CN113511821A - Basalt fiber impregnating compound for electronic fabric and preparation method thereof - Google Patents
Basalt fiber impregnating compound for electronic fabric and preparation method thereof Download PDFInfo
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- CN113511821A CN113511821A CN202110881208.9A CN202110881208A CN113511821A CN 113511821 A CN113511821 A CN 113511821A CN 202110881208 A CN202110881208 A CN 202110881208A CN 113511821 A CN113511821 A CN 113511821A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/465—Coatings containing composite materials
- C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
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Abstract
The invention relates to the technical field of basalt fiber preparation, in particular to a basalt fiber impregnating compound for electronic fabrics and a preparation method thereof, wherein the basalt fiber impregnating compound comprises the following components, by mass, 6-10% of a film-forming agent, 1.0-2.5% of a lubricant, 0.2-1% of an antistatic agent, 0.2-1.5% of a silane coupling agent, 30-50% of double-layer microcapsule particles and the balance of water; the film forming agent comprises, by mass, 5-10% of waterborne polyurethane, 5-10% of waterborne epoxy resin, 0.5-2% of boron trifluoride diethyl etherate, 10-20% of PEG-400, and the balance of water; the double-layer microcapsule particle sequentially comprises cyclodextrin, a curing agent, an organic silicon resin and methyl cellulose mixture and epoxy resin from outside to inside. The cyclodextrin, the waterborne polyurethane and the waterborne epoxy resin form a three-dimensional network structure, and the waterborne polyurethane and the epoxy resin in the impregnating compound form a film on the surface of the basalt fiber, so that the bonding strength of the microcapsule particles and the basalt fiber is improved.
Description
Technical Field
The invention relates to the technical field of basalt fiber preparation, in particular to a basalt fiber impregnating compound for electronic fabrics and a preparation method thereof.
Background
The basalt fiber is an inorganic fiber with high strength, high temperature resistance and corrosion resistance, and has wide application in the fields of aerospace, automobiles, buildings, electronics and the like. The composite material is mainly applied to the electronic field and is used as a reinforced material of a copper clad laminate, namely, basalt fiber cloth is soaked with resin and then coated with copper foil to prepare a plate for manufacturing a circuit board; or the wave-absorbing material is coated on the basalt fiber cloth to shield electromagnetic waves of various electronic devices.
During the drawing process of the basalt fiber, an impregnating compound is required to be used to improve the drawing performance, reduce hairiness, improve the fiber strength and the like, and for the basalt fiber in different application directions, the impregnating compound is required to be selected and matched. For the impregnating compound for electronic fabrics, the coated fibers need to have good spinning performances such as wire drawing, twisting, plying, weaving and the like, so that the impregnating compound needs to have certain affinity; patent CN108558234A discloses a glass fiber impregnating compound for electronic fabrics, which comprises an aqueous epoxy ester emulsion, an epoxy modified polyester emulsion, a silane coupling agent, etc., and the impregnating compound is coated on the surface of a glass fiber, so that when the obtained glass fiber is used for preparing a copper-clad plate, the glass fiber has good compatibility with resin, and also has excellent textile properties, such as improving the problems of adhesion, yarn breakage, hairiness, etc. among yarns, and the obtained fabric also has high mechanical properties. Although the impregnating compound provided by the patent meets the requirements of electronic fabrics, the mechanical properties of the fibers and the fabrics are affected because the impregnating compound is acted by external force in the wire drawing process and the spinning process, cracks and the like are easy to appear on the surfaces of basalt fibers.
In the scheme, melamine-urea-formaldehyde copolymer is coated with epoxy resin to obtain a microcapsule structure, the microcapsule structure is mixed with waterborne polyurethane, the microcapsule structure is loaded on the surface of basalt fiber by taking the waterborne polyurethane as a medium, when the fiber is cracked under external force, the microcapsule structure is cracked, and an epoxy resin core body flows out to repair the cracks, so that the mechanical properties of the fiber in the spinning process and the mechanical properties of fabrics are improved. The scheme of the patent utilizes a microcapsule structure to carry out self-repairing on basalt fibers, but the self-repairing fails because the microcapsule is coated on the surface of the basalt fibers by taking water-based polyurethane as a medium, the bonding force between the microcapsule and the basalt fibers is weak, and the microcapsule is easy to fall off after the wire drawing or spinning process. In the scheme, the water-based polyurethane containing the microcapsule is used for padding treatment of fabrics and is not suitable for infiltration treatment in the basalt fiber drawing process.
Disclosure of Invention
The invention aims to provide a basalt fiber impregnating compound for electronic fabrics and a preparation method thereof, wherein the basalt fiber impregnating compound comprises a film forming agent, a lubricating agent, double-layer microcapsule particles and the like, the wall material of the double-layer microcapsule particles is cyclodextrin, the cyclodextrin, waterborne polyurethane and waterborne epoxy resin form a three-dimensional network structure, and the waterborne polyurethane and the epoxy resin in the impregnating compound form a film on the surface of basalt fibers, so that the bonding strength of the microcapsule particles and the basalt fibers is improved.
The invention is realized by the following technical scheme:
a basalt fiber impregnating compound for electronic fabrics comprises the following components by mass percent,
6 to 10 percent of film forming agent, 1.0 to 2.5 percent of lubricant, 0.2 to 1 percent of antistatic agent, 0.2 to 1.5 percent of silane coupling agent,
30-50% of double-layer microcapsule particles and the balance of water;
the film forming agent comprises, by mass, 5-10% of waterborne polyurethane, 5-10% of waterborne epoxy resin, 0.5-2% of boron trifluoride diethyl etherate, 10-20% of PEG-400, and the balance of water;
the double-layer microcapsule particle sequentially comprises cyclodextrin, a curing agent, an organic silicon resin and methyl cellulose mixture and epoxy resin from outside to inside.
In the invention, the impregnating compound is added with double-layer microcapsule particles, so that when cracks appear on the surface of the basalt fiber, the surface of the basalt fiber can be self-repaired, the cracks can be repaired in time, and the mechanical property of the basalt fiber is improved. The basalt fiber prepared by the impregnating compound has good textile performance, and the fiber cloth obtained by spinning can be directly used for preparing a copper-clad laminate without removing the impregnating compound at high temperature.
Further, the double-layer microcapsule particle comprises, by mass, 20-30% of cyclodextrin, 10-20% of a curing agent, 10-20% of a silicone resin, 10-20% of methylcellulose and 30-40% of an epoxy resin.
Further comprises the following components in percentage by mass,
6-8% of film forming agent, 1.5-2% of lubricant, 0.5-1% of antistatic agent, 0.5-1% of silane coupling agent, 30-40% of microcapsule particles and the balance of water;
the film forming agent comprises 10% of waterborne polyurethane, 10% of waterborne epoxy resin, 1% of boron trifluoride diethyl etherate, 15% of PEG-40015% and the balance of water by mass percent;
further, the double-layer microcapsule particles comprise, by mass, 30% of cyclodextrin, 15% of a curing agent, 20% of silicone resin, 10% of methyl cellulose and 25% of epoxy resin.
Further comprises the following components in percentage by mass,
6% of film forming agent, 1.5-2% of lubricant, 0.5-1% of antistatic agent, 0.5-1% of silane coupling agent, 30% of microcapsule particles and the balance of water;
the film forming agent comprises, by mass, 5% of waterborne polyurethane, 10% of waterborne epoxy resin, 2% of boron trifluoride diethyl etherate, 20% of PEG-40020% and the balance of water;
the double-layer microcapsule particle comprises, by mass, 30% of cyclodextrin, 15% of a curing agent, 10% of an organic silicon resin, 20% of methyl cellulose and 25% of an epoxy resin.
Further, the particle size of the double-layer microcapsule particles is 100-200 μm.
Further, the lubricant is a mixture of polyethylene glycol and fatty acid quaternary ammonium salt, wherein the mass ratio of the polyethylene glycol to the fatty acid quaternary ammonium salt is 1: 2.
The invention also aims to provide a preparation method of the basalt fiber impregnating compound for the electronic fabric, which comprises the following steps,
s1 dissolving methyl cellulose in water of 80-90 ℃, simultaneously adding organic silicon resin into the water, stirring uniformly, cooling to room temperature, adding an emulsifier, and mixing uniformly;
s2, mixing the epoxy resin, the emulsifier and the diluent, and carrying out an emulsification reaction and a defoaming treatment;
s3, dropwise adding the mixture prepared in the step S2 into the mixture prepared in the step S1, simultaneously carrying out emulsification reaction, adjusting the pH value of the mixture after dropwise adding, and solidifying and drying to obtain primary microcapsule particles;
s4, mixing a dispersing agent and a curing agent to prepare a curing agent suspension, adding the primary microcapsule particles prepared in the step S3 into the curing agent suspension, and curing and drying to obtain secondary microcapsule particles;
s5 adding cyclodextrin into water, stirring uniformly, and adding the secondary microcapsule particles prepared in the step S4 while stirring;
s6, uniformly mixing the film-forming agent, the lubricant, the antistatic agent and the silane coupling agent according to the proportion, then adding the mixture into the system in the step S5, grinding the mixture in a sand mill, and then filtering the mixture to obtain the impregnating compound.
Further, in the step S3, the curing temperature is 50 to 70 ℃, and the drying temperature is 30 to 40 ℃. In step S3, dropping an epoxy resin core material into a wall material of methylcellulose and silicone resin to form a microcapsule structure, wherein the methylcellulose is subject to thermal gelation at 50-70 ℃, during the thermal gelation, part of the silicone resin is added into the thermal gelation, and then drying is carried out at 30-40 ℃, the methylcellulose is cooled and melted, and the moisture is evaporated, the methylcellulose is formed into a film, the silicone resin is encapsulated in the methylcellulose film, and a certain pore structure is formed in the film along with the evaporation of the moisture during the film formation; in step S4, the curing agent is loaded on the surface of the methylcellulose and the silicone resin, and the pore structure reduces the loading difficulty of the curing agent and improves the loading rate and the loading capacity of the curing agent. And the coating film with the hole structure is easier to break when being subjected to external force, so that the curing agent and the epoxy resin in the microcapsule structure can flow out, and the surface cracks of the basalt fibers are repaired.
Further, in the step S4, the curing temperature is 30-40 ℃, and the drying temperature is 50-70 DEG C
The technical scheme of the invention at least has the following advantages and beneficial effects:
the impregnating compound comprises a film forming agent, double-layer microcapsule particles and the like, wherein the film forming agent contains waterborne polyurethane and waterborne epoxy resin, the wall material of the double-layer microcapsule particles is cyclodextrin, the waterborne polyurethane and the waterborne epoxy resin form a three-dimensional network structure, and the waterborne polyurethane and the epoxy resin in the impregnating compound form a film on the surface of basalt fibers, so that the bonding strength of the microcapsule particles and the basalt fibers is improved, and the microcapsules are not easy to fall off in the spinning process.
In the invention, double-layer microcapsule particles are loaded on the surface of basalt fiber, and in the process of drawing or spinning, the basalt fiber is acted by external force to cause cracks on the surface of the fiber, because the cyclodextrin of the outermost layer wall material of the microcapsule, polyurethane and epoxy resin in a film forming agent form a three-dimensional network structure, when the crack occurs on the surface of the fiber, the crack can extend to the surface of the microcapsule through a film, so that the structure of the microcapsule is broken, a curing agent and the epoxy resin in an inner layer flow out, and the epoxy resin is cured into a film on the surface of the fiber under the action of the curing agent to play a role in repairing the crack, thereby reducing the crack on the surface of the basalt fiber and improving the mechanical property of the basalt fiber or the fabric thereof.
In the invention, the second layer of wall material in the double-layer microcapsule adopts the mixture of organic silicon resin and methyl cellulose, the methyl cellulose is taken as a coating material, a film is formed on the surface of epoxy resin particles, silicon oxygen groups in the organic silicon resin are loaded on the surface of the methyl cellulose, after the double-layer microcapsule structure is broken, the organic silicon resin is mixed with the epoxy resin in the inner layer and is solidified under the action of a curing agent, the cracks on the surface of the basalt fiber are repaired, and the extension of the tissue cracks is repaired, thereby providing the mechanical property of the basalt fiber.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Examples
The impregnating agents of examples 1 to 10 were prepared by selecting the relevant raw materials according to the formulations shown in tables 1 to 3 and by the following preparation methods.
Preparing a sizing agent:
s1 dissolving methyl cellulose in water of 90 +/-2 ℃, simultaneously adding organic silicon resin into the water, stirring uniformly, cooling to room temperature, adding an emulsifier, and mixing uniformly;
s2, mixing the epoxy resin, the emulsifier and the diluent, and carrying out an emulsification reaction and a defoaming treatment;
s3, dropwise adding the mixture prepared in the step S2 into the substance obtained in the step S1, simultaneously carrying out emulsification reaction, adjusting the pH value of the mixture after the dropwise adding is finished, curing at 60 +/-2 ℃, and immediately drying at 30 +/-2 ℃ to obtain primary microcapsule particles;
s4, mixing the dispersing agent, the curing agent and water to prepare a curing agent suspension, and then adding the primary microcapsule particles prepared in the step S3 into the curing agent suspension, curing and drying at 30 +/-2 ℃ to obtain secondary microcapsule particles;
s5 adding cyclodextrin into water, stirring uniformly, and adding the secondary microcapsule particles prepared in the step S4 while stirring;
s6, uniformly mixing the film-forming agent, the lubricant, the antistatic agent and the silane coupling agent according to the proportion, then adding the mixture into the system in the step S5, grinding the mixture in a sand mill, controlling the particle size of the double-layer microcapsule particles to be 200 mu m, and then filtering the mixture to remove large-particle substances to obtain the impregnating compound.
TABLE 1 Components and proportions of film-forming agents
| Film-forming agent 1 | Film-forming agent 2 | Film-forming agent 3 | Film-forming agent 4 | Film-forming agent 5 | Film-forming agent 6 | |
| Aqueous polyurethane | 5 | 6 | 7 | 8 | 9 | 10 |
| Aqueous epoxy resin | 10 | 5 | 5 | 6 | 9 | 10 |
| Boron trifluoride diethyl etherate | 2 | 1 | 0.5 | 0.8 | 1.5 | 1 |
| PEG-400 | 20 | 10 | 12 | 18 | 15 | 15 |
TABLE 2 Components and proportions of the double-layer microcapsule particles
TABLE 3 Components and compounding ratios of impregnating compounds of examples 1-10
In tables 1 to 3 above, the contents of the respective components are mass percentages, and the balance is water. In table 3, the lubricant used is a mixed lubricant, which is a mixture of polyethylene glycol and a fatty acid quaternary ammonium salt in a mass ratio of 1:2, and specifically, the fatty acid quaternary ammonium salt may be a common quaternary ammonium salt such as dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl hydroxyethyl ammonium bromide, and the like.
Comparative examples 1 to 5:
the self-repairing microcapsules prepared in the patent CN110368879A in the example 1 are adopted, and the rest components are respectively the same as those in the examples 1 to 5, so that the sizing agents of the comparative examples 1 to 5 are prepared.
Comparative examples 6 to 8:
the impregnating compound of the comparative examples 6-8 is obtained by using the raw materials of the impregnating compound of the patent CN108558234A in the examples 1-3 and adding the double-layer microcapsule particles prepared in the examples 6-8 into the impregnating compound.
Comparative examples 9 to 10:
the impregnating compound of examples 1-2 of patent CN108558234A was used as the impregnating compound of comparative examples 9-10.
Experimental example:
for the same basalt fiber, the impregnating compounds of examples 1 to 10 and comparative examples 1 to 10 were drawn to prepare corresponding basalt fibers, respectively.
The tensile strength of the basalt fibers of examples 1 to 10 and comparative examples 1 to 10 was measured using a single fiber strength tester, and the results are shown in table 4.
TABLE 4 tensile Strength of basalt fiber for examples 1 to 10 and comparative examples 1 to 10
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Tensile strength | 0.812 | 0.801 | 0.841 | 0.865 | 0.798 |
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | |
| Tensile strength | 0.752 | 0.823 | 0.841 | 0.835 | 0.841 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Tensile strength | 0.688 | 0.684 | 0.701 | 0.692 | 0.648 |
| Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | |
| Tensile strength | 0.641 | 0.652 | 0.576 | 0.562 | 0.572 |
In Table 4, the tensile strength is expressed in N/Tex.
As can be seen from Table 4, the tensile strength of the basalt fiber prepared by the impregnating compounds of examples 1 to 10 is higher than that of the basalt fiber prepared by the comparative examples 1 to 10, because in the examples 1 to 10, the impregnating compounds contain double-layer microcapsule particles, when the fiber is subjected to an external force, the double-layer microcapsule particles loaded on the surface of the fiber are broken, the flowed epoxy resin and the curing agent act, the epoxy resin and the curing agent are cured on the surface of the fiber, the crack on the surface of the fiber is repaired, the crack is prevented from expanding, and the tensile strength of the fiber is further improved.
In comparative examples 1 to 5, the self-repairing microcapsule disclosed in patent CN110368879A is adopted, wherein an epoxy resin is coated by a melamine-urea-formaldehyde copolymer, a curing agent is loaded, and the melamine-urea-formaldehyde copolymer is coated to obtain a self-repairing double-layer microcapsule structure, the self-repairing microcapsule is added into the impregnating compound raw materials of examples 1 to 5 to obtain a corresponding impregnating compound, the impregnating compound of comparative examples 1 to 5 is different from the impregnating compound of examples 1 to 5 in that the microcapsule in comparative examples 1 to 5 is directly loaded on the surface of a film-forming agent or a fiber and does not form a three-dimensional reticular structure, during the process of stretching the fiber, firstly, the microcapsule is easy to fall off, secondly, the microcapsule structure cannot be broken in time, the crack on the surface of the fiber cannot be repaired in time, and further the crack is easy to extend and expand on the surface of the fiber, the tensile strength of the fiber cannot be increased or is increased less. As can be seen from Table 4, the tensile strength of the fibers of comparative examples 1-5 is improved over that of comparative examples 6-10, and the fibers are much lower than those of examples 1-10 when compared to examples 1-10.
Also, in comparative examples 6 to 8, the microcapsules did not form a three-dimensional structure with the film-forming agent, and the tensile strength of the fibers was lower than that of examples 6 to 8.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A basalt fiber impregnating compound for electronic fabrics is characterized in that: comprises the following components in percentage by mass,
6 to 10 percent of film forming agent, 1.0 to 2.5 percent of lubricant, 0.2 to 1 percent of antistatic agent, 0.2 to 1.5 percent of silane coupling agent,
30-50% of double-layer microcapsule particles and the balance of water;
the film forming agent comprises, by mass, 5-10% of waterborne polyurethane, 5-10% of waterborne epoxy resin, 0.5-2% of boron trifluoride diethyl etherate, 10-20% of PEG-400, and the balance of water;
the double-layer microcapsule particle sequentially comprises cyclodextrin, a curing agent, an organic silicon resin and methyl cellulose mixture and epoxy resin from outside to inside.
2. The basalt fiber sizing material for electronic fabrics according to claim 1, wherein: the double-layer microcapsule particle comprises, by mass, 20-30% of cyclodextrin, 10-20% of a curing agent, 10-20% of an organic silicon resin, 10-20% of methyl cellulose and 30-40% of an epoxy resin.
3. The basalt fiber sizing material for electronic fabrics according to claim 1, wherein: comprises the following components in percentage by mass,
6 to 8 percent of film forming agent, 1.5 to 2 percent of lubricant, 0.5 to 1 percent of antistatic agent, 0.5 to 1 percent of silane coupling agent,
30-40% of microcapsule particles and the balance of water;
the film forming agent comprises, by mass, 10% of waterborne polyurethane, 10% of waterborne epoxy resin, 1% of boron trifluoride diethyl etherate, 15% of PEG-40015% and the balance of water.
4. A basalt fiber sizing agent for electronic textile as claimed in claim 3, wherein: the double-layer microcapsule particle comprises, by mass, 30% of cyclodextrin, 15% of a curing agent, 20% of silicone resin, 10% of methyl cellulose and 25% of epoxy resin.
5. The basalt fiber sizing material for electronic fabrics according to claim 1, wherein: comprises the following components in percentage by mass,
6 percent of film forming agent, 1.5 to 2 percent of lubricant, 0.5 to 1 percent of antistatic agent, 0.5 to 1 percent of silane coupling agent,
30% of microcapsule particles and the balance of water;
the film forming agent comprises, by mass, 5% of waterborne polyurethane, 10% of waterborne epoxy resin, 2% of boron trifluoride diethyl etherate, 20% of PEG-40020% and the balance of water;
the double-layer microcapsule particle comprises, by mass, 30% of cyclodextrin, 15% of a curing agent, 10% of an organic silicon resin, 20% of methyl cellulose and 25% of an epoxy resin.
6. The basalt fiber sizing material for electronic fabrics according to claim 1, wherein: the particle size of the double-layer microcapsule particles is 100-200 μm.
7. The basalt fiber sizing material for electronic fabrics according to claim 1, wherein: the lubricant is a mixture of polyethylene glycol and fatty acid quaternary ammonium salt, wherein the mass ratio of the polyethylene glycol to the fatty acid quaternary ammonium salt is 1: 2.
8. A method for preparing a basalt fiber sizing agent for an electronic textile as claimed in any one of claims 1 to 5, wherein: comprises the following steps of (a) carrying out,
s1 dissolving methyl cellulose in water of 80-90 ℃, simultaneously adding organic silicon resin into the water, stirring uniformly, cooling to room temperature, adding an emulsifier, and mixing uniformly;
s2, mixing the epoxy resin, the emulsifier and the diluent, and carrying out an emulsification reaction and a defoaming treatment;
s3, dropwise adding the mixture prepared in the step S2 into the mixture prepared in the step S1, simultaneously carrying out emulsification reaction, adjusting the pH value of the mixture after dropwise adding, and solidifying and drying to obtain primary microcapsule particles;
s4, mixing a dispersing agent and a curing agent to prepare a curing agent suspension, adding the primary microcapsule particles prepared in the step S3 into the curing agent suspension, and curing and drying to obtain secondary microcapsule particles;
s5 adding cyclodextrin into water, stirring uniformly, and adding the secondary microcapsule particles prepared in the step S4 while stirring;
s6, uniformly mixing the film-forming agent, the lubricant, the antistatic agent and the silane coupling agent according to the proportion, then adding the mixture into the system in the step S5, grinding the mixture in a sand mill, and then filtering the mixture to obtain the impregnating compound.
9. The basalt fiber sizing material for electronic fabrics according to claim 1, wherein: in the step S3, the curing temperature is 50-70 ℃, and the drying temperature is 30-40 ℃.
10. The basalt fiber sizing material for electronic fabrics according to claim 1, wherein: in the step S4, the curing temperature is 30-40 ℃, and the drying temperature is 50-70 ℃.
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| CN114934342A (en) * | 2022-04-27 | 2022-08-23 | 复旦大学 | Self-connection fabric electronic circuit and preparation and application thereof |
| CN114934342B (en) * | 2022-04-27 | 2023-07-04 | 复旦大学 | Self-connecting fabric electronic circuit and preparation and application thereof |
| CN117342804A (en) * | 2023-09-20 | 2024-01-05 | 海南电网有限责任公司电力科学研究院 | Impregnating compound for improving high-temperature and high-humidity resistance of basalt fiber composite material and preparation method thereof |
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| CN113511821B (en) | 2022-10-25 |
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