CN113200527A - Modification treatment method of hexagonal boron nitride - Google Patents
Modification treatment method of hexagonal boron nitride Download PDFInfo
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- CN113200527A CN113200527A CN202110679428.3A CN202110679428A CN113200527A CN 113200527 A CN113200527 A CN 113200527A CN 202110679428 A CN202110679428 A CN 202110679428A CN 113200527 A CN113200527 A CN 113200527A
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- C01B21/00—Nitrogen; Compounds thereof
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- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
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Abstract
The invention discloses a modification treatment method of hexagonal boron nitride, which relates to the technical field of modified material preparation, and comprises the following steps: s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization; and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling and sand milling treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification. The method for preparing the modified hexagonal boron nitride is simple, few in steps, loose in conditions, environment-friendly and safe, short in production period and low in production cost, and the adopted equipment is universal equipment, and a large amount of organic solvents are not used. The obtained modified hexagonal boron nitride has high surface hydroxyl content, strong interface atomic force, small thermal resistance and high thermal conductivity.
Description
Technical Field
The invention relates to the technical field of modified material preparation, in particular to a modification treatment method of hexagonal boron nitride.
Background
Hexagonal boron nitride is also called white graphite and is the simplest boron-nitrogen polymer. Similar to the hexagonal carbon network in graphite, nitrogen and boron in hexagonal boron nitride also form hexagonal network layers, which are overlapped to form crystals. The crystal is similar to graphite, has diamagnetism and high anisotropy, and has similar crystal parameters. The boron nitride is mainly used for refractory materials, semiconductor solid phase doping sources, structural materials of atomic stacks, packaging materials for preventing neutron radiation, rocket engine composition materials, high-temperature lubricants and release agents.
The hexagonal boron nitride is similar to the hexagonal carbon network in graphite, and nitrogen and boron in the hexagonal boron nitride also form a hexagonal network layer and are overlapped to form a crystal. The crystal is similar to graphite, has diamagnetism and high anisotropy, and has similar crystal parameters. Similarly, the hexagonal boron nitride is similar to graphite, has excellent thermal conductivity, heat resistance and thermal stability, and can be used for preparing a thermal conductive material of an electronic product.
However, the surface of hexagonal boron nitride is very stable, the number of active groups is very small, interaction with other high polymer materials and the like is not easy to occur, the application of hexagonal boron nitride to the preparation of a heat conduction layer of an electronic material is not facilitated, the existing solution method is generally to perform surface modification on hexagonal boron nitride and then apply the hexagonal boron nitride to the preparation of the heat conduction layer, but the existing modification method generally has the following problems: most of the modification methods use a large amount of volatile organic solvents, are not environment-friendly and have higher requirements on treatment processes and equipment; the partial modification method has multiple operation steps, complex method, special required equipment, high counterfeiting rate, long modification time and high cost; most modification methods can cause structural changes of the hexagonal boron nitride, influence the thermal/electrical properties of the hexagonal boron nitride, and are not beneficial to subsequent application, so that the practicability is low.
Disclosure of Invention
In order to solve the problems of multiple steps, complex method, large organic solvent consumption, influence on the hexagonal boron nitride structure in the modification process and the like in the hexagonal boron nitride modification method, the invention provides a simple, rapid and environment-friendly hexagonal boron nitride modification method, and the specific scheme is as follows.
A modification treatment method of hexagonal boron nitride comprises the following steps:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
Preferably, the processing of the hexagonal boron nitride in S1 includes processing the hexagonal boron nitride by ball milling and high-pressure homogenization sequentially.
Preferably, the processing of the hexagonal boron nitride in S1 includes processing the hexagonal boron nitride by sand grinding and high-pressure homogenization sequentially.
Preferably, the processing of the hexagonal boron nitride in S1 includes processing the hexagonal boron nitride by ball milling, sand milling and high-pressure homogenization in sequence.
Preferably, the ball milling is carried out in S1, the grinding balls are yttria-stabilized zirconia ceramics, and the mass ratio of the grinding balls with the diameter sizes of 25mm, 15mm, 10mm and 5mm, the diameters of 25mm, 15mm, 10mm and 5mm is (1-4): 1-4: (2-6): 1.
Preferably, the ball milling is carried out according to S1, the ratio of the mass of the milling balls to the mass of the hexagonal boron nitride (10-30): 1.
Preferably, the ball milling is carried out in S1, the ball milling speed is 100-.
Preferably, the ball milling described in S1 is followed by drying.
Preferably, the sand grinding ball is made of yttria-stabilized zirconia ceramic material, the diameter size comprises two or three of 3mm, 1mm and 0.5mm, and the mass ratio of the grinding balls with the diameters of 3mm, 1mm and 0.5mm is (0-2): (0.5-3): 1.
Preferably, the ratio of the mass of the grinding balls to the mass of the hexagonal boron nitride by sanding as described in S1 is (3-8): 1.
Preferably, the sanding is performed at S1, the host speed is 500-1600rpm, and the sanding time is 1-10 h.
Preferably, the sand of S1 is dried.
Preferably, the high pressure homogenization in S1 uses a Z-shaped working chamber or a Y-shaped working chamber.
Preferably, the high-pressure homogenization is carried out in S1, the pressure value is 75-190MPa, the flow rate is 50-8000mL/min, the cyclic homogenization treatment is carried out for 1-10 times, and the total time length is 0.5-4 h.
More preferably, the high-pressure homogenization in S1 is performed, the pressure value is 100-.
Preferably, the step of S1 is drying after high pressure homogenization.
Preferably, the hydroxylation modifying agent of S2 includes any one of dopamine, hydrogen peroxide and glutamic acid.
Preferably, the mass percentage of the hydroxylation modifying agent in S2 to the sum of the mass of the hydroxylation modifying agent and the mass of the treated hexagonal boron nitride is 1-10% wt.
Preferably, the temperature of the mixture of the hydroxylation modifying reagent and the treated hexagonal boron nitride is kept between 20 and 45 ℃ during the ball milling or sanding process of S2.
Preferably, the processing of S2 is performed by ball milling, and the grinding balls are yttria-stabilized zirconia ceramics, and the mass ratio of the grinding balls with the diameter size of 15mm, 10mm and 5mm including the diameters of 15mm, 10mm and 5mm is (1-2): (5-7): 1.
Preferably, the ratio of the mass of the grinding balls to the sum of the mass of the hydroxylated modifying agent and the mass of the treated hexagonal boron nitride (35-40):1 is obtained by ball milling as described in S2.
Preferably, the ball milling is carried out in S2, the ball milling speed is 100-.
Preferably, the grinding balls are sanded according to S2, the grinding balls are made of yttria-stabilized zirconia ceramic material, the mass ratio of the grinding balls with the diameter sizes of 2mm and 0.5mm, and the diameters of 2mm and 0.5mm is (4-7): 1.
Preferably, the ratio of the mass of the sand-milled, grinding balls to the sum of the mass of the hydroxylated modifying agent and the mass of the treated hexagonal boron nitride as described in S2 is (9-15): 1.
Preferably, the sanding is performed at S2, the host speed is 500-1600rpm, and the sanding time is 1-10 h.
Preferably, the sand of S2 is dried.
Preferably, when the hexagonal boron nitride is treated in S1, the method comprises the steps of ball milling and high-pressure homogenization sequentiallyTime t of high pressure homogenization when boron is present3The determination method comprises the following steps:
wherein, t1The ball milling time is; i is a ball milling time correction coefficient, i is a constant and takes a value of 0.2-0.5; t is tcTaking the value as a reference time standard quantity for 15-30 h; k is a correction parameter, and k is a constant with the value of 0.5-0.7. Preferably, among the above parameters, t1Is 10-24 h.
Preferably, when the hexagonal boron nitride is treated in S1, including the steps of sand grinding and high-pressure homogenization, the high-pressure homogenization time t is3The determination method comprises the following steps:
wherein, t2Sanding time; j is a sanding time correction coefficient, j is a constant and takes a value of 1-2; t is tcTaking the value as a reference time standard quantity for 8-30 h; k is a correction parameter, and k is a constant and takes a value of 0.1-0.7. Preferably, t is the parameter2Is 6-10 h.
Preferably, when the hexagonal boron nitride is treated in S1, the method comprises ball milling, sand milling and high-pressure homogenization in sequence, the high-pressure homogenization time t is3The determination method comprises the following steps:
wherein, t1Time of ball milling, t2Sanding time; i is a ball milling time correction coefficient, i is a constant and takes a value of 0.2-0.5; j is the sanding time correction coefficient, j is a constant and takes the value of 0.5-2; t is tcTaking the value as a reference time standard quantity for 2-15 h; k is a correction parameter, and k is a constant with the value of 0.5-0.7. Preferably, among the above parameters，t1Is 2-17h, t2Is 1-6 h.
Advantageous effects
The invention has the beneficial effects that:
the method for preparing the modified hexagonal boron nitride is simple, few in steps, loose in conditions, environment-friendly and safe, short in production period and low in production cost, and the adopted equipment is universal equipment, and a large amount of organic solvents are not used.
The obtained modified hexagonal boron nitride has high surface hydroxyl content, strong interface atomic force, small thermal resistance and high thermal conductivity.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The following examples and comparative examples are parallel runs, with the same processing steps and parameters, unless otherwise indicated.
Example 1 modification treatment of hexagonal boron nitride:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
S1, the processing of the hexagonal boron nitride comprises the steps of sequentially adopting a ball milling method and a high-pressure homogenizing method to process the hexagonal boron nitride.
And S1, performing ball milling, wherein the milling balls are made of yttria-stabilized zirconia ceramics, and the mass ratio of the diameter of the milling balls is 1:1:2:1, wherein the diameter of the milling balls comprises 25mm, 15mm, 10mm and 5 mm.
And S1, performing ball milling, wherein the ratio of the mass of the milling balls to the mass of the hexagonal boron nitride is 10: 1.
And S1, performing ball milling, wherein the ball milling speed is 100rpm in revolution speed, 200rpm in rotation speed, and the ball milling time is 4 hours.
And S1, drying after ball milling.
And S1, homogenizing under high pressure, and using a Z-shaped working cavity or a Y-shaped working cavity.
And S1, homogenizing under high pressure, wherein the pressure value is 100MPa, the flow rate is 800mL/min, and carrying out circular homogenization treatment for 3 times, and the total time length is 1 h.
And S1, drying after high-pressure homogenization.
S2 the hydroxylation modifying agent comprises dopamine.
S2, the mass of the hydroxylation modifying reagent accounts for 1 wt% of the sum of the mass of the hydroxylation modifying reagent and the mass of the treated hexagonal boron nitride.
S2, in the ball milling or sanding process, the temperature of the mixture of the hydroxylation modifying reagent and the processed hexagonal boron nitride is kept at 25 ℃.
And S2, performing ball milling treatment, wherein the milling balls are yttria-stabilized zirconia ceramics, and the mass ratio of the 15mm, 10mm and 5mm diameter milling balls is 1:5: 1.
And S2, performing ball milling, wherein the ratio of the mass of the milling balls to the sum of the mass of the hydroxylated modification reagent and the mass of the treated hexagonal boron nitride is 35: 1.
And S2, performing ball milling, wherein the ball milling speed is 100rpm in revolution speed, 200rpm in rotation speed, and the ball milling time is 2 h.
S2, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, and the mass ratio of the grinding balls with the diameters of 2mm and 0.5mm is 4: 1.
And S2, sanding, wherein the ratio of the mass of the grinding balls to the sum of the mass of the hydroxylated modification agent and the mass of the treated hexagonal boron nitride is 9: 1.
And S2, sanding at the speed of 500rpm of the main machine for 1 h.
And S2, drying after sanding.
Example 2 modification treatment of hexagonal boron nitride:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
S1, the processing of the hexagonal boron nitride comprises the steps of sequentially processing the hexagonal boron nitride by a sanding and high-pressure homogenizing method.
S1, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, the diameters of the yttria-stabilized zirconia ceramic materials comprise two or three of 3mm, 1mm and 0.5mm, and the mass ratio of the 3mm, 1mm and 0.5mm grinding balls is 2:3: 1.
And S1, sanding, wherein the mass ratio of the grinding balls to the hexagonal boron nitride is 8: 1.
And S1, sanding at the main machine speed of 1600rpm for 10 h.
And S1, drying after sanding.
S1 homogenizing under high pressure, and using Y-shaped working chamber.
And S1, performing high-pressure homogenization at a pressure value of 150MPa and a flow rate of 4500mL/min, and performing cyclic homogenization for 10 times, wherein the total time length is 4 h.
And S1, drying after high-pressure homogenization.
S2 the hydroxylation modifying reagent comprises glutamic acid.
S2, the mass of the hydroxylation modifying reagent accounts for 10 wt% of the sum of the mass of the hydroxylation modifying reagent and the mass of the treated hexagonal boron nitride.
S2, in the ball milling or sanding process, the temperature of the mixture of the hydroxylation modifying reagent and the processed hexagonal boron nitride is kept at 45 ℃.
And S2, performing ball milling treatment, wherein the milling balls are yttria-stabilized zirconia ceramics, and the mass ratio of the 15mm, 10mm and 5mm diameter milling balls is 2:7: 1.
And S2, performing ball milling, wherein the ratio of the mass of the milling balls to the sum of the mass of the hydroxylated modification reagent and the mass of the treated hexagonal boron nitride is 40: 1.
And S2, performing ball milling, wherein the ball milling speed is 400rpm in revolution speed, 800rpm in rotation speed and 5h in ball milling time.
S2, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, and the mass ratio of the grinding balls with the diameters of 2mm and 0.5mm is 7: 1.
And S2, sanding, wherein the ratio of the mass of the grinding balls to the sum of the mass of the hydroxylated modification agent and the mass of the treated hexagonal boron nitride is 15: 1.
And S2, sanding at the main machine speed of 1600rpm for 10 h.
And S2, drying after sanding.
Example 3 modification treatment of hexagonal boron nitride:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
S1, the processing of the hexagonal boron nitride comprises the steps of sequentially adopting ball milling, sand milling and high-pressure homogenization to process the hexagonal boron nitride.
And S1, performing ball milling, wherein the milling balls are made of yttria-stabilized zirconia ceramics, and the mass ratio of the diameter of the milling balls is 25mm, 15mm, 10mm and 5mm, and the diameter of the milling balls is 25mm, 15mm, 10mm and 5mm is 2:3:5: 1.
And S1, performing ball milling, wherein the ratio of the mass of the milling balls to the mass of the hexagonal boron nitride is 20: 1.
S1, ball milling, wherein the ball milling speed is 100 and 400rpm in revolution speed, 500rpm in rotation speed and 15h in ball milling time.
And S1, drying after ball milling.
S1, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, the diameters of the yttria-stabilized zirconia ceramic materials comprise two or three of 3mm, 1mm and 0.5mm, and the mass ratio of the 3mm, 1mm and 0.5mm grinding balls is 1:2: 1.
And S1, sanding, wherein the mass ratio of the grinding balls to the hexagonal boron nitride is 5: 1.
And S1, sanding at the host speed of 900rpm for 6 h.
And S1, drying after sanding.
S1 homogenizing under high pressure, and using Y-shaped working chamber.
S1, homogenizing under high pressure, wherein the pressure value is 130MPa, the flow rate is 3000mL/min, and carrying out circular homogenization treatment for 6 times, and the total time length is 2 h.
And S1, drying after high-pressure homogenization.
S2, the hydroxylation modifying reagent comprises hydrogen peroxide.
S2, the mass of the hydroxylation modifying reagent accounts for 6 wt% of the sum of the mass of the hydroxylation modifying reagent and the mass of the treated hexagonal boron nitride.
S2, in the ball milling or sanding process, the temperature of the mixture of the hydroxylation modifying reagent and the processed hexagonal boron nitride is kept at 30 ℃.
And S2, performing ball milling treatment, wherein the milling balls are yttria-stabilized zirconia ceramics, and the mass ratio of the 15mm, 10mm and 5mm diameter milling balls is 1:6: 1.
And S2, performing ball milling, wherein the ratio of the mass of the milling balls to the sum of the mass of the hydroxylated modification reagent and the mass of the treated hexagonal boron nitride is 37: 1.
And S2, performing ball milling, wherein the ball milling speed is 300rpm in revolution speed, 500rpm in rotation speed, and the ball milling time is 4 hours.
S2, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, and the mass ratio of the grinding balls with the diameters of 2mm and 0.5mm is 6: 1.
And S2, sanding, wherein the ratio of the mass of the grinding balls to the sum of the mass of the hydroxylated modification agent and the mass of the treated hexagonal boron nitride is 12: 1.
And S2, sanding at the main machine speed of 1100rpm for 6 h.
And S2, drying after sanding.
Example 4 modification treatment of hexagonal boron nitride:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
S1, the processing of the hexagonal boron nitride comprises the steps of sequentially adopting a ball milling method and a high-pressure homogenizing method to process the hexagonal boron nitride.
And S1, performing ball milling, wherein the milling balls are made of yttria-stabilized zirconia ceramics, and the mass ratio of the diameter of the milling balls is 1:1:2:1, wherein the diameter of the milling balls comprises 25mm, 15mm, 10mm and 5 mm.
And S1, performing ball milling, wherein the ratio of the mass of the milling balls to the mass of the hexagonal boron nitride is 10: 1.
And S1, performing ball milling, wherein the ball milling speed is 100rpm in revolution speed and 200rpm in rotation speed.
And S1, drying after ball milling.
And S1, homogenizing under high pressure, and using a Z-shaped working cavity or a Y-shaped working cavity.
And S1, performing high-pressure homogenization at a pressure value of 100MPa and a flow rate of 800mL/min, and performing cyclic homogenization for 3 times.
And S1, drying after high-pressure homogenization.
S2 the hydroxylation modifying agent comprises dopamine.
S2, the mass of the hydroxylation modifying reagent accounts for 1 wt% of the sum of the mass of the hydroxylation modifying reagent and the mass of the treated hexagonal boron nitride.
S2, in the ball milling or sanding process, the temperature of the mixture of the hydroxylation modifying reagent and the processed hexagonal boron nitride is kept at 25 ℃.
And S2, performing ball milling treatment, wherein the milling balls are yttria-stabilized zirconia ceramics, and the mass ratio of the 15mm, 10mm and 5mm diameter milling balls is 1:5: 1.
And S2, performing ball milling, wherein the ratio of the mass of the milling balls to the sum of the mass of the hydroxylated modification reagent and the mass of the treated hexagonal boron nitride is 35: 1.
And S2, performing ball milling, wherein the ball milling speed is 100rpm in revolution speed, 200rpm in rotation speed, and the ball milling time is 2 h.
S2, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, and the mass ratio of the grinding balls with the diameters of 2mm and 0.5mm is 4: 1.
And S2, sanding, wherein the ratio of the mass of the grinding balls to the sum of the mass of the hydroxylated modification agent and the mass of the treated hexagonal boron nitride is 9: 1.
And S2, sanding at the speed of 500rpm of the main machine for 1 h.
And S2, drying after sanding.
S1, the processing of the hexagonal boron nitride comprises the steps of processing the hexagonal boron nitride by adopting a ball milling method and a high-pressure homogenizing method in sequence, wherein the high-pressure homogenizing time t3The determination method comprises the following steps:
wherein, t1The ball milling time is; i is a ball milling time correction coefficient, i is a constant and takes a value of 0.2-0.5; t is tcTaking the value as a reference time standard quantity for 15-30 h; k is a correction parameter, and k is a constant with the value of 0.5-0.7. Among the above parameters, t1Is 10-24 h.
Using said t3In the determination method, a plurality of groups of combinations within each parameter range are tested (10 groups, the performance verification data are averaged), and subsequent effect verification tests show that the mass of the modified group is 3.1% higher than that of the modified group in the average of example 1, and the thermal conductivity is 7.9% higher than that of example 1 in the average of the modified group. Description Using the above t3The method of (3) is effective in increasing the number of surface modifying groups and improving the thermal properties of the material.
Example 5 modification treatment of hexagonal boron nitride:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
S1, the processing of the hexagonal boron nitride comprises the steps of sequentially processing the hexagonal boron nitride by a sanding and high-pressure homogenizing method.
S1, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, the diameters of the yttria-stabilized zirconia ceramic materials comprise two or three of 3mm, 1mm and 0.5mm, and the mass ratio of the 3mm, 1mm and 0.5mm grinding balls is 2:3: 1.
And S1, sanding, wherein the mass ratio of the grinding balls to the hexagonal boron nitride is 8: 1.
S1 sanding, the main machine speed is 1600 rpm.
And S1, drying after sanding.
S1 homogenizing under high pressure, and using Y-shaped working chamber.
And S1, performing high-pressure homogenization at a pressure value of 150MPa and a flow rate of 4500mL/min, and performing cyclic homogenization for 10 times.
And S1, drying after high-pressure homogenization.
S2 the hydroxylation modifying reagent comprises glutamic acid.
S2, the mass of the hydroxylation modifying reagent accounts for 10 wt% of the sum of the mass of the hydroxylation modifying reagent and the mass of the treated hexagonal boron nitride.
S2, in the ball milling or sanding process, the temperature of the mixture of the hydroxylation modifying reagent and the processed hexagonal boron nitride is kept at 45 ℃.
And S2, performing ball milling treatment, wherein the milling balls are yttria-stabilized zirconia ceramics, and the mass ratio of the 15mm, 10mm and 5mm diameter milling balls is 2:7: 1.
And S2, performing ball milling, wherein the ratio of the mass of the milling balls to the sum of the mass of the hydroxylated modification reagent and the mass of the treated hexagonal boron nitride is 40: 1.
And S2, performing ball milling, wherein the ball milling speed is 400rpm in revolution speed, 800rpm in rotation speed and 5h in ball milling time.
S2, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, and the mass ratio of the grinding balls with the diameters of 2mm and 0.5mm is 7: 1.
And S2, sanding, wherein the ratio of the mass of the grinding balls to the sum of the mass of the hydroxylated modification agent and the mass of the treated hexagonal boron nitride is 15: 1.
And S2, sanding at the main machine speed of 1600rpm for 10 h.
And S2, drying after sanding.
S1, the hexagonal boron nitride treatment method comprises the steps of sequentially adopting a sanding method and a high-pressure homogenizing method to treat the hexagonal boron nitride, wherein the high-pressure homogenizing time t3The determination method comprises the following steps:
wherein, t2Sanding time; j is a sanding time correction coefficient, j is a constant and takes a value of 1-2; t is tcTaking the value as a reference time standard quantity for 8-30 h; k is a correction parameter, and k is a constant and takes a value of 0.1-0.7. T among the above parameters2Is 6-10 h.
Using said t3In the determination method, a plurality of groups of combinations within each parameter range are tested (10 groups, average values of performance verification data are obtained), and subsequent effect verification tests show that the mass of the modified group is 4.4% higher than that of the modified group in average in example 2, and the thermal conductivity is 7.0% higher than that of the modified group in average in example 2. Description Using the above t3The method of (3) is effective in increasing the number of surface modifying groups and improving the thermal properties of the material.
Example 6 modification treatment of hexagonal boron nitride:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
S1, the processing of the hexagonal boron nitride comprises the steps of sequentially adopting ball milling, sand milling and high-pressure homogenization to process the hexagonal boron nitride.
And S1, performing ball milling, wherein the milling balls are made of yttria-stabilized zirconia ceramics, and the mass ratio of the diameter of the milling balls is 25mm, 15mm, 10mm and 5mm, and the diameter of the milling balls is 25mm, 15mm, 10mm and 5mm is 2:3:5: 1.
And S1, performing ball milling, wherein the ratio of the mass of the milling balls to the mass of the hexagonal boron nitride is 20: 1.
S1, ball milling, wherein the ball milling speed has revolution speed of 100 and 400rpm and the rotation speed is 500 rpm.
And S1, drying after ball milling.
S1, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, the diameters of the yttria-stabilized zirconia ceramic materials comprise two or three of 3mm, 1mm and 0.5mm, and the mass ratio of the 3mm, 1mm and 0.5mm grinding balls is 1:2: 1.
And S1, sanding, wherein the mass ratio of the grinding balls to the hexagonal boron nitride is 5: 1.
S1 sanding, the main machine speed is 900 rpm.
And S1, drying after sanding.
S1 homogenizing under high pressure, and using Y-shaped working chamber.
S1, homogenizing under high pressure, wherein the pressure value is 130MPa, the flow rate is 3000mL/min, and circularly homogenizing for 6 times.
And S1, drying after high-pressure homogenization.
S2, the hydroxylation modifying reagent comprises hydrogen peroxide.
S2, the mass of the hydroxylation modifying reagent accounts for 6 wt% of the sum of the mass of the hydroxylation modifying reagent and the mass of the treated hexagonal boron nitride.
S2, in the ball milling or sanding process, the temperature of the mixture of the hydroxylation modifying reagent and the processed hexagonal boron nitride is kept at 30 ℃.
And S2, performing ball milling treatment, wherein the milling balls are yttria-stabilized zirconia ceramics, and the mass ratio of the 15mm, 10mm and 5mm diameter milling balls is 1:6: 1.
And S2, performing ball milling, wherein the ratio of the mass of the milling balls to the sum of the mass of the hydroxylated modification reagent and the mass of the treated hexagonal boron nitride is 37: 1.
And S2, performing ball milling, wherein the ball milling speed is 300rpm in revolution speed, 500rpm in rotation speed, and the ball milling time is 4 hours.
S2, sanding, wherein the grinding balls are made of yttria-stabilized zirconia ceramic materials, and the mass ratio of the grinding balls with the diameters of 2mm and 0.5mm is 6: 1.
And S2, sanding, wherein the ratio of the mass of the grinding balls to the sum of the mass of the hydroxylated modification agent and the mass of the treated hexagonal boron nitride is 12: 1.
And S2, sanding at the main machine speed of 1100rpm for 6 h.
And S2, drying after sanding.
S1, the hexagonal boron nitride treatment method comprises the steps of sequentially adopting ball milling, sanding and high-pressure homogenization to treat the hexagonal boron nitride, wherein the high-pressure homogenization time t3The determination method comprises the following steps:
wherein, t1Time of ball milling, t2Sanding time; i is a ball milling time correction coefficient, i is a constant and takes a value of 0.2-0.5; j is the sanding time correction coefficient, j is a constant and takes the value of 0.5-2; t is tcTaking the value as a reference time standard quantity for 2-15 h; k is a correction parameter, and k is a constant with the value of 0.5-0.7. Preferably, among the above parameters, t1Is 2-17h, t2Is 1-6 h.
Using said t3In the determination method, a plurality of groups of combinations within each parameter range are tested (10 groups, the performance verification data are averaged), and subsequent effect verification tests show that the mass of the modified group is 3.9% higher than that of the modified group in average in example 3, and the thermal conductivity is 6.1% higher than that of the modified group in average in example 3. Description Using the above t3The method of (3) is effective in increasing the number of surface modifying groups and improving the thermal properties of the material.
Effect verification test: the products obtained in the above examples were characterized: detecting the quality of the surface modified group (hydroxyl) by adopting a thermogravimetric analyzer, and adopting the weight loss percentage data measured at the temperature of between 300 and 600 ℃ as the weight ratio of the hydroxyl grafted on the surface of the hexagonal boron nitride to the surface modified hexagonal boron nitride; testing thermal diffusivity coefficient alpha (m) of material by laser thermal conductivity meter2S-1) the density of the material, rho (Kg. m), was tested using a density balance-3) The specific heat capacity c (J.Kg) of the material was measured by a differential scanning calorimeter-1·K-1) Wherein the thermal conductivity is calculated by the following formula:
λ＝α·ρ·c。
the results of some of the tests (examples 1-3) are given in the following table:
| sample source | The mass ratio of the modified group ([ permillage ]) | Thermal conductivity (Wm)-1K-1) |
| Example 1 | 12 | 79 |
| Example 2 | 16 | 86 |
| Example 3 | 19 | 95 |
The modified hexagonal boron nitride prepared by the method has higher proportion of modified groups and higher thermal conductivity, and the hexagonal boron nitride structure is judged to be not damaged from the aspect of performance.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. A modification treatment method of hexagonal boron nitride is characterized by comprising the following steps: the method comprises the following steps:
s1, processing the hexagonal boron nitride by two or three of ball milling, sand milling or high-pressure homogenization;
and S2, adding a hydroxylation modification reagent into the treated hexagonal boron nitride, and performing ball milling, sanding and deionized water cleaning treatment in sequence to obtain the modified hexagonal boron nitride subjected to hydroxylation modification.
2. The method for modifying hexagonal boron nitride according to claim 1, wherein:
processing the hexagonal boron nitride in S1, including processing the hexagonal boron nitride by ball milling and high-pressure homogenizing in sequence;
or the like, or, alternatively,
processing the hexagonal boron nitride in S1, including sequentially processing the hexagonal boron nitride by a sanding and high-pressure homogenizing method;
or the like, or, alternatively,
and the step of processing the hexagonal boron nitride in the step S1 comprises the steps of sequentially processing the hexagonal boron nitride by adopting a ball milling method, a sand milling method and a high-pressure homogenizing method.
3. The method for modifying hexagonal boron nitride according to claim 2, wherein: in S1, grinding balls used in the ball milling are yttria-stabilized zirconia ceramics with diameters of 25mm, 15mm, 10mm, 5mm, 25mm, 15mm, 10mm and 5mm, and the mass ratio is (1-4): 2-6): 1.
4. The method for modifying hexagonal boron nitride according to claim 2, wherein: and (S1) carrying out ball milling, wherein the ratio of the mass of the milling balls to the mass of the hexagonal boron nitride (10-30) is 1.
5. The method for modifying hexagonal boron nitride according to claim 2, wherein: in S1, the revolution speed of ball milling is 100-; drying was carried out after ball milling as described in S1.
6. The method for modifying hexagonal boron nitride according to claim 2, wherein: the grinding balls used for the sanding in the S1 are made of yttria-stabilized zirconia ceramic materials, the diameters of the yttria-stabilized zirconia ceramic materials comprise two or three of 3mm, 1mm and 0.5mm, and the mass ratio of the grinding balls with the diameters of 3mm, 1mm and 0.5mm is (0-2): (0.5-3): 1.
7. The method for modifying hexagonal boron nitride according to claim 2, wherein: the mass ratio of the grinding balls to the hexagonal boron nitride used for the sanding in the S1 is (3-8): 1.
8. The method for modifying hexagonal boron nitride according to claim 2, wherein: sanding is carried out in S1, the speed of a main machine is 500-1600rpm, and the sanding time is 1-10 h; and S1, drying after sanding.
9. The method for modifying hexagonal boron nitride according to claim 2, wherein: homogenizing under high pressure in S1 by using a Z-shaped working cavity or a Y-shaped working cavity; s1, performing high-pressure homogenization at a pressure value of 75-190MPa and a flow rate of 50-8000mL/min, and performing cyclic homogenization for 1-10 times, wherein the total time is 0.5-4 h; and S1, drying after high-pressure homogenization.
10. The method for modifying hexagonal boron nitride according to claim 2, wherein: the hydroxylation modifying reagent comprises any one of dopamine, hydrogen peroxide and glutamic acid; s2, the mass of the hydroxylation modifying reagent accounts for 1-10 wt% of the sum of the mass of the hydroxylation modifying reagent and the mass of the treated hexagonal boron nitride; s2, in the ball milling or sanding process, the temperature of the mixture of the hydroxylation modifying reagent and the processed hexagonal boron nitride is kept between 20 and 45 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114481355A (en) * | 2022-02-17 | 2022-05-13 | 苏州鸿凌达电子科技股份有限公司 | Method for preparing heat-conducting insulating film based on hexagonal boron nitride |
| CN116178642A (en) * | 2023-04-24 | 2023-05-30 | 山东鹏程陶瓷新材料科技有限公司 | Surface grafting modified hexagonal boron nitride and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554514A (en) * | 2016-10-28 | 2017-04-05 | 上海大学 | A kind of method for modifying boron nitride nanosheet surface with poly-dopamine |
| CN112209354A (en) * | 2019-06-26 | 2021-01-12 | 苏州太湖电工新材料股份有限公司 | Method for preparing hydrophobic hexagonal boron nitride nanosheets |
| WO2021005538A1 (en) * | 2019-07-09 | 2021-01-14 | Saudi Arabian Oil Company | Methods for the production of nanocomposites for high temperature electrochemical energy storage devices |
| CN112724677A (en) * | 2020-12-29 | 2021-04-30 | 中山大学 | Dopamine modified boron nitride heat-conducting silicone grease and preparation method thereof |
| CN112919431A (en) * | 2021-02-07 | 2021-06-08 | 辽东学院 | High-yield and high-crystallinity hexagonal boron nitride nanosheet and preparation method thereof |
-
2021
- 2021-06-18 CN CN202110679428.3A patent/CN113200527A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554514A (en) * | 2016-10-28 | 2017-04-05 | 上海大学 | A kind of method for modifying boron nitride nanosheet surface with poly-dopamine |
| CN112209354A (en) * | 2019-06-26 | 2021-01-12 | 苏州太湖电工新材料股份有限公司 | Method for preparing hydrophobic hexagonal boron nitride nanosheets |
| WO2021005538A1 (en) * | 2019-07-09 | 2021-01-14 | Saudi Arabian Oil Company | Methods for the production of nanocomposites for high temperature electrochemical energy storage devices |
| CN112724677A (en) * | 2020-12-29 | 2021-04-30 | 中山大学 | Dopamine modified boron nitride heat-conducting silicone grease and preparation method thereof |
| CN112919431A (en) * | 2021-02-07 | 2021-06-08 | 辽东学院 | High-yield and high-crystallinity hexagonal boron nitride nanosheet and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114481355A (en) * | 2022-02-17 | 2022-05-13 | 苏州鸿凌达电子科技股份有限公司 | Method for preparing heat-conducting insulating film based on hexagonal boron nitride |
| CN116178642A (en) * | 2023-04-24 | 2023-05-30 | 山东鹏程陶瓷新材料科技有限公司 | Surface grafting modified hexagonal boron nitride and preparation method thereof |
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