Basalt fiber composite material having a fiber directional distribution and method of making the same

Abstract

The application discloses a basalt fiber composite material with fiber directional distribution and a preparation method thereof in the field of fiber reinforced composites. CO2 The method comprises the following steps: obtaining original basalt fiber powder by using a supercritical extraction method; sequentially immersing the original basalt fiber powder into a hydrolyzed gamma-aminopropyltrimethoxysilane solution and a polydiallyldimethylammonium chloride solution to obtain co-modified basalt fiber powder; dispersively immersing ferroferric oxide nanoparticles into a phytic acid / polyisobutylene succinimide solution to obtain a magnetic sizing agent of phytic acid-modified ferroferric oxide nanoparticles; immersing the co-modified basalt fiber powder into the magnetic sizing agent to obtain magnetic basalt fiber powder; melt blending and granulating the magnetic basalt fiber powder and acrylonitrile-butadiene-styrene; and using a magnetic field to assist in melt deposition molding to obtain the basalt fiber composite material with fiber directional distribution; and the method significantly improves the mechanical properties of the composite material.

Description

TECHNICAL FIELD

[0001] The present application relates to a basalt fiber composite material with fiber orientation distribution and a preparation method thereof, and belongs to the field of fiber reinforced composite materials. BACKGROUND

[0002] In recent years, basalt fiber composites with basalt fiber as reinforcing phase and thermoplastic material as matrix have been widely used in wind power blades, automotive lightweight components and aerospace structural parts due to their high specific strength, lightweight, excellent chemical corrosion resistance and environmental friendliness. Although basalt fiber composites have shown good comprehensive performance, their limited interfacial bonding force and the resulting insufficient overall mechanical properties still restrict their further application.

[0003] The smooth surface of basalt fiber, low roughness and chemical inertness make it difficult to form a strong interfacial bond with the matrix, which can easily form microcracks and voids during processing, thereby causing stress concentration and ultimately leading to a decrease in the overall mechanical properties of basalt fiber composites. Currently, the main method to enhance the mechanical properties of basalt fiber composites is interface modification, which mainly includes chemical vapor deposition, electrophoretic deposition, plasma treatment, etc. Chemical vapor deposition usually requires high temperature and specific atmosphere, which can damage the internal structure of the fiber and weaken its inherent mechanical properties. The design of catalyst introduction and removal is difficult to operate and the process is complex. Electrophoretic deposition requires high equipment precision and cost. In addition, due to the insulation of basalt fiber, an additional conductive layer is needed to be used as a deposition electrode. The fiber position needs to be adjusted multiple times during the deposition process to ensure uniform coating. Plasma treatment can increase the roughness of the fiber surface through surface etching, thereby improving the mechanical engagement effect. However, the damage to the surface structure of the fiber is irreversible, resulting in a decrease in fiber strength. Compared with the above methods, coating is one of the most effective methods to modify basalt fiber, which is simple to operate.

[0004] Meanwhile, the directional distribution of fibers in the composite material can improve the mechanical properties. However, there are still some limitations in the method of controlling the directional distribution of fibers in the composite material to improve the mechanical properties of basalt fiber composite material. For example, the optimization of the lamination angle by fabric / prepreg layering molding is subject to the lamination process and mold, and it is difficult to achieve high-precision orientation on a microscale simultaneously. The methods such as winding and directional fiber laying have poor practicability for chopped basalt fibers, and it is difficult to achieve local precise fiber directional reinforcement on complex geometry. These methods cannot achieve high-precision fiber orientation, which limits the mechanical property enhancement of basalt fiber composite material. For the above challenges, we propose a method of modifying the surface of basalt fiber to enhance the interfacial bonding force between basalt fiber and matrix, realize the improvement of the strength of basalt fiber composite material, and introduce a magnetic field to assist fiber orientation in fused deposition molding to improve the high-precision orientation of basalt fiber on a microscale, and synergistically improve the mechanical properties of basalt fiber composite material. Compared with other methods of preparing basalt fiber composite material, the method proposed in the present application has the characteristics of mild process, easy integration into the existing fused deposition process, local directional reinforcement and good economy. SUMMARY

[0005] The present application mainly overcomes the deficiencies in the prior art and proposes a basalt fiber composite material with fiber directional distribution and a preparation method thereof. The basalt fiber composite material prepared by the method has the characteristic of fiber directional distribution and realizes significant improvement of mechanical properties.

[0006] The technical scheme provided by the present application to solve the above technical problems is: a basalt fiber composite material with fiber directional distribution and a preparation method thereof, comprising the following steps:

[0007] S1, using supercritical CO2 extraction method to remove sizing agent on the surface of basalt fiber powder, cleaning and drying to obtain original basalt fiber powder;

[0008] S2, immersing the original basalt fiber powder obtained in S1 into hydrolyzed γ-aminopropyltrimethoxysilane solution and polydiallyldimethylammonium chloride solution in sequence, stirring and reacting, filtering and drying to obtain γ-aminopropyltrimethoxysilane / polydiallyldimethylammonium chloride co-modified basalt fiber powder;

[0009] S3, dispersing ferroferric oxide nanoparticles in deionized water by ultrasonic, adding phytic acid and polyisobutylene succinimide, adjusting pH value, and stirring to obtain a magnetic sizing agent composed of phytic acid modified ferroferric oxide nanoparticles;

[0010] S4, immersing the basalt fiber powder co-modified by γ-aminopropyltrimethoxysilane and polydiallyldimethylammonium chloride obtained in S2 into the magnetic sizing agent obtained in S3 to obtain magnetic basalt fiber powder loaded with Fe3O4 nanoparticles on the surface;

[0011] S5, melt blending the magnetic basalt fiber powder obtained in S4 with acrylonitrile-butadiene-styrene, crushing and granulating, and using controllable magnetic field assisted melt deposition molding to obtain basalt fiber composite material with fiber directional distribution.

[0012] Further, the extraction pressure in the supercritical CO2 extraction method in S1 is 25 MPa, and the extraction temperature is 60℃.

[0013] Further, the pressure increasing rate is 2 MPa·min -1 , the pressure decreasing rate is 1 MPa·min -1 , the temperature increasing rate is 10℃·min -1 , and the extraction time is 90 min.

[0014] Further, the extraction co-solvent is ethanol, and the concentration is 5wt%.

[0015] Further, the average length of the basalt fiber powder is 200-300μm, and the average diameter is 13-15μm.

[0016] Further, the concentration of γ-aminopropyltrimethoxysilane in S2 is 5.0×10 - 2 mol·L -1 , and the concentration of polydiallyldimethylammonium chloride is 2.0×10 -3 mol·L -1 , and the average molecular weight is 20000-50000.

[0017] Further, the pH of the γ-aminopropyltrimethoxysilane hydrolysis is 4.5.

[0018] Further, the time of the γ-aminopropyltrimethoxysilane hydrolysis is 20 min.

[0019] Further, the solution for the γ-aminopropyltrimethoxysilane hydrolysis is ethanol and deionized water, and the volume ratio is 4:1.

[0020] Further, the time of immersing the basalt fiber powder into the γ-aminopropyltrimethoxysilane solution is 30 min.

[0021] Further, the basalt fiber powder is immersed in the polydimethyl diallyl ammonium chloride solution for 30 min.

[0022] Further, the concentration of the polyisobutylene succinimide in the step S3 is 6.7×10 -3 mol·L -1 , the average molecular weight is 1500, and the concentration of the ferroferric oxide nanoparticles is 2.0×10 -2 mol·L -1 .

[0023] Further, the molar ratio of the phytic acid to the ferroferric oxide is 1:5.

[0024] Further, the pH for modifying the ferroferric oxide with the phytic acid is 4.0.

[0025] Further, the time for modifying the ferroferric oxide with the phytic acid is 60 min.

[0026] Further, the average particle size of the phytic acid-modified ferroferric oxide is 250-300 nm.

[0027] Further, the mass ratio of the basalt fiber powder co-modified with the gamma-aminopropyl trimethoxysilane and the polydimethyl diallyl ammonium chloride to the phytic acid-modified ferroferric oxide nanoparticles in the step S4 is 7:1.

[0028] Further, the pH for modifying the basalt fiber powder with the ferroferric oxide is 3.5-4.5.

[0029] Further, the time for modifying the basalt fiber powder with the ferroferric oxide is 60 min.

[0030] Further, the surface roughness of the magnetic basalt fiber powder is 55 nm.

[0031] Further, the mass ratio of the ferroferric oxide to the basalt fiber powder in the magnetic basalt fiber powder is 6.5wt%.

[0032] Further, the saturation magnetization of the magnetic basalt fiber powder is ≥5emu·g -1 .

[0033] Further, the step S5 adopts an electrically powered solenoid to form an axial magnetic field to assist the fused deposition modeling.

[0034] Further, the solenoid axis is coaxial with the nozzle axis, the solenoid diameter is 20 mm, the coil length is 30 mm, the number of turns is 600, the peak current is 10 A, and the axial magnetic field is 0.25-0.30 T.

[0035] Further, the composite material is printed in 11 layers, and the printing direction of each layer from bottom to top is 0°, 36°, 72°, 108°, 144°, 180°, 36°, 72°, 108°, 144°, and 180°.

[0036] Further, the layer thickness of the layer with the printing direction of 0° is 0.35 mm, and the layer thickness of the remaining layers is 0.20 mm.

[0037] Further, the printing extrusion flow is 25 mm 3 -1 .

[0038] The second technical problem to be solved by the present application is to provide a basalt fiber composite material with a fiber orientation distribution prepared by the above method.

[0039] The present application has the following beneficial effects:

[0040] (1) The present application removes the sizing agent on the surface of the basalt fiber powder by the supercritical CO2 extraction method, which can effectively avoid damage to the fiber; the phosphate group of phytic acid can form a coordination bond with the exposed iron ions on the surface of the ferroferric oxide, realizing chemical anchoring; at the same time, the ferroferric oxide modified by phytic acid has a net negative charge, which can strongly electrostatically adsorb the basalt fiber powder with a positive quaternary ammonium group chain modified by gamma-aminopropyltrimethoxysilane / polydiallyldimethylammonium chloride on the surface. The coordination bond and electrostatic action synergize, so that the ferroferric oxide nanoparticles can be firmly loaded on the surface of the basalt fiber powder and are not easy to fall off during subsequent melting processing or service; at the same time, the ferroferric oxide modified basalt fiber powder endows the basalt fiber powder with a certain magnetic intensity and improves the surface roughness, which helps to improve the interfacial bonding force between the basalt fiber powder and the matrix, thereby improving the mechanical properties of the basalt fiber composite material.

[0041] ​(2) Phytic acid-modified iron oxide nanoparticles are distributed on the surface of basalt fiber powder through electrostatic adsorption, retaining the original magnetism of iron oxide nanoparticles and endowing basalt fiber powder with a certain magnetism. Using extremely short basalt fiber powder as raw material, the magnetic torque overcomes the viscous damping of the melt during magnetic field-assisted melt deposition molding, causing the fiber to be oriented along the magnetic field direction. Subsequently, it is fixed during the matrix solidification process, realizing high-precision orientation within the cross section of the basalt fiber composite material. This is beneficial for stress transmission in the same direction of the basalt fiber, significantly improving the modulus and strength along the basalt fiber direction. Moreover, the oriented distribution of the fiber reduces the porosity and layer thickness deviation during melt deposition molding, reduces stress concentration in the basalt fiber composite material, and further improves the mechanical properties. Attached Figure Description

[0042] Figure 1 This is a flowchart illustrating the preparation process of the present invention;

[0043] Figure 2 This is a scanning electron microscope image of magnetic basalt fiber powder.

[0044] Figure 3 This is a scanning electron microscope image of basalt fiber composite material;

[0045] Figure 4 The diagram shows the mechanical properties of basalt fiber composite materials.

[0046] Figure 5 The image shows the saturation magnetization test results for basalt fiber composite materials. Detailed Implementation

[0047] The present invention will be further described below with reference to the embodiments and accompanying drawings.

[0048] Example 1

[0049] like Figure 1 As shown, the basalt fiber composite material with oriented fiber distribution and its preparation method of the present invention are prepared through the following steps:

[0050] Step 1: Place basalt fiber powder with an average length of 200-300μm and an average diameter of 13-15μm into a supercritical CO2 extraction device, and after extraction, wash and dry to obtain raw basalt fiber powder.

[0051] The extraction pressure was 25 MPa, the extraction temperature was 60℃, and the pressure increase rate was 2 MPa·min. -1 The pressure reduction rate is 1 MPa·min -1 The heating rate is 10℃·min -1 The co-solvent for extraction was ethanol with a concentration of 5 wt%, and the extraction time was 90 min.

[0052] Step 2: Immerse the raw basalt fiber powder sequentially in a solution with a concentration of 5.0 × 10⁻⁶. -2 mol·L -1 The hydrolyzed γ-aminopropyltrimethoxysilane solution has a concentration of 2.0 × 10⁻⁶. -2 mol·L -3 The basalt fiber powder was prepared by immersing the fibers in a polydiallyldimethylammonium chloride solution with an average molecular weight of 20,000-50,000 for 30 minutes each. After filtration and drying, basalt fiber powder co-modified with γ-aminopropyltrimethoxysilane / polydiallyldimethylammonium chloride was obtained.

[0053] The hydrolysis of γ-aminopropyltrimethoxysilane was carried out at a pH of 4.5 for 20 minutes, and the hydrolysis solution consisted of ethanol and deionized water in a volume ratio of 4:1.

[0054] Step 3: Disperse the iron(III) oxide nanoparticles ultrasonically in deionized water, and add an average molecular weight of 1500 and a concentration of 6.7 × 10⁻⁶. -3 mol·L -1 Polyisobutylene succinimide was mixed with phytic acid, the pH was adjusted to 4.0, and the mixture was stirred for 60 min to obtain phytic acid-modified iron oxide nanoparticles.

[0055] The concentration of iron(III) oxide nanoparticles was 2.0 × 10⁻⁶. -2 mol·L -1 The molar ratio of phytic acid to iron oxide is 1:5, and the average particle size of the phytic acid-modified iron oxide particles is 250-300 nm.

[0056] Step 4: Dissolve basalt fiber powder co-modified with γ-aminopropyltrimethoxysilane / polydiallyldimethylammonium chloride and phytic acid-modified iron oxide nanoparticles in deionized water at a mass ratio of 7:1 for 60 min, filter and dry to obtain magnetic basalt fiber powder with surface-loaded iron oxide nanoparticles.

[0057] The reaction pH was 3.5-4.5, the surface roughness of the magnetic basalt fiber powder was 55 nm, and the saturation magnetization was ≥5 emu·g. -1 The mass ratio of iron oxide to basalt fiber powder is 6.5 wt%.

[0058] Step 5: Magnetic basalt fiber powder is melt-blended with acrylonitrile-butadiene-styrene, pulverized and granulated, and then melt-deposited using a controllable magnetic field to obtain a basalt fiber composite material with oriented fiber distribution.

[0059] Wherein, the axial magnetic field is formed by energized solenoid, the diameter of solenoid is 20mm, the length of coil is 30mm, the number of turns is 600, the peak current is 10A, the axial magnetic field is 0.25-0.30T; 11 layers are printed, and the printing direction of each layer is 0°, 36°, 72°, 108°, 144°, 180°, 36°, 72°, 108°, 144°, 180° respectively; the layer thickness of the layer with printing direction of 0° is 0.35mm, and the layer thickness of the remaining layers is 0.20mm, and the printing extrusion flow is 25mm 3 ·s -1 .

[0060] The basalt fiber composite material prepared in this embodiment 1 is measured by a scanning electron microscope to have an orientation deviation of the magnetic basalt fiber powder in the cross section of ±0.26°, and a layer thickness uniformity deviation of the basalt fiber composite material of ±0.01mm; the mass fraction of the basalt fiber powder is measured by a weighing method to be 10wt%, and the density of the basalt fiber composite material is measured by a weighing method to be 1.12g·cm -3 ; the porosity of the basalt fiber composite material is measured by a mass density method to be 3.9%; the volume resistivity of the basalt fiber composite material is measured by a two-probe method to be 10 12 Ω·cm; the thermal conductivity of the basalt fiber composite material is measured by a transient plane source method to be 0.28W·m -1 ·K -1 ; the saturation magnetization of the basalt fiber composite material is measured by a vibrating sample magnetometer to be 0.63emu·g -1 .

[0061] Comparative example 1

[0062] Step 1: The basalt fiber powder with an average length of 200-300μm and an average diameter of 13-15μm is placed in a supercritical CO2 extraction device, and after extraction, it is cleaned and dried to obtain the original basalt fiber powder.

[0063] Wherein, the extraction pressure is 25MPa, the extraction temperature is 60℃, the pressure increasing rate is 2MPa·min -1 , the pressure decreasing rate is 1MPa·min -1 , the temperature increasing rate is 10℃·min -1 , the co-solvent for extraction is ethanol, the concentration of co-solvent is 5wt%, and the extraction time is 90min.

[0064] Step 2: The original basalt fiber powder is melt-blended with acrylonitrile-butadiene-styrene, crushed and granulated, and a basalt fiber composite material is obtained by using a fused deposition modeling method.

[0065] Wherein, 11 layers are printed, and the printing direction of each layer is 0°, 36°, 72°, 108°, 144°, 180°, 36°, 72°, 108°, 144°, 180° respectively; the layer thickness of the layer with a printing direction of 0° is 0.35 mm, and the layer thickness of the remaining layers is 0.20 mm, and the printing extrusion flow is 25 mm 3 ·s -1 .

[0066] The magnetic basalt fiber powder prepared in steps 1, 2, 3 and 4 in Example 1 was observed for micro morphology, and the results are shown in Figure 2 .

[0067] Figure 2 The morphology feature that the surface of the magnetic basalt fiber powder is covered by a large number of Fe3O4 nanoparticles is disclosed, and the surface is obviously roughened to form a continuous rough covering layer, and the Fe3O4 nanoparticles are in spherical or cluster accumulation, indicating that the Fe3O4 nanoparticles are successfully loaded on the fiber surface and fixed by the co-modification layer, thereby providing a larger contact area and mechanical engagement site for the basalt fiber and the matrix.

[0068] The basalt fiber composite material with fiber directional distribution prepared in steps 1, 2, 3, 4 and 5 in Example 1 was observed for micro morphology, and the results are shown in Figure 3 .

[0069] Figure 3 The layered printing stacking structure of the basalt fiber composite material with fiber directional distribution and the orientation distribution of the magnetic basalt fiber powder are disclosed, and it is shown that the fibers in each layer in the cross section have obvious orientation distribution, and the fiber orientation angle is consistent with the printing setting angle, indicating that the magnetic basalt fiber powder successfully overcomes the viscous damping of the melt under the action of the magnetic field, and has obvious fiber directional distribution characteristics.

[0070] The basalt fiber composite material with fiber directional distribution prepared in Example 1 and the basalt fiber composite material prepared in Comparative Example 1 were tested for tensile properties, and the results are shown in Figure 4 .

[0071] Figure 4 It is disclosed that the tensile strength of the basalt fiber composite material with fiber directional distribution is 135 MPa, the tensile modulus is 6.1 GPa, and the elongation at break is 3.4%, and the tensile strength of the basalt fiber composite material is 65 MPa, the tensile modulus is 4.8 GPa, and the elongation at break is 2.6%, indicating that the tensile properties of the basalt fiber composite material are effectively improved.

[0072] The basalt fiber composite material with fiber orientation distribution prepared in Example 1 and the basalt fiber composite material prepared in Comparative Example 1 were tested for saturation magnetization, and the results are shown in Table 2. Figure 5

[0073] Figure 5 It is disclosed that the saturation magnetization of the basalt fiber composite material with fiber orientation distribution prepared in Example 1 is 0.650 emu·g -1 , while the saturation magnetization of the basalt fiber composite material is 0.002 emu·g -1 , which indicates that the magnetic component is successfully introduced to the surface of the Fe3O4 nanoparticles after the modification of the basalt fiber with phytic acid, so that the composite material exhibits magnetic response characteristics.

[0074] These results show that the basalt fiber composite material with fiber orientation distribution prepared in Example 1 has the characteristics of fiber orientation distribution and excellent mechanical properties.

[0075] The above description is not intended to limit the present application in any form, although the present application has been disclosed by the above examples, however, it is not intended to limit the present application, any person skilled in the art, within the scope of the technical scheme of the present application, can make some changes or modifications of the above disclosed technical content as equivalent examples, but any simple modification, equivalent change and modification of the above examples according to the technical essence of the present application, which does not deviate from the content of the technical scheme of the present application, still belongs to the scope of the technical scheme of the present application.​

Claims

1. A method for the production of a basalt fiber composite material having a fiber- oriented distribution, characterized by, The method comprises the following steps: S1, removing the sizing agent on the surface of basalt fiber powder by supercritical CO2 extraction method, cleaning and drying to obtain original basalt fiber powder; S2, immersing the original basalt fiber powder obtained in S1 into a hydrolyzed γ-aminopropyltrimethoxysilane solution and a polydiallyldimethylammonium chloride solution in sequence, stirring and reacting, filtering and drying to obtain γ-aminopropyltrimethoxysilane / polydiallyldimethylammonium chloride co-modified basalt fiber powder; S3, dispersing ferroferric oxide nanoparticles in deionized water by ultrasonic, adding phytic acid and polyisobutylene succinimide, adjusting pH value, and stirring to obtain a magnetic sizing agent composed of phytic acid modified ferroferric oxide nanoparticles; S4, immersing the γ-aminopropyltrimethoxysilane / polydiallyldimethylammonium chloride co-modified basalt fiber powder obtained in S2 into the magnetic sizing agent obtained in S3 to obtain magnetic basalt fiber powder loaded with ferroferric oxide nanoparticles; S5, melt blending the magnetic basalt fiber powder obtained in S4 with acrylonitrile-butadiene-styrene, crushing and granulating, and using controllable magnetic field assisted fused deposition forming to obtain basalt fiber composite material with fiber directional distribution.

2. The method for producing a basalt fiber composite material having a fiber orientation distribution according to claim 1, characterized by, The basalt fiber powder in step S1 has an average length of 200-300 μm and an average diameter of 13-15 μm; the extraction pressure in the supercritical CO2 extraction method is 25 MPa, the pressure increasing rate is 2 MPa·min -1 , the extraction temperature is 60℃, the temperature increasing rate is 10℃·min -1 , the extraction time is 90 min, the extraction co-solvent is ethanol, and the concentration thereof is 5wt%; the extraction is ended by reducing the pressure to normal pressure at a rate of 1 MPa·min -1 , and the heating and circulation are simultaneously terminated.

3. The method of manufacturing basalt fiber composite material with oriented distribution of fibers according to claim 1, characterized in that, The concentration of the γ-aminopropyl trimethoxysilane in the step S2 is 5.0×10 -2 mol·L -1 -1, the hydrolysis pH is 4.5, the hydrolysis time is 20 min, the hydrolysis solution is ethanol and deionized water with a volume ratio of 4:1; the concentration of the polydiallyldimethylammonium chloride is 2.0×10 -3 mol·L -1 -1, and the average molecular weight is 20000-50000; and the time for the sequential immersion is 30 min.

4. The method of manufacturing basalt fiber composite material with oriented distribution of fibers according to claim 1, characterized in that, The concentration of polyisobutylene succinimide in the step S3 is 6.7×10 -3 mol·L -1 , the average molecular weight is 1500, the concentration of ferroferric oxide nanoparticles is 2.0×10 -2 mol·L -1 , the molar ratio of phytic acid to ferroferric oxide is 1:5, the pH of the reaction is 4.0, the reaction time is 60 min, and the average particle size of the phytic acid modified ferroferric oxide particles is 250-300 nm.

5. The method of manufacturing basalt fiber composite material with oriented distribution of fibers according to claim 1, characterized in that, In the step S4, the mass ratio of the γ-aminopropyltrimethoxysilane / polydiallyldimethylammonium chloride co-modified basalt fiber powder to the phytic acid-modified ferroferric oxide nanoparticles is 7:1, the reaction pH is 3.5-4.5, and the reaction time is 60 min; the surface roughness of the magnetic basalt fiber powder is 55 nm, the mass ratio of the ferroferric oxide in the magnetic basalt fiber powder to the basalt fiber powder is 6.5 wt%, and the saturation magnetization of the magnetic basalt fiber powder is ≥5 emu·g -1 .

6. The method of manufacturing basalt fiber composite material with oriented distribution of fibers according to claim 1, characterized in that, In the step S5, an electric solenoid is used to form an axial magnetic field, the axis of the solenoid is coaxial with the axis of the nozzle, the diameter of the solenoid is 20 mm, the length of the coil is 30 mm, the number of turns is 600, the peak current is 10 A, and the axial magnetic field is 0.25-0.30 T.

7. The method of manufacturing basalt fiber composite material with oriented distribution of fibers according to claim 1, characterized in that, In the step S5, the number of printed layers of the composite material is 11, and the printing direction of each layer from bottom to top is 0°, 36°, 72°, 108°, 144°, 180°, 36°, 72°, 108°, 144°, and 180°, respectively. The thickness of the layer with the printing direction of 0° is 0.35 mm, and the thickness of the remaining layers is 0.20 mm. The printing extrusion flow rate is 25 mm 3 ·s -1 .

8. A basalt fiber composite material having a fiber directional distribution, characterized by: The basalt fiber composite material with fiber directional distribution is prepared by the method according to any one of claims 1-7. The basalt fiber composite material with fiber directional distribution is prepared by the method according to any one of claims 1-7.

9. A basalt fiber composite material having a fiber oriented distribution according to claim 8, characterized in that, The magnetic basalt fiber powder in the basalt fiber composite has a directional distribution in a cross section and an orientation deviation of not more than ±1°; the basalt fiber composite has a porosity of ≤5%, a layer thickness uniformity deviation of ≤±0.02 mm, and a density of 1.12 g·cm -3 ; and the content of the magnetic basalt fiber powder in the basalt fiber composite is 10 wt%.

10. A basalt fiber composite material having a fiber oriented distribution according to claim 8, characterized in that, The basalt fiber composite has a tensile strength of 135 MPa, a tensile modulus of 6.1 GPa, an elongation at break of 3.4%, a volume resistivity of 10 12 Ω·cm, a saturation magnetization of 0.63 emu·g -1 , and a thermal conductivity of 0.28 W·m -1 ·K -1 .

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