A basalt fiber reinforced composite material, its preparation method and application
By blending basalt fiber with glass fiber and performing surface modification treatment, a three-dimensional cross-linked network structure is formed, which solves the problems of high density, high VOC emission, and poor mildew resistance of traditional glass fiber composite materials. This enables the preparation and application of basalt fiber reinforced composite materials that are lightweight, have improved mechanical properties, and excellent environmental performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JILIN UNIVERSITY
- Filing Date
- 2026-06-03
- Publication Date
- 2026-06-30
AI Technical Summary
Traditional glass fiber composite materials have high density, high VOC emissions, and poor mildew resistance, which cannot meet the requirements of lightweighting and environmental protection in automobiles, and their mechanical properties are insufficient.
A composite material with low VOC and good anti-mildew properties was prepared by using a mixture of basalt fiber and glass fiber, and by using silane coupling agent modifier and compatibilizer to form a three-dimensional cross-linked network structure, combined with chitosan and inorganic anti-mildew agent.
It achieves lightweighting, improved mechanical properties, reduced VOC emissions, and excellent mildew resistance in composite materials, making it suitable for automotive interiors and profiles and easy to mass-produce.
Smart Images
Figure CN122302425A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of composite materials technology, and in particular to a basalt fiber reinforced composite material, its preparation method, and its application. Background Technology
[0002] With the rapid development of the automotive industry, lightweighting, environmental protection, and high performance have become the main trends in automotive technology development. Traditional automotive interior parts and structural profiles are mostly made of metal materials, glass fiber reinforced composites (GFRP), or pure organic polymer materials.
[0003] While metallic materials offer high mechanical strength, their high density hinders automotive lightweighting; pure organic polymers suffer from low strength and rigidity, failing to meet the requirements for structural components; and although glass fiber reinforced composites achieve a better balance between strength and weight, they still present the following problems: 1. Glass fiber has a high density (approximately 2.5-2.7 g / cm³). 3 There is limited room for further weight loss; Second, glass fiber composite materials release a large amount of volatile organic compounds (VOCs) during production and use, producing irritating odors and affecting the air quality inside the vehicle. Third, fiberglass has poor weather resistance and mildew resistance, and is prone to mold growth in humid environments, which affects the service life and aesthetics of the material. Fourth, glass fiber has low fracture toughness and its impact resistance needs to be improved.
[0004] In existing technologies, basalt fiber, as a novel green and environmentally friendly reinforcing material, possesses excellent properties such as high strength, high modulus, resistance to high and low temperatures, corrosion resistance, and environmental friendliness and non-toxicity. Furthermore, the raw materials are widely available and inexpensive. However, the interfacial bonding between basalt fiber and the resin matrix is relatively weak, resulting in poor mechanical properties of the composite material. There is a lack of specialized formulations and molding processes tailored to the specific requirements of automotive interior trim and profiles, and quantitative data on its environmental performance and mildew resistance are limited.
[0005] Therefore, there is an urgent need to develop a basalt fiber reinforced composite material with low VOC and high mildew resistance, and to apply it to automotive interiors and profiles. Summary of the Invention
[0006] The purpose of this invention is to provide a basalt fiber reinforced composite material, its preparation method, and its application, which solves the problems of traditional glass fiber composite materials such as large weight, high VOC emission, and poor mildew resistance, while improving mechanical properties and facilitating large-scale process production.
[0007] To achieve the above objectives, the present invention provides a basalt fiber reinforced composite material, comprising the following weight proportions: 10-20 parts glass fiber; 30-60 parts basalt fiber; 35-65 parts resin matrix; 3-5 parts compatibilizer; 1-5 parts interface modifier; 0.1-1 part antioxidant; 0.1-0.5 parts mildew inhibitor; wherein the compatibilizer is maleic anhydride-grafted polypropylene.
[0008] Preferably, the glass fiber is one or a combination of two of E-glass fiber (alkali-free glass fiber reinforced mainly with aluminum borosilicate) or ECR glass fiber (chemically resistant alkali-free glass), and the diameter of the glass fiber is 10~13μm. E-glass fiber is suitable for most automotive parts, while ECR glass fiber is suitable for structural components with high corrosion resistance requirements, such as battery pack frames and chassis components.
[0009] Preferably, the basalt fiber is one or more of continuous basalt fiber, chopped basalt fiber, or basalt fiber fabric, and the diameter of the basalt fiber is 9~17μm.
[0010] Preferably, the resin matrix is a thermoplastic resin, which is selected from one or more of polypropylene (PP), polyethylene, polyamide, polyethylene terephthalate, and polybutylene terephthalate.
[0011] Preferably, the interface modifier is a silane coupling agent selected from one or more of aqueous γ-aminopropyltriethoxysilane (KH-550), aqueous γ-glycidoxypropyltrimethoxysilane (KH-560), and aqueous γ-methacryloyloxypropyltrimethoxysilane (KH-570).
[0012] Preferably, the interface modifier is a mixture of aqueous γ-aminopropyltriethoxysilane and aqueous γ-glycidoxypropyltrimethoxysilane in a mass ratio of 1:1, and the total amount of the interface modifier is 2 to 6% of the total mass of glass fiber and basalt fiber.
[0013] Basalt fiber has high tensile strength (3000~4800MPa) but low elongation at break (3.1~3.3%), belonging to high-strength, low-toughness fibers. Glass fiber has slightly lower tensile strength (2000-3500MPa) but higher elongation at break (3.5~4.5%). When the two are mixed, a "synergistic toughening effect" will be produced: when the material is impacted, the glass fiber will break first to absorb energy, and then the basalt fiber will bear the load, thereby increasing the impact strength of the composite material by 10~20%.
[0014] Basalt fibers are modified with KH-550, while glass fibers should be modified with KH570. The ethoxy group (-OC2H5) in the KH-550 molecule hydrolyzes in aqueous solution to generate silanol groups (-SiOH), which then undergo a dehydration condensation reaction with the hydroxyl groups on the basalt fiber surface to form Si-O-Si and Si-O-Al covalent bonds, thus firmly adhering to the basalt fiber surface. Similarly, the methoxy group (-OCH3) in the KH-570 molecule hydrolyzes to generate silanol groups, which then undergo a dehydration condensation reaction with the hydroxyl groups on the glass fiber surface to form Si-O-Si covalent bonds, adhering to the glass fiber surface. When maleic anhydride-grafted polypropylene (PP-g-MAH) is used as a compatibilizer, the amino group (-NH2) at the end of the KH-550 molecule is a strong nucleophilic group, capable of reacting with the anhydride groups in the PP-g-MAH molecule. The group undergoes a ring-opening addition reaction to generate amide bonds (-CONH-) and carboxyl groups (-COOH), thereby covalently connecting the basalt fiber and the PP matrix. Under the high temperature and shearing action of twin-screw extrusion, the methacryloyloxy double bond (C=C) at the end of the KH-570 molecule can undergo a free radical grafting reaction with the PP molecular chain, thereby covalently connecting the glass fiber and the PP matrix. In the PP matrix, the amino group in the KH-550 molecule can also undergo a Michael addition reaction with the double bond in the KH-570 molecule, forming a covalent bridge between the two fibers, thereby connecting the basalt fiber and the glass fiber into a whole. A three-dimensional cross-linked network structure of fiber-coupling agent-coupling agent-fiber-matrix will be formed in the interface region of the hybrid composite material, improving the overall interfacial bonding force.
[0015] Preferably, the antifungal agent is a mixture of chitosan, inorganic antifungal agent, and citral, wherein the inorganic antifungal agent is selected from one or more of nano silver, nano zinc oxide, and nano titanium dioxide.
[0016] The surface of basalt fibers contains numerous nanoscale micropores, which can adsorb and load antifungal agents, providing a slow-release effect and extending the antifungal lifespan. The positively charged amino groups in chitosan molecules can adsorb negatively charged mold cell membranes, disrupting cell membrane integrity and causing leakage of cell contents. The hydroxyl groups on the basalt fiber surface can form hydrogen bonds with the amino and hydroxyl groups in chitosan molecules, firmly loading chitosan onto the fiber surface. Chitosan also improves the interfacial bonding between basalt fibers and the resin matrix, enhancing the mechanical properties of the composite material. Simultaneously, chitosan coating of inorganic antifungal agents prevents the aggregation of inorganic nanoparticles, improving their dispersibility. The hydrogen bonds formed between chitosan and basalt fibers ensure uniform distribution of the composite antifungal agent on the fiber surface, resulting in a synergistic bactericidal effect between chitosan and the inorganic antifungal agent. Furthermore, citral has deodorizing properties (improving car interior odor) and inhibits the enzyme activity of mold.
[0017] The antioxidant is selected from one or more of hindered phenolic antioxidants (such as 1010, 1076) and phosphite antioxidants (such as 168).
[0018] It also includes other additives, including one or more of toughening agents, lubricants, and colorants.
[0019] This invention also provides a method for preparing basalt fiber reinforced composite materials, comprising the following steps: S1. Fiber pretreatment: Basalt fiber is soaked in an acetic acid aqueous solution of silane coupling agent for 10-30 min, and glass fiber is soaked in an acetic acid aqueous solution of silane coupling agent for 10-30 min. After the solutions are mixed, they are soaked for 3-8 min. After removal, they are dried at 80-120℃ for 2-4 h to obtain modified fiber. S2. Material mixing: Add the resin matrix, compatibilizer, antioxidant, mildew inhibitor and other additives to a high-speed mixer and mix at 80~120℃ for 5~15 minutes to obtain a mixture. S3. Melt blending: Modified fibers and mixed materials are melt blended and extruded through a twin-screw extruder to obtain basalt fiber reinforced composite material particles; or modified basalt fiber fabric is impregnated in a resin matrix and then molded to obtain composite material boards.
[0020] The temperature settings of the twin-screw extruder are as follows: Zone 1 160~180℃, Zone 2 180~200℃, Zone 3 200~220℃, Zone 4 220~240℃, Die head temperature 210~230℃, and screw speed 200~400rpm.
[0021] The present invention also provides an application of basalt fiber reinforced composite material in automotive interiors and profiles, wherein the automotive interiors include door panels, dashboard frames, seat frames, pillar trim panels, roof frames, and trunk trim panels; and the profiles include body anti-collision beams, sill beams, floor beams, and roof longitudinal beams.
[0022] Therefore, the present invention employs the above-mentioned basalt fiber reinforced composite material, its preparation method, and its application, and the beneficial effects are as follows: Significant weight reduction effect: Through the blending of basalt fiber and glass fiber, the density is controlled at 1.12~1.24 g / cm³. 3 This achieves an overall weight reduction of approximately 30%, thereby realizing lightweighting and effectively reducing vehicle fuel consumption and carbon emissions.
[0023] Excellent mechanical properties: Utilizing the complementary characteristics of the high strength of basalt fiber and the high elongation at break of glass fiber, a significant synergistic toughening effect is generated, increasing the impact strength of the composite material by 10-20% compared to pure basalt fiber reinforced composite materials, and improving the tensile strength and flexural strength by more than 14% compared to pure glass fiber reinforced composite materials. Simultaneously, a 1:1 mass ratio of waterborne KH-550 and waterborne KH-570 is used as an interface modifier to form a three-dimensional cross-linked network structure, further enhancing the interfacial bonding force.
[0024] Outstanding environmental performance: Basalt fiber is a natural inorganic material that is non-toxic and odorless. It does not release harmful substances during production and use. At the same time, it uses a low-VOC resin matrix and environmentally friendly additives, which reduces the VOC emission of the composite material compared to traditional glass fiber composite materials, significantly improving the air quality inside the vehicle.
[0025] Excellent anti-mildew performance: This invention uses an inorganic anti-mildew agent, which relies on the adsorption and loading effect of the nano-scale micropores on the surface of basalt fiber to achieve the slow release of the anti-mildew agent, which can effectively prevent the growth of mold in humid environments and extend the service life of materials.
[0026] Significant cost advantages: Basalt fiber raw materials are widely available and inexpensive, and the production process is simple and easy to scale up for industrial production.
[0027] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description
[0028] Figure 1 These are test sample diagrams of embodiments and comparative examples of the present invention; Figure 2 This is a graph showing the theoretical weight reduction potential of Embodiment 2 of the present invention. Detailed Implementation
[0029] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.
[0030] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
[0031] Example 1 A basalt fiber reinforced composite material for use in automotive interior parts, comprising the following components: Short-cut basalt fibers (6 mm in length, 13 μm in diameter): 32 parts; E-glass fiber (6mm in length, 11μm in diameter): 12 parts; Polypropylene (PP): 50 parts; Maleic anhydride-grafted polypropylene (PP-g-MAH, grafting rate 1.2%): 3 parts; Interface modifier (KH-550:KH-570=1:1): 1.8 parts (4% of the total fiber mass); Antioxidant 1010: 0.3 parts; Antioxidant 168: 0.2 parts; Antifungal agent: 0.4 parts (0.2 parts chitosan, 0.15 parts nano zinc oxide, 0.05 parts citral); Calcium stearate lubricant: 0.3 parts.
[0032] Its preparation method is as follows: S1. Fiber pretreatment: Basalt fiber was placed in a 2% (w / w) aqueous solution of KH-550, and the pH was adjusted to 4.5 with acetic acid. The solution was soaked for 20 min. Glass fiber was placed in a 2% (w / w) aqueous solution of KH-570, and the pH was adjusted to 3.5 with acetic acid. The solution was soaked for 15 min. After mixing the solutions, the fiber was soaked for 5 min. After removing the fiber, it was dried at 110℃ for 3 h to obtain the modified fiber. S2. Material mixing: Add the resin matrix, compatibilizer, antioxidant, mildew inhibitor and other additives to a high-speed mixer and mix at 100°C for 10 minutes to obtain a mixture.
[0033] S3. Melt blending: The pretreated fiber and the mixture are added to a twin-screw extruder. The temperature settings are: Zone 1 170℃, Zone 2 190℃, Zone 3 210℃, Zone 4 230℃, Die head 220℃, screw speed 300rpm. The mixture is extruded and granulated to obtain composite material particles.
[0034] S4. Injection molding: Dry the composite material particles at 80℃ for 4 hours, and then injection mold them into standard test specimens. The injection temperature is 210~230℃, and the mold temperature is 40℃.
[0035] Example 2 A basalt fiber reinforced composite material for use in general structural profiles comprises the following components: Short-cut basalt fibers (12 mm in length, 15 μm in diameter): 40 parts; E-glass fiber (6mm in length, 11μm in diameter): 15 parts; PP: 38 copies; PP-g-MAH (grafting rate 1.2%): 4 parts; Interface modifier (KH-550:KH-570=1:1): 2.2 parts (4% of the total fiber mass); Antioxidant 1010: 0.2 parts; Antioxidant 168: 0.2 parts; Antifungal agent: 0.2 parts (0.1 parts chitosan, 0.08 parts nano zinc oxide, 0.02 parts citral); Ethylene bis-stearamide (EBS) lubricant: 0.2 parts.
[0036] The preparation method is the same as in Example 1.
[0037] Example 3 A basalt fiber reinforced composite material for use in battery pack frames comprises the following components: Short-cut basalt fibers (12 mm in length, 13 μm in diameter): 35 parts; ECR glass fiber (12mm in length, 13μm in diameter): 18 parts; PP: 40 copies; PE-g-MAH (grafting rate 1.0%): 4 parts; Interface modifier (KH-550:KH-570=1:1): 2.1 parts (3.8% of the total fiber mass); Antioxidant 1098: 0.3 parts; Antioxidant 168: 0.2 parts; Antifungal agent: 0.3 parts (0.15 parts chitosan, 0.12 parts nano titanium dioxide, 0.03 parts citral); Zinc stearate lubricant: 0.1 parts.
[0038] The preparation method is the same as in Example 1.
[0039] Comparative Example 1 A conventional pure glass fiber reinforced PP composite material comprises the following components: Short-cut E-glass fiber (6mm in length, 11μm in diameter, modified with KH-550): 44 parts; PP: 50 copies; PP-g-MAH (grafting rate 1.2%): 3 parts; KH-550 coupling agent: 1.8 parts; Antioxidant 1010: 0.3 parts; Antioxidant 168: 0.2 parts; Nano zinc oxide antifungal agent: 0.4 parts; Calcium stearate lubricant: 0.3 parts.
[0040] The preparation method is the same as in Example 1.
[0041] Comparative Example 2 A basalt fiber reinforced PP composite material, comprising the following components: Short-cut basalt fibers (6 mm in length, 13 μm in diameter, modified with KH-550): 44 parts; PP: 50 copies; PP-g-MAH (grafting rate 1.2%): 3 parts; KH-550 coupling agent: 1.8 parts; Antioxidant 1010: 0.3 parts; Antioxidant 168: 0.2 parts; Nano zinc oxide antifungal agent: 0.4 parts; Calcium stearate lubricant: 0.3 parts.
[0042] The preparation method is the same as in Example 1.
[0043] Test The composite materials prepared in Examples 1-3 and Comparative Examples 1-2 were tested for density, mechanical properties, gas release, and mildew resistance. Samples before testing were as follows: Figure 1 As shown in Table 1, the test results are as follows.
[0044] Table 1. Test results of composite material properties
[0045] As shown in Table 1, the impact strength of the material in Example 1 was 13.6% higher than that of Comparative Example 2 (pure basalt) and 52.7% higher than that of Comparative Example 1 (pure glass fiber). Simultaneously, the tensile strength was 20.4% higher and the flexural strength was 21.2% higher than that of Comparative Example 1, indicating the formation of a three-dimensional cross-linked interface structure and the synergistic toughening effect of basalt and glass fiber. The addition of citral not only enhanced the anti-mildew effect but also provided natural deodorization, reducing both total VOC and formaldehyde emissions, and lowering the odor level from 3.5 to 2.2. The four-fold synergistic system of basalt fiber carrier, chitosan, inorganic anti-mildew agent, and citral achieved a highly efficient, long-lasting, and environmentally friendly anti-mildew effect.
[0046] Mechanical strength and specific strength were tested on low-carbon steel, aluminum alloy, and the composite material prepared in Example 2. The results are shown in Table 2.
[0047] Table 2 Performance test results of low carbon steel, aluminum alloy, and composite materials
[0048] The formula for calculating its theoretical weight loss potential is as follows: Theoretical weight loss potential = ; In the formula, ρ is the material density, in g / cm³. 3 σ represents tensile strength, in MPa.
[0049] Substitute the above results into the formula to calculate the theoretical weight loss potential, such as Figure 2 As shown.
[0050] From Table 2 and Figure 2 It is known that the specific strength of composite materials is 4.1 times that of low-carbon steel. This means that to achieve the same load-bearing capacity, the wall thickness of composite material components only needs to be increased by about 65%, while the volume is only 1.65 times that of steel components, and the weight is only 24.2% of that of steel components, with a theoretical weight reduction potential of 75.8%. In practical engineering applications, considering structural design, connection methods, and safety margins, a weight reduction of 25-35% can usually be achieved.
[0051] Therefore, the present invention adopts the above-mentioned basalt fiber reinforced composite material, its preparation method and application, and achieves synergistic toughening, improved interfacial bonding force, long-lasting grade 0 mildew resistance, and VOC emission reduction of more than 60%. Under the same mechanical properties, it reduces weight by 30% compared with steel parts and can be widely used in automotive interior parts and structural profiles.
[0052] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.
Claims
1. A basalt fiber reinforced composite material, characterized in that, Includes the following weight groups: 10-20 parts glass fiber; 30-60 parts basalt fiber; 35-65 parts resin matrix; 3-5 parts compatibilizer; 1-5 parts interface modifier; 0.1-1 part antioxidant; 0.1-0.5 parts mildew inhibitor; wherein the compatibilizer is maleic anhydride-grafted polypropylene.
2. The basalt fiber reinforced composite material according to claim 1, characterized in that: The glass fiber is one or a combination of E glass fiber or ECR glass fiber, and the diameter of the glass fiber is 10~13μm.
3. The basalt fiber reinforced composite material according to claim 1, characterized in that: The basalt fiber is one or more of continuous basalt fiber, chopped basalt fiber, or basalt fiber fabric, and the diameter of the basalt fiber is 9~17μm.
4. The basalt fiber reinforced composite material according to claim 1, characterized in that: The interface modifier is a silane coupling agent selected from one or more of aqueous γ-aminopropyltriethoxysilane, aqueous γ-glycidoxypropyltrimethoxysilane, and aqueous γ-methacryloyloxypropyltrimethoxysilane.
5. The basalt fiber reinforced composite material according to claim 4, characterized in that: The interface modifier is a mixture of aqueous γ-aminopropyltriethoxysilane and aqueous γ-glycidoxypropyltrimethoxysilane in a mass ratio of 1:1, and the total amount of the interface modifier is 2 to 6% of the total mass of glass fiber and basalt fiber.
6. The basalt fiber reinforced composite material according to claim 1, characterized in that: The antifungal agent is a mixture of chitosan, inorganic antifungal agent, and citral, wherein the inorganic antifungal agent is selected from one or more of nano silver, nano zinc oxide, and nano titanium dioxide.
7. The basalt fiber reinforced composite material according to claim 1, characterized in that: The antioxidant is selected from one or more of hindered phenolic antioxidants and phosphite antioxidants.
8. The basalt fiber reinforced composite material according to claim 1, characterized in that: The resin matrix is one or more of polypropylene, polyethylene, polyamide, polyethylene terephthalate, and polybutylene terephthalate.
9. A method for preparing a basalt fiber reinforced composite material as described in any one of claims 1 to 8, characterized in that, Includes the following steps: S1. Fiber pretreatment: Basalt fiber is soaked in an acetic acid aqueous solution of silane coupling agent for 10-30 min, and glass fiber is soaked in an acetic acid aqueous solution of silane coupling agent for 10-30 min. After the solutions are mixed, they are soaked for 3-8 min. After removal, they are dried at 80-120℃ for 2-4 h to obtain modified fiber. S2. Material mixing: Add the resin matrix, compatibilizer, antioxidant, mildew inhibitor and other additives to a high-speed mixer and mix at 80~120℃ for 5~15 minutes to obtain a mixture. S3. Melt blending: Modified fibers and mixtures are melt blended and extruded through a twin-screw extruder to obtain basalt fiber reinforced composite material particles.
10. The application of a basalt fiber reinforced composite material as described in any one of claims 1 to 8 in automotive interior trim and profiles.