CN116925500A - Buffer material and preparation method thereof - Google Patents

Buffer material and preparation method thereof Download PDF

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Publication number
CN116925500A
CN116925500A CN202210345902.3A CN202210345902A CN116925500A CN 116925500 A CN116925500 A CN 116925500A CN 202210345902 A CN202210345902 A CN 202210345902A CN 116925500 A CN116925500 A CN 116925500A
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China
Prior art keywords
epoxy resin
porous ceramic
inorganic filler
buffer material
alumina
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CN202210345902.3A
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Chinese (zh)
Inventor
余非凡
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Triple Win Technology Shenzhen Co Ltd
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Triple Win Technology Shenzhen Co Ltd
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Priority to CN202210345902.3A priority Critical patent/CN116925500A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

The application provides a buffer material and a preparation method thereof, wherein the buffer material is a porous ceramic/epoxy resin composite material, and the weight ratio of the porous ceramic to the epoxy resin is (10-80) to (15-85). The raw materials of the porous ceramic comprise inorganic filler, and the inorganic filler is at least one of aluminum oxide, magnesium oxide, boron nitride or beryllium oxide. The thermal conductivity of the porous ceramic/epoxy resin composite material is 4.5-5.7W.m ‑1 ·k ‑1 . The buffer material has extremely high heat conductivity, high heating speed and good mechanical property, and can effectively improve the production efficiency and reduce the cost.

Description

Buffer material and preparation method thereof
Technical Field
The application relates to the technical field of buffer materials, in particular to a buffer material and a preparation method thereof.
Background
In the electronic assembly process, a buffer material is generally required to be arranged between the hot press head and the pressed product, so as to buffer the pressure on the hot press head and protect the pressed product from being damaged by the hot press head or being scalded at high temperature. Therefore, the cushioning material is required to have high heat resistance, high thermal conductivity, excellent mechanical properties, and the like.
However, the existing buffer material has poor thermal conductivity and mechanical property, and can not meet the requirement of the existing electronic assembly industry on the buffer material. The epoxy resin composite material has excellent mechanical property and insulating property, but the thermal conductivity of the epoxy resin body is very low (0.17-0.21 W.m) -1 ·k -1 ) Adding intoThe thermal conductivity of the epoxy composite material obtained after a large amount of inorganic filler can only reach 0.8-0.9W.m -1 ·k -1 (2 s for rising to 100 ℃ C.) is far from meeting the practical production application requirements.
Disclosure of Invention
In order to solve the above problems, the present application provides a cushioning material.
Another object of the present application is to provide a method for preparing a cushioning material.
The application provides a buffer material which is a porous ceramic/epoxy resin composite material, wherein the weight ratio of the porous ceramic to the epoxy resin is (10-80): (15-85);
wherein, the raw materials of the porous ceramic comprise inorganic filler, and the inorganic filler is at least one of alumina, magnesia, boron nitride or beryllium oxide;
the thermal conductivity of the porous ceramic/epoxy resin composite material is 4.5-5.7W.m -1 ·k -1
The application also provides a preparation method of the buffer material, which comprises the following steps:
ball milling inorganic filler powder, starch and polyvinyl alcohol in the weight ratio of (70-80) to (15-25) to 5, stoving, mixing, sieving to obtain mold pressing split; molding the mold to obtain inorganic filler blanks by two-way compression molding;
sintering the inorganic filler blank at a high temperature of 1200-1400 ℃ for 2-3 hours, grinding, placing the inorganic filler blank in absolute ethyl alcohol containing 3-5wt.% of silane coupling agent for surface modification, and preserving heat for 5-8 hours at 70-90 ℃ to obtain modified porous ceramic;
epoxy resin, curing agent, accelerator and nano alumina are mixed according to the following ratio of 1:0.8:0.03:0.0864, stirring at 60-80deg.C for 1.5-3 hr, and vacuum defoaming for 2.5-3.5 hr to obtain mixed solution;
preheating the modified porous ceramic at 70-90 ℃, immersing in the mixed solution for 1h, and heating and curing to obtain the buffer material.
Compared with the prior art, the application has the beneficial effects that:
the buffer material provided by the application is a porous ceramic/epoxy resin composite material, and the thermal conductivity of the buffer material can reach 5.7W.m -1 ·k -1 The temperature rising speed is high, the mechanical property is good, the production efficiency can be effectively improved by using the high-temperature-rising-speed ceramic material to be practically applied, and the cost is reduced.
Drawings
Fig. 1 is an SEM image of the buffer material prepared in example 1.
FIG. 2 is a schematic diagram showing the performance test of the buffer material and the conventional silica gel sheet in example 1.
Fig. 3 (a) is a diagram showing a process of heating the conventional silica gel sheet to 100 ℃, and fig. 3 (B) is a diagram showing a process of heating the cushioning material provided in example 1 to 100 ℃.
Detailed Description
The application is further illustrated below with reference to examples. These examples are only for illustrating the present application and are not intended to limit the scope of the present application. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the application as claimed.
The application provides a buffer material which is used for buffering the pressure between a hot press head and a pressed product and protecting the pressed product from being damaged, wherein the buffer material is a porous ceramic/epoxy resin composite material, and the weight ratio of the porous ceramic to the epoxy resin is (10-80): 15-85);
wherein, the raw materials of the porous ceramic comprise inorganic filler, and the inorganic filler is at least one of alumina, magnesia, boron nitride or beryllium oxide;
the thermal conductivity of the porous ceramic/epoxy resin composite material is 4.5-5.7W.m -1 ·k -1
The inorganic filler has the advantages of high purity, high dispersibility, high thermal conductivity, low price and the like, and compared with the pure epoxy resin, the epoxy resin doped with the inorganic filler particles not only can overcome the defects of poor heat resistance, low mechanical strength and the like of the pure epoxy resin, but also can fully exert the advantages of high thermal conductivity, corrosion resistance and the like of the inorganic particles.
However, in the prior art, the epoxy composite material is mainly prepared by adopting a solution mixing method, and inorganic filler particles are difficult to independently exist in an epoxy resin matrix, so that an effective heat conduction channel cannot be formed, and high heat conductivity is difficult to realize.
The buffer material provided by the application is a porous ceramic/epoxy resin composite material, wherein the inorganic filler in the composite material is a continuous phase, so that the high-low temperature mechanical property, the heat conductivity and the high-temperature creep resistance of the composite material can be further improved. The thermal conductivity of the material can reach 5.7W.m at most when the material is used in the buffer process of the electronic assembly industry -1 ·k -1 The temperature rising speed is high, the production efficiency can be effectively improved, and the cost is reduced.
In this embodiment, the porosity of the cushioning material is 1% to 5% and the flexural strength is 80 to 150MPa.
Further, the inorganic filler is alumina, and the weight ratio of the porous ceramic to the epoxy resin in the buffer material is 65:34.
The alumina particles have a dense atomic crystal structure and phonons as carriers enable high thermal conductivity of the composite material. When the mass parts of the inorganic fillers reach a certain proportion, the interaction between the inorganic fillers can form a net-like or chain-like heat conducting net chain in the whole composite material system, and when the heat conducting net chain is consistent with the heat flow direction, the heat conducting performance of the composite material is best. In the application, the inorganic filler is alumina, and when the weight ratio of the porous alumina ceramic to the epoxy resin in the buffer material is 65:34, the heat conductivity of the buffer material is the highest and can reach 5.7W.m -1 ·k -1
In this embodiment, the porous ceramic in the buffer material has a porosity of 45% to 55%.
The application also provides a preparation method of the buffer material, which comprises the following steps:
ball milling inorganic filler powder, starch and polyvinyl alcohol in the weight ratio of (70-80) to (15-25) to 5, stoving, mixing, sieving to obtain mold pressing split; molding the mold to obtain inorganic filler blanks by two-way compression molding;
sintering the inorganic filler blank at a high temperature of 1200-1400 ℃ for 2-3 hours, grinding, placing the inorganic filler blank in absolute ethyl alcohol containing 3-5wt.% of silane coupling agent for surface modification, and preserving heat for 5-8 hours at 70-90 ℃ to obtain modified porous ceramic;
epoxy resin, curing agent, accelerator and nano alumina are mixed according to the following ratio of 1:0.8:0.03:0.0864, stirring at 60-80deg.C for 1.5-3 hr, and vacuum defoaming for 2.5-3.5 hr to obtain mixed solution;
preheating the modified porous ceramic at 70-90 ℃, immersing in the mixed solution for 1h, and heating and curing to obtain the buffer material.
According to the preparation method, the porous ceramic is prepared firstly, then the epoxy resin is filled into the pores of the porous ceramic by adopting an impregnation method, and the bicontinuous phase porous ceramic/epoxy resin composite material is prepared, so that the thermal conductivity of the composite material can be effectively improved, and meanwhile, the high-low temperature mechanical property of the composite material is improved.
In this embodiment, the inorganic filler powder has an average particle diameter of 0.1 to 200 μm; the solid phase content of the polyvinyl alcohol was 8wt.%.
The pore size and porosity of the prepared porous ceramic can be controlled by controlling the average particle size of the inorganic filler powder, the solid phase content of the polyvinyl alcohol and the like.
In this embodiment, the number of the sieving holes is 150 mesh; the bidirectional pressurizing pressure is 80MPa, and the time is 5-10min.
In this embodiment, the rate of temperature rise in the high-temperature sintering is 3 ℃/min at 600 ℃ or lower and 5 ℃/min at 600 ℃ or higher.
In this embodiment, the epoxy resin is bisphenol F type epoxy resin; the nanometer alumina is vapor phase nanometer alumina, the average grain diameter is 5-200nm, and the purity is 98.00% -99.99%.
In the application, a small amount of nano aluminum oxide is additionally added into the composite material system, and the nano aluminum oxide is gas phase nano aluminum oxide, so that the compactness, cold and hot fatigue property, fracture toughness, creep deformation resistance and wear resistance of the porous ceramic can be further improved.
In this embodiment, the temperature of the heat curing is 70-90 ℃ for 1 hour.
The preparation and properties of the cushioning material of the present application are described below using specific examples and comparative examples.
Example 1
The embodiment provides a buffer material, and the preparation method thereof comprises the following steps:
s1: ball milling alumina powder (average particle size of 10 mu m) and starch and PVA (solid phase content of 8 wt.%) in a weight ratio of 75:20:5 in absolute ethyl alcohol for 24 hours, drying, and sieving with a 150-mesh screen to obtain a mould pressing split; then, carrying out bidirectional compression molding for 5min under the pressure of 80MPa to obtain an alumina blank; placing the pressed alumina blank into a high-temperature air furnace, and sintering and preserving heat for 2 hours at 1400 ℃ under normal pressure (the heating rate below 600 ℃ is 3 ℃/min, and the heating rate above 600 ℃ is 5 ℃/min), thus obtaining porous alumina ceramic with the porosity of 55%; and (3) grinding the surface of the obtained porous alumina ceramic to be flat, placing the surface of the porous alumina ceramic in absolute ethyl alcohol containing 3wt.% of silane coupling agent for surface modification, and preserving heat for 6 hours at 80 ℃ to obtain the modified porous alumina ceramic.
S2: bisphenol F type epoxy resin, platinum, alkali gel and nano alumina (average grain diameter 5nm, purity 98%) are mixed according to a ratio of 1:0.8:0.03:0.0864 is stirred at a high speed for 2 hours at 70 ℃, and is subjected to vacuum defoaming for 3 hours after being uniformly mixed to obtain a mixed solution;
preheating the modified porous alumina ceramic obtained in the step S1 at 80 ℃, then placing the preheated porous alumina ceramic in the mixed solution for soaking for 1h, and curing for 1h at 80 ℃ in an oven to obtain a bicontinuous-phase porous ceramic/epoxy resin composite material; wherein the weight ratio of the modified porous alumina ceramic to the bisphenol F type epoxy resin is 65:34.
The porous alumina ceramic/epoxy resin composite material has a porosity of 1% and is resistant to bendingStrength is 139.8MPa, and thermal conductivity is 5.7W.m -1 ·k -1 . Fig. 1 is an SEM image of the porous ceramic/epoxy resin composite material prepared in example 1. As can be seen from fig. 1, the epoxy resin was uniformly impregnated into the porous ceramic skeleton in a bicontinuous phase and in a good interface bonding state.
Example 2
The embodiment provides a buffer material, and the preparation method thereof comprises the following steps:
s1: ball milling alumina powder (average particle size of 10 mu m) and starch and PVA (solid phase content of 8 wt.%) in a weight ratio of 75:20:5 in absolute ethyl alcohol for 24 hours, drying, and sieving with a 150-mesh screen to obtain a mould pressing split; then, carrying out bidirectional compression molding for 5min under the pressure of 80MPa to obtain an alumina blank; placing the pressed alumina blank into a high-temperature air furnace, sintering at normal pressure at 1200 ℃ and preserving heat for 2 hours (the heating rate below 600 ℃ is 3 ℃/min, the heating rate above 600 ℃ is 5 ℃/min), thus obtaining porous alumina ceramic with the porosity of 50%; grinding and flattening the surface of the obtained porous alumina ceramic, and then placing the ceramic in absolute ethyl alcohol containing 3wt.% of silane coupling agent for surface modification, and preserving heat for 6 hours at 80 ℃ to obtain modified porous alumina ceramic;
s2: bisphenol F type epoxy resin, platinum, alkali gel and nano alumina (average particle diameter 190nm, purity 99.99%) are mixed according to a ratio of 1:0.8:0.03:0.0864 is stirred at a high speed for 2 hours at 70 ℃, and is subjected to vacuum defoaming for 3 hours after being uniformly mixed to obtain a mixed solution;
preheating the modified porous alumina ceramic obtained in the step S1 at 80 ℃, then placing the preheated porous alumina ceramic in the mixed solution for soaking for 1h, and curing for 1h at 80 ℃ in an oven to obtain a bicontinuous-phase porous alumina ceramic/epoxy resin composite material; wherein the weight ratio of the modified porous alumina ceramic to the bisphenol F type epoxy resin is 65:34.
The porous alumina ceramic/epoxy resin composite material prepared in example 2 has the same morphology as that in example 1, a porosity of 5%, a flexural strength of 85.9MPa and a thermal conductivity of 4.5 W.m -1 ·k -1
Performance testing
The porous alumina ceramic/epoxy resin composite material prepared in example 1 was subjected to performance test and compared with a buffer material commonly used in the prior art, and the results are shown in table 1. It can be seen that the buffer material provided in the present application has higher thermal conductivity while other properties remain excellent, compared to the prior art.
Table 1 comparative buffer material performance test
Note that: in example 1, the heat conductive material is porous ceramic, and the base resin is epoxy resin.
The porous alumina ceramic/epoxy resin composite material prepared in example 1 was compared with a silica gel skin buffer material commonly used in the prior art for performance test, and the schematic diagram is shown in fig. 2.
Fig. 3 (a) is a diagram showing a process of heating up the conventional silica gel sheet buffer material to 100 c, and fig. 3 (B) is a diagram showing a process of heating up the buffer material provided in example 1 to 100 c. As can be seen from fig. 3 (a), the temperature of the silica gel skin buffer material used in the prior art needs to be raised to 100 ℃ for 2 seconds, and the temperature is increased and lost in actual production. As is clear from FIG. 3 (B), the time required for heating to 100℃was shortened to 0.2s by using the porous alumina ceramic/epoxy resin composite material prepared in example 1.
The porous alumina ceramic/epoxy resin composite material prepared in example 1 is used in actual production, and compared with the silica gel skin buffer material adopted in the prior art, the production efficiency can be improved by 15% (see table 2).
TABLE 2 comparison of example 1 with prior art Productivity
Finally, it should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present application without departing from the spirit and scope of the technical solution of the present application.

Claims (9)

1. The buffer material is characterized by being a porous ceramic/epoxy resin composite material, wherein the weight ratio of the porous ceramic to the epoxy resin is (10-80): (15-85);
wherein, the raw materials of the porous ceramic comprise inorganic filler, and the inorganic filler is at least one of alumina, magnesia, boron nitride or beryllium oxide;
the thermal conductivity of the porous ceramic/epoxy resin composite material is 4.5-5.7W.m -1 ·k -1
2. The cushioning material of claim 1, wherein the cushioning material has a porosity of 1% to 5% and a flexural strength of 80 to 150MPa.
3. The cushioning material of claim 1, wherein the porous ceramic of said cushioning material has a porosity of 45% to 55%.
4. A method of producing a cushioning material according to any one of claims 1 to 3, comprising the steps of:
ball milling inorganic filler powder, starch and polyvinyl alcohol in the weight ratio of (70-80) to (15-25) to 5, stoving, mixing, sieving to obtain mold pressing split; molding the mold to obtain inorganic filler blanks by two-way compression molding;
sintering the inorganic filler blank at a high temperature of 1200-1400 ℃ for 2-3 hours, grinding, placing the inorganic filler blank in absolute ethyl alcohol containing 3-5wt.% of silane coupling agent for surface modification, and preserving heat for 5-8 hours at 70-90 ℃ to obtain modified porous ceramic;
epoxy resin, curing agent, accelerator and nano alumina are mixed according to the following ratio of 1:0.8:0.03:0.0864, stirring at 60-80deg.C for 1.5-3 hr, and vacuum defoaming for 2.5-3.5 hr to obtain mixed solution;
preheating the modified porous ceramic at 70-90 ℃, immersing in the mixed solution for 1h, and heating and curing to obtain the buffer material.
5. The method according to claim 4, wherein the inorganic filler powder has an average particle diameter of 0.1 to 200. Mu.m; the solid phase content of the polyvinyl alcohol was 8wt.%.
6. The method of claim 4, wherein the number of the sieve is 150 mesh; the pressure of the bidirectional pressurization is 80MPa, and the time is 5-10min.
7. The method according to claim 4, wherein the high-temperature sintering is performed at a temperature rise rate of 3 ℃/min at 600 ℃ or lower and at 5 ℃/min at 600 ℃ or higher.
8. The method of claim 4, wherein the epoxy resin is bisphenol F type epoxy resin; the curing agent is platinum; the catalyst is alkali gel; the nanometer alumina is vapor phase nanometer alumina, the average grain diameter is 5-200nm, and the purity is 98.00% -99.99%.
9. The method of claim 4, wherein the heat curing is carried out at a temperature of 70-90 ℃ for a period of 1h.
CN202210345902.3A 2022-03-31 2022-03-31 Buffer material and preparation method thereof Pending CN116925500A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210345902.3A CN116925500A (en) 2022-03-31 2022-03-31 Buffer material and preparation method thereof

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Application Number Priority Date Filing Date Title
CN202210345902.3A CN116925500A (en) 2022-03-31 2022-03-31 Buffer material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116925500A true CN116925500A (en) 2023-10-24

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