High-performance low-cost mixed fiber composite material and preparation method thereof

Abstract

The invention relates to the technical field of fiber composite material manufacturing, in particular to a high-performance and low-cost mixed fiber composite material and a preparation method thereof. The mixed fiber composite material specifically comprises the following components in percentage by mass: 60-90% of mixed fibers; 10-40% of a resin composite matrix; the stretching, compression and bending elastic modulus of the mixed fiber composite material is 45-75 Gpa. All the components of the mixed fiber composite material are subjected to melt blending and then are prepared through a thermocuring pultrusion process; according to the mixed fiber composite material and the sectional material prepared by the manufacturing method, the material with low cost, light weight, high strength, corrosion resistance, aging resistance, insulation and heat insulation can be obtained, and the mixed fiber composite material is suitable for various products with high requirements on self weight, strength, corrosion resistance, insulativity, heat insulation, service life and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber composite material manufacturing, and in particular to a high-performance and low-cost hybrid fiber composite material and a preparation method thereof. Background Art

[0002] In the existing fiber composite material production field, the main formula system is a single fiber and a single resin, but there is usually a balance problem between mechanical properties, material life, and cost. For example, the formula of glass fiber plus unsaturated resin and glass fiber plus modified epoxy resin usually has problems such as low strength, low elastic modulus, poor UV resistance, and poor heat and oxygen aging resistance. The formula system of basalt fiber plus epoxy resin has problems such as high production difficulty, excessive mechanical properties, and high cost. The above balance problems make it difficult to promote and apply fiber composite material profiles on a large scale in the field of structure.

[0003] Therefore, we consider using a hybrid fiber composite material formulation system so that the fiber composite material can simultaneously meet the comprehensive performance requirements of low cost, high strength, high elastic modulus, resistance to UV aging, resistance to heat and oxygen aging, insulation, and thermal insulation, so that it can take into account the requirements of both structural materials and functional materials. In view of this, we propose a high-performance and low-cost hybrid fiber composite material and its preparation method.

[0004] The above contents are only used to assist in understanding the technical solution of the present invention, and do not constitute an admission that the above contents are the closest prior art. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a high-performance, low-cost hybrid fiber composite material and a preparation method thereof. The profiles prepared by the hybrid fiber composite material and the manufacturing method can obtain low-cost, lightweight, high-strength, corrosion-resistant, aging-resistant, and heat-insulating materials, which are suitable for various products that have high requirements on the material's self-weight, strength, corrosion resistance, insulation, heat insulation, and life.

[0006] To achieve the above-mentioned purpose, the technical solution of the present invention is implemented as follows: a high-performance, low-cost hybrid fiber composite material and a preparation method thereof, wherein the components of the hybrid fiber composite material are specifically as follows by mass fraction: hybrid fiber is 60-90%; resin composite matrix is ​​10-40%; the tensile, compressive and bending elastic moduli of the hybrid fiber composite material are 45-75Gpa.

[0007] Preferably, the mixed fiber includes basalt fiber and glass fiber, and the ratio of the basalt fiber to the glass fiber is 1:4-1:1.

[0008] Preferably, the hybrid fibers are arranged in a manner such that the basalt fibers are uniformly coated on the outer layer of the glass fibers, and the thickness ratio of the basalt fiber layer to the glass fiber layer is 1:2-1:1.

[0009] Preferably, the mass fraction percentages of the basalt fiber components are as follows: basalt fiber roving is 70-90%; basalt felt cloth is 10-30%.

[0010] Preferably, the glass fiber components are specifically as follows in terms of mass fraction: glass fiber roving is 70-90%; polyester glass fiber mat is 10-30%; or: glass fiber roving is 70-90%; glass fiber mat is 10-30%.

[0011] Preferably, the components of the resin composite matrix are specifically as follows by mass fraction: epoxy resin is 50-85%; vinyl resin is 0-40%; unsaturated resin is 10-40%; additives are 5-10%; inorganic filler powder is 2-5%; color paste is 0-2%.

[0012] Preferably, the inorganic filler powder is any one or more of calcium carbonate, silicon carbide, calcium hydroxide, aluminum hydroxide, titanium dioxide, nano-montmorillonite, silicon dioxide, silicon micropowder, and ceramic powder.

[0013] Preferably, the components of the additives are specifically composed of 10-40% by mass of anti-ultraviolet additives, 10-30% of functional thermoplastic resin powders, 10-30% of curing accelerators, 10%-20% of coupling agents, 5-10% of anti-aging additives, 5-10% of organic peroxide initiators, 0-10% of dispersants, 0-20% of external release agents, and 0-5% of internal release agents.

[0014] Preferably, the anti-ultraviolet additive is UV-234; the functional thermoplastic resin powder is POM resin particles, the curing accelerator is DMP-30 epoxy accelerator, the coupling agent is silane KH560, the anti-aging additive is BASF Y-180 anti-aging agent, the organic peroxide initiator is dibenzoyl peroxide initiator, the dispersant is zinc stearate, the external release agent is epoxy resin release agent, and the internal release agent is E155 epoxy resin internal release agent.

[0015] Preferably, the components of the hybrid fiber composite material are melt-blended and then prepared by a heat curing pultrusion process; the heat curing pultrusion process comprises the following steps:

[0016] 1) Mixing: Add all inorganic filler powder, adhesion promoter, functional thermoplastic resin powder, internal release agent, UV-resistant additive, coupling agent and color paste to vinyl resin or unsaturated resin, stir for 10 minutes in a stirrer at 500r / min-1000r / min at a temperature above 10°C, then add all epoxy resin and DMP-30 epoxy resin promoter, stir for 20 minutes at a temperature above 10°C and a speed of 500r / min-1000r / min, until it is uniform and no bubbles are precipitated;

[0017] 2) Yarn threading: First, pull the fiber strands from the yarn rack to the yarn threading plate, then pass through the preformed plate in sequence according to the mold preformed design, and finally close and pass through the mold to collect single or double strands. After being tied firmly, connect the traction belt, and the traction belt is connected to the production line gantry;

[0018] 3) Dipping: Press the fibers between the preformed plate and the threading plate down into the resin tank to fully soak them. Arrange a reflux guide device at the mold mouth to guide and collect the resin refluxed from the mold mouth, filter it, and then add it back into the tank for recycling;

[0019] 4) Mold heating and curing: Turn on the temperature control on the production line console, adjust to the designed temperature, and use a thermometer to test until it is heated to the specified temperature;

[0020] 5) Traction: Use an intermittent hydraulic press or crawler machine to pull the profile, and the travel speed of the hydraulic press or crawler machine is set to the same as the production speed;

[0021] 6) Cutting: Use alloy saw blades to cut profiles that have reached the predetermined production length.

[0022] Preferably, the mold heating and curing needs to be divided into three temperature control intervals, namely the entrance section, the middle section and the exit section. The temperatures of the three temperature control intervals are continuously adjusted according to the resin formula. The entrance section temperature of the temperature control interval is 120-150°C, the middle section temperature is 140-190°C, the exit section temperature is 100-160°C, and the production speed is 20cm / min-50cm / min; the starting test temperature of the entrance section is 120°C, the starting test temperature of the middle section is 120°C, the starting test temperature of the exit section is 100°C, and the starting test production speed is 20cm / min. The straightness of the profile is observed and the strength of the produced profile is tested with a universal testing instrument. When the actual measured strength does not reach the preset strength, the temperature of each section is increased. When the actual measured strength exceeds the preset strength, it is regarded as an ideal temperature control interval and production speed. If you want to increase the production speed at this time, you can further increase the temperature until the strength is lower than the preset strength or the production line slips, blocks the mold, or deforms. The temperature and speed cannot be increased any further.

[0023] The beneficial effects of the present invention are embodied in:

[0024] (1) The profiles prepared by the hybrid fiber composite material manufacturing method of the present invention are low-cost, lightweight, high-strength, corrosion-resistant, aging-resistant, and heat-insulating materials, and can be used in various products that have high requirements on the material's self-weight, strength, corrosion resistance, insulation, heat insulation, and lifespan.

[0025] (2) Since part of the glass fiber is replaced by basalt fiber, the strength and modulus of the profile are significantly improved and the friction resistance during production is reduced.

[0026] (3) Since the basalt fibers are arranged in the outer layer, the bending elastic modulus of the profile is significantly improved.

[0027] (4) The present invention significantly improves the surface smoothness and hardness of the profile and reduces the friction resistance during pultrusion production by adding functional thermoplastic resin powder.

[0028] (5) The invention adds a coupling agent, which significantly improves the bonding force between the resin and the fiber, and improves the mechanical properties and elastic modulus of the profile.

[0029] (6) In the method provided by the present invention, in the mixing step, since "the inorganic filler powder, functional thermoplastic resin powder, adhesion promoter, internal release agent, UV resistant additive, coupling agent and color paste are first added to vinyl resin or unsaturated resin as the first step of mixing, and then the epoxy resin and its promoter are added as the second step of mixing", compared with completing the mixing all at once, the difficulty of mixing the mixed resin is significantly reduced, the viscosity of the resin is reduced, the uniformity, fluidity and workability are improved, the wetting effect during the pultrusion process is improved, and the profile has more uniform mechanical properties and surface effects.

[0030] (7) In the method provided by the present invention, in the resin dipping step, since "a reflux guiding device is arranged at the mold mouth to guide and collect the resin refluxed from the mold mouth, and then add it back into the material tank for recycling after filtering", compared with the conventional method of directly refluxing the resin into the material tank, the viscosity of the refluxed resin is significantly reduced, the smoothness of the pultrusion process is improved, and the probability of mold blockage is reduced. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. In the absence of conflict, the embodiments in this application and the features in the embodiments can be combined with each other. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Examples and Comparative Examples

[0033] Example 1

[0034] The invention provides a high-performance and low-cost mixed fiber composite material. The components of the mixed fiber composite material are specifically as follows by mass fraction: 14.25% of basalt fiber roving, 4.75% of basalt felt cloth, 45.6% of glass fiber roving, 11.4% of polyester glass fiber felt, 13.92% of epoxy resin E44, 6.96% of unsaturated resin, 1.2% of oxide ceramic powder, 0.3864% of DMP-30 epoxy resin curing agent, 0% of coupling agent, 0% of POM resin particles, 0.42% of ASA resin particles, 0.3024% of UV-resistant additive UV-234, 0.084% of BASF Y-180 anti-aging agent, 0.168% of dibenzoyl peroxide initiator, 0.252% of external mold release agent, 0.0672% of internal mold release agent and 0.24% of color paste.

[0035] Example 2

[0036] The invention provides a high-performance and low-cost mixed fiber composite material. The components of the mixed fiber composite material are specifically as follows by mass fraction: 14.25% of basalt fiber roving, 4.75% of basalt felt cloth, 45.6% of glass fiber roving, 11.4% of polyester glass fiber felt, 13.92% of epoxy resin E44, 6.96% of unsaturated resin, 1.2% of oxide ceramic powder, 0.3024% of DMP-30 epoxy resin curing agent, 0.084% of coupling agent, 0% of POM resin particles, 0.42% of ASA resin particles, 0.3024% of UV-resistant additive UV-234, 0.084% of BASF Y-180 anti-aging agent, 0.168% of dibenzoyl peroxide initiator, 0.252% of external mold release agent, 0.0672% of internal mold release agent and 0.24% of color paste.

[0037] Example 3

[0038] The invention provides a high-performance and low-cost mixed fiber composite material. The components of the mixed fiber composite material are specifically as follows by mass fraction: 14.25% of basalt fiber roving, 4.75% of basalt felt cloth, 45.6% of glass fiber roving, 11.4% of polyester glass fiber felt, 13.92% of epoxy resin E44, 6.96% of unsaturated resin, 1.2% of oxide ceramic powder, 0.3024% of DMP-30 epoxy resin curing agent, 0.168% of coupling agent, 0.168% of POM resin particles, 0.168% of ASA resin particles, 0.3024% of UV-resistant additive UV-234, 0.084% of BASF Y-180 anti-aging agent, 0.168% of dibenzoyl peroxide initiator, 0.252% of external mold release agent, 0.0672% of internal mold release agent and 0.24% of color paste.

[0039] Example 4

[0040] The present invention provides a high-performance and low-cost mixed fiber composite material. The components of the mixed fiber composite material are specifically as follows by mass fraction: 14.625% of basalt fiber roving, 4.875% of basalt felt cloth, 46.8% of glass fiber roving, 11.7% of polyester glass fiber felt, 12.76% of epoxy resin E44, 6.38% of unsaturated resin, 1.1% of oxide ceramic powder, and 1.2% of DMP-30 The epoxy resin curing agent is 0.2772%, the coupling agent is 0.154%, the POM resin particles are 0.231%, the ASA resin particles are 0.077%, the anti-UV additive UV-234 is 0.2772%, the BASF Y-180 anti-aging agent is 0.077%, the dibenzoyl peroxide initiator is 0.154%, the external release agent is 0.231%, the internal release agent is 0.0616%, and the color paste is 0.22%.

[0041] Example 5

[0042] The invention provides a high-performance and low-cost mixed fiber composite material. The components of the mixed fiber composite material are specifically as follows by mass fraction: 15% of basalt fiber roving, 5% of basalt felt cloth, 48% of glass fiber roving, 12% of polyester glass fiber felt, 11.6% of epoxy resin E44, 5.8% of unsaturated resin, 1% of oxide ceramic powder, 0.252% of DMP-30 epoxy resin curing agent, 0.14% of coupling agent, 0.21% of POM resin particles, 0.07% of ASA resin particles, 0.252% of UV-resistant additive UV-234, 0.07% of BASF Y-180 anti-aging agent, 0.14% of dibenzoyl peroxide initiator, 0.21% of external mold release agent, 0.056% of internal mold release agent and 0.2% of color paste.

[0043] Comparative Example

[0044] The invention provides a high-performance and low-cost mixed fiber composite material. The components of the mixed fiber composite material are specifically as follows by mass fraction: 0% of basalt fiber roving, 0% of basalt felt cloth, 65% of glass fiber roving, 15% of polyester glass fiber felt, 16% of epoxy resin E44, 0% of unsaturated resin, 1.5% of oxide ceramic powder, 1% of DMP-30 epoxy resin curing agent, 0% of coupling agent, 0% of POM resin particles, 0% of ASA resin particles, 0.4% of UV-resistant additive UV-234, 0.1% of BASF Y-180 anti-aging agent, 0.2% of dibenzoyl peroxide initiator, 0.45% of external mold release agent, 0.05% of internal mold release agent and 0.3% of color paste.

[0045] The specific mass fraction percentages of the components in the above examples 1-5 and the comparative examples are shown in the following table:

[0046]

[0047] The composite materials obtained by the heat curing pultrusion process provided by the present invention are prepared by the above-mentioned Examples 1-5 and Comparative Example 1, and the density, tensile strength / modulus, compressive strength / modulus, bending strength / modulus, stamping shear strength and interlaminar shear strength of each composite material are tested according to GB / T 1463-2005 "Test Method for Density and Relative Density of Fiber Reinforced Plastics", GB / T 1447-2005 "Test Method for Tensile Properties of Fiber Reinforced Plastics", GB / T 1448-2005 "Test Method for Fiber Reinforced Compression and Tensile Properties", GB / T 1449-2005 "Test Method for Flexural Properties of Fiber Reinforced Plastics", GB / T 1450.2-2005 "Test Method for Punching Shear Strength of Fiber Reinforced Plastics", and JC / T 773-2010 "Fiber Reinforced Plastics Short Beam Method for Determining Interlaminar Shear Strength". The following table is obtained.

[0048] Composite material sample test report

[0049]

[0050]

[0051] It can be seen from the test report of the embodiments that the average values ​​of tensile, compressive and bending elastic moduli of each embodiment within the preparation process range are in the range of 45-75 GPa.

[0052] It can be seen from the above table that the average tensile strength in this embodiment is 1041.5MPa, which is 39.4% higher than that of the comparative example; the average compressive strength is 954.6MPa, which is 15.9% higher than that of the comparative example; the average compressive strength is 1262.7MPa, which is 54.9% higher than that of the comparative example; the enhancement of tensile, compressive and bending strength makes the profile more suitable for axially loaded components or bending components, which can improve product safety.

[0053] In this example, the average value of tensile, compressive and bending elastic moduli is 61.8 GPa, which is 12.5% ​​higher than that of the control example, making the profile more suitable for preparing beam-type components, improving structural rigidity and reducing material consumption.

[0054] During the production process, because the basalt fiber bundles are thinner than the glass fiber bundles, the threading process is significantly smoother than the control example, and the production speed is also higher than the control example. After adding oxide ceramic powder, POM resin particles, and ASA resin particles, there are almost no scratches on the surface of the profile during the production process, and the wear resistance is significantly better than the control example.

[0055] It should be noted that if there are descriptions involving "first", "second", etc. in the embodiments of the present invention, the descriptions of "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes. Taking "A and / or B" as an example, it includes scheme A, or scheme B, or schemes that satisfy both A and B. In addition, "multiple" refers to more than two. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist.

[0056] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-performance, low-cost hybrid fiber composite material, characterized in that: The components of the mixed fiber composite material are specifically as follows according to mass fraction percentage: mixed fiber is 60-90%; resin composite matrix is ​​10-40%; the tensile, compressive and bending elastic moduli of the mixed fiber composite material are 45-75Gpa.

2. A high-performance, low-cost hybrid fiber composite material according to claim 1, characterized in that: The mixed fiber includes basalt fiber and glass fiber, and the ratio of the basalt fiber to the glass fiber is 1:4-1:

1.

3. A high-performance, low-cost hybrid fiber composite material according to claim 1 or 2, characterized in that: The basalt fibers are uniformly coated on the outer layer of the glass fibers, and the thickness ratio of the basalt fiber layer to the glass fiber layer is 1:2-1:

1.

4. A high-performance, low-cost hybrid fiber composite material according to claim 3, characterized in that: The mass fraction percentage of the basalt fiber components is as follows: basalt fiber roving is 70-90%; basalt felt cloth is 10-30%.

5. A high-performance, low-cost hybrid fiber composite material according to claim 4, characterized in that: The glass fiber components are specifically as follows in terms of mass fraction: glass fiber roving is 70-90%; polyester glass fiber mat is 10-30% or high temperature resistant glass fiber mat cloth is 10-30%.

6. A high-performance, low-cost hybrid fiber composite material according to claim 1, characterized in that: The components of the resin composite matrix are specifically as follows in terms of mass fraction: epoxy resin is 50-85%, vinyl resin is 0-40%, unsaturated resin is 10-40%, additives are 5-10%, inorganic filler powder is 2-5%, and color paste is 0-2%.

7. A high-performance, low-cost hybrid fiber composite material according to claim 6, characterized in that: The inorganic filler powder is one or more of calcium carbonate, silicon carbide, calcium hydroxide, aluminum hydroxide, titanium dioxide, nano-montmorillonite, silicon dioxide, silicon micropowder, and ceramic powder.

8. A high-performance, low-cost hybrid fiber composite material according to claim 7, characterized in that: The specific mass fraction percentages of the additive components are: 10-40% of anti-ultraviolet additive; 10-30% of functional thermoplastic resin powder; 10-30% of curing accelerator; 10%-20% of coupling agent; 5-10% of anti-aging additive; 5-10% of organic peroxide initiator; 0-10% of dispersant; 0-20% of external release agent; and 0-5% of internal release agent.

9. A method for manufacturing a high-performance and low-cost hybrid fiber composite material according to any one of claims 1 to 8, characterized in that: The components of the hybrid fiber composite material are melt-blended and then prepared by a heat curing pultrusion process; the heat curing pultrusion process comprises the following steps: 1) Mixing: Add all inorganic filler powder, adhesion promoter, internal release agent, anti-ultraviolet additive, coupling agent and color paste to vinyl resin or unsaturated resin, stir for 10 minutes in a stirrer at 500r / min-1000r / min at a temperature above 10°C, then add all epoxy resin and DMP-30 epoxy resin accelerator, and stir for 20 minutes at 500r / min-1000r / min at a temperature above 10°C; 2) Yarn threading: First, pull the fiber strands from the yarn rack to the yarn threading plate, then pass through the preformed plate in sequence according to the mold preformed design, and finally close and pass through the mold to collect single or double strands. After being tied firmly, connect the traction belt, and the traction belt is connected to the production line gantry; 3) Dipping: Press the fibers between the preformed plate and the threading plate down into the resin tank to fully soak them. Arrange a reflux guide device at the mold mouth to guide and collect the resin refluxed from the mold mouth, filter it, and then add it back into the tank for recycling; 4) Mold heating and curing: Turn on the temperature control on the production line console, adjust to the designed temperature, and use a thermometer to test until it is heated to the specified temperature; 5) Traction: Use an intermittent hydraulic press or crawler machine to pull the profile, and the travel speed of the hydraulic press or crawler machine is set to the same as the production speed; 6) Cutting: Use alloy saw blades to cut profiles that have reached the predetermined production length.

10. The method for manufacturing a high-performance and low-cost hybrid fiber composite material according to claim 9, characterized in that: The mold heating and curing needs to be divided into three temperature control zones: entrance section, middle section, and exit section; the entrance section temperature of the temperature control zone is 120-150°C, the middle section temperature is 140-190°C, the exit section temperature is 100-160°C, and the production speed is 20cm / min-50cm / min.

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