CN107640913A - A kind of preparation method and applications of Basalt fiber surface modification coating - Google Patents
A kind of preparation method and applications of Basalt fiber surface modification coating Download PDFInfo
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- CN107640913A CN107640913A CN201710724783.1A CN201710724783A CN107640913A CN 107640913 A CN107640913 A CN 107640913A CN 201710724783 A CN201710724783 A CN 201710724783A CN 107640913 A CN107640913 A CN 107640913A
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- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 115
- 238000012986 modification Methods 0.000 title claims abstract description 30
- 230000004048 modification Effects 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 39
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 22
- 238000005530 etching Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000005543 nano-size silicon particle Substances 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 238000001994 activation Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000006179 pH buffering agent Substances 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 1
- 239000012876 carrier material Substances 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000000813 microbial effect Effects 0.000 abstract description 4
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 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 abstract 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- 230000002459 sustained effect Effects 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 244000005700 microbiome Species 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002715 modification method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 238000010170 biological method Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910005084 FexOy Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 premium grade pure Chemical compound 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VLCQZHSMCYCDJL-UHFFFAOYSA-N tribenuron methyl Chemical compound COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)N(C)C1=NC(C)=NC(OC)=N1 VLCQZHSMCYCDJL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention belongs to inorfil technical field of modification, is related to Basalt fiber surface modification, more particularly to the preparation method of Basalt fiber surface modification coating.Silane coupler, surfactant solution, polyacrylamide solution and 1/3 aqueous epoxy resins, back flow reaction are first added in proper amount of nano silica dispersions；Then remaining aqueous epoxy resins and initiator solution are added dropwise in heating simultaneously, are made after alkaline system sustained response.The invention also discloses obtained Basalt fiber surface modification coating application, first with dense H2SO4/H2O2Mixed solution activates to basalt fibre surface group, then with hydrochloric acid, is then infiltrated and be grafted in the coating, be finally dried to constant weight.Coating emulsion prepared by the present invention is free of any organic solvent, and green, operating technology is convenient and simple, strong applicability, stable performance can fast and effeciently treated basalt fiber, its surface roughness is substantially increased, can be applied to microbial membrane carrier Material Field.
Description
Technical Field
The invention belongs to the technical field of inorganic fiber modification, relates to a method for surface modification of basalt fiber, and particularly relates to a preparation method and application of a basalt fiber surface modified coating.
Background
At present, the water resource shortage and the water pollution problem coexist in China, the surface water pollution condition is still severe, the water resource is protected, the water environment is improved, and the sewage/wastewater treatment efficiency is improved. The conventional process for sewage/wastewater treatment covers physical, chemical and biological methods, and most of the sewage/wastewater treatment in China is mainly based on the biological method. Among the sewage/wastewater treatment processes by biological methods, the biofilm process is the most widely used technology. The biomembrane waste water treatment technology is a technology for fixing microorganisms on a carrier to form a biomembrane to degrade pollutants in waste water, both the growth and the propagation of the biomembrane are carried out by using a carrier material as a place, the carrier material is the core of the biomembrane water treatment technology, the performance of the carrier material affects the species, the quantity, the activity and the mass transfer of metabolites of the microorganisms in a biological pond, and the performance of the carrier material also directly influences the efficiency of the biomembrane water treatment technology. Therefore, proper selection of the carrier is very important to improve the effect of wastewater treatment.
The requirements of the biofilm carrier material are: easy film forming and no toxic action; can provide large specific surface area to increase the biological attachment amount; low cost and easily available materials. Currently, biofilm carrier materials can be divided into organic carriers and inorganic carriers. Organic carriers such as PVC, PE, PS, PP, various resins, plastics, soft or semi-soft fibers and the like are not environment-friendly in production process, have more pollutant discharge, are easy to have the phenomena of aging, broken filaments and the like in waste water, influence the service life, are difficult to regenerate and are easy to cause secondary pollution to the environment.
The Basalt Fiber (BF) is a high-performance inorganic silicate fiber, is formed by melting basalt ore at 1450-1500 ℃, and then rapidly drawing through a platinum-rhodium alloy wire drawing bushing plate, and mainly comprises SiO2、Al2O3、CaO、FexOy、MgO、TiO2、Na2O、K2O, etc., and the diameter is generally 7 to 13 μm. The BF is generated without discharging boron or alkali metal oxide, and can be obtained without introducing any new component, so the preparation process of the basalt fiber does not cause adverse effects on environment and human beings, and the basalt fiber is a 100 percent pure natural green industrial material. The defects that the traditional materials consume a large amount of energy and resources in the production, use and waste processes, cause environmental pollution and the like are avoided.
The basalt fiber has excellent mechanical properties, has higher tensile strength and elastic modulus, even higher than those of glass fiber and aramid fiber, and has equivalent tensile strength to carbon fiber. In addition, the basalt fiber has outstanding chemical stability, the basalt ore belongs to silicate ore, and the basalt fiber has natural compatibility with silicate and has high acid and alkali resistance. Therefore, the basalt fiber has the strength and the acid and alkali resistance which can meet the requirements of the biomembrane carrier material, and is an ideal biomembrane carrier material; however, the basalt fiber has a smooth surface, and the generally commercially available basalt fiber has poor surface hydrophilicity, which affects the attachment of microorganisms and reduces the mass transfer efficiency of a biofilm, so the basalt fiber surface needs to be treated before being applied to a biofilm carrier material, and the surface performance of the basalt fiber is improved.
The fiber surface modification method mainly comprises a surface oxidation modification method, an acid-base etching method, a plasma modification method, a surface coating modification method and the like. Currently, researchers in various countries around the world are carrying out research work on the aspect of fiber surface modification technology with great enthusiasm, and the main achievements obtained at present are as follows:
[1]Surface modification and characterizations of basalt fibers withnon-thermal plasma,Surface&coatings Technology,2007,201(15):6565-2OH, etc.). However, the plasma modification technology requires high equipment requirement and high cost, the plasma modification strength is not large, and the research work is scattered, so the application of the plasma modification technology is limited.
[2] The acid etching has influence on the adsorption quantity of the coupling agent on the surface of the basalt fiber and the mechanical property of the fiber/epoxy resin composite material, which is reported in the composite material science, 2014, 31(4): 888-.
[3]Strengthening of basalt fibers with nano-SiO2Epoxy composition, Materials and Design,2011, (32):4180-2The composite material is used as a basalt fiber coating, and the result shows that the modified basalt fiber can effectively improve the mechanical property and the surface roughness of the basalt fiber.
In the research of the basalt fiber surface modification technology, the research focuses on the mechanical properties of the basalt fiber before and after modification, and the research on the improvement of the hydrophilicity of the basalt fiber surface is not reported at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention discloses a method for modifying the surface of basalt fiber, which is used for preparing polyacrylamide/waterborne epoxy resin/nano SiO2The composite emulsion is used as a surface coating of basalt fiber, and the modified basalt fiber is obtained through the processes of activation, etching, infiltration, grafting, drying and the like, so that the surface hydrophilicity of the basalt fiber is improved, the surface biological affinity of the basalt fiber is improved, and the requirement of the basalt fiber as a biological membrane carrier material is met.
One purpose of the invention is to disclose a preparation method of a basalt fiber surface modified coating, which comprises the following steps:
A. stirring and mixing tetraethyl orthosilicate (TEOS), deionized water and absolute ethyl alcohol according to the mass ratio of 1.18:4.00:6.31, adjusting the pH to be about 3-4 by hydrochloric acid, and continuously stirring for 3 hours at 30 ℃ to obtain a nano silicon dioxide dispersion liquid;
B. adding a proper amount of nano-silica dispersion into a reaction container equipped with a mechanical stirrer, a reflux condenser tube and a thermometer, adding a silane coupling agent, a surfactant solution, a polyacrylamide solution and 1/3 aqueous epoxy resin into the mixed solution, and stirring until the mixture is uniform, wherein the reflux reaction temperature is 40-50 ℃, and preferably 45 ℃;
C. raising the reaction temperature to 65-80 ℃, simultaneously dropwise adding the rest aqueous epoxy resin and the rest initiator solution, adjusting the pH value to 12-14 by using a pH buffering agent, and continuously stirring for 3-5 h, wherein the reaction temperature is preferably 75 ℃, the pH value is preferably 13, the reaction time is preferably 4h, and the pH buffering agent is one of potassium hydroxide or sodium hydroxide, preferably potassium hydroxide;
D. after the reaction is completed, cooling to room temperature, dropwise adding hydrochloric acid to adjust the pH value to 7-8, and filtering to obtain polyacrylamide/waterborne epoxy resin/nano SiO2Composite emulsion, namely a basalt fiber surface modified coating.
Wherein the mass percentages of all substances participating in the reaction are as follows:
1.17-5.88%, preferably 3.52% of nano silicon dioxide dispersion liquid;
0.09-0.47% of silane coupling agent, preferably 0.28%;
0.06-0.2% of surfactant, preferably 0.15%;
0.12-0.59% of polyacrylamide, preferably 0.35%;
2.18-31.57% of water-based epoxy resin, preferably 19.14%;
0.07-0.12% of initiator, preferably 0.09%;
61.17-96.31% of deionized water, preferably 76.47%.
Further, the silane coupling agent is one or two of gamma-aminopropyltriethoxysilane (KH-550), gamma-glycidoxypropyltrimethoxysilane (KH-560) and gamma-methacryloxypropyltrimethoxysilane (KH-570), preferably gamma-aminopropyltriethoxysilane (KH-550);
the waterborne epoxy resin is bisphenol A type epoxy resin, preferably E-51;
the surfactant is one of quaternary ammonium salt surfactant, cetyl trimethyl ammonium chloride (HTMAC) and octadecyl trimethyl ammonium chloride (ODAC), preferably cetyl trimethyl ammonium chloride (HTMAC);
the initiator is one of potassium persulfate (KPS) and Ammonium Persulfate (APS), and preferably potassium persulfate (KPS).
The invention also discloses an application of the prepared basalt fiber surface modified coating, which comprises the following steps:
A. basalt fiber surface groupsAnd (3) activation: by using concentrated H2SO4/H2O2Mixed solution (H)2SO4/H2O2The volume ratio is 7:3) to activate the surface of the fiber, so that more silanol groups are generated on the surface of the fiber. The specific operation is to soak the basalt fiber in H2SO4/H2O2Placing the mixed solution in a hydrothermal synthesis reaction kettle at the temperature of 80-120 ℃, wherein the activation time is 0.5-2 h, the preferred temperature is 90 ℃, and the preferred activation time is 1 h;
B. etching basalt fibers: soaking the activated basalt fiber in a hydrochloric acid solution, wherein the concentration of the hydrochloric acid solution is 0.5-2M, preferably 1M, the etching temperature is 30-50 ℃, preferably 40 ℃, and the etching time is 30-90 min, preferably 60 min;
C. infiltration and grafting process: the pretreated basalt fiber surface contains a large amount of silanol groups, the surface roughness is increased by acid etching, and the basalt fiber surface is soaked in polyacrylamide/waterborne epoxy resin/nano SiO2The composite emulsion is prepared by soaking the basalt fiber surface modification coating, silanol groups on the fiber surface are easy to react with a soaking agent, so that organic polymer chains in the composite emulsion are grafted to the fiber surface, in addition, due to the existence of the silane coupling agent, one end of the coupling agent can react with organic components in the soaking agent, and the other end of the coupling agent can generate a Si-O-Si structure with nano silicon dioxide in the soaking agent or silicon dioxide in the basalt fiber, so that the modified basalt fiber is obtained, the soaking time is 60-150 min, preferably 120min, the soaking temperature is 25-60 ℃, and preferably the temperature is 40 ℃;
D. and (3) drying: and taking out the soaked basalt fibers, and drying at 100 ℃ to constant weight.
Tetraethyl orthosilicate, absolute ethyl alcohol, concentrated hydrochloric acid, potassium hydroxide, a silane coupling agent (KH-550, KH-560 or KH-570) and polyacrylamide used in the invention, analytically pure, national pharmaceutical group chemical reagents, Inc.; epoxy resin (E-51), cetyltrimethylammonium chloride (HTMAC) and octadecyltrimethylammonium chloride (ODAC), analytically pure, Shandong Youth chemical science and technology Co., Ltd; potassium persulfate and ammonium persulfate, premium grade pure, cameo chemical reagents ltd, tianjin; the basalt fiber is commercially available, and the science and technology development company of the new material of Jiangsu green grains is limited.
One of the basic requirements of the microbial film carrier material is that the carrier material must have certain biocompatibility, and the static water contact angle and the surface energy of the basalt fiber monofilaments before and after modification are measured. The epoxy resin has excellent adhesive performance because the structure contains amino, ether bond and other polar groups. In addition, polyacrylamide is a linear polymer which is easy to dissolve in water, contains a large number of amide groups, can react with epoxy groups under a strong alkaline condition, is easy for other substances to generate hydrogen bonding, can obviously reduce the hydrophilicity of the aqueous epoxy resin by adding the polyacrylamide, and can improve the roughness of the surface of the basalt fiber by doping nano silicon dioxide. The data show that the polyacrylamide/water-based epoxy resin/nano SiO prepared by the invention2The composite emulsion modified basalt fiber does not destroy the mechanical property of the basalt fiber, can improve the surface hydrophilicity of the basalt fiber, obviously reduces the water contact angle of the fiber, and improves the affinity between the fiber and microorganisms.
Advantageous effects
The modification method of the basalt fiber disclosed by the invention is simple to operate, and the prepared polyacrylamide/water-based epoxy resin/nano SiO2The composite emulsion and the fiber have good compatibility, the materials used for modification are all green and environment-friendly raw materials, the epoxy resin is also water-based epoxy resin, and the impregnating compound does not contain organic solvent, so that the environment and human are not polluted and damaged. In addition, the organic impregnating compound and the inorganic fiber are connected through the silane coupling agent, the surface of the basalt fiber is coated with a layer of organic coating, the hydrophilicity of the fiber is reduced, the dispersibility of the fiber in water is improved, and the modified basalt fiber has certain softness and meets the requirement of the fiber as a microbial carrier material.
Drawings
FIG. 1 is SEM images before and after modification of basalt fiber, wherein a is a microscopic morphology of Basalt Fiber (BF) before modification, and b is a microscopic Morphology of Basalt Fiber (MBF) after modification.
FIG. 2 FTIR patterns before and after modification of basalt fiber.
FIG. 3 is a graph showing the change of water contact angle before and after the basalt fiber is modified.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
(1) Adding 1.18g of TEOS, 40g of deionized water and 63.12g of absolute ethyl alcohol into a 250ml three-neck flask, stirring and mixing uniformly, adjusting the pH to be about 3 by hydrochloric acid, and stirring and reacting for 3 hours at the temperature of 30 ℃ to obtain the nano silicon dioxide dispersion liquid.
(2) 1g of nano-silica dispersion, 0.077g of silane coupling agent KH-550, 0.1g of Polyacrylamide (PAM), 0.051g of hexadecyltrimethylammonium chloride (HTMAC), 0.62g of epoxy resin and 5g of deionized water are sequentially added into a 250mL four-mouth bottle provided with a stirrer and a reflux condenser, and the mixture is fully and uniformly stirred, wherein the reflux reaction temperature is 40 ℃.
(3) Heating the reaction temperature to 65 ℃, simultaneously dropwise adding 1.24g of epoxy resin and 0.06g of APS initiator solution (dissolved in 10g of deionized water), adding NaOH buffer solution, adjusting the pH value to about 12, continuously stirring for 3h, cooling to room temperature after the reaction is complete, adjusting the pH value to 7-8, and obtaining polyacrylamide/aqueous epoxy resin/nano SiO2Composite Emulsion (Emulsion-1). Wherein,in this example, the total amount of all the deionized water was 81.86g (mass ratio: 96.31%, ratio relative to the total mass of all the monomer components in the sizing agent).
(4) Placing basalt fiber in H2SO4/H2O2Mixed solution (H)2SO4/H2O27:3 by volume), and placing the mixture in a hydrothermal synthesis reaction kettle at the temperature of 80 ℃ for 30 min. And soaking the activated basalt fiber in 0.5M hydrochloric acid, wherein the etching temperature is 30 ℃, and the etching time is 30min, so as to obtain the pretreated basalt fiber.
(5) Soaking the pretreated basalt fiber in Emulsion-1 composite Emulsion for 60min at 25 ℃. And after 1 hour, taking out the soaked basalt fiber, placing in a constant-temperature drying oven at 100 ℃ and drying to constant weight to obtain the modified basalt fiber (MBF-1).
Example 2
(1) Adding 1.18g of TEOS, 40g of deionized water and 63.12g of absolute ethyl alcohol into a 250ml three-neck flask, stirring and mixing uniformly, adjusting the pH to be about 3 by hydrochloric acid, and stirring and reacting for 3 hours at the temperature of 30 ℃ to obtain the nano silicon dioxide dispersion liquid.
(2) 2g of nano-silica dispersion, 0.2g of silane coupling agent (KH-560), 0.3g of Polyacrylamide (PAM), 0.1g of cetyltrimethylammonium chloride (HTMAC), 4.53g of epoxy resin and 10g of deionized water are sequentially added into a 250mL four-neck flask provided with a stirrer and a reflux condenser tube, and the mixture is fully and uniformly stirred, wherein the reflux reaction temperature is 45 ℃.
(3) Heating the reaction temperature to 70 ℃, simultaneously dropwise adding 9.06g of epoxy resin and 0.085g of KPS initiator solution (dissolved in 10g of deionized water), adding KOH buffer solution to adjust the pH value to about 13, continuously stirring for 4 hours, cooling to room temperature after the reaction is complete, adjusting the pH value to 7-8, and obtaining polyacrylamide/waterborne epoxy resin/nano SiO 22Composite emulsion (Emuls)ion-2). In this example, the total amount of all the deionized water was 68.72g (mass ratio: 80.85% of the total mass of all the monomer components in the sizing agent).
(4) Placing basalt fiber in H2SO4/H2O2Mixed solution (H)2SO4/H2O27:3 by volume), and the mixture is placed in a hydrothermal synthesis reaction kettle at the temperature of 90 ℃ for activation time of 1 h. And soaking the activated basalt fiber in 2M hydrochloric acid, wherein the etching temperature is 40 ℃, and the etching time is 60min, so as to obtain the pretreated basalt fiber.
(5) Soaking the pretreated basalt fiber in Emulsion-2 composite Emulsion for 120min at 40 ℃. And after 2 hours, taking out the soaked basalt fiber, placing in a constant-temperature drying oven at 100 ℃ and drying to constant weight to obtain the modified basalt fiber (MBF-2).
Example 3
(1) Adding 1.18g of TEOS, 40g of deionized water and 63.12g of absolute ethyl alcohol into a 250ml three-neck flask, stirring and mixing uniformly, adjusting the pH to be about 3 by hydrochloric acid, and stirring and reacting for 3 hours at the temperature of 30 ℃ to obtain the nano silicon dioxide dispersion liquid.
(2) In a 250mL four-necked flask equipped with a stirrer and a reflux condenser, 3g of the nano-silica dispersion, 0.24g of the silane coupling agent (KH-550), 0.3g of the Polyacrylamide (PAM), 0.128g of the cetyltrimethylammonium chloride (HTMAC), 5.42g of the epoxy resin and 10g of the deionized water were sequentially added, and the mixture was sufficiently and uniformly stirred at a reflux reaction temperature of 45 ℃.
(3) Heating the reaction temperature to 75 ℃, simultaneously dropwise adding 10.85g of epoxy resin and 0.077g of initiator solution (dissolved in 10g of deionized water), adding KOH buffer solution to adjust the pH value to about 13, continuously stirring for 4 hours, cooling to room temperature after the reaction is complete, adjusting the pH value to 7-8, and obtaining the polyacrylamide/aqueous epoxy resin/nano SiO2Composite Emulsion (Emulsion-3). In this example, the total amount of all the deionized water was 64.99g (76.47% by mass relative to the total mass of all the monomer components in the sizing agent).
(4) Placing basalt fiber in H2SO4/H2O2Mixed solution (H)2SO4/H2O27:3 by volume), and the mixture is placed in a hydrothermal synthesis reaction kettle at the temperature of 90 ℃ for activation time of 1 h. And soaking the activated basalt fiber in 1M hydrochloric acid, wherein the etching temperature is 40 ℃, and the etching time is 60min, so as to obtain the pretreated basalt fiber.
(5) Soaking the pretreated basalt fiber in Emulsion-3 composite Emulsion for 120min at 40 ℃. And after 2 hours, taking out the soaked basalt fiber, placing in a constant-temperature drying oven at 100 ℃ and drying to constant weight to obtain the modified basalt fiber (MBF-3).
Example 4
(1) Adding 1.18g of TEOS, 40g of deionized water and 63.12g of absolute ethyl alcohol into a 250ml three-neck flask, stirring and mixing uniformly, adjusting the pH to be about 3 by hydrochloric acid, and stirring and reacting for 3 hours at the temperature of 30 ℃ to obtain the nano silicon dioxide dispersion liquid.
(2) 4g of nano-silica dispersion, 0.3g of silane coupling agent (KH-550), 0.4g of Polyacrylamide (PAM), 0.15g of octadecyl trimethyl ammonium chloride (ODAC), 7.15g of epoxy resin and 15g of deionized water are sequentially added into a 250mL four-mouth bottle provided with a stirrer and a reflux condenser, and the mixture is fully and uniformly stirred, wherein the reflux reaction temperature is 50 ℃.
(3) Heating the reaction temperature to 80 ℃, simultaneously dropwise adding 14.31g of epoxy resin and 0.085g of APS initiator solution (dissolved in 15g of deionized water), adding NaOH buffer solution to adjust the pH value to about 14, continuously stirring for 5 hours, cooling to room temperature after the reaction is complete, adjusting the pH value to 7-8, and obtaining the polyacrylamide/waterborne epoxy resin/nano epoxy resinSiO2Composite Emulsion (Emulsion-4). In this example, the total amount of all the deionized water was 58.6g (68.94% by mass, based on the total mass of all the monomer components in the sizing agent).
(4) Placing basalt fiber in H2SO4/H2O2Mixed solution (H)2SO4/H2O27:3 by volume), and the mixture is placed in a hydrothermal synthesis reaction kettle at the temperature of 120 ℃ for activation time of 1.5 h. And soaking the activated basalt fiber in 2M hydrochloric acid, wherein the etching temperature is 50 ℃, and the etching time is 90min, so as to obtain the pretreated basalt fiber.
(5) Soaking the pretreated basalt fiber in Emulsion-4 composite Emulsion for 120min at 50 ℃. And after 2 hours, taking out the soaked basalt fiber, placing in a constant-temperature drying oven at 100 ℃ and drying to constant weight to obtain the modified basalt fiber (MBF-4).
The results of the basalt fiber performance tests before and after modification made in the above examples are shown in table 1.
TABLE 1 basalt fiber Performance test results before and after modification
Example 5
(1) Adding 1.18g of TEOS, 40g of deionized water and 63.12g of absolute ethyl alcohol into a 250ml three-neck flask, stirring and mixing uniformly, adjusting the pH to be about 3 by hydrochloric acid, and stirring and reacting for 3 hours at the temperature of 30 ℃ to obtain the nano silicon dioxide dispersion liquid.
(2) 5g of nano-silica dispersion, 0.4g of silane coupling agent (KH-570), 0.5g of Polyacrylamide (PAM), 0.17g of octadecyl trimethyl ammonium chloride (ODAC), 8.94g of epoxy resin and 15g of deionized water are sequentially added into a 250mL four-necked flask provided with a stirrer and a reflux condenser, and the mixture is fully and uniformly stirred, wherein the reflux reaction temperature is 50 ℃.
(3) Heating the reaction temperature to 80 ℃, simultaneously dropwise adding 17.89g of epoxy resin and 0.102g of APS initiator solution (dissolved in 15g of deionized water), adding KOH buffer solution to adjust the pH value to about 14, continuously stirring for 5 hours, cooling to room temperature after the reaction is complete, adjusting the pH value to 7-8, and obtaining the polyacrylamide/aqueous epoxy resin/nano SiO2Composite Emulsion (Emulsion-5). In this example, the total amount of all the deionized water was 51.99g (61.17% by mass relative to the total mass of all the monomer components in the sizing agent).
(4) Placing basalt fiber in H2SO4/H2O2Mixed solution (H)2SO4/H2O27:3 by volume), and the mixture is placed in a hydrothermal synthesis reaction kettle at the temperature of 120 ℃ for 2 h. And soaking the activated basalt fiber in 1M hydrochloric acid, wherein the etching temperature is 50 ℃, and the etching time is 90min, so as to obtain the pretreated basalt fiber.
(5) Soaking the pretreated basalt fiber in Emulsion-5 composite Emulsion for 150min at 60 ℃. After 2.5 hours, taking out the soaked basalt fiber, placing in a constant-temperature drying oven at 100 ℃ and drying to constant weight to obtain the modified basalt fiber (MBF-5).
The basalt fiber modified by the method has increased surface roughness, a micropore structure appears on the surface, and the method is favorable for the attachment of microorganisms, and the basalt fiber modified in an infrared spectrogram is 1276cm-1A bending vibration peak of-CONH-appears at 3300cm-1Is in the form of-NH2And a large amount of hydrophilic groups appear in a stretching vibration peak, and a contact angle test result also shows that the hydrophilicity is obviously improved, the surface energy is obviously improved, the affinity of microorganisms on the surface of the fiber is improved, and the modified basalt fiber can be applied to the field of microbial membrane carrier materials.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (9)
1. The preparation method of the basalt fiber surface modified coating is characterized by comprising the following steps:
A. tetraethyl orthosilicate TEOS, deionized water and absolute ethyl alcohol are stirred and mixed according to the mass ratio of 1.18:4.00:6.31, the pH value is adjusted to about 3-4 by hydrochloric acid, and the mixture is continuously stirred for 3 hours at 30 ℃ to obtain nano silicon dioxide dispersion liquid;
B. adding a proper amount of nano-silica dispersion into a reaction container equipped with a mechanical stirrer, a reflux condenser tube and a thermometer, adding a silane coupling agent, a surfactant solution, a polyacrylamide solution and 1/3 aqueous epoxy resin into the mixed solution, and stirring until the mixture is uniform, wherein the reflux reaction temperature is 40-50 ℃, and preferably 45 ℃;
C. raising the reaction temperature to 65-80 ℃, simultaneously dropwise adding the rest aqueous epoxy resin and the rest initiator solution, adjusting the pH value to 12-14 by using a pH buffering agent, and continuously stirring for 3-5 h, wherein the reaction temperature is preferably 75 ℃, the pH value is preferably 13, and the pH buffering agent is one of potassium hydroxide or sodium hydroxide, preferably potassium hydroxide;
D. after the reaction is completed, cooling to room temperature, dropwise adding hydrochloric acid to adjust the pH value to 7-8, and filtering to obtain polyacrylamide/waterborne epoxy resin/nano SiO2Composite emulsion, namely a basalt fiber surface modified coating.
2. The preparation method of the basalt fiber surface modified coating according to claim 1, wherein the mass percentages of the substances participating in the reaction are as follows:
1.17-5.88%, preferably 3.52% of nano silicon dioxide dispersion liquid;
0.09-0.47% of silane coupling agent, preferably 0.28%;
0.06-0.2% of surfactant, preferably 0.15%;
0.12-0.59% of polyacrylamide, preferably 0.35%;
2.18-31.57% of water-based epoxy resin, preferably 19.14%;
0.07-0.12% of initiator, preferably 0.09%;
61.17-96.31% of deionized water, preferably 76.47%.
3. The preparation method of the basalt fiber surface modified coating according to claim 1, wherein: the silane coupling agent is one or two of gamma-aminopropyl triethoxysilane KH-550, gamma-glycidoxypropyl trimethoxysilane KH-560 and gamma-methacryloxypropyl trimethoxysilane KH-570, preferably gamma-aminopropyl triethoxysilane KH-550;
the waterborne epoxy resin is bisphenol A type epoxy resin, preferably E-51;
the surfactant is quaternary ammonium salt surfactant, one of hexadecyl trimethyl ammonium chloride HTMAC and octadecyl trimethyl ammonium chloride ODAC, and hexadecyl trimethyl ammonium chloride HTMAC is preferably selected;
the initiator is one of potassium persulfate KPS and ammonium persulfate APS, preferably potassium persulfate KPS.
4. A basalt fiber surface modified coating made according to the method of any one of claims 1 to 3.
5. The use of the basalt fiber surface modifying coating of claim 4 comprising the steps of:
A. soaking basalt fiber in H2SO4/H2O2Putting the mixed solution into a hydrothermal synthesis reaction kettle at the temperature of 80-120 ℃, wherein the activation time is 0.5-2H, and the H2SO4/H2O2H in the mixed solution2SO4/H2O2The volume ratio is 7: 3;
B. soaking the activated basalt fiber in a hydrochloric acid solution, wherein the concentration of the hydrochloric acid solution is 0.5-2M, the etching temperature is 30-50 ℃, and the etching time is 30-90 min;
C. soaking the basalt fiber surface modification coating in the basalt fiber surface modification coating of claim 4 for 60-150 min at a temperature of 25-60 ℃;
D. and taking out the soaked basalt fibers, and drying at 100 ℃ to constant weight.
6. The use of the basalt fiber surface modification coating according to claim 5, wherein: and step A, placing the mixture in a hydrothermal synthesis reaction kettle at the temperature of 90 ℃, wherein the activation time is 1 h.
7. The use of the basalt fiber surface modification coating according to claim 5, wherein: and the concentration of the hydrochloric acid solution in the step B is 1M.
8. The use of the basalt fiber surface modification coating according to claim 5, wherein: and the etching temperature in the step B is 40 ℃, and the etching time is 60 min.
9. The use of the basalt fiber surface modification coating according to claim 5, wherein: and C, soaking for 120min in the step C, wherein the soaking temperature is 40 ℃.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329580A (en) * | 1998-10-13 | 2002-01-02 | Ppg工业俄亥俄公司 | Impregnated glass fiber stands and products including the same |
| JP2008031451A (en) * | 2006-06-29 | 2008-02-14 | Sumitomo Chemical Co Ltd | Inorganic fiber-containing polyolefin resin composition and molded product formed therefrom |
| EP1897862A1 (en) * | 2006-09-05 | 2008-03-12 | Rockwool International A/S | Mineral wool composite moldings |
| US20090143524A1 (en) * | 2005-09-29 | 2009-06-04 | Yoshifumi Nakayama | Fiber-Reinforced Thermoplastic Resin Composition, Method for Producing the Same, and Carbon Fiber for Thermoplastic Resin |
| CN102942826A (en) * | 2010-10-20 | 2013-02-27 | 威士伯采购公司 | Water-based coating system with improved moisture and heat resistance |
| CN103143067A (en) * | 2013-02-21 | 2013-06-12 | 宁波保税区安杰脉德医疗器械有限公司 | Antimicrobial coat on surface of water system, and its preparation method |
| CN105492406A (en) * | 2013-08-27 | 2016-04-13 | 建筑研究和技术有限公司 | Novel fibers, methods for their preparation and use in the manufacture of reinforced elements |
| CN105776896A (en) * | 2016-03-18 | 2016-07-20 | 江苏大学 | Surface modification method of basalt fiber |
| CN106046694A (en) * | 2016-08-08 | 2016-10-26 | 山西晋投玄武岩开发有限公司 | Basalt fiber composite-material photovoltaic support profile and photovoltaic panel support manufactured by use of profile |
-
2017
- 2017-08-22 CN CN201710724783.1A patent/CN107640913B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329580A (en) * | 1998-10-13 | 2002-01-02 | Ppg工业俄亥俄公司 | Impregnated glass fiber stands and products including the same |
| US20090143524A1 (en) * | 2005-09-29 | 2009-06-04 | Yoshifumi Nakayama | Fiber-Reinforced Thermoplastic Resin Composition, Method for Producing the Same, and Carbon Fiber for Thermoplastic Resin |
| JP2008031451A (en) * | 2006-06-29 | 2008-02-14 | Sumitomo Chemical Co Ltd | Inorganic fiber-containing polyolefin resin composition and molded product formed therefrom |
| EP1897862A1 (en) * | 2006-09-05 | 2008-03-12 | Rockwool International A/S | Mineral wool composite moldings |
| CN102942826A (en) * | 2010-10-20 | 2013-02-27 | 威士伯采购公司 | Water-based coating system with improved moisture and heat resistance |
| CN103143067A (en) * | 2013-02-21 | 2013-06-12 | 宁波保税区安杰脉德医疗器械有限公司 | Antimicrobial coat on surface of water system, and its preparation method |
| CN105492406A (en) * | 2013-08-27 | 2016-04-13 | 建筑研究和技术有限公司 | Novel fibers, methods for their preparation and use in the manufacture of reinforced elements |
| CN105776896A (en) * | 2016-03-18 | 2016-07-20 | 江苏大学 | Surface modification method of basalt fiber |
| CN106046694A (en) * | 2016-08-08 | 2016-10-26 | 山西晋投玄武岩开发有限公司 | Basalt fiber composite-material photovoltaic support profile and photovoltaic panel support manufactured by use of profile |
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|---|---|---|---|---|
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| CN110407591A (en) * | 2019-08-01 | 2019-11-05 | 山东耀华特耐科技有限公司 | Using basaltic castable |
| CN110407591B (en) * | 2019-08-01 | 2022-01-28 | 山东耀华特耐科技有限公司 | Castable using basalt |
| CN110565364A (en) * | 2019-08-09 | 2019-12-13 | 天津大学 | Quinone modified basalt fiber carrier and preparation method and application thereof |
| CN110565364B (en) * | 2019-08-09 | 2022-01-28 | 天津大学 | Quinone modified basalt fiber carrier and preparation method and application thereof |
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