA flexible film, comprising the following steps:
(1) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(2) And (3) placing the PVA solution on a glass sheet by using a spin coater, spin-coating the PVA solution to form a film, and naturally air-drying the film in a room temperature environment for 48 hours.
(3) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Comparative example 2
The comparative example provides a preparation method of an h-BN/PVA flexible heat-conducting film, which comprises the following steps:
(1) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(2) 2g of unpeeled h-BN are weighed out and added to the PVA solution.
(3) And spin-coating the uniform mixed solution into a film by using a spin-coating instrument, and naturally air-drying the film for 48 hours in a room temperature environment.
(4) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Comparative example 3
The embodiment provides a preparation method of an h-BN/PEI/PVA flexible heat-conducting film, which comprises the following steps:
(1) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(2) 2g of PEI, 2g of unpeeled h-BN are weighed and added to the PVA solution.
(3) And spin-coating the uniform mixed solution into a film by using a spin-coating instrument, and naturally air-drying the film for 48 hours in a room temperature environment.
(4) Finally, the film is hot-pressed for 15min at 100 ℃ and 15 MPa.
Comparative example 4
The embodiment provides a preparation method of an h-BN/PEI/PVA flexible heat-conducting film, which comprises the following steps:
(1) 10g of PVA was placed in a beaker with 90ml of deionized water and heated at 100℃until the PVA particles were completely dissolved in the water.
(2) 2g of PEI, 2g of unpeeled h-BN are weighed and added to the PVA solution.
(3) And spin-coating the uniform mixed solution into a film by using a spin-coating instrument, and naturally air-drying the film for 48 hours in a room temperature environment.
Analysis of experimental results:
FIG. 1 is a morphological characterization of raw materials BN and BNSs, wherein (a) and (b) are SEM images of the original h-BN; (c) An SEM image of exfoliated BNSs, (d) an SEM magnified image of exfoliated BNSs; from FIGS. 1 (a) and (b), it was found that h-BN was present as a lamellar structure having a lamellar diameter of about < 5. Mu.m, but it was mostly present in a state of being superimposed with a plurality of layers. The morphology of the stripped BNSs is shown in fig. 1 (c) and (d), and the thickness reduction of the boron nitride can be obviously observed.
FIG. 2 is an SEM image of a 10 BNSs/20 PEI/PVA composite, wherein the red curve surrounding area is the PVA phase, and the remainder is the enriched phase of BNSs/PEI. The PVA phase is of a sea-island phase structure, the BNSs/PEI phase is of a continuous phase structure, and an efficient heat conduction path is provided for BNSs.
FIG. 3 shows the thermal conductivity of BNSs/PEI/PVA composite films of examples 1, 2, and 3. From the data, when the PEI content is 20wt% of PVA, the TC of the composite material is highest, and the phase structure of the 10 BNSs/20 PEI/PVA composite material system is superior to that of the other two systems, so that a continuous and more efficient heat conduction path is formed.
The TC of BNSs/20 PEI/PVA composite films of examples 4, 5 and 6 were 0.85 W.multidot.m, respectively -1 K -1 、1.3W·m -1 K -1 、1.08W·m -1 K -1 . The BNSs/20 PEI/PVA composite System of example 5 reached TC 1.3 W.m at a BNSs loading of 10wt% -1 K -1 Is pure PVA material TC (0.15 W.m -1 K -1 ) 8.7 times (comparative example 1). In example 6, when the BNSs loading was 20wt%, the TC (1.08 W.multidot.m) -1 K -1 ) On the contrary, the effect of the contribution of the filler content to the heat conduction performance is reduced after the heat conduction path is constructed, and the interface thermal resistance between the fillers is obviously improved due to the excessively high filler content, which is not beneficial to the improvement of the heat conduction performance of the composite material. TC of the composite films of comparative example 1, comparative example 2, comparative example 3, comparative example 4 were 0.15 W.multidot.m, respectively -1 K -1 、0.38W·m -1 K -1 、0.61W·m -1 K -1 、0.48W·m -1 K -1 It can be seen that the thermal conductivity of the material film is less improved after the unpeeled heat conducting filler h-BN is added, and the thermal performance of the film after hot pressing is more excellent than that of the film after non-hot pressing.
Table 1 shows the tensile strength and elongation at break of the BNSs/PEI/PVA composite films of examples 4, 5, and 6. As the BNNSs content in the system increases, the tensile strength of the composite material gradually increases. The tensile strength of the pure PVA is 13.8MPa, the tensile strength of the 10 BNSs/20 PEI/PVA composite material is 27.4MPa, and the mechanical properties of the composite material are further improved. Meanwhile, BNSs completely exist in PEI phase when the system is subjected to phase separation, so that partial PVA material is reserved in the composite material
Good toughness. The elongation at break of the 10 BNSs/20 PEI/PVA composite material can still reach 17.9 percent.
TABLE 1
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A method for preparing a flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride is characterized by comprising the following steps:
(1) Weighing a certain amount of h-BN and (NH) 3 PO 4 ·3H 2 O, stripping and functionalizing the h-BN to obtain BNSs;
(2) Placing a proper amount of PVA and deionized water into a container, and heating until PVA particles are completely dissolved in water;
(3) Adding a silane coupling agent into the BNSs dispersion solution prepared in the step (1), and uniformly dispersing by using ultrasonic waves; weighing a certain mass of PEI, adding the PEI, and mechanically stirring to completely dissolve the PEI in BNSS aqueous dispersion containing a silane coupling agent; adding PVA water solution with certain mass into BNSs/PEI water solution prepared in the previous step, heating and stirring to obtain uniformly mixed solution;
(4) Under certain spin coating conditions, placing the uniform mixed solution on a glass sheet to spin-coat the glass sheet into a film by using a spin coater, naturally air-drying the glass sheet in a room temperature environment to obtain a single-layer composite material film, and then superposing the single-layer composite material films together;
(5) And finally, hot-pressing the stacked single-layer composite material film under a certain hot-pressing condition to obtain a finished product.
2. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: the specific steps of stripping and functionalizing the h-BN in the step (1) are as follows: weighing a certain amount of h-BN sum (NH) 3 PO 4 ·3H 2 O is added into a ball milling tank for ball milling; washing the ball milled BNSs with deionized water until the pH is 7 to remove (NH) 3 PO 4 ·3H 2 O; crushing the solution obtained after cleaning, and crushing for 1-2 hours under the power of 500W by using a point-to-point cell crusher; centrifuging to obtain supernatant, removing the unpeeled h-BN, wherein the centrifuging time is 10min, and the rotating speed is 1500-2500 rpm.
3. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 2, wherein the method comprises the following steps: in the specific step of stripping and functionalizing the h-BN described in step (1), the h-BN and (NH) are weighed 3 PO 4 ·3H 2 The mass ratio of O is 1:25 to 1:100; ball milling conditions are 560-720 r/min; the ball milling time is 20h.
4. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the ratio of the PVA to the deionized water is 90ml of deionized water corresponding to 10g of PVA.
5. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the silane coupling agent is KH-570 or KH-550; the ultrasonic power is 200-400W.
6. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the mass of BNSs is 5-20wt% of the total mass of the composite material.
7. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the mass ratio of the PEI to the PVA is 1:10-3:10.
8. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the spin coating conditions are as follows: 3000rpm, 20s.
9. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: in the step (4), after a single-layer composite material film is obtained, the composite material film is placed in a room temperature environment for natural air drying for 48 hours.
10. The method for preparing the flexible polyvinyl alcohol composite material heat conduction film based on low-content boron nitride as claimed in claim 1, wherein the method comprises the following steps: in the step (5), the hot pressing condition is 80-100 ℃,15MPa and 15min.
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