CN112662134A - Preparation method of epoxy resin composite material filled with MOF nanosheets - Google Patents
Preparation method of epoxy resin composite material filled with MOF nanosheets Download PDFInfo
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- CN112662134A CN112662134A CN202110078846.7A CN202110078846A CN112662134A CN 112662134 A CN112662134 A CN 112662134A CN 202110078846 A CN202110078846 A CN 202110078846A CN 112662134 A CN112662134 A CN 112662134A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 74
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000012621 metal-organic framework Substances 0.000 description 49
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 230000017525 heat dissipation Effects 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Abstract
The invention discloses a preparation method of an epoxy resin composite material filled with MOF nanosheets, which comprises the following steps: s1, synthesis of MOF nanosheets: mixing DMF and ethanol solution to obtain a first mixed solution; dissolving polyvinylpyrrolidone in a trifluoroacetic acid solution, and dissolving a copper nitrate trihydrate crystal in the solution to obtain a second mixed solution; adding TCPP into a mixed solution of DMF and an ethanol solution to dissolve to obtain a third mixed solution; dripping the third mixed solution into the second mixed solution, stirring uniformly, performing ultrasonic treatment, and heating at the temperature of 80 ℃ to obtain MOF nanosheets; centrifuging the MOF nanosheet by using ethanol, and cleaning; s2, preparing the epoxy resin composite material filled with the MOF nanosheets. According to the invention, the MOF nanosheet is prepared by a solution mixing method and is compounded with the epoxy resin material, so that the performance advantages of the MOF nanosheet and the epoxy resin material are combined, the synergistic effect of the MOF nanosheet and the epoxy resin material is exerted, and the heat-conducting property of the composite material is greatly improved.
Description
Technical Field
The invention relates to the technical field of new material processing, in particular to a preparation method of an epoxy resin composite material filled with MOF nanosheets.
Background
With the increasing demand of terminal products for thinning and high efficiency, the development direction of semiconductor schemes has not only improved performance, but also the heat generation and heat dissipation become important factors in semiconductor design. The heat generation is mainly related to the chip manufacturing process and the temperature control algorithm, and the heat dissipation performance can be improved in material and product structure. The heat conduction material is a novel industrial material designed aiming at the heat conduction requirement of equipment in recent years, has excellent and reliable performance, and is widely applied to the fields of various consumer electronics, communication power stations, power batteries and the like. The higher the performance of electronic products, the more difficult thermal management becomes, because with increasing power density of semiconductor components, the heat flux will be larger and larger, some even up to tens of kilowatts per square centimeter, which is 5 times the surface of the sun. If the large heating value can not be led out and diffused from the components in time, the stability of the electronic product can be seriously threatened, and researches show that the majority of faults in the electronic device are caused by heat related problems. As electronic devices are becoming smaller, integrated, and multifunctional, their power density is increasing, and the amount of heat generated per unit volume is increasing. The heat generated by electronic components during operation is a key factor affecting the performance and service life of the electronic components, and the problem of heat dissipation has become a bottleneck restricting the development and application of microelectronic devices and systems. Especially with the rapid deployment of 5G and autopilot technologies, new challenges are presented to the thermal management materials. With the increasing demand for high heat conduction materials in China, the development of novel high heat conduction materials, especially heat conduction silica gel, is becoming the focus of research day by day, and it is believed that in the near future, not only new energy automobile industry, heat conduction materials will be developed in various fields.
Epoxy resins (EP) are a class of thermosetting polymer synthetic materials with good corrosion resistance, insulation properties, and high strength, which have chemical resistance, good dimensional stability, high bonding strength, excellent overall properties, and low price, and thus are widely used. However, EP is an amorphous polymer, which mainly relies on phonon heat transfer, and due to its huge molecular weight and polydispersity of molecular weight, the molecular size is different and molecular chains are randomly entangled, phonon scattering is severe, making the heat conductivity of EP poor (the thermal conductivity of EP is about 0.2W/(m.k)). Electronic packaging is mainly based on filled heat conduction EP, and generally needs to be added with inorganic filler to improve heat conduction performance. The inorganic filler has the main functions of reducing the thermal expansion coefficient, the water absorption rate, the molding shrinkage rate and the production cost, and also has the functions of reinforcing and improving the reliability. Research shows that the heat-conducting silica gel matrix is filled with the heat-conducting filler according to the same volume fraction or mass fraction, the higher the heat conductivity of the heat-conducting filler is, the more excellent the heat-conducting performance of the composite material is, so that the composite material with higher heat conductivity can be prepared by selecting the filler with higher heat conductivity, and the same heat-conducting effect can be achieved by adopting less fillers. As a porous organic-inorganic hybrid crystal, a Metal Organic Framework (MOFs) material has high specific surface area and good structure adjustability, is easy to build an effective pore channel, increases the thermal conductivity, and is just complementary with epoxy resin in the aspects of electric conductivity and thermal conductivity. If the advantages of GE and EP materials with excellent performance can be combined to prepare a new composite heat-conducting and electricity-conducting material, the advantages of the GE and EP materials can be combined, the application of the GE and EP materials in the field of heat dissipation materials is realized, and great economic benefits are brought while great contribution is made to the development and popularization of energy-saving and environment-friendly career. Therefore, the MOFs material is filled into the epoxy resin matrix, so that the composite heat dissipation material with high thermal conductivity can be prepared, and the thermal conductivity is far superior to that of the heat dissipation material prepared by other traditional fillers.
Disclosure of Invention
With the continuous development of semiconductor technology, high-voltage, high-power and high-efficiency high-power semiconductor devices are emerging continuously, and are widely applied to the fields of wireless communication, radar and countermeasure, power electronics and the like. However, the high power semiconductor device has not enough good chips, and must have a reasonable package structure with high light extraction efficiency, and the thermal resistance is as low as possible, so as to ensure the photoelectric performance and reliability. In practical applications, in order to make the power device perform the maximum efficacy brought by advanced processes, the problem of good heat dissipation must be solved in the packaging and assembly of the device. The heat dissipation performance becomes a key factor for restricting the service performance and the service life of the high-power semiconductor device. The invention provides an epoxy resin composite material filled with MOF nano sheets, which has super-strong heat dissipation performance and can greatly improve the heat dissipation problem of a semiconductor device. The MOF nanosheet/epoxy resin composite material is an ideal interface packaging material and has a wide application prospect.
In order to achieve the purpose, the technical scheme of the invention is realized in such a way that the preparation method of the epoxy resin composite material filled with the MOF nanosheets comprises the following steps:
s1, synthesis of MOF nanosheets: mixing DMF and ethanol solution to obtain a first mixed solution; dissolving polyvinylpyrrolidone in a trifluoroacetic acid solution, and dissolving a copper nitrate trihydrate crystal in the solution to obtain a second mixed solution; adding TCPP into a mixed solution of DMF and an ethanol solution to dissolve to obtain a third mixed solution; dripping the third mixed solution into the second mixed solution, stirring uniformly, performing ultrasonic treatment, and heating at the temperature of 80 ℃ to obtain MOF nanosheets; centrifuging the MOF nanosheet by using ethanol, and cleaning;
s2, preparing an epoxy resin composite material filled with MOF nanosheets: dispersing the MOF nanosheets in water, and carrying out ultrasonic treatment to obtain a suspension; adding epoxy resin into the suspension, and stirring in a water bath kettle at 60 ℃ to obtain a mixture of MOF nanosheets and the epoxy resin; then dehydrating, taking out the product, mixing with a curing agent 4:1, and injecting into a mold; and then curing at the temperature of 60-120 ℃ to obtain the epoxy resin composite material filled with the MOF nanosheets.
After the MOF nanosheets and the epoxy resin are mixed in S2, the filling percentage of the MOF nanosheets is 2.0%.
And in S1, adding ethanol into the MOF nanosheets, centrifuging at a centrifuge rotation speed of 9500r/min for 10 min.
The curing temperature in S2 was 100 ℃.
And (S1) dropping the third mixed solution into the second mixed solution, uniformly stirring, performing ultrasonic treatment for 30min, and heating at 80 ℃ for 4h to obtain the MOF nanosheet.
In S2, dispersing the MOF nano-sheets in water at the concentration of 2mg/ml, and carrying out ultrasonic treatment for 10min to obtain a suspension.
And S2, adding epoxy resin into the suspension, and stirring for 4 hours in a water bath kettle at 60 ℃ to obtain a mixture of the MOF nanosheet and the epoxy resin.
The advantages of the invention are as follows:
1. according to the invention, the MOF nanosheet is prepared by a solution mixing method and is compounded with the epoxy resin material, so that the performance advantages of the MOF nanosheet and the epoxy resin material are combined, the synergistic effect of the MOF nanosheet and the epoxy resin material is exerted, and the heat-conducting property of the composite material is greatly improved.
2. According to the invention, the properties of the epoxy resin composite material filled with the MOF nanosheets with different mass percentages are explored to obtain the MOF nanosheet/epoxy resin composite material with different electrical conductivity and heat resistance.
3. According to the invention, the properties of the MOF nanosheet filled epoxy resin composite material at different curing temperatures are explored to obtain the MOF nanosheet/epoxy resin composite material with different electrical conductivity and heat resistance.
4. The invention adopts solution processing and other conventional processing methods in the whole process, has simple process, can reduce the consumption of inorganic materials, reduces the cost, is very beneficial to industrial mass production and has great economic value.
5. The MOF nanosheet/epoxy resin composite material prepared by the invention is an ideal interface packaging material and has a wide application prospect.
Detailed Description
The present invention will be further illustrated with reference to the following examples.
The invention adopts a chemical synthesis method to prepare the MOF-filled epoxy resin composite material, firstly, a coupling agent is used for modification, and the modified epoxy resin composite material is added into epoxy resin as a nano filler to obtain the functional MOF nano sheet/epoxy resin composite material.
< specific examples >
Synthesis of MOF nanosheet
9 mL of DMF (dimethylformamide) and 3 mL of ethanol solution were mixed in a beaker to obtain a mixture 1.
10.0 mg of polyvinylpyrrolidone (PVP) was dissolved in 40. mu.L of a 1.0M trifluoroacetic acid solution, and 2.4 mg of copper nitrate trihydrate crystals were dissolved in the above solution to obtain a mixed solution 2.
4.4 mg of TCPP was dissolved in a mixture of DMF and ethanol (mixture 3)
Slowly dripping the mixed solution 3 into the mixed solution 2, and uniformly stirring.
And (3) carrying out ultrasonic treatment on the solution for 30min, and then heating the solution at 80 ℃ for 4h to obtain the MOF nanosheet.
The MOF nanosheets were washed 2 times with ethanol centrifugation (9500 r/min, 10 min).
Preparation of MOF nanosheet filled epoxy resin composite material with different mass percentages
The MOF nanosheets were dispersed in water at a concentration of 2mg/ml and sonicated for 10 minutes to give a suspension.
0ml, 7.5ml, 15ml, 30ml and 45ml of the above-obtained suspension was added to a dry 100ml three-necked flask, respectively. To the different volumes of suspension, 30g of epoxy resin was added in sequence.
The mixed solution is stirred at a high speed in a water bath kettle at 60 ℃ for 4 hours to obtain a mixture of MOF nanosheets and epoxy resin with different mass percentages (respectively 0%, 0.5%, 1.0%, 2.0% and 3.0%).
The flask was evacuated to reduce pressure for dehydration, and the product was taken out separately and mixed with a curing agent 4:1 and poured into a mold.
Curing at 60 ℃ to obtain the MOF nanosheet filled epoxy resin composite material with different mass fractions.
Preparation of epoxy resin composite material filled with MOF nanosheets at different curing temperatures
Dispersing the obtained MOF nano-sheets in deionized water at the concentration of 2mg/ml, and carrying out ultrasonic treatment for 10 minutes to obtain a suspension.
7.5ml of the suspension obtained above was added to a dry 100ml three-necked flask.
And then adding 30g of epoxy resin into the solution to obtain a mixture of the MOF nanosheet and the epoxy resin with the mass percentage of 2.0%.
The mixture was stirred at high speed in a 60 ℃ water bath for 4h, and the flask was evacuated to reduce the pressure and dewater.
The product was taken out and mixed with a curing agent at a mass ratio of 4:1 and injected into a mold.
The product is respectively cured at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ to obtain the MOF nanosheet and epoxy resin composite material at different curing temperatures.
< assay >
The MOF nanosheet/epoxy resin composite material obtained under different mass percentages is subjected to mechanical property test and thermal property test respectively, and specifically shown in the following table 1:
TABLE 1
The MOF nanosheet/epoxy resin composite material obtained at different curing temperatures is subjected to mechanical property test and thermal property test respectively, and specifically shown in the following table 2:
TABLE 2
According to the invention, the MOF nanosheet is filled in the epoxy resin material for compounding, so that the performance advantages of the MOF nanosheet and the epoxy resin material are combined, the synergistic effect of the MOF nanosheet and the epoxy resin material is exerted, and the heat-conducting property of the composite material is greatly improved.
The invention determines that the optimal filling percentage of the MOF nano-sheet/epoxy resin is 2.0%, and the optimal curing temperature is 100 ℃.
The MOF nano-sheets involved in the invention can be replaced by other two-dimensional nano-materials with similar properties.
The above-mentioned embodiments are only examples of the present invention, and not intended to limit the scope of the present invention, and various modifications made according to the above-mentioned embodiments are within the scope of the present invention.
Claims (7)
1. A preparation method of an epoxy resin composite material filled with MOF nanosheets is characterized by comprising the following steps:
s1, synthesis of MOF nanosheets: mixing DMF and ethanol solution to obtain a first mixed solution; dissolving polyvinylpyrrolidone in a trifluoroacetic acid solution, and dissolving a copper nitrate trihydrate crystal in the solution to obtain a second mixed solution; adding TCPP into a mixed solution of DMF and an ethanol solution to dissolve to obtain a third mixed solution; dripping the third mixed solution into the second mixed solution, stirring uniformly, performing ultrasonic treatment, and heating at the temperature of 80 ℃ to obtain MOF nanosheets; centrifuging the MOF nanosheet by using ethanol, and cleaning;
s2, preparing an epoxy resin composite material filled with MOF nanosheets: dispersing the MOF nanosheets in water, and carrying out ultrasonic treatment to obtain a suspension; adding epoxy resin into the suspension, and stirring in a water bath kettle at 60 ℃ to obtain a mixture of MOF nanosheets and the epoxy resin; then dehydrating, taking out the product, mixing with a curing agent 4:1, and injecting into a mold; and then curing at the temperature of 60-120 ℃ to obtain the epoxy resin composite material filled with the MOF nanosheets.
2. The preparation method of the MOF nanosheet filled epoxy resin composite material of claim 1, wherein the filling percentage of the MOF nanosheets after mixing of the MOF nanosheets and the epoxy resin in S2 is 2.0%.
3. The preparation method of the MOF nanosheet-filled epoxy resin composite material according to claim 1, wherein the MOF nanosheets are subjected to ethanol centrifugation treatment in S1 at a centrifuge rotation speed of 9500r/min for 10 min.
4. A method of making a MOF nanosheet filled epoxy resin composite according to claim 1, wherein the curing temperature in S2 is 100 ℃.
5. The preparation method of the epoxy resin composite material filled with the MOF nanosheets, according to claim 1, characterized in that the third mixed solution in S1 is dripped into the second mixed solution, uniformly stirred, ultrasonically treated for 30min, and then heated at 80 ℃ for 4h to obtain the MOF nanosheets.
6. The preparation method of the MOF nanosheet-filled epoxy resin composite material according to claim 1, wherein the MOF nanosheets are dispersed in water at a concentration of 2mg/ml in S2, and subjected to ultrasonic treatment for 10min to obtain a suspension.
7. The preparation method of the MOF nanosheet filled epoxy resin composite material according to claim 6, wherein the epoxy resin is added to the suspension in S2 and stirred in a water bath kettle at 60 ℃ for 4h to obtain a mixture of MOF nanosheets and epoxy resin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113105719A (en) * | 2021-04-21 | 2021-07-13 | 广东创辉鑫材科技股份有限公司 | Environment-friendly flame-retardant high-thermal-conductivity metal-based copper-clad plate |
| CN113932954A (en) * | 2021-10-13 | 2022-01-14 | 北京化工大学 | Preparation method of ZIF-8-doped flexible wearable pressure sensor and product thereof |
| CN114410185A (en) * | 2022-01-28 | 2022-04-29 | 扬州大学 | Preparation method and application of electrostatic spinning film-silicate mineral-2D Co-MOFs epoxy resin coating |
| CN115025243A (en) * | 2022-04-08 | 2022-09-09 | 南京师范大学 | Preparation method and application of silver nanoparticle loaded on two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105719A (en) * | 2021-04-21 | 2021-07-13 | 广东创辉鑫材科技股份有限公司 | Environment-friendly flame-retardant high-thermal-conductivity metal-based copper-clad plate |
| CN113105719B (en) * | 2021-04-21 | 2022-10-25 | 深圳市鑫荣进绝缘材料有限公司 | Environment-friendly flame-retardant high-thermal-conductivity metal-based copper-clad plate |
| CN113932954A (en) * | 2021-10-13 | 2022-01-14 | 北京化工大学 | Preparation method of ZIF-8-doped flexible wearable pressure sensor and product thereof |
| CN113932954B (en) * | 2021-10-13 | 2024-02-02 | 北京化工大学 | Preparation method of ZIF-8 doped flexible wearable pressure sensor and product thereof |
| CN114410185A (en) * | 2022-01-28 | 2022-04-29 | 扬州大学 | Preparation method and application of electrostatic spinning film-silicate mineral-2D Co-MOFs epoxy resin coating |
| CN115025243A (en) * | 2022-04-08 | 2022-09-09 | 南京师范大学 | Preparation method and application of silver nanoparticle loaded on two-dimensional sheet metal organic framework modified by mercaptophenylboronic acid |
| CN115025243B (en) * | 2022-04-08 | 2024-02-23 | 南京师范大学 | Preparation method and application of mercaptophenylboronic acid modified two-dimensional sheet metal organic framework loaded silver nanoparticle |
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Application publication date: 20210416 |