A continuous basalt fiber composite material and a method for manufacturing the same

Abstract

The present application relates to the technical field of composite materials, in particular to a continuous basalt fiber composite material and a preparation method thereof.The continuous basalt fiber composite material comprises continuous basalt fiber, aluminum borate whisker, carbon nanotube, epoxy resin, curing agent, silane coupling agent, titanate coupling agent and dispersing agent.In the continuous basalt fiber composite material and the preparation method thereof, the continuous basalt fiber is used as a reinforcing body to provide strength, the aluminum borate whisker is inserted between the fibers to play a bridge connecting role, and the carbon nanotube forms a three-dimensional network structure to tightly combine the components, thereby effectively improving the mechanical properties of the composite material, enhancing the hardness, wear resistance and impact resistance of the composite material.Meanwhile, the use of the silane coupling agent and the titanate coupling agent enhances the interfacial bonding force between the fibers, the whisker and the matrix, reduces the delamination and debonding phenomenon, improves the safety and durability of the ship structure, reduces the ship operation cost and improves the economic benefit.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of composite materials, in particular to a continuous basalt fiber composite material and a preparation method thereof. BACKGROUND

[0002] Currently, in the development process of the marine field of ships, the demand for lightweight and high-performance of ships is increasing, and fiber composite materials are widely used in the manufacturing of structural parts of ships, such as hulls, decks, etc., due to their advantages of lightweight and high strength. However, the marine environment is extremely complex and harsh, and the fiber composite material needs to withstand the impact of waves, mechanical vibration and repeated action of alternating load during the navigation of the ship.

[0003] In the prior art, some measures such as surface treatment of fibers and optimization of matrix resin formula have been taken for the application of fiber composite materials in the marine field of ships, which can improve the performance of the composite material. However, when the fiber composite material is subjected to external forces such as wave impact and vibration for many times, the delamination and debonding phenomenon between the fiber and the matrix still occurs frequently. This phenomenon not only leads to the decrease of the mechanical properties of the composite material, but also reduces the carrying capacity of the structure, the safety and durability of the ship structure, and affects the service life and normal operation of the ship. Therefore, it increases the maintenance cost and replacement frequency of the ship, increases the operating cost of the ship, and reduces the economic benefit of the ship operation.

[0004] Therefore, there is an urgent need for a continuous basalt fiber composite material and a preparation method thereof. SUMMARY

[0005] The present application aims to provide a continuous basalt fiber composite material and a preparation method thereof to solve the problems raised in the background.

[0006] To achieve the above-mentioned purpose, on the one hand, the present application provides a continuous basalt fiber composite material, which comprises the following raw materials:

[0007] The amount of continuous basalt fiber is 120-140 parts; the amount of aluminum borate whisker is 6-8 parts; the amount of carbon nanotube is 3-4 parts; the amount of epoxy resin is 110-126 parts; the amount of curing agent (such as amine curing agent) is 22-26 parts; the amount of silane coupling agent is 2.2-2.5 parts; the amount of titanate coupling agent is 0.5-0.8 parts; the amount of dispersing agent (such as sodium dodecyl benzene sulfonate) is 0.2-0.4 parts; wherein:

[0008] The continuous basalt fiber serves as a reinforcing body, the epoxy resin serves as a matrix, the continuous basalt fiber is wrapped to bond the fibers together to form an integral structure for stress transmission and fiber protection, so that the fibers are prevented from being directly contacted with the external environment to be chemically eroded and abraded, thereby prolonging the service life of the composite material; in addition, the aluminum borate whiskers and the carbon nanotubes are distributed around the continuous basalt fiber to form a reinforced interface region, and the aluminum borate whiskers are needle-shaped and can be inserted between the fibers to play a role of bridge connection.

[0009] The aluminum borate whiskers serve as a reinforcing phase and are dispersed in the epoxy resin matrix to improve the hardness, wear resistance and impact resistance of the composite material; after the surface modification of the aluminum borate whiskers by the titanate coupling agent, the aluminum borate whisker surface is provided with active groups that can react with the epoxy resin, so that the aluminum borate whiskers and the epoxy resin molecules can chemically react to form chemical bonds, thereby enhancing the compatibility and bonding strength between the aluminum borate whiskers and the epoxy resin.

[0010] The carbon nanotubes have high strength, electrical conductivity and thermal conductivity, and after being uniformly dispersed in the epoxy resin, the carbon nanotubes form a network structure to enhance the strength and toughness of the epoxy resin matrix; meanwhile, the carbon nanotubes have a one-dimensional tubular structure and a high specific surface area, and under the action of the dispersant, the molecules in the dispersant can be adsorbed on the surface of the carbon nanotubes to form a protective film, thereby reducing the interaction force between the carbon nanotubes and making the carbon nanotubes uniformly distributed in the epoxy resin; the carbon nanotubes can be intertwined and interwoven with the continuous basalt fiber and the aluminum borate whiskers to form a three-dimensional network structure, so that the continuous basalt fiber, the aluminum borate whiskers and the epoxy resin are closely combined together to jointly bear external force, thereby effectively reducing the delamination and debonding between the fiber and the matrix.

[0011] In the present application, the silane coupling agent molecule has amphiphilic properties, one end of which can react with the hydroxyl group on the surface of the continuous basalt fiber to form a stable silicon-oxygen bond, so that the silane coupling agent is grafted to the fiber surface; the other end of which has an organic functional group that can physically entangle and chemically react (such as forming a hydrogen bond) with the epoxy resin molecules, so that the combination between the fiber and the resin is more compact; this action enhances the interfacial bonding force between the continuous basalt fiber and the epoxy resin, so that the stress transmission between the matrix and the fiber is more efficient, and the overall mechanical properties of the composite material are effectively improved; the reaction between the silane coupling agent (represented as Si(OR)4, R is an organic group) and the fiber surface hydroxyl group (represented as F-OH, F represents the fiber) is as follows: Si(OR)4+nF-OH→(F-O) n Si(OR) 4-n +nROH; (wherein n is the stoichiometric number of the reaction, and 1≤n≤4), and then the silane coupling agent grafted on the fiber surface reacts with the epoxy resin.

[0012] However, when the titanate coupling agent is used to modify the surface of aluminum borate whiskers, the functional groups (such as alkoxy) at one end of the titanate coupling agent molecule will react with the hydroxyl groups on the surface of the aluminum borate whiskers to form chemical bonds, thereby grafting the titanate coupling agent onto the surface of the whiskers; the active groups (such as acyloxy) at the other end can chemically react with the active sites (such as hydroxyl groups, carboxyl groups) in the epoxy resin molecules to form chemical bonds (such as ester bonds); taking the reaction of the titanate coupling agent (R1O4Ti) with the aluminum borate whiskers (represented by AlBO3) and the epoxy resin (represented by containing active groups A) as an example, the reaction process is as follows: R1O4Ti + AlBO3-OH → R1O3Ti-O-AlBO3 + R1OH; then the active groups on R1O3Ti react with A in the epoxy resin, so that the aluminum borate whiskers are firmly combined with the epoxy resin; the formation of such chemical bonds enhances the compatibility and bonding strength between the aluminum borate whiskers and the epoxy resin, effectively improves the hardness, wear resistance and impact resistance of the composite material, thereby reducing the delamination and debonding phenomena at the interface.

[0013] On the other hand, according to Figure 1 The present application provides a method for preparing continuous basalt fiber composite material, comprising the following steps:

[0014] S1, surface treatment of continuous basalt fiber: put the continuous basalt fiber into a solution of silane coupling agent (KH-560) in xylene with a concentration of 1%-2% and soak for 2h-3h, so that the silane coupling agent molecules can fully react with the hydroxyl groups on the surface of the continuous basalt fiber; after soaking, rinse with xylene to remove the residual silane coupling agent, and then dry in an oven at 85°C-95°C for 3h-4h;

[0015] S2, surface modification of aluminum borate whiskers: add aluminum borate whiskers to a solution of titanate coupling agent (NDZ-201) with a concentration of 1%-2%, stir and react at a temperature of 65°C-75°C for 2h-3h, filter after the reaction is completed, rinse with xylene, and then dry in an oven at 105°C-115°C for 4h-5h;

[0016] S3, dispersion of carbon nanotubes: add carbon nanotubes and a dispersing agent to xylene, first perform ultrasonic dispersion for 2h-3h to effectively break the agglomeration of the carbon nanotubes, and then stir at a speed of 4500r / min-5500r / min for 2h-3h to further uniformly disperse the carbon nanotubes in the organic solvent, forming a uniform carbon nanotube suspension;

[0017] S4, epoxy resin mixing: pour the epoxy resin into a container, add dimethylbenzene to adjust the viscosity, the amount of dimethylbenzene is 0.3-0.8 times (mass ratio) of the amount of epoxy resin, then add the surface modified aluminum borate whisker and carbon nanotube suspension in sequence, use stirring equipment to mix at a speed of 800-1000 r / min for 2-3 h, so that the aluminum borate whisker and carbon nanotube are fully and uniformly dispersed in the epoxy resin, forming a uniformly mixed resin system;

[0018] S5, fiber impregnation: immerse the continuous basalt fiber after surface treatment in the uniformly mixed resin system, through shaking operation, let the resin fully impregnate the continuous basalt fiber, so that the epoxy resin, aluminum borate whisker and carbon nanotube are uniformly and closely wrapped on the surface of the fiber;

[0019] S6, curing forming: place the impregnated continuous basalt fiber into the mold according to the layering mode, the layering number is 3-9, the layering mode uses one of the mixed layering mode, the orthogonal layering mode and the angle layering mode, add the curing agent and uniformly mix with the resin system in the mold, put the mold into the heating equipment, first keep at a temperature of 120-150 DEG C for 2-3 h, so that the epoxy resin is preliminarily crosslinked; then raise the temperature to 150-180 DEG C, continue to keep for 1-2 h for post-curing, so that the epoxy resin is completely cured, finally obtain the continuous basalt fiber composite material.

[0020] Compared with the prior art, the beneficial effects of the present application are:

[0021] 1、The continuous basalt fiber composite material and the preparation method thereof, by the raw material amount of continuous basalt fiber, aluminum borate whisker, carbon nanotube and epoxy resin, a reinforcing structure is formed, the continuous basalt fiber provides strength as a reinforcing body, the aluminum borate whisker is inserted between the fibers to play a bridge connecting role, the carbon nanotube forms a three-dimensional network structure, which tightly combines each component, effectively improves the mechanical properties of the composite material, enhances the hardness, wear resistance and impact resistance, at the same time, the use of silane coupling agent and titanate coupling agent enhances the interfacial bonding force between the fiber, whisker and matrix, reduces the delamination and debonding phenomenon, improves the safety and durability of the ship structure, reduces the ship operation cost, thereby improving the economic benefit.

[0022] 2、The continuous basalt fiber composite material and the preparation method thereof, the surface treatment is carried out to the continuous basalt fiber, and silane coupling agent is grafted to make the combination with the epoxy resin matrix more firm, which is favorable for the effective transmission of stress;After the surface modification of aluminum borate whisker, chemical bond is formed with the epoxy resin, and the dispersibility and compatibility in the matrix are enhanced;Carbon nanotubes are uniformly distributed in the network structure of the epoxy resin by ultrasonic dispersion and high-speed stirring, which not only enhances the strength and toughness of the matrix itself, but also tightly winds and interweaves with the fiber and whisker, improves the resistance of the composite material to complex external load, reduces the delamination and debonding problems, and thus prolongs the service life of the material in the harsh marine environment. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The flowchart of the preparation method of the continuous basalt fiber composite material of the present application. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0025] Embodiment 1: The present application provides a preparation method of a continuous basalt fiber composite material, which is used in the manufacturing scene of ship hull structural parts, and includes the following steps:

[0026] Surface treatment of continuous basalt fiber: 120 parts of continuous basalt fiber are weighed and soaked in a 1% silane coupling agent (KH-560) xylene solution for 2h, then washed with xylene, and then dried in an oven at 85℃ for 3h to obtain the surface-treated continuous basalt fiber;

[0027] Surface modification of aluminum borate whisker: 6 parts of aluminum borate whisker are weighed and added to a 1% titanate coupling agent (NDZ-201) solution, stirred and reacted at 65℃ for 2h, filtered after the reaction, washed with xylene, and then dried in an oven at 105℃ for 4h to obtain the surface-modified aluminum borate whisker;

[0028] Dispersion of carbon nanotubes: 3 parts of carbon nanotubes and 0.2 parts of dispersant (sodium dodecyl benzene sulfonate) are added to xylene, ultrasonically dispersed for 2h, and then stirred at a speed of 4500r / min for 2h to form a uniform carbon nanotube suspension;

[0029] Epoxy resin mixing: 110 parts of epoxy resin was weighed into a container, 22 parts (0.4 times the mass ratio of the amount of epoxy resin) of dimethylbenzene was added to adjust the viscosity; then the surface modified aluminum borate whisker and carbon nanotube suspension were added in turn, and the stirring device was used to mix at a speed of 800 r / min for 2 h to form a uniformly mixed resin system;

[0030] Fiber impregnation: the continuous basalt fiber after surface treatment was immersed in the uniformly mixed resin system, and the resin was fully impregnated into the continuous basalt fiber by shaking operation, so that the epoxy resin, aluminum borate whisker and carbon nanotube were uniformly and closely wrapped on the surface of the fiber;

[0031] Curing forming: the impregnated continuous basalt fiber was placed in the mold according to the layering mode, the layering number was 3-5 layers, and the orthogonal layering mode (i.e. 0° / 90° alternating mode) was adopted, 22 parts of curing agent (amine curing agent) was added and uniformly mixed with the resin system in the mold, the mold was placed in the heating device, first kept at 120℃ for 2h to make the epoxy resin preliminary crosslinking; then the temperature was raised to 150℃, and the post-curing was continued for 1h to make the epoxy resin completely cured, and finally the continuous basalt fiber composite material for ship hull structure parts was obtained.

[0032] Comparative Example 1: A preparation method of continuous basalt fiber composite material was provided, which was used in the manufacturing scene of ship hull structure parts, including the following steps:

[0033] Surface treatment of continuous basalt fiber: the same as Example 1, but the continuous basalt fiber was 110 parts, which was soaked in water;

[0034] Surface modification of aluminum borate whisker: the same as Example 1, but the aluminum borate whisker was 10 parts;

[0035] Carbon nanotube dispersion: the same as Example 1, but the carbon nanotube was 2 parts and the dispersing agent was 0.1 part;

[0036] Epoxy resin mixing: the same as Example 1, but the epoxy resin was 130 parts;

[0037] Fiber impregnation: the same as Example 1;

[0038] Curing forming: the same as Example 1.

[0039] Comparative Example 2: A preparation method of continuous basalt fiber composite material was provided, which was used in the manufacturing scene of ship hull structure parts, including the following steps:

[0040] Surface treatment of continuous basalt fiber: the same as Example 1;

[0041] Aluminum borate whisker surface modification: the same as example 1, but aluminum borate whisker is taken 10 parts;

[0042] Carbon nanotube dispersion, epoxy resin mixing and fiber impregnation steps are the same as example 1;

[0043] Curing forming: the same as example 1, but the number of layers is 6, and unidirectional layering is used (all layers are 0°).

[0044] Comparative example 3: in the prior art, a single glass fiber reinforced epoxy resin composite material is used in the manufacturing scenario of ship hull structural parts, including the following steps:

[0045] Fiber preparation: take 120 parts of glass fiber without special surface treatment;

[0046] Resin mixing: take 110 parts of epoxy resin and add 22 parts (1 times the mass ratio of epoxy resin) of dimethylbenzene to adjust the viscosity;

[0047] Fiber impregnation: immerse the glass fiber in the epoxy resin, and let the resin soak the glass fiber by shaking operation;

[0048] Curing forming: the impregnated glass fiber is extruded into the mold using an extruder, 22 parts of curing agent (amine curing agent) is added, and the resin system in the mold is uniformly mixed, the mold is placed in a heating device, first at a temperature of 120℃ for 2h, the epoxy resin is preliminarily crosslinked; then the temperature is raised to 150℃, and the epoxy resin is completely cured by continuing to keep for 1h, finally the glass fiber reinforced epoxy resin composite material for ship hull structural parts is obtained.

[0049] Example 2: the present application provides a preparation method of continuous basalt fiber composite material, which is used in the manufacturing scenario of ship deck, including the following steps:

[0050] Continuous basalt fiber surface treatment: take 130 parts of continuous basalt fiber, immerse in a 2% silane coupling agent (KH-560) dimethylbenzene solution for 3h, then rinse with dimethylbenzene, and then place in a 95℃ oven for drying for 4h, to obtain the surface treated continuous basalt fiber;

[0051] Aluminum borate whisker surface modification: take 8 parts of aluminum borate whisker, add to a 2% solution of titanate coupling agent (NDZ-201), stir at a temperature of 75℃ for 3h, filter after reaction, rinse with dimethylbenzene, and then dry in a 115℃ oven for 5h, to obtain the surface modified aluminum borate whisker;

[0052] Carbon nanotube dispersion: 4 parts of carbon nanotubes and 0.4 parts of dispersant (sodium dodecyl benzene sulfonate) were weighed and added to xylene, first ultrasonic dispersion for 3 h, then stirred at a speed of 5500 r / min for 3 h to form a uniform carbon nanotube suspension;

[0053] Epoxy resin mixing: 126 parts of epoxy resin were weighed into a container, 100.8 parts (0.6 times the mass ratio of the amount of epoxy resin) of xylene were added to adjust the viscosity, then the surface modified aluminum borate whisker and carbon nanotube suspension were added in sequence, and a stirring device was used to mix at a speed of 1000 r / min for 3 h to form a uniformly mixed resin system;

[0054] Fiber impregnation: the surface treated continuous basalt fiber was immersed in the uniformly mixed resin system, and the resin was fully impregnated into the continuous basalt fiber by shaking operation, so that the epoxy resin, aluminum borate whisker and carbon nanotube were uniformly and tightly wrapped on the surface of the fiber;

[0055] Curing forming: the impregnated continuous basalt fiber was placed in the mold according to the layering mode, the layering number was 6-9 layers, the mixed layering mode (such as 0° / +45° / 90° / -45°) was adopted, 26 parts of curing agent (amine curing agent) was added and uniformly mixed with the resin system in the mold, the mold was placed in the heating device, first kept at 150℃ for 3 h to make the epoxy resin preliminary crosslinking; then the temperature was raised to 180℃, and the post-curing was continued for 2 h to make the epoxy resin completely cured, and finally the continuous basalt fiber composite material for ship deck was obtained.

[0056] Comparative example 4: a preparation method of a continuous basalt fiber composite material was provided, which was used in the manufacturing scene of ship deck, including the following steps:

[0057] Surface treatment of continuous basalt fiber: 140 parts of continuous basalt fiber were weighed without any surface treatment;

[0058] Surface modification of aluminum borate whisker: 8 parts of aluminum borate whisker were weighed without any surface modification treatment;

[0059] Carbon nanotube dispersion: 4 parts of carbon nanotubes were directly added to xylene, stirred at a speed of 5500 r / min for 3 h, without ultrasonic dispersion, and the carbon nanotubes may have agglomeration phenomenon;

[0060] The steps of epoxy resin mixing and fiber impregnation were the same as example 2;

[0061] Curing forming: the same as example 2, but the layering number was 11 layers, and the angle layering (±45° alternately) was adopted.

[0062] Comparative Example 5: A method for preparing a continuous basalt fiber composite material is provided for a ship deck manufacturing scenario, comprising the following steps:

[0063] The continuous basalt fiber surface treatment, carbon nanotube dispersion, epoxy resin mixing, fiber impregnation and curing forming steps are the same as Example 2, but the aluminum borate whisker surface modification step is not used, and no aluminum borate whisker is added.

[0064] Comparative Example 6: In the prior art, a single carbon fiber reinforced epoxy resin composite material is used in a ship deck manufacturing scenario, comprising the following steps:

[0065] Fiber preparation: 140 parts of carbon fiber are weighed without special surface treatment;

[0066] Resin mixing: 126 parts of epoxy resin are weighed into a container, and 100.8 parts (0.8 times the mass ratio of the amount of epoxy resin) of dimethylbenzene are added to adjust the viscosity;

[0067] Fiber impregnation: immerse the carbon fiber in the epoxy resin to allow the resin to impregnate the carbon fiber;

[0068] Curing forming: the impregnated carbon fiber is extruded into a mold using an extruder, 26 parts of a curing agent (an amine curing agent) is added, and the resin system in the mold is uniformly mixed, the mold is placed in a heating device, first at a temperature of 150°C for 3h to preliminarily crosslink the epoxy resin; then the temperature is raised to 180°C, and the post-curing is continued for 2h to completely cure the epoxy resin, and finally a carbon fiber reinforced epoxy resin composite material for a ship deck is obtained.

[0069] Test Example 1: The continuous basalt fiber composite material provided in Example 1 is compared with Comparative Example 1, Comparative Example 2 and Comparative Example 3

[0070] Test conditions: The test is carried out under standard room temperature environment (23°C ± 2°C) and relative humidity (55% ± 5%), simulating the static and dynamic load conditions that the ship may withstand in the marine environment, while avoiding external environmental factors from causing greater interference to the test results.

[0071] The test method is as follows:

[0072] Tensile strength test: according to the ASTM D3039 standard, the composite material is made into a standard tensile specimen (length 250mm, width 25mm, thickness 3mm), and tested on a universal material testing machine at a constant tensile speed of 5mm / min, the load change during the tensile process is recorded, the maximum tensile load is recorded when the specimen breaks, and the tensile strength is calculated by the formula, the calculation formula is: Wherein, σ represents tensile strength, unit is megapascal (MPa); F represents the maximum tensile load when the sample is broken, unit is Newton (N); b represents the width of the sample, unit is millimeter (mm), b=25mm in the standard tensile sample; t represents the thickness of the sample, unit is millimeter (mm), t=3mm in the standard tensile sample.

[0073] Bending strength test: according to the standard of ASTM D790, three-point bending test is carried out on the universal material testing machine; the span is set to 64mm, the loading speed is 2mm / min, the maximum bending load is recorded, the bending strength is calculated, and the calculation formula is: Wherein, σ is the bending strength (unit: MPa or N / mm 2 ); P is the maximum bending load (unit: N); L is the sample span (unit: mm); b is the sample width (unit: mm); h is the sample thickness (unit: mm).

[0074] Impact strength test: according to the standard of ASTM D256, simple beam impact test is carried out by using a pendulum impact testing machine; the impact pendulum energy is set to 5J, the impact strength is calculated according to the damage degree of the sample after impact, and the calculation formula is: Wherein, I represents the impact strength (unit: kJ / m 2 ); A represents the impact absorbed work (unit: J), that is, the initial energy of the impact pendulum minus the remaining energy of the pendulum after impact; b represents the sample width (unit: m); h represents the sample thickness (unit: m).

[0075] Interlaminar shear strength test: according to GB / T1450.1-2005 "Fiber Reinforced Plastic Interlaminar Shear Strength Test Method", interlaminar shear samples with a size of 20mm in length, 6mm in width and 4mm in thickness are prepared, and the test is carried out on the universal material testing machine at a speed of 2mm / min, the load when the sample is broken is recorded, and the calculation formula is: Wherein: τ is the interlaminar shear strength, unit is megapascal (MPa); P is the load when the sample is broken, unit is Newton (N); b is the width of the sample, unit is millimeter (mm); h is the thickness of the sample, unit is millimeter (mm).

[0076] Table 1 is the composite material detection index for ship hull structure parts

[0077]

[0078]

[0079] According to Table 1, when used for ship hull structure parts, the continuous basalt fiber composite material of Example 1 is obviously superior to Comparative Example 1, Comparative Example 2 and Comparative Example 3 in tensile strength, bending strength, interlaminar shear strength and impact toughness; the continuous basalt fiber in Comparative Example 1 is not properly treated (soaked with water) and the amount of each raw material is not properly proportioned, resulting in a significant decrease in mechanical properties; the unidirectional layering method used in Comparative Example 2 makes the material not as good as the orthogonal layering method of Example 1 in multi-directional mechanical properties, limiting the performance of the material; the single glass fiber reinforced epoxy resin composite material used in Comparative Example 3 has a comprehensive performance far inferior to that of the composite material of the present application; this fully shows that the continuous basalt fiber composite material and the preparation method thereof of the present application can effectively improve the comprehensive performance of the material, reduce the occurrence of delamination and debonding, and enhance the safety and durability of the ship hull structure parts.

[0080] Test Example 2: Comparative test of the continuous basalt fiber composite material provided in Example 2 with Comparative Example 4, Comparative Example 5 and Comparative Example 6

[0081] Test conditions: Under standard room temperature environment (23℃±2℃) and relative humidity (55%±5%), simulate the complex load (such as sea wave impact, mechanical vibration) and environmental erosion (such as salt spray corrosion, seawater immersion) that the ship deck may be subjected to in actual use; when testing salt spray corrosion, the salt solution concentration is set to 5% (mass fraction) and the test temperature is controlled at 35℃±2℃.

[0082] Test method:

[0083] Tensile strength test: same as the tensile strength test method of Test Example 1.

[0084] Bending strength test: same as the bending strength test method of Test Example 1.

[0085] Interlaminar shear strength test: same as the interlaminar shear strength test method of Test Example 1.

[0086] Salt spray corrosion resistance test: according to GB / T10125-2012 "Salt Spray Test for Artificial Atmosphere Corrosion Test", place the composite material sample in a salt spray test box, the salt solution concentration is 5% (mass fraction), the test temperature is 35℃±2℃, and the test time is 1200h; after the test, observe the corrosion condition of the sample surface (such as rust spots, coating peeling), and test the change rate of tensile strength, the calculation formula is: Wherein: Δσ represents the change rate of tensile strength; σ0 represents the tensile strength of the composite material before the test; σ1 represents the tensile strength of the composite material after the test.

[0087] Table 2 is the detection index of the composite material for ship deck

[0088] Example 2 Comparative Example 4 Comparative Example 5 Comparative Example 6 Tensile strength (MPa) 920 750 800 680 Flexural strength (MPa) 750 600 630 560 Interlaminar shear strength (MPa) 62 48 53 42 Change rate of tensile strength after salt spray corrosion resistance (%) 8 20 13 25

[0089] According to Table 2, when used for ship deck, the continuous basalt fiber composite material of Example 2 is obviously superior to Comparative Example 4, Comparative Example 5 and Comparative Example 6 in tensile strength, bending strength, interlaminar shear strength and salt spray corrosion resistance; the continuous basalt fiber and aluminum borate whisker in Comparative Example 4 are not surface treated, and the carbon nanotubes are not sufficiently dispersed (not ultrasonically dispersed), resulting in a significant decrease in the comprehensive performance and corrosion resistance of the material; Comparative Example 5 does not add aluminum borate whisker, so that the reinforcing effect of the material is weakened, and the performance indicators are relatively low; Comparative Example 6 uses a single carbon fiber reinforced epoxy resin composite material, which is not as good as the composite material of the application in salt spray corrosion resistance and comprehensive mechanical properties; this shows that the continuous basalt fiber composite material and the preparation method thereof can make the comprehensive performance and durability of the material better in the application of ship deck, effectively reduce the delamination and debonding problems caused by environmental erosion and external force, thereby prolonging the service life of the material.

[0090] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited by the above examples, and the above examples and descriptions in the specification are only preferred examples of the present application and are not intended to limit the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A continuous basalt fiber composite material, characterized by, The raw materials include the following: Continuous basalt fiber, aluminum borate whisker, carbon nanotube, epoxy resin, curing agent, silane coupling agent, titanate coupling agent and dispersant, wherein: The amount of the continuous basalt fiber is 120-140 parts; the amount of the aluminum borate whisker is 6-8 parts; the amount of the carbon nanotube is 3-4 parts; the amount of the epoxy resin is 110-126 parts; the amount of the curing agent is 22-26 parts; the amount of the silane coupling agent is 2.2-2.5 parts; the amount of the titanate coupling agent is 0.5-0.8 parts; and the amount of the dispersant is 0.2-0.4 parts; The continuous basalt fiber serves as a reinforcing body, and the epoxy resin serves as a matrix to wrap the continuous basalt fiber to form an overall structure for transmitting stress and protecting the fiber, in addition, the aluminum borate whisker and the carbon nanotube are distributed around the continuous basalt fiber to form an enhanced interface region; The aluminum borate whisker serves as a reinforcing phase and is dispersed in the epoxy resin matrix to improve the hardness, wear resistance and impact resistance of the composite material, and after the surface modification of the aluminum borate whisker by the titanate coupling agent, the surface of the aluminum borate whisker has active groups that can react with the epoxy resin to form a chemical bond; The carbon nanotube forms a network structure after being uniformly dispersed in the epoxy resin, and the carbon nanotube can be intertwined and interwoven with the continuous basalt fiber and the aluminum borate whisker to form a three-dimensional network structure; The aluminum borate whisker has a needle shape and can be inserted between the fibers; The carbon nanotube has a one-dimensional tubular structure and a high specific surface area, and under the action of the dispersant, the molecules in the dispersant can be adsorbed on the surface of the carbon nanotube to form a protective film, so that the carbon nanotube is uniformly distributed in the epoxy resin; The preparation method of the continuous basalt fiber composite material comprises the following steps: S1, surface treatment of continuous basalt fiber: immerse the continuous basalt fiber in a 1%-2% silane coupling agent xylene solution for 2-3 hours, then rinse with xylene, and then dry in an oven at 85-95°C for 3-4 hours; S2, surface modification of aluminum borate whisker: add the aluminum borate whisker to a 1%-2% titanate coupling agent solution, stir and react at 65-75°C for 2-3 hours, then filter, rinse with xylene, and then dry in an oven at 105-115°C for 4-5 hours; S3, dispersion of carbon nanotube: add the carbon nanotube and the dispersant to xylene, ultrasonically disperse for 2-3 hours to preliminarily disperse the carbon nanotube in the solution, and then stir at 4500-5500 r / min for 2-3 hours to further uniformly disperse the carbon nanotube in the organic solvent to form a uniform carbon nanotube suspension; S4, mixing of epoxy resin: pour the epoxy resin into a container, add xylene to adjust the viscosity, then add the surface-modified aluminum borate whisker and the carbon nanotube suspension in sequence, and mix using a stirring device to form a uniformly mixed resin system; S5, fiber impregnation: the surface treated continuous basalt fiber is immersed in the mixed uniform resin system, and the resin is fully impregnated into the continuous basalt fiber by shaking operation; S6, curing forming: the impregnated continuous basalt fiber is placed in the mold according to the layering mode, the curing agent is added, and the resin system in the mold is uniformly mixed, the mold is placed in the heating equipment for curing, and the continuous basalt fiber composite material is obtained. The layering mode is one of mixed layering mode, orthogonal layering mode and angle layering mode; the layering number of the layering mode is 3-9 layers.

2. A method for the production of the continuous basalt fiber composite material as claimed in claim 1, characterized in that, The method comprises the following steps: S1, continuous basalt fiber surface treatment: the continuous basalt fiber is immersed in a 1%-2% silane coupling agent xylene solution for 2-3 hours, then washed with xylene, and then dried in an oven at 85-95℃ for 3-4 hours; S2, aluminum borate whisker surface modification: the aluminum borate whisker is added to a 1%-2% titanate coupling agent solution, stirred and reacted at 65-75℃ for 2-3 hours, filtered after the reaction, washed with xylene, and then dried in an oven at 105-115℃ for 4-5 hours; S3, carbon nanotube dispersion: the carbon nanotube and the dispersant are added to xylene, ultrasonic dispersion is carried out for 2-3 hours to preliminarily disperse the carbon nanotube in the solution, and then stirring is carried out at a speed of 4500-5500 r / min for 2-3 hours to further uniformly disperse the carbon nanotube in the organic solvent, forming a uniform carbon nanotube suspension; S4, epoxy resin mixing: the epoxy resin is poured into a container, xylene is added to adjust the viscosity, then the surface modified aluminum borate whisker and the carbon nanotube suspension are sequentially added, and a mixed uniform resin system is formed by mixing with a stirring device; S5, fiber impregnation: the surface treated continuous basalt fiber is immersed in the mixed uniform resin system, and the resin is fully impregnated into the continuous basalt fiber by shaking operation; S6, curing forming: the impregnated continuous basalt fiber is placed in the mold according to the layering mode, the curing agent is added, and the resin system in the mold is uniformly mixed, the mold is placed in the heating equipment for curing, and the continuous basalt fiber composite material is obtained.

3. The method of claim 2, wherein the continuous basalt fiber composite material is characterized by, In S4, the amount of xylene is 0.3-0.8 times the amount of epoxy resin.

4. The method of claim 2, wherein the continuous basalt fiber composite material is characterized by, In S4, the stirring device is mixed at a speed of 800-1000 r / min for 2-3 hours.

5. The method of claim 2, wherein the continuous basalt fiber composite material is characterized by, In S6, the layering number of the layering mode is 3-9 layers.

6. The method of claim 2, wherein the continuous basalt fiber composite material is characterized by, In S6, the layering mode is one of mixed layering mode, orthogonal layering mode and angle layering mode.

7. The method of claim 2, wherein the continuous basalt fiber composite material is characterized by, In S6, during the curing process, the heating equipment is first kept at a temperature of 120-150℃ for 2-3 hours to preliminarily crosslink the epoxy resin; then the temperature is raised to 150-180℃, and the post-curing is continued for 1-2 hours to completely cure the epoxy resin.

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