CN115093605B - Preparation method and application of aluminum hydroxide-tin bismuth alloy hybrid powder material - Google Patents
Preparation method and application of aluminum hydroxide-tin bismuth alloy hybrid powder material Download PDFInfo
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Abstract
The application relates to the technical field of insulating and heat-conducting fillers, in particular to a preparation method and application of an aluminum hydroxide-tin bismuth alloy hybrid powder material. The preparation method of the hybrid powder material comprises the steps of dissolving stannous chloride and bismuth chloride in ethanol according to a molar ratio of 57:43 to obtain a mixed solution; dissolving sodium borohydride in water, adding aluminum hydroxide powder, stirring and dispersing uniformly to obtain dispersion liquid; dropwise adding the mixed solution into the dispersion liquid, continuously reacting for 30min after the dropwise adding is finished, standing, pouring out supernatant, adding water, standing, pouring out supernatant, repeating the steps for 3-5 times, and vacuum heating and drying the obtained precipitate to obtain the aluminum hydroxide-tin-bismuth alloy hybrid powder material, wherein the tin-bismuth molar ratio of the tin-bismuth alloy in the hybrid material is 57:43, and the melting point is 138-145 ℃. When the tin-bismuth alloy is used for heat conduction insulating filler, aluminum hydroxide is mutually and tightly connected in a resin matrix by melting tin-bismuth alloy, so that a heat conduction path is formed, and the heat conduction performance is effectively improved.
Description
Technical Field
The application relates to the technical field of insulating heat-conducting fillers, in particular to a preparation method and application of an aluminum hydroxide-tin bismuth alloy hybrid powder material.
Background
Insulating materials are key base materials for electrical equipment, and the performance of the insulating materials directly affects the reliability and service life of the equipment. The main reasons affecting the reliability and service life of the device operation are as follows: in the running process of the electrical equipment, heat generated by the current thermal effect must be conducted outwards or dissipated out in time, otherwise, the internal temperature rise of the equipment is too high, the working stability is affected, and even faults or accidents occur in serious cases.
As modern electrical devices develop to high power density, high overload capability, etc., the direct consequence is that the effective heat dissipation space inside the device is insufficient and the heat generation amount increases. The following problems are brought about: if such heat cannot be timely transferred outwards, insulation aging of the material can be accelerated, and the operation efficiency, reliability and service life of the equipment are seriously affected.
In order to solve the above problems, a high heat conduction insulating material is generally used to replace an insulating material with lower heat conduction, that is, the high heat conduction insulating material is the most effective way to solve the heat dissipation problem of the electrical equipment structure. At present, epoxy resins in insulating materials used for electrical equipment are most widely used, but pure ringsThe thermal conductivity of the oxygen resin material is low, about 0.20W (m.times.K) -1 It is increasingly difficult to meet the timely and efficient heat dissipation requirements of modern electrical equipment, and the heat dissipation requirements become one of main technical bottlenecks in the development of the electrical industry.
In order to break through the technical bottleneck of development of the electrical industry, the filled heat-conducting insulating epoxy resin is widely applied in the field of electrical insulation. Common thermally conductive and insulating fillers are alumina, boron nitride, magnesia, aluminum nitride, and the like. Wherein the boron nitride and aluminum nitride have high thermal conductivity coefficients of about 280W (m.times.K), respectively -1 、320W(m*K) -1 But are expensive. The aluminum oxide and magnesium oxide have relatively low thermal conductivity, respectively about 33W (m.times.K) -1 、36W(m*K) -1 But is inexpensive. Aluminum hydroxide and magnesium hydroxide have lower thermal conductivity but are the least expensive and are flame retardant.
Although boron nitride and aluminum nitride have high thermal conductivity, in practice, the thermal conductivity of the filled epoxy is very limited. For example: at a filler volume level of 25%, the boron nitride filled epoxy resin composite has a thermal conductivity of about 0.90 to 1.00W (m x K) -1 Less than 0.36% of pure boron nitride has not yet been used to much advantage of the high thermal conductivity of boron nitride. Similarly, an alumina-filled epoxy resin composite material has a thermal conductivity of about 1.30W (m x K) when the filler is present in an amount of 50% by volume -1 Only about 4.0% of pure alumina.
Disclosure of Invention
In order to solve the technical defect that the prior heat conduction insulating filler filled resin matrix composite material has limited improvement of heat conductivity, the invention provides a preparation method of aluminum hydroxide-tin bismuth alloy hybrid powder material, and application of the powder material as filler in heat conduction insulating epoxy resin composition and cured product thereof.
In a first aspect, the preparation method of the aluminum hydroxide-tin bismuth alloy hybrid powder material is realized by the following technical scheme:
the preparation method of the aluminum hydroxide-tin bismuth alloy hybrid powder material comprises the following steps:
step one, stannous chloride (SnCl) is carried out under the condition of room temperature and inert gas protection 2 ) Bismuth chloride (BiCl) 3 ) Dissolving in ethanol; stannous chloride (SnCl) 2 ) Bismuth chloride (BiCl) 3 ) The molar ratio of (2) is controlled at 57:43;
step two, sodium borohydride (NaBH) is added under the protection of inert gas at room temperature 4 ) Dissolving in water, adding aluminum hydroxide powder, stirring and dispersing uniformly;
step three, dropwise adding the solution obtained in the step one into the dispersion liquid obtained in the step two under the conditions of room temperature and inert gas protection, and continuing to react for 30-40min after the dropwise adding is finished;
fourthly, standing the product obtained in the third step, pouring out supernatant, adding deionized water, standing, pouring out supernatant, and repeating the steps for 3-5 times;
and fifthly, vacuum heating and drying the precipitate obtained in the step four to obtain the aluminum hydroxide-tin bismuth alloy hybrid powder material.
In the technical scheme adopted by the application, aluminum hydroxide-tin bismuth alloy hybrid powder material takes aluminum hydroxide powder as a base material, the tin bismuth alloy is adsorbed on the surface of the base material, the tin bismuth molar ratio of the tin bismuth alloy is 57:43, and the melting point is 138-145 ℃. The hybridized powder material is used as heat conducting insulating filler to be mixed with epoxy resin and curing agent to obtain heat conducting insulating epoxy resin composition, and then the composition is heated to about 150 ℃ to be cured.
Preferably, the aluminum hydroxide-tin bismuth alloy hybrid powder material comprises aluminum hydroxide and tin bismuth alloy, and the tin bismuth alloy is adsorbed on the surface of the aluminum hydroxide.
When the heat-conducting insulating filler is used as the heat-conducting insulating epoxy resin composition, the composition is heated to about 150 ℃ to be solidified, so that the tin-bismuth alloy adsorbed on the surface of the aluminum hydroxide powder is melted, the filler is tightly connected to form a heat-conducting passage, the heat-conducting performance of a composite system is improved, and the composite system still maintains good electric insulation due to the fact that the tin-bismuth alloy is partitioned by insulating aluminum hydroxide and an epoxy matrix, therefore, the heat-conducting insulating epoxy resin composition has good heat-conducting performance and flame retardant performance, still maintains good insulating performance, and can be used for various electric insulating materials.
Preferably, the molar ratio of tin to bismuth of the tin to bismuth alloy in the aluminum hydroxide-tin to bismuth alloy hybrid powder material is 57:43; the tin-bismuth alloy is low-melting-point alloy, and the melting point is 138-145 ℃.
The melting point of the tin-bismuth alloy reaches the lowest (139.0 ℃) when the tin-bismuth molar ratio is 57:43, so that the tin-bismuth alloy adsorbed on the surface of aluminum hydroxide powder can be ensured to be melted, and the fillers are tightly connected to form a heat conduction path. However, above or below this molar ratio, the melting point of the aluminum hydroxide-tin bismuth alloy hybrid powder material will be significantly increased, and thus it is not possible to satisfy the melting of the tin bismuth alloy adsorbed on the surface of the aluminum hydroxide powder at the curing temperature (about 150 ℃) of the heat conductive insulating epoxy resin composition, and the filler is tightly connected to form a heat conductive path. In addition, the aluminum hydroxide is adopted, and as the-OH has electronegativity, more tin and bismuth ions can be adsorbed, so that the hybrid material with higher tin-bismuth alloy content is obtained, and the combination of the tin-bismuth alloy and the aluminum hydroxide is tighter.
By adopting the technical scheme, the tin-bismuth alloy on the surface of the aluminum hydroxide is melted at the temperature of more than 139.0 ℃, the filler is tightly connected to form a heat conduction path, the heat conduction performance of the composite system is improved, and the composite system still maintains good electric insulation because the tin-bismuth alloy is separated by the insulating aluminum hydroxide and the epoxy matrix.
Preferably, in the second step, naBH 4 Is SnCl in mole number 2 +BiCl 3 0.5 to 0.8 times of the total mole number.
NaBH in the preparation process of the application 4 Is excessive, adopt NaBH 4 Is SnCl in mole number 2 +BiCl 3 The technical proposal of 0.5 to 0.8 times of the total mole number is to ensure the sufficient reduction reaction and avoid SnCl in the hybrid material 2 Or BiCl 3 Residue.
Preferably, in the second step, naBH 4 Is SnCl in mole number 2 +BiCl 3 0.6 times the total moles.
By adopting the technical scheme, the full reduction reaction is further ensured, and SnCl in the hybrid material is avoided 2 Or BiCl 3 Residue.
Preferably, the temperature of the vacuum heating and drying in the fifth step is 80-100 ℃, the vacuum degree is 0.1-10Pa, and the time is 20-26 hours.
By adopting the technical scheme, the quality of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared by the preparation method can be ensured, the production energy consumption is reduced, and the preparation method is more environment-friendly.
In a second aspect, the application provides an application of an aluminum hydroxide-tin bismuth alloy hybrid powder material:
an aluminum hydroxide-tin bismuth alloy hybrid powder material is used for heat conduction and insulation filler.
The aluminum hydroxide-tin bismuth alloy hybrid powder material provided by the application is used as a heat conduction insulating filler for a heat conduction insulating epoxy resin composition, is simple and convenient to mix, and has a remarkably improved heat conduction coefficient.
Preferably, the aluminum hydroxide-tin bismuth alloy hybrid powder material can be used for preparing a heat-conducting insulating epoxy resin composition and a condensate thereof; the heat-conducting insulating epoxy resin composition and the condensate thereof comprise epoxy resin, curing agent and aluminum hydroxide-tin bismuth alloy hybrid powder material.
The aluminum hydroxide-tin bismuth alloy hybrid powder material can be tightly connected with each other in an epoxy resin matrix to form a heat conduction path, so that the overall insulation performance and the flame retardant performance are ensured, and the heat conduction performance is effectively improved.
In summary, the present application has the following advantages:
1. when the tin-bismuth alloy is used for heat conduction insulating filler, aluminum hydroxide is mutually and tightly connected in a resin matrix by melting tin-bismuth alloy, so that a heat conduction path is formed, the overall insulating property is ensured, and meanwhile, the heat conduction property is effectively improved.
2. When the epoxy resin composition is applied to epoxy resin combination, when the composition is heated (about 150 ℃) to solidify, the tin-bismuth alloy adsorbed on the surface of aluminum hydroxide is melted, and the filler is tightly connected to form a heat conduction path, so that the heat conduction performance of the composite system is improved. In addition, the tin-bismuth alloy is separated by the insulating aluminum hydroxide and the epoxy matrix, so that the composite system still maintains good electrical insulation, and can be used for various electrical insulation materials.
3. The preparation method of the aluminum hydroxide-tin bismuth alloy hybrid powder material provided by the application takes water and ethanol as solvents, the production process is environment-friendly, the process is simple, and the industrial production is easy.
4. The aluminum hydroxide-tin bismuth alloy hybrid powder material provided by the application is used as a filler for a heat-conducting and insulating epoxy resin composition, is simple and convenient to mix, and has a remarkably improved heat conductivity coefficient.
5. The aluminum hydroxide-tin bismuth alloy hybrid powder material provided by the application has the advantages that under the condition of obtaining the same heat conductivity coefficient, the viscosity of an epoxy resin system filled with the aluminum hydroxide-tin bismuth alloy hybrid powder material is lower, and the product has the characteristics of low viscosity and high heat conductivity.
6. The aluminum hydroxide is adopted in the application, and as the-OH of the aluminum hydroxide has electronegativity, more tin and bismuth ions can be adsorbed, so that the hybrid material with higher tin-bismuth alloy content is obtained, and the combination of the tin-bismuth alloy and the aluminum hydroxide is tighter.
Detailed Description
The present application is described in further detail below with reference to examples.
Examples
Example 1
The preparation method of the aluminum hydroxide-tin bismuth alloy hybrid powder material comprises the following steps:
step one, 21.61 g (0.114 mol) of SnCl is reacted under the condition of room temperature and nitrogen protection 2 (CAS number: 7772-99-8, analytical grade), 27.12 g (0.086 mol) BiCl 3 (CAS number 7787-60-2, analytical grade) in 400 ml ethanol;
step two, 4.54 g (0.12 mol) NaBH is added under nitrogen protection at room temperature 4 (CAS number: 16940-66-2, chemically pure) in 500 ml of water, then 25 g of aluminum hydroxide powder (Buddha Jin Ge New Material Co., ltd., FA-06TA, median diameter 15-21 μm) was added;
step three, dripping the solution obtained in the step one into the dispersion liquid obtained in the step two under the conditions of room temperature and nitrogen protection, and continuing to react for 30min after the dripping is finished;
step four, standing the dispersion liquid obtained in the step three, and then pouring out supernatant; adding 500 ml of water, standing, pouring out supernatant, and repeating the above steps for 4 times to obtain precipitate;
and fifthly, drying the precipitate obtained in the fourth step by vacuum heating, wherein the temperature of the vacuum heating and drying is 80 ℃, the vacuum degree is 0.1Pa, and the time is 24 hours, so that the aluminum hydroxide-tin bismuth alloy hybrid powder material is obtained. The density of the obtained aluminum hydroxide-tin bismuth alloy hybrid material is 4.03 g/cm 3 The mass content of the tin-bismuth alloy in the hybrid material is 55.8%, the volume content is 26.4%, and the melting point is 139.0deg.C (DSC test).
The application of the aluminum hydroxide-tin bismuth alloy hybrid powder material is that the aluminum hydroxide-tin bismuth alloy hybrid powder material is used as a filler for a heat-conducting and insulating epoxy resin composition.
The formula of the heat-conducting insulating epoxy resin composition comprises the following components:
9g of YDF-170 epoxy resin;
1g of 594 curing agent;
10g of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared by the method.
The preparation method of the heat-conducting insulating epoxy resin composition comprises the following steps:
the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared by 9g of YDF-170 epoxy resin, 1g of 594 curing agent and 10g is uniformly dispersed at high speed to obtain a heat-conducting insulating epoxy resin composition,
the preparation of the cured epoxy resin composition comprises the following steps:
the prepared heat-conducting insulating epoxy resin composition is defoamed for 1h under the vacuum condition of 90 ℃, and then is cured for 4h under the temperature of 150 ℃ to obtain a heat-conducting insulating epoxy resin cured product which is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler mass content of the cured product was 50.0% and the volume content was 22.9%.
Example 2
Example 2 differs from example 1 in that:
the formula of the heat-conducting insulating epoxy resin composition comprises the following components:
9g of YDF-170 epoxy resin;
1g of 594 curing agent;
20g of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared in example 1.
The filler mass content of the obtained epoxy cured product was 66.7% and the volume content was 37.3%.
Example 3
Example 3 differs from example 1 in that:
the formula of the heat-conducting insulating epoxy resin composition comprises the following components:
9g of YDF-170 epoxy resin;
1g of 594 curing agent;
30g of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared in example 1.
The filler mass content of the obtained epoxy cured product was 75%, and the volume content was 47.2%.
Example 4
The preparation method of the aluminum oxide-tin bismuth alloy hybrid powder material comprises the following steps:
step one: 10.81 g (0.057 mol) of SnCl are reacted under the protection of nitrogen at room temperature 2 13.56 g (0.043 mol) BiCl 3 Dissolving in 200 ml of ethanol;
step two: 2.27 g (0.06 mol) NaBH was added at room temperature under nitrogen blanket 4 Dissolving in 500 ml of water, then adding 25 g of aluminum hydroxide powder, stirring and dispersing uniformly;
step three, dripping the solution obtained in the step one into the dispersion liquid obtained in the step two under the conditions of room temperature and nitrogen protection, and continuing to react for 30 minutes after the dripping is finished;
step four, standing the dispersion liquid obtained in the step three, and then pouring out supernatant; adding 500 ml of water, standing, pouring out supernatant, and repeating the above steps for 4 times to obtain precipitate;
and fifthly, drying the precipitate obtained in the fourth step by vacuum heating, wherein the temperature of the vacuum heating and drying is 80 ℃, the vacuum degree is 0.1Pa, and the time is 24 hours, so that the aluminum hydroxide-tin bismuth alloy hybrid powder material is obtained. The density of the obtained aluminum hydroxide-tin bismuth alloy hybrid powder material is 3.35 g/cm 3 The mass content of the tin-bismuth alloy in the hybrid material is 38.7 percent, and the volume content is 15.2 percent.
The application of the aluminum hydroxide-tin bismuth alloy hybrid powder material is that the aluminum hydroxide-tin bismuth alloy hybrid powder material is used as a filler for a heat-conducting and insulating epoxy resin composition.
The formula of the heat-conducting insulating epoxy resin composition comprises the following components:
9g of YDF-170 epoxy resin;
1g of 594 curing agent;
10g of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared by the method.
The preparation method of the heat-conducting insulating epoxy resin composition comprises the following steps:
9g of YDF-170 epoxy resin, 1g of 594 curing agent and 10g of aluminum hydroxide-tin bismuth alloy hybrid powder material prepared by the method are uniformly dispersed at high speed to obtain a heat-conducting insulating epoxy resin composition,
the preparation of the cured epoxy resin composition comprises the following steps:
the prepared heat-conducting insulating epoxy resin composition is defoamed for 1h under the vacuum condition of 90 ℃, and then is cured for 4h under the temperature of 150 ℃ to obtain a heat-conducting insulating epoxy resin cured product which is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler mass content of the cured product was 50% and the volume content was 26.4%.
Example 5
Example 5 differs from example 4 in that:
the formula of the heat-conducting insulating epoxy resin composition comprises the following components:
9g of YDF-170 epoxy resin;
1g of 594 curing agent;
20g of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared in example 4.
The filler mass content of the obtained cured product was 66.7% and the volume content was 41.7%.
Example 6
Example 6 differs from example 4 in that:
the formula of the heat-conducting insulating epoxy resin composition comprises the following components:
9g of YDF-170 epoxy resin;
1g of 594 curing agent;
30g of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared in example 4.
The filler mass content of the obtained cured product was 75.0% and the volume content was 51.8%.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 and example 4 in that:
the formula of the heat-conducting insulating epoxy resin composition comprises the following components: 9g of YDF-170 epoxy resin, 1g of 594 curing agent and 10g of aluminum hydroxide powder.
The filler mass content of the obtained cured product was 50.0% and the volume content was 33.1%.
Comparative example 2
Comparative example 2 differs from example 2 and example 5 in that:
the formula of the heat-conducting insulating epoxy resin composition comprises the following components: 9g of YDF-170 epoxy resin, 1g of 594 curing agent and 20g of aluminum hydroxide powder.
The filler mass content of the obtained cured product was 66.7% and the volume content was 49.8%.
Comparative example 3
Comparative example 3 differs from example 3 and example 6 in that:
the formula of the heat-conducting insulating epoxy resin composition comprises the following components: 9g of YDF-170 epoxy resin, 1g of 594 curing agent and 30g of aluminum hydroxide powder.
The filler mass content of the obtained cured product was 75.0% and the volume content was 59.8%.
Comparative example 4
Comparative example 4 differs from example 1 in that:
the preparation method of the aluminum hydroxide-tin bismuth alloy hybrid powder material comprises the following steps:
step one, 18.39 g (0.097 mol) of SnCl is reacted under nitrogen at room temperature 2 30.58 g (0.097 mol) BiCl 3 Dissolving in 400 ml of ethanol;
step two, 4.54 g (0.12 mol) NaBH is added under nitrogen protection at room temperature 4 Dissolving in 500 ml of water, adding 24.5 g of aluminum hydroxide powder, and stirring and dispersing uniformly;
step three, dripping the solution obtained in the step one into the dispersion liquid obtained in the step two under the conditions of room temperature and nitrogen protection, and continuing to react for 30min after the dripping is finished;
step four, standing the dispersion liquid obtained in the step three, and then pouring out supernatant; adding 500 ml of water, standing, pouring out supernatant, and repeating the above steps for 4 times to obtain precipitate;
and fifthly, drying the precipitate obtained in the fourth step by vacuum heating, wherein the temperature of the vacuum heating and drying is 80 ℃, the vacuum degree is 0.1Pa, and the time is 24 hours, so that the aluminum hydroxide-tin bismuth alloy hybrid powder material is obtained. The density of the obtained aluminum hydroxide-tin bismuth alloy hybrid powder material is 4.09 g/cm 3 The mass content of the tin-bismuth alloy in the hybrid material is 56.5 percent, the volume content is 26.5 percent, and the melting point of the tin-bismuth alloy is 156.1 ℃ (DSC test).
The application of the aluminum hydroxide-tin bismuth alloy hybrid powder material is that the aluminum hydroxide-tin bismuth alloy hybrid powder material is used as a filler for a heat-conducting and insulating epoxy resin composition.
The formula of the heat-conducting insulating epoxy resin composition comprises the following components:
9g of YDF-170 epoxy resin;
1g of 594 curing agent;
30.5g of the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared by the method.
The preparation method of the heat-conducting insulating epoxy resin composition comprises the following steps:
the aluminum hydroxide-tin bismuth alloy hybrid powder material prepared by 9g of YDF-170 epoxy resin, 1g of 594 curing agent and 30.5g is uniformly dispersed at high speed to obtain a heat-conducting insulating epoxy resin composition,
the preparation of the cured epoxy resin composition comprises the following steps:
the prepared heat-conducting insulating epoxy resin composition is defoamed for 1h under the vacuum condition of 90 ℃, and then is cured for 4h under the temperature of 150 ℃ to obtain a heat-conducting insulating epoxy resin cured product which is used for testing and analyzing the heat conductivity coefficient and the resistivity. The filler mass content of the cured product was 75.3% and the volume content was 47.2%.
Performance test
Detection method/test method
1. And (3) testing the heat conductivity coefficient of the cured product: according to GB/T10295-2008 heat-insulating material steady state thermal resistance and related characteristics.
2. And (3) testing the volume resistivity of the cured object: the volume resistivity test method of conductive and antistatic plastics is described in GB/T15662-1995.
3. Composition viscosity test: according to GB/T12007.4-1989 method for measuring the viscosity of epoxy resins.
Data analysis
Table 1 shows the performance parameters of the aluminum hydroxide-tin bismuth alloy hybrid powder materials and aluminum hydroxide-filled heat conductive insulating epoxy resin compositions and cured products of examples 1-6 and comparative examples 1-4
Note that: the densities of the epoxy resin matrix (cured product) and aluminum hydroxide were 1.20g/cm, respectively 3 And 2.42g/cm 3 。
As can be seen from the combination of examples 1-6 and comparative examples 1-4 and Table 1, when the filler mass contents are equal, the thermal conductivity of the aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy resin composite material (examples 1-6) is significantly greater than that of the aluminum hydroxide filled epoxy composite materialThe thermal conductivity of the composite material (comparative examples 1-3), but the volume resistivity of the aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy resin composite material is significantly less than the volume resistivity of the aluminum hydroxide filled epoxy composite material. For the aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy resin composite material with the tin bismuth alloy mass content of 55.8 percent (examples 1-3), when the filler mass content is 75.0 percent (example 3), the volume resistivity of the material is 9.56 multiplied by 10 10 Omega.m, still has electrical insulation properties (volume resistivity>10 9 Ω·m). Therefore, the heat conduction performance is improved and the insulating performance is good.
As can be seen in combination with examples 1-6 and with table 1, for the aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy composite (examples 1-6), when the filler mass content was equal, the hybrid material filled epoxy composite (examples 1-3) having a tin bismuth alloy mass content of 55.8% had a thermal conductivity greater than the hybrid material filled epoxy composite (examples 4-6) having a tin bismuth alloy mass content of 38.7%, but the hybrid material filled epoxy composite having a tin bismuth alloy mass content of 55.8% had a volume resistivity less than the hybrid material filled epoxy composite having a tin bismuth alloy mass content of 38.7%.
It can be seen in combination with examples 1-6 and comparative examples 1-3 and with Table 1 that when the filler mass contents are equal, the filler volume content of the aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy resin composite (examples 1-6) is smaller than that of the aluminum hydroxide filled epoxy composite (comparative examples 1-3). For aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy resin composite materials, when the filler mass content is equal, the filler volume content of the hybrid material filled epoxy resin composite material (examples 1-3) with the tin bismuth alloy mass content of 55.8% is less than the filler volume content of the hybrid material filled epoxy resin composite material (examples 4-6) with the tin bismuth alloy mass content of 38.7%.
It can be seen from the combination of examples 1 to 6 and comparative examples 1 to 3 and the combination of table 1 that when the filler mass contents are equal, the viscosity of the aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy resin composition (examples 1 to 6) is smaller than that of the aluminum hydroxide filled epoxy resin composition (comparative examples 1 to 3). For the aluminum hydroxide-tin bismuth alloy hybrid powder filled epoxy resin composition, when the filler mass content was equal, the viscosity of the hybrid material filled epoxy resin composition (examples 1-3) with a tin bismuth alloy mass content of 55.8% was less than the viscosity of the hybrid material filled epoxy resin composition (examples 4-6) with a tin bismuth alloy mass content of 38.7%.
As can be seen from the combination of examples 1 to 6 and comparative examples 1 to 3 and Table 1, when the filler mass contents were 50.0%, 66.7% and 75.0%, the viscosity of the hybrid material-filled epoxy resin compositions (examples 1 to 3) having the tin-bismuth alloy mass contents of 55.8% were 36400, 97100 and 274200cP, respectively, and the thermal conductivity of the cured products thereof were 1.86, 2.43 and 2.98W (m.K), respectively -1 The method comprises the steps of carrying out a first treatment on the surface of the The viscosity of the epoxy resin compositions filled with the hybrid material (examples 4 to 6) containing 38.7% by mass of the tin-bismuth alloy was 54200, 128200 and 489000cP, respectively, and the thermal conductivity of the cured products thereof was 1.75, 2.17 and 2.54W (m.K), respectively -1 The method comprises the steps of carrying out a first treatment on the surface of the The viscosities of the aluminum hydroxide-filled epoxy resin compositions (comparative examples 1-3) were 77800, 304500 and 849600cP, respectively, and the thermal conductivities of the cured products thereof were 1.01, 1.38 and 1.72W (m.K), respectively -1 。
In view of the above analysis, it can be seen that: compared with aluminum hydroxide filler, the epoxy resin system is filled with the aluminum hydroxide-tin bismuth alloy hybrid material, so that higher heat conductivity coefficient can be obtained under lower filler volume content and system viscosity, and the volume resistivity is reduced to some extent, but good electrical insulation performance can be maintained. The epoxy resin is filled with the hybridization material with the mass content of the tin-bismuth alloy of 55.8 percent, and compared with the epoxy resin system filled with the hybridization material with the mass content of the tin-bismuth alloy of 38.7 percent, the epoxy resin system can obtain lower viscosity and higher heat conductivity coefficient, but the volume resistivity is also reduced. If the content of the tin-bismuth alloy in the hybrid material is further increased, the volume resistivity of the system is further lowered and the insulation performance may be lost.
As can be seen in combination with example 3 and comparative example 4, and with table 1, the tin-bismuth alloy contents of the two hybrid materials are very close (comparative example 4 is slightly higher),alloy with tin-bismuth mole ratio of 50:50 and melting point of 156.1 ℃ and aluminum hydroxide hybrid material filled epoxy composite material (comparative example 4) under the condition of same filler volume content (the mass content is very close to the mass content) has heat conductivity coefficient (1.03W (m.K) -1 ) The thermal conductivity (2.98W (m.K)) of the alloy with the tin-bismuth molar ratio of 57:43 and the melting point of 139.0 ℃ and the aluminum hydroxide hybrid material filled epoxy composite material (example 3) is significantly lower than that of the alloy -1 ) And is also lower than the thermal conductivity of any of the aluminum hydroxide-tin bismuth alloy hybrid material filled epoxy resin composites of examples 1-6.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (6)
1. A preparation method of an aluminum hydroxide-tin bismuth alloy hybrid powder material is characterized by comprising the following steps: the method comprises the following steps:
step one, stannous chloride (SnCl) is carried out under the condition of room temperature and inert gas protection 2 ) Bismuth chloride (BiCl) 3 ) Dissolving in ethanol; stannous chloride (SnCl) 2 ) Bismuth chloride (BiCl) 3 ) The molar ratio of (2) is controlled at 57:43;
step two, sodium borohydride (NaBH) is added under the protection of inert gas at room temperature 4 ) Dissolving in water, adding aluminum hydroxide, stirring and dispersing uniformly;
step three, dropwise adding the solution obtained in the step one into the dispersion liquid obtained in the step two under the conditions of room temperature and inert gas protection, and continuing to react for 30-40min after the dropwise adding is finished;
fourthly, standing the product obtained in the third step, pouring out supernatant, adding deionized water, standing, pouring out supernatant, and repeating the steps for 3-5 times;
fifthly, vacuum heating and drying the precipitate obtained in the step four to obtain an aluminum hydroxide-tin bismuth alloy hybrid powder material;
the aluminum hydroxide-tin bismuth alloy hybrid powder material comprises aluminum hydroxide and tin bismuth alloy, wherein the tin bismuth alloy is adsorbed on the surface of the aluminum hydroxide; the molar ratio of tin to bismuth of the tin to bismuth alloy in the aluminum hydroxide-tin to bismuth alloy hybrid powder material is 57:43; the tin-bismuth alloy is low-melting-point alloy, and the melting point is 138-145 ℃.
2. The preparation method of the aluminum hydroxide-tin bismuth alloy hybrid powder material according to claim 1, which is characterized in that: in the second step, naBH 4 Is SnCl in mole number 2 +BiCl 3 0.5 to 0.8 times of the total mole number.
3. The method for preparing the aluminum hydroxide-tin bismuth alloy hybrid powder material according to claim 2, which is characterized in that: in the second step, naBH 4 Is SnCl in mole number 2 +BiCl 3 0.6 times the total moles.
4. The preparation method of the aluminum hydroxide-tin bismuth alloy hybrid powder material according to claim 1, which is characterized in that: and in the fifth step, the temperature of vacuum heating and drying is 80-100 ℃, the vacuum degree is 0.1-10Pa, and the time is 20-26 hours.
5. Use of an aluminium hydroxide-tin bismuth alloy hybrid powder material according to claims 1-4, characterized in that: the aluminum hydroxide-tin bismuth alloy hybrid powder material is used for heat conduction and insulation filler.
6. The use of an aluminum hydroxide-tin bismuth alloy hybrid powder material according to claim 5, wherein the aluminum hydroxide-tin bismuth alloy hybrid powder material is characterized in that: the aluminum hydroxide-tin bismuth alloy hybrid powder material can be used for preparing a heat-conducting insulating epoxy resin composition and a cured product thereof; the heat-conducting insulating epoxy resin composition and the condensate thereof comprise epoxy resin, curing agent and aluminum hydroxide-tin bismuth alloy hybrid powder material.
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