CN116462423A - Alkali-resistant basalt fiber sizing agent and preparation method of basalt fiber - Google Patents
Alkali-resistant basalt fiber sizing agent and preparation method of basalt fiber Download PDFInfo
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- CN116462423A CN116462423A CN202310614964.4A CN202310614964A CN116462423A CN 116462423 A CN116462423 A CN 116462423A CN 202310614964 A CN202310614964 A CN 202310614964A CN 116462423 A CN116462423 A CN 116462423A
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- alkali
- basalt fiber
- sizing agent
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- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 59
- 239000003513 alkali Substances 0.000 title claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 44
- 238000004513 sizing Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims abstract description 18
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 11
- 229910006251 ZrOCl2.8H2O Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 3
- SADUZRTZUBZVBK-UHFFFAOYSA-N didecyl oxalate Chemical group CCCCCCCCCCOC(=O)C(=O)OCCCCCCCCCC SADUZRTZUBZVBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 34
- 239000000835 fiber Substances 0.000 abstract description 31
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 239000004567 concrete Substances 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- -1 titanium ions Chemical class 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000011241 protective layer Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000004568 cement Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Classifications
-
- 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
- C03C25/12—General methods of coating; Devices therefor
- C03C25/16—Dipping
-
- 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
- C03C25/48—Coating with two or more coatings having different compositions
- C03C25/54—Combinations of one or more coatings containing organic materials only with one or more coatings containing inorganic materials only
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the technical field of impregnating compounds, and discloses an alkali-resistant basalt fiber impregnating compound and a preparation method thereof, wherein the alkali-resistant basalt fiber impregnating compound comprises 6-10% of ZrOCl2 sol, 20-22% of film forming agent, 0.4-0.6% of coupling agent, 0.1-0.3% of lubricant, 1.0-3.0% of antioxidant, 0.1-0.3% of pH regulator and the balance of deionized water; after the alkali-resistant basalt fiber sizing agent provided by the invention is formed into a film, titanium ions are gathered on the surface of basalt fibers, so that a protective layer is formed, and meanwhile, a compact ZrO2 coating can be formed to block mass transfer between the surface of fibers and an alkali solution, so that the alkali resistance of the fibers is improved, the film forming effect is good, and the bonding property with concrete is good.
Description
Technical Field
The invention relates to the technical field of impregnating compounds, in particular to an alkali-resistant basalt fiber impregnating compound and a preparation method of basalt fibers.
Background
In the modern building industry, building structures are towering, huge and diversified, and in order to meet the development requirements of building structures, a large number of fibers are needed for reinforcing cement-based composite materials; cement is an alkaline substance, and the interior of cement-based materials is in alkaline environment all the time, so that when the fiber is adopted for compounding, the alkali resistance of the fiber needs to be ensured.
In the prior art, two main methods for improving the alkali resistance of the fiber are provided, namely, one method is to change the formula of the fiber; secondly, changing the formula of the impregnating compound;
the patent with the publication number of CN113321429A discloses an alkali-resistant basalt fiber sizing agent, which is characterized in that ZrO2 emulsion is added into the sizing agent to enrich ZrO2 on the surface of the fiber, thereby protecting the fiber from being corroded by an alkali environment and improving alkali resistance; when the sizing agent is used, alkali-resistant components are required to be uniformly coated on the surface of basalt fibers, and meanwhile, the concentration of zirconia on the surface of the fibers is required to be used for further promoting the adhesive force of the sizing agent on the surface of the fibers, ensuring that basalt fiber tows are not scattered and improving the overall alkali resistance;
however, the stability of the ZrO2 emulsion is poor, not only is the emulsion required to be stirred continuously and dispersed by means of ultrasound during the preparation, but also the emulsion can be settled at the bottom during the use process if not used in time, thereby affecting the coating effect and blocking the pipeline; further, the zirconia occupies the defect positions of the fibers, and influences the strengthening effect of the impregnating compound.
For another example, the patent with the publication number of CN103466963A discloses an alkali-resistant chopped glass fiber sizing agent, specifically, a certain proportion of polyacrylate film forming agent, epoxy resin emulsion film forming agent and water-soluble epoxy resin film forming agent are added into the sizing agent formula, and the alkali resistance of the fiber is enhanced by improving the film thickness of the surface sizing agent;
however, the impregnating compound adopts a large amount of organic film forming agent, has poor bonding effect in the process of mixing with concrete, and is inconvenient for mass mixing.
Disclosure of Invention
Aiming at the technical problems that the existing basalt fiber sizing agent is poor in film forming effect and poor in combination effect after being mixed with concrete, so that the alkali resistance of the fiber is affected, the first aim of the invention is to provide an alkali-resistant basalt fiber sizing agent; the second aim of the invention is to provide a preparation method of alkali-resistant basalt fiber;
in order to achieve the above purpose, the present invention adopts the following technical scheme:
the alkali-resistant basalt fiber impregnating compound comprises, by mass, 6% -10% of ZrOCl2 sol, 20% -22% of a film forming agent, 0.4% -0.6% of a coupling agent, 0.1% -0.3% of a lubricant, 1.0% -3.0% of an antioxidant, 0.1% -0.3% of a pH regulator and the balance of deionized water.
The method for preparing basalt fiber by impregnating with the impregnating compound comprises the following steps:
s1, preparing ZrOCl2 sol, namely adding ZrOCl2.8H2O powder into ethanol-water solution, and uniformly mixing under stirring;
s2, hydrolysis of the coupling agent, namely fully dissolving the pH regulator in deionized water, adding the coupling agent while stirring, wherein the stirring time is 20-40 min, and the rotating speed is 50-150 r/min.
And S3, preparing the impregnating compound, namely sequentially adding the film forming agent, the lubricant, the ZrOCl2 sol, the antioxidant and the rest deionized water into the mixed coupling agent hydrolysate while stirring, and continuously stirring for 20-40 min after fully mixing at a stirring speed of 50-150 r/min to obtain the prepared reinforcing impregnating compound.
S4, preparing alkali-resistant basalt fiber, namely uniformly coating the sizing agent on the surface of the basalt fiber, and heating to 400-500 ℃ for curing for 8-15 hours to obtain a sample. The inventor researches show that the epoxy resin-ZrO 2 film-basalt fiber can be obtained at the heating curing temperature, and if the temperature is lower than 400 ℃, the conversion of ZrOCl2 molecules into ZrO2 is not facilitated.
< beneficial effects achieved by the present application >
Firstly, compared with common basalt fibers, the invention has better alkali resistance, wherein titanium ions on the surface of the basalt fibers are gathered after film formation, so as to form a protective layer; and at the same time, a compact ZrO2 coating can be formed to obstruct mass transfer between the fiber surface and the alkali solution, so that the alkali resistance of the fiber is improved. Compared with the reinforcing method of adding ZrO2 suspension, the method has the advantages that ZrO2 is suspended in a system in the form of dissolved ZrOCl2 molecules before heating and curing, and the phenomena of pipeline blockage, poor coating effect and the like caused by sedimentation of ZrO2 particles in the production process can be avoided.
In addition, the novel addition of the non-silane coupling agent changes the interface energy between basalt fiber and cement, and forms firm chemical bonds between the interfaces, so that the impregnating compound forms a more compact film on the surface of the basalt fiber, and the film forming effect is better.
In addition, the binding property with concrete is better, compared with changing the interface energy between basalt fiber and concrete after a large amount of organic impregnating compound is adopted, the titanium ion-containing composite material can be better combined with various inorganic matters in the concrete when being doped with the concrete after being aggregated on the surface of a fiber film, and the strength, the water resistance, the ageing resistance and the service life of the reinforced concrete are further improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides an alkali-resistant basalt fiber impregnating compound which comprises, by mass, 6% -10% of ZrOCl2 sol, 20% -22% of a film forming agent, 0.4% -0.6% of a coupling agent, 0.1% -0.3% of a lubricant, 1.0% -3.0% of an antioxidant, 0.1% -0.3% of a pH regulator and the balance of deionized water.
Among them, zrOCl2 sol mainly provides ZrO2 with alkali resistance. ZrO2 is suspended in a system in a form of dissolved ZrOCl2 molecules before heating and curing, zrOCl2 sol particles are distributed in a range of several to hundreds of nanometers in a dispersing process, are easy to form a film on the surface of a fiber, do not need a special chemical treatment process, have low heat curing treatment temperature, can be suitable for a basalt fiber normal production process, and a nano film of hundreds of nanometers does not cause other influence on a fiber body.
The preparation method of ZrOCl2 sol comprises the steps of adding ZrOCl2.8H2O powder into ethanol-water solution, and uniformly mixing under stirring;
in the application, the molar ratio of ethanol to water in the ethanol-water solution is 1:8, and the molar ratio of ZrOCl2.8H2O to the ethanol-water solution is 1:4-10. The ZrOCl2 sol prepared in the application is added into stable epoxy resin impregnating compound emulsion, and the emulsion is formed into a sol-like state by adjusting the content of ethanol.
The film forming agent is a key component in the impregnating compound, and the maximum dosage has important influence on the action and performance of the impregnating compound. The film forming agent in the invention is specifically epoxy resin emulsion (TH-811) which has excellent bonding capability, can protect basalt fibers from fracture and mechanical abrasion, and simultaneously provides good bundling property for the basalt fibers.
The coupling agent combines glass fiber with high molecular polymer such as resin, and has two different reaction properties, thereby playing a role of a bridge and realizing good interface combination between inorganic matters and organic matters. The coupling agent comprises a silane coupling agent and a titanate non-silane coupling agent. Specifically, the silane coupling agent is at least one of A187, A151 and A171; the titanate non-silane coupling agent is at least one of n-butyl titanate and tetrapropyl titanate.
The titanate non-silane coupling agent in the coupling agent is a key for enhancing alkali resistance, in the production process, externally active hydroxyl groups after the non-silane coupling agent is hydrolyzed are combined with hydroxyl groups on the surface of basalt fibers in a hydrogen bond form, and under the action of drying high temperature, the hydroxyl groups combined by the hydrogen bond are subjected to etherification reaction to remove water and form firm covalent bonds, so that the coupling effect is realized. Titanium ions are enriched on the surface of basalt fibers, so that the compactness of film formation can be improved, the titanium ions can prevent alkaline solution from reacting with basalt fibers, and the alkali resistance of the fibers is improved.
The lubricant has the functions of lubricating the surface of basalt fiber and reducing abrasion. The lubricant comprises at least one of lithium nitrate, ammonium chloride and polyethyleneimine polyamide salt;
preferably, the lubricant comprises polyethyleneimine polyamide salt and ammonium chloride in a mass ratio of 1-2:10-20.
The antioxidant is mainly used for delaying and inhibiting the oxidation process of organic components in the impregnating solution, preventing the aging of the organic components and prolonging the service life of the organic components. The antioxidant in the invention is specifically didecyl oxalate.
The pH regulator can regulate the pH value of the soaking liquid in the preparation process. The pH regulator in the application is at least one of glacial acetic acid and citric acid.
The alkali-resistant basalt fiber impregnating solution provided by the application can enhance the wear resistance and corrosion resistance of basalt fibers, promote the bundling property of the fibers so as to reduce yarn scattering and breakage, prevent static accumulation on the surfaces of the fibers and improve the interaction between the fibers and different matrixes (including cement, high polymers and the like).
Meanwhile, the invention provides a method for preparing basalt fiber by impregnating with the impregnating compound, which comprises the following steps:
s1, preparing ZrOCl2 sol, namely adding ZrOCl2.8H2O powder into ethanol-water solution, and uniformly mixing under stirring;
s2, hydrolysis of the coupling agent, namely fully dissolving the pH regulator in deionized water, adding the coupling agent while stirring, wherein the stirring time is 20-40 min, and the rotating speed is 50-150 r/min.
And S3, preparing the impregnating compound, namely sequentially adding the film forming agent, the lubricant, the ZrOCl2 sol, the antioxidant and the rest deionized water into the mixed coupling agent hydrolysate while stirring, and continuously stirring for 20-40 min after fully mixing at a stirring speed of 50-150 r/min to obtain the prepared reinforcing impregnating compound.
S4, preparing alkali-resistant basalt fiber, namely uniformly coating the sizing agent on the surface of the basalt fiber, and heating to 400-500 ℃ for curing for 8-15 hours to obtain a sample. The inventor researches show that the epoxy resin-ZrO 2 film-basalt fiber can be obtained at the heating curing temperature, and if the temperature is lower than 400 ℃, the conversion of ZrOCl2 molecules into ZrO2 is not facilitated.
After the sizing agent is coated on basalt fibers, the bundling property and the flexibility of the fibers can be effectively changed, so that the mechanical properties of the fibers are improved, and a compact ZrO2 coating is formed to block mass transfer between the surfaces of the fibers and an alkali solution, so that the alkali resistance of the fibers is improved.
Example 1
The invention provides an alkali-resistant basalt fiber sizing agent which comprises the following components in percentage by mass:
10% of ZrOCl2 sol, 22% of film forming agent (epoxy resin emulsion), 0.6% of coupling agent (A187: n-butyl titanate=1:1), 0.3% of lubricant (polyethyleneimine polyamide salt: lithium nitrate=1:12.5), 3.0% of antioxidant (didecyl oxalate), 0.1% of pH regulator (glacial acetic acid) and the balance of deionized water.
The preparation method comprises the following steps:
s1, preparing ZrOCl2 sol, namely adding ZrOCl2.8H2O powder into ethanol-water solution, and uniformly mixing under stirring; the mol ratio of the ethanol to the water in the ethanol-water solution is 1:8, and the mol ratio of ZrOCl2.8H2O to the ethanol-water solution is 1:4.
S2, hydrolyzing the coupling agent, namely fully dissolving the pH regulator in deionized water, adding the coupling agent while stirring, wherein the stirring time is 30min, and the rotating speed is 100r/min.
And S3, preparing the impregnating compound, namely sequentially adding the film forming agent, the lubricant, the ZrOCl2 sol, the antioxidant and the rest deionized water into the mixed coupling agent hydrolysate while stirring, and continuously stirring for 30min after fully mixing at the stirring speed of 100r/min to obtain the prepared reinforcing impregnating compound.
S4, preparing alkali-resistant basalt fibers, namely uniformly coating the sizing agent on the surfaces of the basalt fibers, and heating to 450 ℃ for curing for 15 hours to obtain samples.
Example 2
This embodiment differs from embodiment 1 in that: zrOCl2 sol 8%; the mol ratio of ZrOCl2.8H2O to the ethanol-water solution is 1:10; after the impregnating compound is coated on the surface of basalt fiber, heating to 500 ℃ and curing for 8 hours to obtain a plurality of groups of parallel samples
Example 3
This embodiment differs from embodiment 1 in that: 20% of film forming agent and 0.5% of coupling agent; the molar ratio of ZrOCl2.8H2O to the ethanol-water solution is 1:10.
Example 4
This embodiment differs from embodiment 1 in that: 20% of film forming agent and 0.3% of pH regulator; the molar ratio of ZrOCl2.8H2O to the ethanol-water solution is 1:10.
Comparative example 1
The difference between this comparative example and example 1 is that: zrOCl2 sol is replaced by ZrO2 emulsion.
Comparative example 2
The difference between this comparative example and example 1 is that: the coupling agent is replaced by at least one of KH550 (gamma-aminopropyl triethoxysilane), KH560 (gamma-glycidoxypropyl trimethoxysilane) and KH570 (gamma-methacryloxypropyl trimethoxysilane).
And under the optimized condition, testing results of basalt fibers coated by the alkali-resistant impregnating solution are obtained. Specific test contents include tensile breaking strength, tensile strength of the monofilament, tensile modulus of the monofilament, tensile strength of the monofilament after alkali resistance and retention rate of strength after alkali resistance.
TABLE 1
As shown in Table 1, after the sizing agent obtained under the optimal conditions in the examples is coated on basalt fibers, the bundling property and the flexibility of the fibers can be effectively changed, so that the mechanical properties of the fibers are improved, and a compact ZrO2 coating is formed to block mass transfer between the surfaces of the fibers and an alkali solution, so that the alkali resistance of the fibers is improved. Compared with the comparative example, the alloy has stronger mechanical property and better strength retention after alkali resistance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The alkali-resistant basalt fiber sizing agent is characterized by comprising, by mass, 6% -10% of ZrOCl2 sol, 20% -22% of a film forming agent, 0.4% -0.6% of a coupling agent, 0.1% -0.3% of a lubricant, 1.0% -3.0% of an antioxidant, 0.1% -0.3% of a pH regulator and the balance of deionized water.
2. The alkali-resistant basalt fiber sizing agent according to claim 1, wherein ZrOCl2 sol is prepared by adding ZrOCl2.8H2O powder to a mixed solution of ethanol and water.
3. The alkali-resistant basalt fiber sizing agent of claim 1, wherein the film forming agent is an epoxy resin emulsion.
4. The alkali-resistant basalt fiber sizing agent of claim 1, wherein the coupling agent comprises a silane coupling agent and a titanate non-silane coupling agent.
5. The alkali-resistant basalt fiber sizing agent of claim 4, wherein the silane coupling agent is at least one of A187, A151 and A171; the titanate non-silane coupling agent is at least one of n-butyl titanate and tetrapropyl titanate.
6. The alkali-resistant basalt fiber sizing agent of claim 1, wherein said lubricant comprises a cationic lubricant and a polyethyleneimine polyamide salt.
7. The alkali-resistant basalt fiber sizing agent of claim 6, wherein the mass ratio of the cationic lubricant to the polyethyleneimine polyamide salt is 10-20:1-2.
8. The alkali-resistant basalt fiber sizing agent of claim 1, wherein the antioxidant is didecyl oxalate.
9. The alkali-resistant basalt fiber sizing agent of claim 1, wherein the pH regulator is at least one of glacial acetic acid and citric acid.
10. A method for preparing alkali-resistant basalt fiber, characterized in that basalt fiber is immersed in the alkali-resistant basalt fiber impregnating compound according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360200A (en) * | 1970-06-19 | 1974-07-17 | Ici Ltd | Fibres |
| JPH0383832A (en) * | 1989-08-29 | 1991-04-09 | Koroido Res:Kk | Preparation of silica-zirconia viscous sol |
| RU2011106415A (en) * | 2011-02-21 | 2012-08-27 | Общество с ограниченной ответственностью "Научно-производственное объединение "Вулкан" (RU) | METHOD FOR PRODUCING CONTINUOUS BASALT FIBER |
| CN113321429A (en) * | 2021-07-07 | 2021-08-31 | 四川玄武岩纤维新材料研究院(创新中心) | Alkali-resistant basalt fiber impregnating compound and preparation method thereof |
| CN114230800A (en) * | 2021-12-30 | 2022-03-25 | 东北大学 | Zirconium modified silicon resin impregnating compound and preparation method and application thereof |
-
2023
- 2023-05-29 CN CN202310614964.4A patent/CN116462423A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360200A (en) * | 1970-06-19 | 1974-07-17 | Ici Ltd | Fibres |
| JPH0383832A (en) * | 1989-08-29 | 1991-04-09 | Koroido Res:Kk | Preparation of silica-zirconia viscous sol |
| RU2011106415A (en) * | 2011-02-21 | 2012-08-27 | Общество с ограниченной ответственностью "Научно-производственное объединение "Вулкан" (RU) | METHOD FOR PRODUCING CONTINUOUS BASALT FIBER |
| CN113321429A (en) * | 2021-07-07 | 2021-08-31 | 四川玄武岩纤维新材料研究院(创新中心) | Alkali-resistant basalt fiber impregnating compound and preparation method thereof |
| CN114230800A (en) * | 2021-12-30 | 2022-03-25 | 东北大学 | Zirconium modified silicon resin impregnating compound and preparation method and application thereof |
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