CN115547691A - Heat-conducting diaphragm for high-frequency capacitor and preparation method thereof - Google Patents
Heat-conducting diaphragm for high-frequency capacitor and preparation method thereof Download PDFInfo
- Publication number
- CN115547691A CN115547691A CN202211374582.0A CN202211374582A CN115547691A CN 115547691 A CN115547691 A CN 115547691A CN 202211374582 A CN202211374582 A CN 202211374582A CN 115547691 A CN115547691 A CN 115547691A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- heat
- diaphragm
- prepare
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052582 BN Inorganic materials 0.000 claims abstract description 64
- 239000004743 Polypropylene Substances 0.000 claims abstract description 28
- -1 polypropylene Polymers 0.000 claims abstract description 28
- 229920001155 polypropylene Polymers 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003292 glue Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000001815 facial effect Effects 0.000 abstract 1
- 238000005276 aerator Methods 0.000 description 15
- 238000007599 discharging Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0003—Protection against electric or thermal overload; cooling arrangements; means for avoiding the formation of cathode films
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a heat-conducting diaphragm for a high-frequency capacitor and a preparation method thereof, and belongs to the technical field of high-frequency capacitors. The diaphragm comprises the following components in parts by weight: 80-100 parts of modified base rubber, 1.2-2.5 parts of branched boron nitride and 1-3 parts of flatting agent; the modified base glue is prepared by dissolving polypropylene, decomposing the polypropylene by ultraviolet irradiation and matching chlorine, grafting-C l on the polypropylene, bridging the polypropylene with a silane coupling agent KH550 to fix lamellar boron nitride along a polymer chain of the polypropylene, accelerating migration of branch-shaped boron nitride by infrared irradiation, and forming a facial line interweaving type heat conduction network with the lamellar boron nitride, so that the diaphragm has good heat conductivity, and the heat conductivity coefficient of the manufactured diaphragm is 0.76-0.82W/m.K through testing, thereby solving the problem that the existing capacitive diaphragm is applied to high-frequency capacitors to cause higher capacitance temperature.
Description
Technical Field
The invention belongs to the technical field of high-frequency capacitors, and particularly relates to a heat-conducting diaphragm for a high-frequency capacitor and a preparation method thereof.
Background
Capacitors are one of the important components in the electronics industry, and in addition to their functions of filtering, decoupling and signal coupling, they also play a special role in special circuits such as rectifier circuits, power supply circuits and ac motor starting circuits. The method is widely applied to the fields of automobile industry, security industry, medical electronics, computer televisions, electronic toys, industrial control and the like. The diaphragm is used as a lining material for adsorbing electrolyte in the capacitor, and the performance of the diaphragm directly influences the quality of the capacitor.
When a capacitor is charged and discharged, charges obviously flow on a capacitor plate, namely the flows of the charges are currents, an electrode of the capacitor in reality is obviously not a superconductor, loss in the charging and discharging process can be released in the form of heat, particularly for a high-frequency capacitor, the heating phenomenon is more obvious, and the service life of the capacitor is greatly shortened under the high-temperature working condition; the heat dissipation performance of an electrode plate and a shell of a capacitor is generally good, a diaphragm is usually made of organic materials, the heat conductivity of the diaphragm is poor, and the diaphragm becomes a main reason for hindering the heat dissipation of the capacitor, and the heat conductivity coefficient of a mature capacitor diaphragm in the prior art is 0.2-0.3W/m.K, so that heat cannot be quickly led out when the diaphragm is applied to a high-frequency capacitor.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention aims to provide a heat-conducting diaphragm for a high-frequency capacitor and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a heat-conducting diaphragm for a high-frequency capacitor comprises the following components in parts by weight: 80-100 parts of modified base rubber, 1.2-2.5 parts of branched boron nitride and 1-3 parts of flatting agent;
the modified base rubber adopts a continuous preparation process, and the specific method comprises the following steps: adding polypropylene master batches and methylbenzene into a stirrer, heating and stirring until the polypropylene master batches are dissolved, then transferring the mixture into a reaction kettle with an aerator pipe arranged at the bottom and a stirrer arranged at the top, heating to 88-95 ℃, slowly introducing chlorine gas into the reaction kettle through the aerator pipe under the condition of ultraviolet irradiation, reacting for 2-4 hours, decomposing the chlorine gas into chlorine radicals under the ultraviolet irradiation, attacking a polymerization chain of polypropylene, grafting-Cl on the polypropylene, improving the activity of the polypropylene, introducing nitrogen gas from the aerator pipe for gas washing after the reaction is finished, eluting the chlorine gas mixed in a reaction system, simultaneously adding lamellar boron nitride and silane coupling agent KH550 under the stirring state, stirring at a high speed, introducing ammonia gas for reacting for 30-50 minutes, reacting the silane coupling agent KH550 with-Cl groups grafted on the polymerization chain, improving the compatibility of a polypropylene matrix, simultaneously reacting siloxane of the silane coupling agent KH550 with oxygen-containing groups on the surface of the lamellar boron nitride, dispersing and fixing the lamellar boron nitride in the polypropylene matrix to prepare the modified base adhesive.
Further, the dosage ratio of the polypropylene master batch to the toluene to the lamellar boron nitride to the silane coupling agent KH550 is 100g:300-360mL:2.7-3.5g:6 to 10mL, and the introduction amount of chlorine is 0.12vvm.
The lamellar boron nitride is prepared by the following method:
step A1: mixing boron nitride micro powder and a small amount of potassium permanganate, putting the mixture into a crucible, transferring the mixture into a muffle furnace, roasting the mixture for 2 to 3 hours at the temperature of between 180 and 200 ℃ in the air atmosphere, transferring the roasted mixture into dilute sulfuric acid for quenching, centrifugally separating, washing the lower-layer precipitate for several times by using water, and preparing oxidizing slag;
further, the mass ratio of the boron nitride micro powder to the potassium permanganate is 10:0.6-0.8, the mode particle size of the boron nitride micro powder is 2 μm, and the mass fraction of the dilute sulfuric acid is 10%.
Step A2: mixing ethylene amine and isopropanol to prepare stripping liquid, adding oxidation slag, mixing, transferring into an ultrasonic disperser, ultrasonically stripping at 55kHz for 3-5h, standing for 30min, taking supernatant, dropwise adding hydrochloric acid to adjust pH value to 6, centrifuging, taking the supernatant, precipitating, and vacuum drying to obtain lamellar boron nitride.
Further, the dosage ratio of the ethylene amine to the isopropanol is 7.5-9g:1L, and the concentration of the oxidation slag in the stripping liquid is 50-80g/L.
The branched boron nitride is prepared by the following method:
step B1: adding boric acid and melamine into a stirrer, adding into an ethanol solution, heating, stirring and mixing, then cooling to precipitate floccules, centrifugally separating out floccules, and drying in vacuum to prepare a batch mixture;
and step B2: introducing nitrogen into a well type crucible furnace, flatly spreading the batch in a crucible, heating to 1200-1300 ℃, keeping the temperature and calcining for 5-7h, cooling, and taking a calcined product to prepare a boron nitride master batch;
and step B3: adding the boron nitride master batch and water into a grinder for circular wet grinding, adding a silane coupling agent KH550 into the slurry, stirring and mixing overnight, and spray-drying to prepare the branched boron nitride.
Further, the mass ratio of the used boric acid to the melamine is 2.6-2.8:1-1.2.
A preparation method of a heat-conducting diaphragm for a high-frequency capacitor comprises the following steps:
step S1: adding the modified base rubber, the branched boron nitride and the leveling agent into an internal mixer, heating to 90-100 ℃ in a nitrogen atmosphere, and carrying out internal mixing for 40-60min to prepare composite rubber;
step S2: spinning the composite glue into a film, irradiating the film for 20min by infrared rays, immersing the film into a sodium chloride solution, and stripping the film to prepare the heat-conducting diaphragm.
Furthermore, medium-frequency infrared rays are adopted for infrared irradiation, and the irradiation distance is 10-15cm.
The invention has the beneficial effects that:
the invention provides a modification method for improving the thermal conductivity of a polypropylene diaphragm, which comprises the steps of dissolving polypropylene, decomposing the polypropylene by ultraviolet irradiation and matching with chlorine, attacking a polypropylene polymer chain by generated chlorine free radicals, grafting-Cl on the polypropylene to improve the activity of the polypropylene, bridging by using a silane coupling agent KH550, fixing lamellar boron nitride along the polypropylene polymer chain, adding branch boron nitride, firing and grinding the branch boron nitride to form a ball-thorn-shaped structure, mixing the branch boron nitride with a modified sizing material, uniformly dispersing the branch boron nitride among the sheet boron nitride under infrared irradiation because the branch boron nitride is not fixed and has a high migration rate, forming a surface-wire interlaced heat conduction network with the sheet boron nitride, further enabling the diaphragm to have good thermal conductivity, being applied to high-frequency capacitors and being beneficial to rapid heat dissipation, and testing shows that the prepared diaphragm has a thermal conductivity of about 0.76-0.82W/m.K.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment prepares a heat-conducting diaphragm for a high-frequency capacitor, and the specific implementation process is as follows:
1. preparation of lamellar boron nitride
Step A1: metering 10g of boron nitride micro powder (commercially available hexagonal boron nitride, mode particle size of 2 mu m) and 0.6g of potassium permanganate, mixing for 10min by a powder mixer, uniformly mixing the two, then putting the mixture into a crucible, transferring the mixture into a muffle furnace, roasting the mixture for 3h at the temperature of 180 ℃ in the air atmosphere, discharging the roasted mixture into 10% dilute sulfuric acid for quenching, centrifugally separating, washing the lower-layer precipitate for 2 times by using water, and preparing oxidation slag;
step A2: taking ethylene amine and isopropanol according to the proportion of 7.5g: stirring and mixing 1L to prepare stripping liquid, mixing the oxidizing slag and the stripping liquid according to 50g/L, transferring into an ultrasonic disperser, ultrasonically stripping for 3h at 55kHz, standing for 30min, taking supernatant, dropwise adding hydrochloric acid to adjust the pH value to 6, centrifuging, taking lower layer, and vacuum drying to prepare the lamellar boron nitride.
2. Preparation of branched boron nitride
Step B1: taking boric acid and melamine according to the mass ratio of 2.6:1, adding the mixture into a stirrer, adding an ethanol solution, heating to 60 ℃, stirring and mixing, then cooling to separate out floccules, centrifugally separating out the floccules, and drying in vacuum to prepare a batch mixture;
and step B2: introducing nitrogen into a well-type crucible furnace, flatly laying the batch in a crucible, heating to 1200 ℃, keeping the temperature, calcining for 7 hours, cooling, and taking a calcined product to prepare a boron nitride master batch;
and step B3: adding the boron nitride master batch and water into a grinding mill for circular wet grinding until the particle size of particles in the slurry reaches 0.5 mu m, adding 0.7wt% of silane coupling agent KH550 into the slurry, stirring, mixing overnight, and spray drying to prepare the branched boron nitride.
3. Preparation of modified base rubber by using lamellar boron nitride
100g of polypropylene master batch and 300mL of methylbenzene are put into a stirrer, the mixture is quickly heated and stirred to dissolve the polypropylene master batch, an aerator pipe is arranged at the bottom of a reaction kettle, the stirrer is arranged at the top of the reaction kettle, the oil bath is heated to 88 ℃, short-wave ultraviolet radiation is carried out, chlorine gas is slowly introduced into the reaction kettle through the aerator pipe, the introduction amount of the chlorine gas is controlled to be 0.12vvm, the reaction is carried out for 2 hours, nitrogen gas is introduced from the aerator pipe after the reaction is finished and is cleaned for 5 minutes, the chlorine gas mixed in the reaction system is eluted, then 2.7g of lamellar boron nitride and 6mL of silane coupling agent KH550 are simultaneously added under the stirring state, the stirring speed is set to be 500rpm, the reaction is carried out for 20 minutes, ammonia gas is introduced from the aerator pipe while the reaction is carried out, the introduction amount of the ammonia gas is 0.1vvm, and the modified base adhesive is prepared after the reaction is finished.
4. Preparation of Heat-conducting Membrane
Step S1: adding 80 parts of modified base rubber, 1.2 parts of branched boron nitride and 1 part of flatting agent (type TEGO Glide 100) into an internal mixer, heating to 90 ℃ in a nitrogen atmosphere, and internally mixing for 60min to prepare composite rubber;
step S2: spinning the composite glue into a film, wherein the spinning temperature is 65 ℃, the voltage is 30kV, the receiving distance is 18cm, the spinning wet film is placed under an infrared irradiator, medium-frequency infrared rays are adopted, the irradiation distance is 10cm, the irradiation is carried out for 20min, and then the spinning wet film is immersed into a sodium chloride solution to be peeled off, so that the heat-conducting diaphragm is prepared.
Example 2
The embodiment prepares a heat-conducting diaphragm for a high-frequency capacitor, and the specific implementation process is as follows:
1. preparation of lamellar boron nitride
Step A1: metering 10g of boron nitride micro powder (commercially available hexagonal boron nitride, with mode particle size of 2 μm) and 0.7g of potassium permanganate, mixing for 12min by a powder mixer, uniformly mixing the two, then putting the mixture into a crucible, transferring the mixture into a muffle furnace, roasting the mixture for 2.5h at the temperature of 200 ℃ in the air atmosphere, discharging the roasted mixture into 10% dilute sulfuric acid for quenching, centrifugally separating, washing the lower-layer precipitate for 2 times by using water, and preparing oxide slag;
step A2: taking ethylene amine and isopropanol according to the proportion of 8.2g: stirring and mixing 1L to prepare stripping liquid, mixing the oxidizing slag and the stripping liquid according to 70g/L, transferring into an ultrasonic disperser, ultrasonically stripping for 4h at 55kHz, standing for 30min, taking supernatant, dropwise adding hydrochloric acid to adjust the pH value to 6, centrifuging, taking lower layer, and vacuum drying to prepare the lamellar boron nitride.
2. Preparation of branched boron nitride
Step B1: taking boric acid and melamine according to the mass ratio of 2.7:1.1, adding the mixture into a stirrer, adding an ethanol solution, heating to 60 ℃, stirring and mixing, then cooling to separate out floccules, centrifugally separating out the floccules, and drying in vacuum to prepare a batch mixture;
and step B2: introducing nitrogen into a well type crucible furnace, flatly spreading the batch in a crucible, heating to 1250 ℃, preserving heat, calcining for 6 hours, cooling, and taking a calcined product to prepare a boron nitride master batch;
and step B3: adding the boron nitride master batch and water into a grinding mill for circular wet grinding until the particle size of particles in the slurry reaches 0.5 mu m, adding 0.7wt% of silane coupling agent KH550 into the slurry, stirring, mixing overnight, and spray drying to prepare the branched boron nitride.
3. Preparation of modified base rubber by using lamellar boron nitride
Adding 100g of polypropylene master batches and 340mL of methylbenzene into a stirrer, quickly heating and stirring to dissolve the polypropylene master batches, installing an aerator pipe at the bottom of a reaction kettle, installing a stirrer at the top of the reaction kettle, heating the oil bath to 92 ℃, carrying out short-wave ultraviolet irradiation, simultaneously slowly introducing chlorine into the reaction kettle through the aerator pipe, controlling the introduction amount of the chlorine to be 0.12vvm, reacting for 3 hours, introducing nitrogen from the aerator pipe after the reaction is finished, cleaning for 5 minutes, eluting the chlorine mixed in the reaction system, simultaneously adding 3.1g of lamellar boron nitride and 8mL of silane coupling agent KH550 under a stirring state, stirring and reacting for 25 minutes at a stirring speed of 500rpm, introducing ammonia from the aerator pipe while stirring and at an introduction amount of 0.1vvm, and preparing the modified base adhesive after the reaction is finished.
4. Preparation of Heat-conducting diaphragm
Step S1: adding 90 parts of modified base rubber, 1.8 parts of branched boron nitride and 2 parts of a flatting agent (type TEGO Glide 100) into an internal mixer, heating to 95 ℃ in a nitrogen atmosphere, and internally mixing for 50min to prepare composite rubber;
step S2: spinning the composite glue into a film, wherein the spinning temperature is 65 ℃, the voltage is 30kV, the receiving distance is 18cm, the spinning wet film is placed under an infrared irradiator, medium-frequency infrared rays are adopted, the irradiation distance is 15cm, the irradiation is carried out for 20min, and then the spinning wet film is immersed into a sodium chloride solution to be peeled off, so that the heat-conducting diaphragm is prepared.
Example 3
The embodiment of the invention provides a heat-conducting diaphragm for a high-frequency capacitor, which is prepared by the following specific implementation processes:
1. preparation of lamellar boron nitride
Step A1: metering 10g of boron nitride micro powder (commercially available hexagonal boron nitride, mode particle size of 2 mu m) and 0.8g of potassium permanganate, mixing for 14min by a powder mixer, uniformly mixing the two, then putting the mixture into a crucible, transferring the mixture into a muffle furnace, roasting the mixture for 2h at the temperature of 220 ℃ in the air atmosphere, discharging the roasted mixture into 10% dilute sulfuric acid for quenching, centrifugally separating, washing the lower-layer precipitate for 3 times by using water, and preparing oxidizing slag;
step A2: taking ethylenediamine and isopropanol according to a ratio of 9g: stirring and mixing 1L to prepare stripping liquid, mixing the oxidation slag and the stripping liquid according to the ratio of 80g/L, transferring the mixture into an ultrasonic dispersion instrument, ultrasonically stripping for 5 hours at 55kHz, standing for 30 minutes, taking supernatant, dropwise adding hydrochloric acid to adjust the pH value to 6, centrifuging, taking the lower layer, and drying in vacuum to prepare the lamellar boron nitride.
2. Preparation of branched boron nitride
Step B1: taking boric acid and melamine according to the mass ratio of 2.8:1.2, adding the mixture into a stirrer, adding an ethanol solution, heating to 60 ℃, stirring and mixing, then cooling to separate out floccules, centrifugally separating out the floccules, and drying in vacuum to prepare a batch mixture;
and step B2: introducing nitrogen into a well type crucible furnace, flatly laying the batch in a crucible, heating to 1300 ℃, keeping the temperature and calcining for 5 hours, and taking a calcined product after cooling to prepare a boron nitride master batch;
and step B3: adding the boron nitride master batch and water into a grinding mill for circular wet grinding until the particle size of particles in the slurry reaches 0.5 mu m, adding 0.7wt% of silane coupling agent KH550 into the slurry, stirring, mixing overnight, and spray drying to prepare the branched boron nitride.
3. Preparation of modified base rubber by using lamellar boron nitride
100g of polypropylene master batch and 360mL of methylbenzene are put into a stirrer, the mixture is quickly heated and stirred to dissolve the polypropylene master batch, an aerator pipe is arranged at the bottom of a reaction kettle, the stirrer is arranged at the top of the reaction kettle, the oil bath is heated to 95 ℃, short-wave ultraviolet radiation is carried out, meanwhile, chlorine is slowly introduced into the reaction kettle through the aerator pipe, the introduction amount of the chlorine is controlled to be 0.12vvm, the reaction is carried out for 4 hours, nitrogen is introduced from the aerator pipe after the reaction is finished to clean for 5 minutes, the chlorine mixed in the reaction system is eluted, then, 3.5g of lamellar boron nitride and 10mL of silane coupling agent KH550 are simultaneously added under the stirring state, the stirring speed is set to be 500rpm, the stirring reaction is carried out for 30 minutes, ammonia is introduced from the aerator pipe while the stirring reaction is carried out, the introduction amount of the ammonia is 0.1vvm, and the modified base adhesive is prepared after the reaction is finished.
4. Preparation of Heat-conducting diaphragm
Step S1: adding 100 parts of modified base rubber, 2.5 parts of branched boron nitride and 3 parts of flatting agent (type TEGO Glide 100) into an internal mixer, heating to 100 ℃ in a nitrogen atmosphere, and internally mixing for 40min to prepare composite rubber;
step S2: spinning the composite glue into a film, wherein the spinning temperature is 65 ℃, the voltage is 30kV, the receiving distance is 18cm, the spinning wet film is placed under an infrared irradiator, medium-frequency infrared rays are adopted, the irradiation distance is 15cm, the irradiation is carried out for 20min, and then the spinning wet film is immersed into a sodium chloride solution to be peeled off, so that the heat-conducting diaphragm is prepared.
The heat conductive membranes prepared in examples 1 to 3 were subjected to the relevant performance tests, and the test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the diaphragm prepared by the method has the thickness of 40-42 μm, the tensile strength of 34.7-38.1MPa, uniform film thickness and good mechanical property; the porosity is 53.5-59.7%, the liquid absorption rate is 304-343%, the lyophilic and liquid retention capacity is excellent, the internal resistance for charging is 2.27-2.71 mOmega, the internal resistance is good, the heat conductivity coefficient reaches 0.76-0.82W/m.K, the thermal conductivity is excellent, the thermal conductivity is far higher than that of the existing capacitance diaphragm, and the high-frequency high-power capacitance diaphragm is suitable for high-frequency high-power capacitors.
In the description of the specification, reference to the description of "one embodiment," "an example," "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. A preparation method of a heat-conducting diaphragm for a high-frequency capacitor is characterized by comprising the following steps:
step S1: adding the modified base rubber, the branched boron nitride and the leveling agent into an internal mixer, heating to 90-100 ℃ in a nitrogen atmosphere, and carrying out internal mixing for 40-60min to prepare composite rubber;
step S2: spinning the composite glue into a film, irradiating the film for 20min by infrared rays, immersing the film into a sodium chloride solution, and peeling the film to prepare a heat-conducting diaphragm;
the preparation method of the modified base rubber comprises the following steps: heating and dissolving polypropylene master batch and toluene, keeping the temperature at 88-95 ℃, introducing chlorine gas under the condition of ultraviolet irradiation for reaction for 2-4h, introducing nitrogen gas for gas washing after the reaction is finished, then simultaneously adding lamellar boron nitride and a silane coupling agent KH550 under the stirring state, introducing ammonia gas, and stirring for reaction for 30-50min to prepare the modified base adhesive.
2. The method for preparing a heat-conducting diaphragm for a high-frequency capacitor as claimed in claim 1, wherein the infrared radiation is medium frequency infrared radiation, and the radiation distance is 10-15cm.
3. The preparation method of the heat-conducting diaphragm for the high-frequency capacitor, according to claim 1, wherein the dosage ratio of the polypropylene master batch, the toluene, the lamellar boron nitride and the silane coupling agent KH550 is 100g:300-360mL:2.7-3.5g:6 to 10mL, and the introduction amount of chlorine is 0.12vvm.
4. The method for preparing a heat-conducting diaphragm for a high-frequency capacitor as claimed in claim 1, wherein the lamellar boron nitride is prepared by the following method:
step A1: mixing boron nitride micro powder and potassium permanganate, heating to 180-200 ℃ in the air atmosphere, roasting for 2-3h, transferring into dilute sulfuric acid for quenching after roasting, centrifugally separating, washing the lower-layer precipitate with water for several times, and preparing oxidation slag;
step A2: mixing ethylene amine and isopropanol to prepare stripping liquid, adding oxidation slag, mixing, ultrasonically stripping at 55kHz for 3-5h, standing for 30min, taking supernatant, dropwise adding hydrochloric acid to adjust pH value to 6, centrifuging, taking the lower layer precipitate, and vacuum drying to obtain lamellar boron nitride.
5. The preparation method of the heat-conducting diaphragm for the high-frequency capacitor as claimed in claim 4, wherein the mass ratio of the boron nitride micro powder to the potassium permanganate is 10:0.6-0.8, the mode particle size of the boron nitride micro powder is 2 μm, and the mass fraction of the dilute sulfuric acid is 10%.
6. The method for preparing a heat-conducting diaphragm for a high-frequency capacitor as claimed in claim 4, wherein the amount ratio of ethylene amine to isopropyl alcohol is 7.5-9g:1L, and the concentration of the oxidation slag in the stripping liquid is 50-80g/L.
7. The method of claim 1, wherein the branched boron nitride is prepared by the following steps:
step B1: mixing boric acid and melamine, adding an ethanol solution, heating, stirring and mixing, then cooling to separate out floccules, centrifugally separating out the floccules, and drying in vacuum to prepare a batch mixture;
and step B2: introducing nitrogen into a well type crucible furnace, flatly spreading the batch in a crucible, heating to 1200-1300 ℃, keeping the temperature and calcining for 5-7h, cooling, and taking a calcined product to prepare a boron nitride master batch;
and step B3: and (3) carrying out circulating wet grinding on the boron nitride master batch and water, adding a silane coupling agent KH550 into the slurry, stirring and mixing overnight, and carrying out spray drying to prepare the branched boron nitride.
8. The method for preparing the heat-conducting diaphragm for the high-frequency capacitor as claimed in claim 7, wherein the mass ratio of the boric acid to the melamine is 2.6-2.8:1-1.2.
9. The heat-conducting membrane prepared by the method according to any one of claims 1 to 8, wherein the heat-conducting membrane comprises 80 to 100 parts by weight of modified base adhesive, 1.2 to 2.5 parts by weight of branched boron nitride and 1 to 3 parts by weight of leveling agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211374582.0A CN115547691A (en) | 2022-11-04 | 2022-11-04 | Heat-conducting diaphragm for high-frequency capacitor and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211374582.0A CN115547691A (en) | 2022-11-04 | 2022-11-04 | Heat-conducting diaphragm for high-frequency capacitor and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN115547691A true CN115547691A (en) | 2022-12-30 |
Family
ID=84720882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211374582.0A Pending CN115547691A (en) | 2022-11-04 | 2022-11-04 | Heat-conducting diaphragm for high-frequency capacitor and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115547691A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116535139A (en) * | 2023-03-18 | 2023-08-04 | 嘉兴市韶华塑胶新材料股份有限公司 | Heat-conducting high-temperature-resistant balanced cement and preparation method thereof |
Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5700517A (en) * | 1993-11-26 | 1997-12-23 | Commissariat A L'energie Atomique | Process for the densification of a porous structure by boron nitride |
CN102070899A (en) * | 2010-12-30 | 2011-05-25 | 广东银禧科技股份有限公司 | Insulating and heat-conducting polyamide composite material and preparation method thereof |
JP2013194223A (en) * | 2012-03-22 | 2013-09-30 | Mitsubishi Chemicals Corp | Heat conductive material |
CN105255183A (en) * | 2015-09-16 | 2016-01-20 | 蚌埠高华电子股份有限公司 | Magnesium oxide whisker-nanometer boron nitride filling-modified PPS/PBT composite thermal conductive plastic for LEDs and preparation method thereof |
CN106084219A (en) * | 2016-06-02 | 2016-11-09 | 黑龙江科技大学 | A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film |
CN106397934A (en) * | 2016-10-18 | 2017-02-15 | 安徽福日光电科技有限公司 | Heat-conduction thermal-insulation reinforced composite cable material prepared via adding of modified boron nitride silicone rubber |
CN107629458A (en) * | 2017-08-21 | 2018-01-26 | 潘明华 | A kind of preparation method of high heat conduction composite heat interfacial material |
CN107881651A (en) * | 2017-11-03 | 2018-04-06 | 上海电力学院 | Suitable for the high heat conduction electrostatic spinning film and preparation method and application of dye separation |
CN107987389A (en) * | 2017-12-19 | 2018-05-04 | 会通新材料股份有限公司 | Polypropylene material of the purposes of modified boron nitride filler parent granule reinforced polypropylene material and modified boron nitride and preparation method thereof |
CN109337596A (en) * | 2018-08-17 | 2019-02-15 | 佛山市森昂生物科技有限公司 | A kind of preparation method of the thermally conductive compound cutan of EVA |
CN110305302A (en) * | 2019-06-27 | 2019-10-08 | 福建工程学院 | A kind of preparation method of In Situ Compatibilization polyester/boron nitride composite |
CN110718659A (en) * | 2019-10-21 | 2020-01-21 | 重庆云天化纽米科技股份有限公司 | Boron nitride coated battery separator and method of making same |
CN110734644A (en) * | 2019-06-24 | 2020-01-31 | 上海大学 | heat-conducting insulating boron nitride polymer composite material and preparation method thereof |
CN112552604A (en) * | 2020-12-09 | 2021-03-26 | 哈尔滨理工大学 | Heat-conducting and insulating polypropylene composite material and preparation method and application thereof |
CN112549700A (en) * | 2019-09-25 | 2021-03-26 | 深圳大学 | Metal-polymer composite material and preparation method and application thereof |
CN113583361A (en) * | 2021-07-30 | 2021-11-02 | 东莞市港鑫实业有限公司 | Heat-conducting polyvinyl chloride and preparation method thereof |
CN114395193A (en) * | 2022-03-04 | 2022-04-26 | 安徽飞达电气科技有限公司 | Polypropylene film and preparation method thereof |
CN114427145A (en) * | 2022-01-24 | 2022-05-03 | 江苏斯迪克新材料科技股份有限公司 | Heat-conducting polymer composite material and preparation method thereof |
CN114456487A (en) * | 2021-12-27 | 2022-05-10 | 国家能源集团宁夏煤业有限责任公司 | Polypropylene composition and application thereof |
CN114752129A (en) * | 2022-04-27 | 2022-07-15 | 安徽超星新材料科技有限公司 | HDPE-based heat-conducting composite material and preparation method and application thereof |
-
2022
- 2022-11-04 CN CN202211374582.0A patent/CN115547691A/en active Pending
Patent Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5700517A (en) * | 1993-11-26 | 1997-12-23 | Commissariat A L'energie Atomique | Process for the densification of a porous structure by boron nitride |
CN102070899A (en) * | 2010-12-30 | 2011-05-25 | 广东银禧科技股份有限公司 | Insulating and heat-conducting polyamide composite material and preparation method thereof |
JP2013194223A (en) * | 2012-03-22 | 2013-09-30 | Mitsubishi Chemicals Corp | Heat conductive material |
CN105255183A (en) * | 2015-09-16 | 2016-01-20 | 蚌埠高华电子股份有限公司 | Magnesium oxide whisker-nanometer boron nitride filling-modified PPS/PBT composite thermal conductive plastic for LEDs and preparation method thereof |
CN106084219A (en) * | 2016-06-02 | 2016-11-09 | 黑龙江科技大学 | A kind of preparation method of high-performance polyimide/ultrathin boron nitride laminated film |
CN106397934A (en) * | 2016-10-18 | 2017-02-15 | 安徽福日光电科技有限公司 | Heat-conduction thermal-insulation reinforced composite cable material prepared via adding of modified boron nitride silicone rubber |
CN107629458A (en) * | 2017-08-21 | 2018-01-26 | 潘明华 | A kind of preparation method of high heat conduction composite heat interfacial material |
CN107881651A (en) * | 2017-11-03 | 2018-04-06 | 上海电力学院 | Suitable for the high heat conduction electrostatic spinning film and preparation method and application of dye separation |
CN107987389A (en) * | 2017-12-19 | 2018-05-04 | 会通新材料股份有限公司 | Polypropylene material of the purposes of modified boron nitride filler parent granule reinforced polypropylene material and modified boron nitride and preparation method thereof |
CN109337596A (en) * | 2018-08-17 | 2019-02-15 | 佛山市森昂生物科技有限公司 | A kind of preparation method of the thermally conductive compound cutan of EVA |
CN110734644A (en) * | 2019-06-24 | 2020-01-31 | 上海大学 | heat-conducting insulating boron nitride polymer composite material and preparation method thereof |
CN110305302A (en) * | 2019-06-27 | 2019-10-08 | 福建工程学院 | A kind of preparation method of In Situ Compatibilization polyester/boron nitride composite |
CN112549700A (en) * | 2019-09-25 | 2021-03-26 | 深圳大学 | Metal-polymer composite material and preparation method and application thereof |
CN110718659A (en) * | 2019-10-21 | 2020-01-21 | 重庆云天化纽米科技股份有限公司 | Boron nitride coated battery separator and method of making same |
CN112552604A (en) * | 2020-12-09 | 2021-03-26 | 哈尔滨理工大学 | Heat-conducting and insulating polypropylene composite material and preparation method and application thereof |
CN113583361A (en) * | 2021-07-30 | 2021-11-02 | 东莞市港鑫实业有限公司 | Heat-conducting polyvinyl chloride and preparation method thereof |
CN114456487A (en) * | 2021-12-27 | 2022-05-10 | 国家能源集团宁夏煤业有限责任公司 | Polypropylene composition and application thereof |
CN114427145A (en) * | 2022-01-24 | 2022-05-03 | 江苏斯迪克新材料科技股份有限公司 | Heat-conducting polymer composite material and preparation method thereof |
CN114395193A (en) * | 2022-03-04 | 2022-04-26 | 安徽飞达电气科技有限公司 | Polypropylene film and preparation method thereof |
CN114752129A (en) * | 2022-04-27 | 2022-07-15 | 安徽超星新材料科技有限公司 | HDPE-based heat-conducting composite material and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
张冬丽: ""导热/介电聚合物基复合材料结构与性能研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 02, 15 February 2019 (2019-02-15), pages 020 - 26 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116535139A (en) * | 2023-03-18 | 2023-08-04 | 嘉兴市韶华塑胶新材料股份有限公司 | Heat-conducting high-temperature-resistant balanced cement and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2023274068A9 (en) | Modified boron nitride, composite material containing same, preparation method therefor, and application thereof | |
CN107418204B (en) | Preparation method of graphene @ calcium copper titanate-polybenzoxazole three-phase composite film | |
CN115547691A (en) | Heat-conducting diaphragm for high-frequency capacitor and preparation method thereof | |
TW440544B (en) | Electroconductive composition | |
CN106366409B (en) | A kind of ultra-high molecular weight polyethylene/graphite alkene/nickel composite material and preparation method | |
CN109399965A (en) | A kind of high intensity toughening type modified glass-fiber and preparation method thereof | |
CN107233852A (en) | A kind of preparation method of magnetic self-repairing microcapsule | |
CN111592738A (en) | EP/h-BN/MWCNTs @ Al2O3Heat-conducting, insulating and heat-conducting composite material and preparation method thereof | |
CN109402765B (en) | Heat-storage warm-keeping chinlon 6 staple fiber and preparation method thereof | |
CN114015231B (en) | Polyimide film with high heat conductivity and preparation method thereof | |
CN105837772B (en) | The preparation method of poly- melamine-formaldehyde polymer microballoon three-dimensional template material | |
CN103214674B (en) | Method for efficiently producing an organic silicone resin microsphere | |
CN114409939B (en) | Preparation method of polyimide coated magnesium oxide/polypropylene nano dielectric film | |
CN116021855A (en) | Dielectric composite film with high energy storage density, preparation method and application | |
CN110627411B (en) | Ceramic slurry for high-temperature-resistant lithium ion battery diaphragm and application thereof | |
CN111698797B (en) | Preparation method of far infrared electric heating film | |
CN114014326A (en) | White carbon black modification method and modified white carbon black | |
CN117089116B (en) | Sodium polyol heat-conducting filler modifier, modified heat-conducting filler and polyurethane heat-conducting adhesive | |
CN115181324A (en) | Sodium bicarbonate microcapsule and preparation method thereof | |
CN105297183A (en) | Preparation method of inorganic porous nanometer fiber | |
CN112795122A (en) | Nano powder-based heat insulation material and preparation method thereof | |
CN111205579A (en) | High-efficiency high-temperature-resistant aluminum nitride/polymer composite material and preparation method thereof | |
CN111286217A (en) | Cobalt blue sepiolite nano composite pigment, preparation method and application thereof | |
CN113637227B (en) | Phthalonitrile-based composite material and preparation method and application thereof | |
CN110010822A (en) | A kind of preparation method of rail traffic cadmium-nickel accumulator dedicated diaphragm |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |