Phytic acid / silane coupling agent modified basalt fiber as well as preparation method and application thereof
By modifying basalt fibers with phytic acid and silane coupling agents, a dense protective film is generated and interfacial compatibility is enhanced, solving the corrosion problem of basalt fibers in acidic environments and improving acid resistance and interfacial stability.
Patent Information
- Application Number
- CN202511925743.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-19
- Publication Date
- 2026-01-23
AI Technical Summary
Basalt fiber is easily corroded in acidic environments, leading to performance degradation and shortened lifespan. Existing technologies are insufficient to effectively improve its acid resistance.
Phytic acid and silane coupling agent were used to synergistically modify basalt fibers. A dense protective film was formed by the complexation of the phosphate groups of phytic acid with metal cations, and the interfacial compatibility between the fiber and the resin matrix was enhanced by the silane coupling agent, thus constructing a dual protection mechanism of inner passivation and outer sealing.
Significantly improves the acid resistance and interfacial stability of basalt fiber, reduces the weight loss rate of the composite material in acidic environments, and increases the flexural strength retention rate, meeting the requirements of green and sustainable development.
Smart Images
Figure CN121377567A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of surface and interface modification of basalt fibers, and particularly relates to a phytic acid / silane coupling agent modified basalt fiber and a preparation method and application thereof. BACKGROUND
[0002] Basalt fiber reinforced polymer (BFRP) is widely used in the fields of construction engineering, aerospace, etc. due to its excellent mechanical, electrical properties, high temperature resistance, and high cost performance. However, in the actual operation process, BFRP is often in a complex and changeable service environment. Acid rain is formed by the conversion of SO2, NO x , etc. in the atmosphere, in addition, the resin-based material is easily degraded and releases acidic by-products when exposed to high temperature environment for a long time, so that the basalt fiber composite material is exposed to various acidic environments for a long time.
[0003] In this process, acid ions will react with metal cations such as Ca 2+ , Mg 2+ , Fe 3+ , etc. on the surface of the fiber to selectively dissolve out, causing the fiber surface to gradually crack, and further accelerating the performance degradation and shortening the service life of the fiber composite material. Therefore, how to enhance the acid resistance of basalt fiber through efficient, green and sustainable surface modification methods has become one of the current research hotspots and difficulties. SUMMARY
[0004] The purpose of the present application is to provide a phytic acid / silane coupling agent modified basalt fiber and a preparation method and application thereof. The basalt fiber is modified by phytic acid and silane coupling agent to effectively improve the acid resistance of the basalt fiber.
[0005] To achieve the above purpose, the present application provides the following technical solutions.
[0006] One of the technical solutions of the present application is to provide a preparation method of a phytic acid / silane coupling agent modified basalt fiber, comprising the following steps:
[0007] First, the basalt fiber is immersed in a solution containing phytic acid, taken out and dried, and then immersed in a solution containing silane coupling agent, taken out and dried to obtain the phytic acid / silane coupling agent modified basalt fiber.
[0008] Phytic acid is a natural organic acid extracted from rice bran. The abundant phosphate groups in its molecule have high hydrophilicity. On the one hand, they can form stable complexes with metal cations and form a dense protective film on the surface of the material, thereby effectively preventing corrosive media from entering the metal surface and inhibiting the corrosion of the metal. On the other hand, the -OH in the phytic acid molecule can provide active sites for the subsequent grafting of silane coupling agents, thereby imparting excellent interfacial compatibility to basalt fibers. As a widely available, green, environmentally friendly, non-toxic and biodegradable natural substance, phytic acid can be used to treat the surface of basalt fibers. Not only can it improve the stability of the basalt fibers, but it also meets the current green and sustainable technology trend, and has important popularization and application value.
[0009] Preferably, the mass fraction of phytic acid in the phytic acid-containing solution is 1% to 5%; more preferably, 5%.
[0010] Preferably, the silane coupling agent includes but is not limited to KH550; the mass fraction of the silane coupling agent in the silane coupling agent-containing solution is 1% to 5%, and the solvent is a mixture of ethanol and water with a volume ratio of (1 to 5):1.
[0011] Preferably, the basalt fiber is immersed in the phytic acid-containing solution for 1 to 3 hours, and is immersed in the silane coupling agent-containing solution for 6 to 9 hours.
[0012] Preferably, the basalt fiber further comprises a pretreatment step before being immersed in the phytic acid-containing solution.
[0013] Optionally, the drying temperature is 80°C, and the time is 1 to 3 hours; the baking temperature is 80°C.
[0014] The second technical scheme of the present application provides a phytic acid / silane coupling agent modified basalt fiber prepared by the above method.
[0015] The third technical scheme of the present application provides a preparation method of a basalt fiber composite material, comprising the following steps:
[0016] The resin, the curing agent and the phytic acid / silane coupling agent modified basalt fiber are mixed and stirred uniformly, and the basalt fiber composite material is obtained after curing.
[0017] Optionally, the resin is bisphenol A diglycidyl ether (DGEBA); the curing agent is methylhexahydrophthalic anhydride (MHHPA) and dimethyl ether tetramine (DMP-30); and the mass ratio of the bisphenol A diglycidyl ether, the methylhexahydrophthalic anhydride and the dimethyl ether tetramine is (95 to 105):(80 to 85):0.5.
[0018] Preferably, the curing includes hot-press curing and post-curing. The hot-press curing pressure is 10-15 MPa, the temperature is 140-150°C, and the time is 45-60 min. The post-curing temperature is 120-140°C, and the time is 4-6 h.
[0019] The fourth technical solution of the present invention provides a basalt fiber composite material prepared according to the above-mentioned method for preparing basalt fiber composite materials.
[0020] The beneficial technical effects of the present invention are as follows:
[0021] The modification mechanism of this invention is as follows: the phosphate groups in phytic acid undergo a complexation reaction with the metal cations in basalt fibers, forming a stable phytic acid film on the fiber surface, effectively preventing the invasion of acidic media. Simultaneously, the -OH groups in the phytic acid molecules provide active sites for subsequent grafting of silane coupling agents. This enhances the interfacial adhesion strength between the basalt fibers and the resin matrix, and the stable bridging structure between phytic acid and the silane coupling agent further constructs a dense organic-inorganic interface layer, thus achieving dual protection of "inner passivation + outer sealing," thereby improving the acid resistance and interfacial stability of the basalt fibers.
[0022] This invention addresses the acid resistance of fibers by employing a synergistic treatment of the fiber surface with phytic acid and a silane coupling agent to improve the fiber's acid resistance. This strategy expands the application of novel organic acids in the acid-resistant modification of composite materials. The modification technique is simple, low-cost, and environmentally friendly.
[0023] The composite material prepared using basalt fiber reinforced epoxy resin based on synergistic modification with phytic acid / silane coupling agent according to this invention, after treatment with 1 mol / L hydrochloric acid for 7 days, showed a significant improvement in acid resistance compared with the unmodified composite material. Characterization revealed that when the phytic acid mass fraction was 5%, the weight loss rate of the composite material was only 0.218%, and the flexural strength retention rate was as high as 91.22%. Attached Figure Description
[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0025] Figure 1 The image shows the surface morphology of the modified basalt fiber BF-1 in Example 1.
[0026] Figure 2Weight loss rate of basalt fiber composite prepared in Examples 1-3 and Comparative Example 1 after acid treatment.
[0027] Figure 3 Bending strength and bending strength retention rate of basalt fiber composite prepared in Examples 1-3 and Comparative Example 1 before and after acid treatment. DETAILED DESCRIPTION
[0028] The detailed description set forth below is intended as a description of various example embodiments of the application and is not intended to represent the only embodiments in which the application can be practiced. It is also not intended to represent that the application will necessarily be implemented in the
[0029] It should be noted that any of the methods described herein can be implemented by a computer using executable instructions. In other words, the methods described herein can be implemented in software and / or firmware. The executable instructions can be any set of instructions that when executed by one or more processors cause the processor(s) to perform the operations described herein. The executable instructions can be stored in any computer readable medium, which can be any available media that can be accessed by a computer.
[0030] Also, for ranges of values, the disclosure includes each intervening value between the upper and lower limits. For example, a range of "1 to 5" includes each intervening value between 1 and 5. The same applies to ranges including integers within the
[0031] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice of the present application.
[0032] As used herein, the terms "comprise", "comprising", "include", "including", "have", "having", and the like are open-ended terms that are intended to mean including, but not limited to.
[0033] The basalt fiber cloth used in the examples and comparative examples of the present application was purchased from Sichuan Kenyi Composite Materials Co., Ltd., and had a density of 300 g / m 2 .
[0034] Example 1
[0035] This example provides the preparation steps of basalt fiber composite modified by 1% KH550 and 1% phytic acid solution:
[0036] 1) The basalt fiber cloth was placed in a Soxhlet extractor, washed with acetone for 18 h to remove the textile type of the fiber surface, then washed with deionized water for 3 times and placed in an oven to dry at 80°C for 1 h. The obtained fiber was marked as UN-BF.
[0037] 2) Measure a certain volume of phytic acid solution with a measuring cylinder, add deionized water and stir thoroughly with a magnetic stirrer to prepare a 1% mass fraction phytic acid solution.
[0038] 3) Prepare a 1% mass fraction silane coupling agent-ethanol aqueous solution with KH550 as the coupling agent, wherein the volume ratio of the ethanol solution to the aqueous solution is 2:1, then ultrasonically shake the coupling agent solution for 10 min and stand for 12 h.
[0039] 4) Soak the UN-BF of step 1) in a 1% mass fraction phytic acid solution for 1 h, dry in an 80°C oven for 1 h, then soak in the coupling agent solution for 6 h, and dry in an 80°C oven for standby, marked as BF-1.
[0040] 5) According to the mass ratio of 100:80:0.5, respectively, 50 g of DGEBA, 40 g of MHHPA and 0.25 g of DMP-30 are weighed to prepare a resin mixture, then placed in a planetary mixer for uniform blending, and then placed in a vacuum oven for defoaming treatment under vacuum for 1 h to obtain a resin mixture.
[0041] 6) Cut the BF-1 in step 4) into a fiber cloth with a length of 20 cm and a width of 10 cm, lay 6 layers in a metal mold, add the prepared resin mixture until the fiber cloth is completely soaked, then place the metal mold in a vulcanizing machine at 140°C and 10 MPa pressure for 45 min, take out the prepared laminate and place it in an oven for post-curing at 120°C for 4 h to obtain BFRP-1.
[0042] Example 2
[0043] This example provides the preparation steps of basalt fiber composite material modified by 1% mass fraction KH550 and 3% mass fraction phytic acid solution:
[0044] 1) Place the basalt fiber cloth in a Soxhlet extractor, wash with acetone for 18 h to remove the textile type sizing agent on the surface of the fiber, then wash with deionized water for 3 times, and then dry in an oven at 80°C for 1 h. The obtained fiber is marked as UN-BF.
[0045] 2) Measure a certain volume of phytic acid solution with a measuring cylinder, add deionized water and stir with a magnetic stirrer to prepare a 3% mass fraction phytic acid solution.
[0046] 3) Prepare a 1% mass fraction silane coupling agent-ethanol aqueous solution with KH550 as the coupling agent, wherein the volume ratio of the ethanol solution to the aqueous solution is 2:1, then ultrasonically shake the coupling agent solution for 10 min and stand for 12 h.
[0047] 4) The UN-BF of step 1) is soaked in a 3% mass fraction phytic acid solution for 1 h and dried in an 80°C oven for 1 h, then soaked in a coupling agent solution for 6 h and dried in an 80°C oven for standby, recorded as BF-2.
[0048] 5) According to the mass ratio of 100:80:0.5, 50 g of DGEBA, 40 g of MHHPA and 0.25 g of DMP-30 are weighed respectively to prepare the resin mixture, and then placed in a planetary mixer for uniform blending, and then placed in a vacuum oven for defoaming treatment under vacuum for 1 h to obtain the resin mixture.
[0049] 6) The BF-2 in step 4) is cut into a fiber cloth with a length of 20 cm and a width of 10 cm, placed in a metal mold with 6 layers, and then the prepared resin mixture is added until the fiber cloth is completely soaked. After that, the metal mold is placed in a vulcanizing machine and hot-pressed at 140°C and 10 MPa pressure for 45 min. The prepared laminate is taken out and placed in an oven for post-curing at 120°C for 4 h to obtain BFRP-2.
[0050] Example 3
[0051] This example provides the preparation steps of basalt fiber composite material modified by 1% mass fraction KH550 and 5% mass fraction phytic acid solution:
[0052] 1) The basalt fiber cloth is placed in a Soxhlet extractor, washed with acetone for 18 h to remove the textile type infiltrant on the surface of the fiber, then washed with deionized water for 3 times and dried in an oven at 80°C for 1 h. The obtained fiber is recorded as UN-BF.
[0053] 2) A certain volume of phytic acid solution is measured by a graduated cylinder, added to deionized water and stirred with a magnetic stirrer to prepare a 5% mass fraction phytic acid solution.
[0054] 3) Using KH550 as the coupling agent, a 1% mass fraction silane coupling agent-ethanol aqueous solution is prepared, wherein the volume ratio of ethanol solution to water solution is 2:1, then the coupling agent solution is ultrasonically oscillated for 10 min and left for 12 h.
[0055] 4) The UN-BF of step 1) is soaked in a 5% mass fraction phytic acid solution for 1 h and dried in an 80°C oven for 1 h, then soaked in a coupling agent solution for 6 h and dried in an 80°C oven for standby, recorded as BF-3.
[0056] 5) 50 g of DGEBA, 40 g of MHHPA and 0.25 g of DMP-30 were weighed according to a mass ratio of 100:80:0.5 to prepare a resin mixture, which was then uniformly blended in a planetary stirrer, and then defoaming treatment was performed in a vacuum oven for 1 h in a vacuumized form to obtain the resin mixture.
[0057] 6) The BF-3 in step 4) was cut into a fiber cloth with a length of 20 cm and a width of 10 cm, 6 layers of which were placed in a metal mold, and the prepared resin mixture was added until the fiber cloth was completely infiltrated, and then the metal mold was placed in a vulcanizing machine and hot-pressed at 140°C and a pressure of 10 MPa for 45 min, and the prepared laminated plate was taken out and placed in an oven for post-curing at 120°C for 4 h to obtain BFRP-3.
[0058] Comparative Example 1
[0059] The present comparative example provides a preparation step of unmodified basalt fiber composite material:
[0060] 1) The basalt fiber cloth was placed in a Soxhlet extractor, washed with acetone for 18 h to remove the textile-type infiltrant on the surface of the fiber, washed with deionized water for 3 times, and then dried in an oven at 80°C for 1 h to obtain the fiber UN-BF.
[0061] 2) DGEBA, MHHPA and DMP-30 were prepared according to a mass ratio of 100:80:0.5 to prepare a resin mixture, which was then uniformly blended in a planetary stirrer, and then defoaming treatment was performed in a vacuum oven for 1 h in a vacuumized form to obtain the resin mixture.
[0062] 3) The UN-BF was cut into a fiber cloth with a length of 20 cm and a width of 10 cm, 6 layers of which were placed in a metal mold, and the prepared resin mixture was added until the fiber cloth was completely infiltrated, and then the metal mold was placed in a vulcanizing machine and hot-pressed at 140°C and a pressure of 10 MPa for 45 min, and the prepared laminated plate was taken out and placed in an oven for post-curing at 120°C for 4 h to obtain UN-BFRP.
[0063] Comparative Example 2
[0064] The present comparative example provides a preparation step of basalt fiber composite material modified only by a silane coupling agent:
[0065] 1) The basalt fiber cloth was placed in a Soxhlet extractor, washed with acetone for 18 h to remove the textile-type infiltrant on the surface of the fiber, washed with deionized water for 3 times, and then dried in an oven at 80°C for 1 h to obtain the fiber UN-BF.
[0066] 2) KH550 as a coupling agent, the preparation of mass fraction of 1% silane coupling agent-ethanol aqueous solution, wherein the volume ratio of ethanol solution and aqueous solution is 2:1, then the coupling agent solution ultrasonic oscillation 10 min, 12 h.
[0067] 3) the UN-BF of step 1) is infiltrated in the coupling agent solution for 6 h and dried in an oven at 80℃ for standby, denoted as BF-0.
[0068] 4) according to the mass ratio of 100:80:0.5, respectively, 50 g of DGEBA, 40 g of MHHPA and 0.25 g of DMP-30 are weighed to prepare resin mixture, and then placed in a planetary mixer for uniform blending, and then placed in a vacuum oven for defoaming treatment under vacuum for 1 h to obtain the resin mixture.
[0069] 5) BF-0 is cut into a fiber cloth with a length of 20 cm and a width of 10 cm, and placed in a metal mold with 6 layers, and the prepared resin mixture is added until the fiber cloth is completely infiltrated, then the metal mold is placed in a vulcanizing machine, and hot-pressed at 140℃ and 10 MPa pressure for 45 min, the prepared laminate is taken out and placed in an oven for post-curing at 120℃ for 4 h to obtain BFRP-0.
[0070] Figure 1 The surface morphology of the modified basalt fiber BF-1 in Example 1 is shown.
[0071] Figure 1 It is shown that a uniform and dense film layer appears on the surface of the phytic acid / silane coupling agent modified basalt fiber prepared by the present application, and local micro-particles can be observed, which is a complex layer generated by the complexation of phosphate groups in phytic acid molecules with metal ions.
[0072] The basalt fiber composites prepared in Examples 1-3 and Comparative Examples 1 and 2 are immersed in 1 mol / L hydrochloric acid, and after 7 days, the weight loss rate and the bending strength and bending strength retention rate of the basalt fiber composites before and after acid treatment are counted, and the results are shown in Table 1. Figure 2 and Figure 3 .
[0073] Figure 2 It is shown that after the sample is treated with acid for 7 days, the mass of the sample changes, and the weight loss rate gradually decreases with the increase of the mass fraction of phytic acid.
[0074] Figure 3It is shown that the flexural strength of the basalt fiber composite prepared in the example is improved compared with the unmodified and the fiber modified only by silane coupling agent, which is due to the fact that the silane coupling agent enhances the interface compatibility between the fiber and the matrix. After the sample is treated by acid for 7 days, the flexural strength retention of the composite is improved, and the flexural strength retention of the basalt fiber composite gradually increases with the increase of the mass fraction of phytic acid, and when the mass fraction of phytic acid is 5%, the flexural strength retention is as high as 91.22%.
[0075] The above-described examples only describe the preferred modes of the present application, and do not limit the scope of the present application. Without departing from the design spirit of the present application, various modifications and improvements to the technical solutions of the present application made by those skilled in the art shall fall within the protection scope determined by the claims of the present application.
Claims
1. A method for preparing basalt fibers modified with phytic acid / silane coupling agent, characterized in that, The method comprises the following steps: The basalt fiber is first immersed in a solution containing phytic acid, taken out and dried, and then immersed in a solution containing silane coupling agent, taken out and dried to obtain the phytic acid / silane coupling agent modified basalt fiber.
2. The method of claim 1, wherein the basalt fiber modified with phytic acid / silane coupling agent is prepared by the steps of: (a) mixing basalt fibers with a silane coupling agent; (b) mixing the basalt fibers with phytic acid; and (c) drying the basalt fibers. The mass fraction of phytic acid in the solution containing phytic acid is 1-5%.
3. The method of claim 1, wherein the basalt fiber modified with phytic acid / silane coupling agent is prepared by the steps of: (a) mixing basalt fibers with a silane coupling agent; (b) mixing the basalt fibers with phytic acid; and (c) drying the basalt fibers. The silane coupling agent comprises KH550, and the mass fraction of silane coupling agent in the solution containing silane coupling agent is 1-5%, and the solvent is a mixture of ethanol and water with a volume ratio of 1-5):
1.
4. The method of claim 1, wherein the basalt fiber modified with phytic acid / silane coupling agent is prepared by the steps of: (1) mixing basalt fiber, phytic acid, and silane coupling agent; (2) drying the mixture; and (3) heating the dried mixture. The basalt fiber is immersed in the solution containing phytic acid for 1-3 hours and in the solution containing silane coupling agent for 6-9 hours.
5. The method of claim 1, wherein the basalt fiber modified with phytic acid / silane coupling agent is prepared by the steps of: (1) mixing basalt fiber, phytic acid, and silane coupling agent; (2) drying the mixture; and (3) heating the dried mixture. The basalt fiber further comprises a pretreatment step before being immersed in the solution containing phytic acid.
6. The phytic acid / silane coupling agent modified basalt fiber prepared by the method according to any one of claims 1-5.
7. A method of manufacturing a basalt fiber composite material, characterized by, The method comprises the following steps: The resin, the curing agent and the phytic acid / silane coupling agent modified basalt fiber according to claim 6 are mixed and stirred uniformly, and the basalt fiber composite material is obtained after curing.
8. The method for preparing the basalt fiber composite material according to claim 7, characterized in that, The resin is bisphenol A diglycidyl ether, the curing agent is methylhexahydrophthalic anhydride and dimethyl ether tetramine, and the mass ratio of the bisphenol A diglycidyl ether, the methylhexahydrophthalic anhydride and the dimethyl ether tetramine is (95-105):(80-85):0.
5.
9. The method for preparing the basalt fiber composite material according to claim 8, characterized in that, The curing comprises hot-pressing curing and post-curing, the pressure of the hot-pressing curing is 10-15 MPa, the temperature is 140-150 DEG C, and the time is 45-60 min, and the temperature of the post-curing is 120-140 DEG C, and the time is 4-6 h.
10. The basalt fiber composite material prepared by the method according to any one of claims 7-9.