Fiber reinforced composite material and preparation method and application thereof, road traffic signboard

Abstract

The application belongs to the technical field of signboard materials, and particularly relates to a fiber-reinforced composite material, a preparation method and application thereof, and a road traffic signboard. The fiber-reinforced composite material provided by the application comprises a matrix and a reinforcing body embedded in the matrix; the reinforcing body is a laminated basalt fiber cloth; the basalt fiber cloths on the upper and lower surfaces of the reinforcing body are all plain cloths woven by basalt fibers; the included angle of the basalt fibers in any two adjacent layers of the basalt fiber cloths is 0-90 DEG; and the matrix is a resin. The composite material provided by the application improves the mechanical properties, ultraviolet aging resistance and salt mist corrosion resistance of the fiber-reinforced composite material under the joint action of the basalt fibers and the resin, and the traffic signboard prepared by using the composite material has a longer service life.

Description

Technical Field

[0001] This invention belongs to the field of signboard material technology, specifically relating to a fiber-reinforced composite material, its preparation method and application, and road traffic signs. Background Technology

[0002] Road traffic signs are safety facilities that use graphic symbols and text to convey specific information in order to manage road traffic. They are generally installed on the side of the road or above the road (gantry type).

[0003] Most existing road traffic signs are made of aluminum alloy, generally using grade 3003 aluminum alloy sheets; large signs (15m) 2 (The above) or signs used in coastal and windy areas generally use aluminum alloy sheets of grade 3004 or 3104. Although aluminum alloy materials are relatively lightweight and strong, they are easily contaminated, corroded and damaged after long-term exposure to wind and rain, temperature fluctuations, ultraviolet radiation, and salt spray in complex outdoor environments. They have poor aging resistance and short service life, which seriously affects road driving safety.

[0004] Therefore, developing a new material with strong durability to replace aluminum alloy materials in the manufacture of road traffic signs is of great significance for maintaining the long-term stable and high-quality operation of highway facilities. Summary of the Invention

[0005] In view of this, the present invention provides a fiber-reinforced composite material, its preparation method and application, and a road traffic sign. The fiber-reinforced composite material provided by the present invention has the advantages of being lightweight, high-strength and having good aging resistance, and the traffic signs made from it have a long service life.

[0006] To address the aforementioned technical problems, the present invention provides a fiber-reinforced composite material, comprising a matrix and a reinforcement embedded in the matrix;

[0007] The reinforcement is a layered basalt fiber cloth; the basalt fiber cloth on the upper and lower surfaces of the reinforcement is plain weave cloth woven from basalt fibers; the included angle between the basalt fibers in any two adjacent layers of basalt fiber cloth is 0 to 90°.

[0008] The matrix is ​​resin.

[0009] Preferably, the basalt fiber cloth in the reinforcement, excluding the upper and lower surfaces, includes one or more of plain weave cloth, unidirectional cloth, and multiaxial cloth woven from basalt fibers.

[0010] Preferably, the resin includes epoxy resin, vinyl resin, or unsaturated resin;

[0011] The resin also includes a modified metal oxide; the modified metal oxide is a metal oxide with a coupling agent grafted onto its surface;

[0012] The mass ratio of modified metal oxide to resin in the matrix is ​​0.3 to 6:100.

[0013] Preferably, the modified metal oxide includes one or more of modified cerium oxide, modified zinc oxide, and modified titanium oxide.

[0014] Preferably, the method for preparing the modified cerium oxide includes the following steps:

[0015] The first coupling agent is dissolved in a first aqueous ethanol solution to obtain a coupling agent solution;

[0016] The nano-cerium oxide particles were first dispersed in water to obtain a cerium oxide dispersion.

[0017] The coupling agent solution and cerium oxide dispersion were first mixed and the pH value was adjusted to 7-11 before the first grafting modification was performed to obtain the modified cerium oxide.

[0018] The method for preparing the modified zinc oxide includes the following steps:

[0019] The nano-zinc oxide particles were further dispersed in a second aqueous ethanol solution to obtain a zinc oxide dispersion.

[0020] The zinc oxide dispersion and the second coupling agent are mixed for a second grafting modification to obtain the modified zinc oxide.

[0021] The method for preparing the modified titanium oxide includes the following steps:

[0022] The nano-titanium oxide particles were dispersed in water to obtain a titanium oxide dispersion.

[0023] The titanium dioxide dispersion, the third coupling agent, and ethanol were mixed and the pH was adjusted to 5-7 before the third grafting modification was performed to obtain the modified titanium dioxide.

[0024] The present invention also provides a method for preparing the fiber-reinforced composite material described in the above technical solution, comprising the following steps:

[0025] The resin and curing agent are mixed to obtain a composite resin;

[0026] Basalt fiber cloth is layered to obtain a reinforcing body; the basalt fiber cloth on the upper and lower surfaces of the reinforcing body is plain weave cloth woven from basalt fibers; the included angle between the basalt fibers in any two adjacent layers of basalt fiber cloth is 0 to 90°.

[0027] The composite resin and the reinforcing agent are mixed and molded to obtain the fiber-reinforced composite material.

[0028] Preferably, the mass ratio of the curing agent to the resin is 60-100:100;

[0029] Modified metal oxides are also added during the mixing process;

[0030] The molding method includes vacuum injection molding;

[0031] The vacuum injection molding process is carried out at a temperature of 150–200°C, a pressure of 3–5 MPa, and a time of 80–120 min.

[0032] The present invention also provides the application of the fiber-reinforced composite material described in the above technical solution or the fiber-reinforced composite material prepared by the preparation method described in the above technical solution in the preparation of road traffic signs.

[0033] The present invention also provides a road traffic sign, including a base plate, a groove disposed on one side of the base plate, and a reflective film disposed on the other side of the base plate;

[0034] The base plate is the fiber-reinforced composite material described in the above technical solution or the fiber-reinforced composite material prepared by the preparation method described in the above technical solution.

[0035] Preferably, the groove is made of aluminum alloy.

[0036] The connection method between the slide and the base plate includes riveting or adhesive riveting; the adhesive used for adhesive riveting includes epoxy resin, vinyl resin or unsaturated resin.

[0037] This invention provides a fiber-reinforced composite material, comprising a matrix and a reinforcement embedded in the matrix; the reinforcement is a layered basalt fiber cloth; the basalt fiber cloth on both the upper and lower surfaces of the reinforcement is a plain weave fabric made of basalt fibers; the included angle between the basalt fibers in any two adjacent layers of basalt fiber cloth is 0–90°; the matrix is ​​resin. This invention lays up basalt fiber cloth in a specific order to form the reinforcement, significantly improving the mechanical properties of the composite material while ensuring its lightweight; the use of resin as the matrix material ensures good corrosion resistance; the composite material provided by this invention, through the combined action of basalt fibers and resin, improves the mechanical properties, UV aging resistance, and salt spray corrosion resistance of the fiber-reinforced composite material, resulting in traffic signs with a longer service life. Attached Figure Description

[0038] Figure 1 This is a rear view of the road traffic sign prepared according to the present invention;

[0039] Figure 2This is a side view of the road traffic sign prepared according to the present invention;

[0040] Figure 3 A cross-sectional view (AA) of the road traffic sign prepared according to the present invention;

[0041] In the figure, 1 is the base plate, 2 is the aluminum alloy slide, 3 is the reflective film, and 4 is the rivet. Detailed Implementation

[0042] The present invention provides a fiber-reinforced composite material, comprising a matrix and a reinforcement embedded in the matrix.

[0043] In this invention, the matrix is ​​a resin; the resin may include epoxy resin, vinyl resin, or unsaturated resin. As a specific embodiment of this invention, the resin may further include a modified metal oxide; the modified metal oxide is a metal oxide with a coupling agent grafted onto its surface; the mass ratio of the modified metal oxide to the resin in the matrix can be 0.3 to 6:100, specifically 0.5:100, 1:100, 2:100, 3:100, 4:100, 5:100, or 6:100.

[0044] As a specific embodiment of the present invention, the modified metal oxide may include one or more of modified cerium oxide, modified zinc oxide, and modified titanium oxide, and may specifically be a mixture of modified cerium oxide, modified zinc oxide, and modified titanium oxide, a mixture of modified cerium oxide and modified zinc oxide, a mixture of modified cerium oxide and modified titanium oxide, a mixture of modified zinc oxide and modified titanium oxide, or modified cerium oxide, modified zinc oxide, or modified titanium oxide. In one specific embodiment of the present invention, when the modified metal oxide is a mixture of modified cerium oxide, modified zinc oxide, and modified titanium oxide, the mass ratio of the modified cerium oxide, modified zinc oxide, and modified titanium oxide can be 1.0–2.5:0.5–1.5:1.0, specifically 2.5:1.5:1.0; when the modified metal oxide is a mixture of modified cerium oxide and modified zinc oxide, the mass ratio of the modified cerium oxide and modified zinc oxide can be 1.5–3.0:1; when the modified metal oxide is a mixture of modified cerium oxide and modified titanium oxide, the mass ratio of the modified cerium oxide and modified titanium oxide can be 1.0–2.0:1; when the modified metal oxide is a mixture of modified zinc oxide and modified titanium oxide, the mass ratio of the modified zinc oxide and modified titanium oxide can be 0.5–1.5:1. In one specific embodiment of the present invention, when the modified metal oxide is modified cerium oxide, the mass ratio of the modified cerium oxide to the resin can be 3 to 5:100; when the modified metal oxide is modified zinc oxide, the mass ratio of the modified zinc oxide to the resin can be 0.5 to 3:100; and when the modified metal oxide is modified titanium oxide, the mass ratio of the modified titanium oxide to the resin can be 1 to 5:100.

[0045] As a specific embodiment of the present invention, the method for preparing the modified cerium oxide may include the following steps:

[0046] The first coupling agent is dissolved in a first aqueous ethanol solution to obtain a coupling agent solution;

[0047] The nano-cerium oxide particles were first dispersed in water to obtain a cerium oxide dispersion.

[0048] After the coupling agent solution and cerium oxide dispersion are first mixed and the pH value is adjusted to 7-11, the first grafting modification is performed to obtain the modified cerium oxide.

[0049] In one specific embodiment of the present invention, the first coupling agent can be a silane coupling agent, specifically KH550, KH560, or KH570 coupling agent; the volume fraction of ethanol in the first ethanol aqueous solution can be 70-80%, or even 70-75%; the volume ratio of the first coupling agent to the first ethanol aqueous solution can be 4-6:100, or even 5-6:100. In another specific embodiment of the present invention, the first dissolution can be carried out under stirring conditions, and the stirring time can be 20-30 minutes; the present invention has no special requirements for the stirring speed, as long as complete dissolution is achieved.

[0050] In one specific embodiment of the present invention, the average particle size of the nano-cerium oxide particles can be 30-100 nm, or 50-80 nm; the water can be deionized water; the mass ratio of the nano-cerium oxide particles to water can be 10-15:100, or 12-14:100. In another specific embodiment of the present invention, the first dispersion can be carried out under stirring conditions, and the stirring time can be 40-60 min; the present invention has no special requirements on the stirring speed, as long as uniform dispersion is achieved.

[0051] This invention does not impose any particular limitation on the first mixture, as long as it can be mixed evenly. In one specific embodiment of this invention, the pH value of the system after the first mixture is 7-11, and can also be 8-10; this invention does not impose any particular requirements on the method of adjusting the pH value, and conventional methods in the art can be used. In one specific embodiment of this invention, the temperature of the first grafting modification can be 65-75℃, and can also be 68-70℃; the time of the first grafting modification can be 6-8 hours; this invention can involve stirring during the first grafting modification process, and this invention does not impose any particular requirements on the stirring, as long as the reaction is sufficient.

[0052] In one specific embodiment of the present invention, the first grafting modification may further include: performing solid-liquid separation on the first grafted modified system, washing the solid obtained from the solid-liquid separation with water, and then freeze-drying it to obtain the modified cerium oxide. In another specific embodiment of the present invention, the solid-liquid separation may be centrifugation; the freeze-drying temperature may be -80 to -40°C, or -60 to -50°C; and the freeze-drying time may be more than 24 hours, or 24 to 30 hours.

[0053] As a specific embodiment of the present invention, the method for preparing the modified zinc oxide may include the following steps:

[0054] The nano-zinc oxide particles were further dispersed in a second aqueous ethanol solution to obtain a zinc oxide dispersion.

[0055] The zinc oxide dispersion and the second coupling agent are mixed for a second grafting modification to obtain the modified zinc oxide.

[0056] In one specific embodiment of the present invention, the average particle size of the nano-zinc oxide particles can be 30-100 nm, or even 50-80 nm; the volume fraction of ethanol in the second ethanol aqueous solution can be 70-80%, or even 70-75%; the mass ratio of the nano-zinc oxide particles to the volume ratio of the second ethanol aqueous solution can be 5-8 mg:1 mL, or even 6-7 mg:1 mL. In another specific embodiment of the present invention, the second dispersion can be carried out under ultrasonic conditions for 20-30 minutes; the present invention has no special requirements for the power of the ultrasonic waves, as long as uniform dispersion is achieved.

[0057] In one specific embodiment of the present invention, the second coupling agent can be a silane coupling agent or a titanate coupling agent, specifically KH550 coupling agent, KH560 coupling agent or KH570 coupling agent; the volume ratio of the second coupling agent and the second ethanol aqueous solution can be 3 to 5:100, or it can be 4 to 5:100.

[0058] The present invention has no special requirements for the second mixing, as long as it can be mixed evenly.

[0059] In one specific embodiment of the present invention, the temperature of the second grafting modification can be 50-80°C or 60-70°C; the time of the second grafting modification can be 6-8 hours; the present invention can be accompanied by stirring and reflux during the second grafting modification process, and the present invention has no special requirements for the stirring, as long as the reaction can be fully achieved.

[0060] In one specific embodiment of the present invention, the second grafting modification may further include: performing solid-liquid separation on the second grafted modified system, washing the solid obtained from the solid-liquid separation with water, and then vacuum drying to obtain the modified zinc oxide. In another specific embodiment of the present invention, the solid-liquid separation may be centrifugation; the water used for washing may be deionized water; the temperature of the vacuum drying may be 35–45°C, or 35–40°C; and the vacuum drying time may be 8–12 hours or more, or 9–10 hours.

[0061] As a specific embodiment of the present invention, the method for preparing the modified titanium oxide may include the following steps:

[0062] The nano-titanium oxide particles were dispersed in water to obtain a titanium oxide dispersion.

[0063] The titanium dioxide dispersion, the third coupling agent, and ethanol were mixed and the pH was adjusted to 5-7 before the third grafting modification was performed to obtain the modified titanium dioxide.

[0064] In one specific embodiment of the present invention, the average particle size of the nano-titanium oxide particles can be 30-100 nm, or 50-80 nm; the water can be deionized water; the mass ratio of the nano-titanium oxide particles to water can be 3-5:100, or 4-5:100. In another specific embodiment of the present invention, the third dispersion can be carried out under stirring conditions, and the stirring time can be 20-30 minutes; the present invention has no special requirements for the stirring speed, as long as uniform dispersion is achieved.

[0065] In one specific embodiment of the present invention, the third coupling agent may be a silane coupling agent or a titanate coupling agent, specifically KH550 coupling agent, KH560 coupling agent or KH570 coupling agent; the ethanol may be anhydrous ethanol; the mass ratio of the nano-titanium oxide particles to the third coupling agent may be 1 to 2:1; the volume ratio of ethanol to water may be 1:2.

[0066] The present invention has no special requirements for the third mixing, as long as it can be mixed evenly; the present invention has no special requirements for the method of adjusting the pH value of the system after the third mixing, and conventional methods in the art can be used.

[0067] In one specific embodiment of the present invention, the temperature of the third grafting modification can be 40-60°C or 45-50°C; the time of the third grafting modification can be 1-2 hours; the present invention may be accompanied by stirring during the third grafting modification process, and the present invention has no special requirements for the stirring, as long as the reaction can be fully achieved.

[0068] In one specific embodiment of the present invention, the third grafting modification may further include: performing solid-liquid separation on the third grafting modified system, and drying the solid obtained from the solid-liquid separation to obtain the modified titanium oxide. In another specific embodiment of the present invention, the solid-liquid separation may be filtration; the drying may be baking, and the baking temperature may be 100–120°C or 100–110°C; the present invention has no special requirements for the baking time, as long as the surface solvent is removed.

[0069] The modified metal oxide added to the resin in this invention has the function of absorbing ultraviolet rays, which can further improve the UV aging resistance of the composite material, and at the same time has the effect of strengthening and toughening the resin.

[0070] In this invention, the reinforcement is a layered basalt fiber cloth; the basalt fiber cloth on both the upper and lower surfaces of the reinforcement is a plain weave cloth woven from basalt fibers; the included angle between the basalt fibers in any two adjacent layers of basalt fiber cloth is 0–90°, specifically 0°, 45°, or 90°. As a specific embodiment of this invention, the basalt fiber cloth in the reinforcement, excluding the upper and lower surfaces, may include one or more of the following: plain weave cloth, unidirectional cloth, and multiaxial cloth woven from basalt fibers. In this invention, when the basalt fiber cloth in the reinforcement, excluding the upper and lower surfaces, is a plain weave cloth, a multiaxial cloth, or a unidirectional cloth, the plain weave is arranged on the outer layer of the composite material, the unidirectional cloth is arranged in the middle of the composite material, and the multiaxial cloth is arranged between the plain weave and unidirectional cloth layers. This invention does not have special requirements on the number of basalt fiber cloth layers in the reinforcement; the design can be based on the thickness of the fiber-reinforced composite material.

[0071] The present invention also provides a method for preparing the fiber-reinforced composite material described in the above technical solution, comprising the following steps:

[0072] The resin and curing agent are mixed to obtain a composite resin;

[0073] Basalt fiber cloth is layered to obtain a reinforcing body; the basalt fiber cloth on the upper and lower surfaces of the reinforcing body is plain weave cloth woven from basalt fibers; the included angle between the basalt fibers in any two adjacent layers of basalt fiber cloth is 0 to 90°.

[0074] The composite resin and the reinforcing agent are mixed and molded to obtain the fiber-reinforced composite material.

[0075] In one specific embodiment of the present invention, the mass ratio of the curing agent to the resin can be 60-100:100, or it can be 70-90:100.

[0076] In one specific embodiment of the present invention, a modified metal oxide may be added during the mixing process; the mass ratio of the total mass of the resin and curing agent to the mass of the modified metal oxide can be 100:0.3 to 6, specifically 100:0.5, 100:1, 100:2, 100:3, 100:4, 100:5, or 100:6. The present invention does not impose any particular limitation on the mixing method, as long as the mixture is homogeneous.

[0077] In one specific embodiment of the present invention, the pre-molding process may further include the following steps: during the layup of basalt fibers, the surface of each layer of basalt fiber cloth is coated with the composite resin, and then pre-molding is performed. In another specific embodiment of the present invention, the mass of the composite resin coated on the unit surface of each layer of basalt fiber cloth can be 120–180 g / m². 2 It can also be 140-160 g / m2 In one specific embodiment of the present invention, the preforming method can be compression molding; the compression molding temperature can be 80-100℃, or 85-95℃; the compression molding pressure can be 0.8-1.2MPa, or 1MPa; the compression molding holding time can be 55-65min, or 60min.

[0078] As a specific embodiment of the present invention, the molding method may include vacuum injection molding; the temperature of the vacuum injection molding may be 150-200℃ or 160-180℃; the pressure of the vacuum injection molding may be 3-5MPa or 3-4MPa; the heat preservation and pressure holding time of the vacuum injection molding may be 80-120min or 90-110min.

[0079] In one specific embodiment of the present invention, the molding process may further include: demolding followed by edge trimming to obtain the fiber-reinforced composite material. The present invention does not impose special requirements on the demolding and edge trimming processes; conventional methods in the art can be employed.

[0080] The present invention also provides the application of the fiber-reinforced composite material described in the above technical solution or the fiber-reinforced composite material prepared by the preparation method described in the above technical solution in the preparation of road traffic signs.

[0081] The present invention also provides a road traffic sign, including a base plate, a groove disposed on one side of the base plate, and a reflective film disposed on the other side of the base plate;

[0082] The base plate is the fiber-reinforced composite material described in the above technical solution or the fiber-reinforced composite material prepared by the preparation method described in the above technical solution.

[0083] In one specific embodiment of this invention, the slide groove can be made of aluminum alloy, specifically grade 3004 or 3104. The slide groove can be shaped into a circle, triangle, rectangle, or regular hexagon, depending on actual needs. In another specific embodiment, the connection between the slide groove and the base plate includes riveting or adhesive riveting. The adhesive used for adhesive riveting includes epoxy resin, vinyl ester resin, or unsaturated resin, which can be consistent with the matrix resin in fiber-reinforced composite materials. The riveting or adhesive riveting connection method used in this invention ensures a flat surface on the marking plate and provides high connection strength.

[0084] In one specific embodiment of the present invention, the reflective film can be adhered to the other side of the base plate.

[0085] Figure 1This is a rear view of the road traffic sign prepared according to the present invention. Figure 2 Its side view, Figure 3 Here is its AA cross-sectional view, where 1 is the base plate, 2 is the aluminum alloy slide, 3 is the reflective film, and 4 is the rivet.

[0086] The traffic sign prepared by this invention has the following advantages:

[0087] 1. This invention uses basalt fiber reinforced resin composite material as the sign base plate. A combination of adhesive and riveting is used to connect the sliding groove to the sign base plate before installation onto the post. The sign plate with the basalt fiber reinforced resin composite material layer as the base plate meets all relevant national standards. Compared with aluminum alloy traffic sign plates, it has higher mechanical properties, better resistance to ultraviolet aging, and better resistance to salt spray corrosion, resulting in a longer service life.

[0088] 2. While ensuring a long-term reliable connection (bonding) between the structural components and the reflective film and the base plate, this invention effectively reduces the number of processes, improves manufacturing efficiency, and correspondingly further reduces costs. The cost of the sign plate using basalt fiber reinforced resin composite material as the base plate is more than 30% lower than that of the aluminum alloy sign plate.

[0089] 3. This invention uses basalt fiber reinforced resin composite material as the base plate to manufacture traffic sign boards, which can reduce the use of aluminum and lower the consumption of raw materials and energy during aluminum production. At the same time, basalt fiber, as a green and environmentally friendly material, greatly reduces carbon emissions during the production process.

[0090] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0091] In this embodiment, the layup angle of the basalt fiber cloth is defined as follows: the orientation of each layer of fiber cloth is determined by the orientation of the fiber cloth product. The initial layup direction (i.e., the system coordinate axis direction) is defined as 0°. Positive and negative direction angles are used to define the fiber cloth layup direction, with a range of 0° to 90°. Fiber cloth with an orientation direction between 0° and 90° is represented by the angle between the fiber cloth orientation direction and 0°, plus "+" or "-". If the fiber cloth is arranged in the positive quadrant of the coordinate axis, it is represented by "+", and if the fiber cloth is arranged in the negative quadrant of the coordinate axis, it is represented by "-". The layers are arranged in a top-to-bottom layup order, separated by " / ".

[0092] Example 1

[0093] Modified metal oxides were prepared according to the following method:

[0094] Modified CeO2 nanoparticles were prepared by the following method:

[0095] The silane coupling agent KH550 was dissolved in a 75% (v / v) aqueous ethanol solution under stirring (25 min) to obtain silane coupling agent aqueous solution A; wherein the volume ratio of coupling agent KH550 to aqueous ethanol solution was 5:100.

[0096] Add nano-CeO2 particles with an average particle size of 60 nm to deionized water of the same volume as silane coupling agent KH550, and stir for 50 min to obtain cerium oxide dispersion; wherein the mass ratio of nano-CeO2 particles to water is 13:100.

[0097] The cerium oxide dispersion was poured into an aqueous solution of silane coupling agent A, and the pH was adjusted to 10 using glacial acetic acid. The first grafting modification was carried out by stirring at 70°C for 7 hours. After centrifugation, the solid obtained by centrifugation was washed three times with deionized water and then freeze-dried at -80°C for 24 hours to obtain modified nano CeO2 particles.

[0098] Modified ZnO nanoparticles were prepared by the following method:

[0099] Zinc oxide dispersion was obtained by ultrasonically dispersing ZnO nanoparticles with an average particle size of 50 nm in a 75% (v / v) ethanol aqueous solution for 25 min; wherein the mass ratio of ZnO nanoparticles to the volume of ethanol aqueous solution was 7 mg: 1 mL.

[0100] The silane coupling agent KH550 was poured into the zinc oxide dispersion and stirred under reflux at 60°C for 7 hours for the second grafting modification, followed by centrifugation. The solid obtained by centrifugation was washed with deionized water and vacuum dried at 40°C for 10 hours to obtain modified ZnO nanoparticles. The volume ratio of silane coupling agent KH550 to aqueous ethanol solution was 4:100.

[0101] Modified TiO2 nanoparticles were prepared by the following method:

[0102] TiO2 nanoparticles with an average particle size of 70 nm were stirred in deionized water for 25 min, and then silane coupling agent KH550 and anhydrous ethanol were added. The pH of the system was adjusted to 6 using citric acid, and the mixture was stirred at 50 °C for 2 h for third grafting modification. The third grafted modified system was filtered, and the solid obtained by filtration was dried at 100 °C and ground to obtain modified TiO2 nanoparticles. The mass ratio of TiO2 nanoparticles to deionized water was 4:100, the mass ratio of TiO2 nanoparticles to silane coupling agent KH550 was 2:1, and the volume ratio of anhydrous ethanol to deionized water was 1:2.

[0103] Epoxy resin and curing agent (5313A / B) were mixed at a mass ratio of 1:1 and stirred evenly. Then, the mixture was combined with modified CeO2 nanoparticles, modified ZnO nanoparticles, and modified TiO2 nanoparticles at a mass ratio of 2.5:1.5:1.0 to obtain a composite epoxy resin. The total mass ratio of the modified CeO2 nanoparticles, modified ZnO nanoparticles, and modified TiO2 nanoparticles to the total mass ratio of epoxy resin and curing agent was 5:100.

[0104] Using a mold that matches the size of the reinforcement and applying a release agent, basalt fiber cloth is cut and laid up. The layup sequence from top to bottom is: plain weave 0° / plain weave -45° / plain weave 0° / plain weave +45° / plain weave 0°.

[0105] During the layup of basalt fibers, the surface of each layer of basalt fiber cloth is coated with the composite epoxy resin, and the mass of resin coated per unit surface of each layer of basalt fiber cloth is 150 g / m². 2 Then, a preforming process is performed. The preforming method is compression molding. The compression molding temperature is 80℃, the pressure is 1.0 MPa, and the heat and pressure holding time is 60 min.

[0106] After the preforming process is completed, the layered basalt fiber cloth and composite resin are molded and cured using a vacuum injection molding process, and then demolded and trimmed to obtain fiber-reinforced composite material; the molding temperature is 170℃, the pressure is 4MPa, and the heat and pressure holding time is 100min.

[0107] Example 2

[0108] The fiber-reinforced composite material was prepared according to the method of Example 1, except that the layup sequence of the basalt fiber cloth from top to bottom was: plain weave 0° / unidirectional cloth -45° / unidirectional cloth 0° / unidirectional cloth +45° / plain weave 0°.

[0109] Example 3

[0110] The fiber-reinforced composite material was prepared according to the method of Example 1, except that the modified metal oxide in the composite resin was a single modified TiO2 nanoparticle.

[0111] Example 4

[0112] The fiber-reinforced composite material was prepared according to the method of Example 1, except that the layup sequence of the basalt fiber cloth from top to bottom was: plain weave 0° / unidirectional cloth 0° / unidirectional cloth 90° / unidirectional cloth 0° / plain weave 0°; no modified metal oxides were added to the resin.

[0113] Comparative Example 1

[0114] Fiber-reinforced composite materials were prepared according to the method of Example 1, except that basalt fiber cloth was replaced with glass fiber cloth.

[0115] Comparative Example 2

[0116] Fiber-reinforced composite materials were prepared according to the method of Example 2, except that basalt fiber cloth was replaced with glass fiber cloth.

[0117] Comparative Example 3

[0118] A 3mm thick aluminum alloy sheet of model 3004 was used as a comparative example.

[0119] Traffic signs were prepared using the materials from Examples 1-4 and Comparative Examples 1-3 according to the following method: The materials from Examples 1-4 and Comparative Examples 1-3 were used as the base plates. One side of the base plate was riveted to an aluminum alloy groove using adhesive. The adhesive used was epoxy resin, a resin material derived from the same source as that used in the preparation of the basalt fiber composite board. The adhesive riveting process was carried out according to the following steps:

[0120] Drill holes in the pre-overlapping area using a drilling machine; the hole size should be slightly larger than the rivet diameter. After thoroughly mixing the adhesive, immediately apply it to the pre-overlapping area. Then, insert the rivets into the holes and use a press-fit connection method. Hammer the rivet heads firmly to rivet the aluminum alloy groove and the sign base plate together. Finally, cure the sign plate by placing it in a 60℃ constant temperature oven for 1 hour. After curing, remove it and cure at room temperature for 24 hours. Engrave the lettering on the reflective film according to the design requirements, then clean and dry the flat surface of the base plate. After drying, paste the reflective film onto the other side of the base plate to obtain the traffic sign plate.

[0121] The traffic sign boards obtained in Examples 1-4 and Comparative Examples 1-3 were tested for relevant performance according to the national standards GB / T 1447-2005 "Test Method for Tensile Properties of Fiber Reinforced Plastics" and GB / T 1449-2005 "Test Method for Bending Properties of Fiber Reinforced Plastics". The test results are shown in Table 1. Table 1 is a comparison table of the tensile strength and bending strength of the traffic sign boards obtained in Examples 1-4 and Comparative Examples 1-3 at room temperature. The performance of the traffic sign boards obtained in Examples 1-4 and Comparative Examples 1-3 after being exposed to ultraviolet light at different temperatures was tested under the following conditions: The test environment conditions were in accordance with GB / T 16422-1997 "Laboratory Light Source Exposure Test Method", the wavelength of the ultraviolet aging test chamber was 315-400nm, and the selected ultraviolet irradiance was 0.68W / m². 2The relative humidity inside the test chamber was 45%–55%. The strength retention rate was calculated as (σ1 / σ0) × 100%, where σ1 is the tensile strength measured after UV irradiation, and σ0 is the tensile strength measured at room temperature. Table 2 shows the tensile strength and strength retention rate of Examples 1–4 and Comparative Examples 1–3 after 1000 hours of UV irradiation at different temperatures.

[0122] Table 1. Tensile strength and flexural strength of traffic signboards obtained in Examples 1-4 and Comparative Examples 1-3

[0123] Example Tensile strength / MPa Flexural strength / MPa Example 1 632.51 763.35 Example 2 475.69 674.95 Example 3 553.73 576.22 Example 4 421.11 525.89 Comparative Example 1 301.29 534.88 Comparative Example 2 292.34 324.03 Comparative Example 3 119.64 270.35

[0124] Table 2. Tensile properties of traffic signboards obtained in Examples 1-4 and Comparative Examples 1-3 after UV aging.

[0125]

[0126] Table 1 compares the results obtained from Examples 1-4 with those from Comparative Example 3, showing that the fiber-reinforced composite traffic sign panel provided by this invention has higher tensile and flexural strength than the aluminum alloy traffic sign panel. The use of fiber-reinforced composite materials fundamentally improves the mechanical properties of the traffic sign panel, enabling it to withstand greater forces.

[0127] Comparing the traffic sign panels made of basalt fiber composite material with those made of glass fiber composite material, Table 1 shows that the fiber-reinforced composite material traffic sign panels of the present invention have higher tensile strength and flexural strength than those made of glass fiber composite material.

[0128] Table 2 shows a comparison of the results obtained in Example 1 and Comparative Example 1. It is evident that the tensile strength retention rate of the fiber-reinforced composite traffic sign board of the present invention is higher than that of the glass fiber composite traffic sign board under prolonged ultraviolet irradiation. Furthermore, as the temperature increases, the tensile strength retention rate of the basalt fiber composite traffic sign board remains almost unchanged, while the tensile strength retention rate of the glass fiber composite traffic sign board decreases significantly.

[0129] Comparing different layup sequences and nanoparticle addition schemes for basalt fiber composite traffic sign panels, Table 1 compares the results obtained in Examples 1 to 4. It can be seen that when the layup sequence and nanoparticle addition scheme are selected as described in Example 1, that is, the layup sequence from top to bottom is: plain weave 0° / plain weave -45° / plain weave 0° / plain weave +45° / plain weave 0°, and three modified nanoparticles, CeO2, ZnO and TiO2, are mixed and added to the resin matrix, the total amount of nanoparticles accounts for 5.0% of the resin mass, and the mass ratio of the three modified nanoparticles is CeO2:ZnO:TiO2 = 2.5:1.5:1.0, the tensile strength and flexural strength of the sign panel are the greatest. When the layup sequence and nanoparticle addition scheme are selected as described in Example 4, i.e., the layup sequence from top to bottom is: plain weave 0° / unidirectional weave 0° / unidirectional weave 90° / unidirectional weave 0° / plain weave 0°, and no nanoparticles are added to the resin matrix, the tensile strength and flexural strength of the marking plate are the lowest.

[0130] Comparing the results of Example 1 and Example 2, it can be seen that using plain weave fabric significantly improves the mechanical properties of the signboard compared to using unidirectional fabric inside. Plain weave fabric has yarns woven in both the warp and weft directions, so under load, fibers in both directions provide tension. Simultaneously, the fiber bundles in both directions generate mutual friction and mechanical interlocking force, thus improving the overall mechanical properties of the fabric. However, the production cost of plain weave fabric is higher than that of unidirectional fabric. Multiple layers of unidirectional fabric with different layup directions can also improve the anisotropic mechanical properties of composite signboards, but the mass and thickness will be greater compared to laminates made from plain weave fabric with the same mechanical properties.

[0131] Comparing the results obtained in Example 1 and Example 3, it can be seen that the tensile strength of the marker plate using the mixed addition scheme of nanoparticles is 12.5% ​​higher than that of the marker plate using the single addition scheme of nanoparticles.

[0132] In this invention, surface modification of nanoparticles adds new chemical functional groups to their surface, improving their bonding with the resin. This modification enhances the UV resistance of the resin nanoparticles, significantly improving the matrix's UV aging resistance and increasing the contact area between the resin matrix and the basalt fiber surface, thus improving the mechanical properties of the marking plate.

[0133] In summary, the basalt fiber composite traffic sign board prepared by the present invention using modified nanoparticle reinforced resin and basalt fiber material with excellent mechanical properties and corrosion resistance has superior mechanical properties, UV aging resistance, and service life. It aligns with the development goals of green and environmental protection and has broad development and application prospects.

[0134] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A fiber-reinforced composite material, characterized in that, Includes a matrix and a reinforcing element embedded in the matrix; The reinforcement is a layered basalt fiber cloth; the basalt fiber cloth on the upper and lower surfaces of the reinforcement is plain weave cloth woven from basalt fibers; the basalt fiber cloth in the reinforcement except on the upper and lower surfaces is plain weave cloth woven from basalt fibers; the included angle between the basalt fibers in any two adjacent layers of basalt fiber cloth is 0~90°. The matrix is ​​a resin; the resin includes epoxy resin, vinyl resin, or unsaturated resin. The resin also includes modified metal oxides; the modified metal oxides are metal oxides with coupling agents grafted onto their surfaces; the modified metal oxides are a mixture of modified cerium oxide, modified zinc oxide, and modified titanium oxide, wherein the mass ratio of modified cerium oxide, modified zinc oxide, and modified titanium oxide is 1.0~2.5:0.5~1.5:1.0; and the mass ratio of modified metal oxides to resin in the matrix is ​​0.3~6:

100. The method for preparing the modified cerium oxide includes the following steps: The first coupling agent is dissolved in a first aqueous ethanol solution to obtain a coupling agent solution; The nano-cerium oxide particles were first dispersed in water to obtain a cerium oxide dispersion. The coupling agent solution and cerium oxide dispersion were first mixed and the pH value was adjusted to 7-11 before the first grafting modification was performed to obtain the modified cerium oxide. The method for preparing the modified zinc oxide includes the following steps: The nano-zinc oxide particles were further dispersed in a second aqueous ethanol solution to obtain a zinc oxide dispersion. The zinc oxide dispersion and the second coupling agent are mixed for a second grafting modification to obtain the modified zinc oxide. The method for preparing the modified titanium oxide includes the following steps: The nano-titanium oxide particles were dispersed in water to obtain a titanium oxide dispersion. The titanium dioxide dispersion, the third coupling agent, and ethanol were mixed and the pH was adjusted to 5-7 before the third grafting modification was performed to obtain the modified titanium dioxide.

2. The method for preparing the fiber-reinforced composite material according to claim 1, characterized in that, Includes the following steps: A composite resin is obtained by mixing a resin and a curing agent; a modified metal oxide is also added during the mixing process. Basalt fiber cloth is layered to obtain a reinforcing body; the basalt fiber cloth on the upper and lower surfaces of the reinforcing body is plain weave cloth woven from basalt fibers; the included angle between the basalt fibers in any two adjacent layers of basalt fiber cloth is 0~90°. The composite resin and the reinforcing agent are mixed and molded to obtain the fiber-reinforced composite material.

3. The preparation method according to claim 2, characterized in that, The mass ratio of the curing agent to the resin is 60~100:100; The molding method includes vacuum injection molding; The vacuum injection molding process involves a temperature of 150-200℃, a pressure of 3-5MPa, and a time of 80-120min.

4. The application of the fiber-reinforced composite material according to claim 1 or the fiber-reinforced composite material prepared by the preparation method according to claim 2 or 3 in the preparation of road traffic signs.

5. A road traffic sign, characterized in that, It includes a base plate, a groove disposed on one side of the base plate, and a reflective film disposed on the other side of the base plate; The base plate is the fiber-reinforced composite material according to claim 1 or the fiber-reinforced composite material prepared by the preparation method according to claim 2 or 3.

6. The road traffic sign according to claim 5, characterized in that, The slide is made of aluminum alloy. The connection method between the slide and the base plate includes riveting or adhesive riveting; the adhesive used for adhesive riveting includes epoxy resin, vinyl resin or unsaturated resin.

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