Explosion-proof bulletproof coating material and preparation method thereof

Abstract

The invention discloses an explosion-proof and bulletproof coating material and a preparation method thereof, and belongs to the technical field of chemical coating materials, the explosion-proof and bulletproof coating material comprises a substrate layer and composite layers, the composite layers are coated on the two surfaces of the substrate layer, and composite ceramic microsphere layers, nanoneedle composite carbon fiber layers and elastic layers are alternately arranged in sequence; the zinc oxide microneedle structures and the carbon fibers are interspersed to serve as a second layer, so that transverse shear stress is effectively borne, and transverse microcracks among composite material layers can be prevented from extending; the growth of nano zinc oxide increases the surface roughness and friction coefficient between the fibers, which is beneficial to better dispersion and absorption of energy when being impacted, and can improve the bonding effect of the fibers and resin, amino groups on the surface of the nanoneedle composite carbon fibers are bonded with carboxyl groups of acrylic acid, and the surface roughness and friction coefficient of the fibers are improved. Therefore, the interface performance of the fiber reinforced composite material is improved, the integrity of the composite material can be kept when the composite material is impacted, and the bulletproof performance of the composite material is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical coating materials, and in particular relates to an explosion-proof and bullet-proof coating material and a preparation method thereof. Background Art

[0002] When an explosion occurs, it usually produces extremely strong shock waves and fragments, which have very serious consequences and greatly endanger the safety of people's lives and property. Therefore, in the face of such a serious emergency, the protective material needs to have the highest possible explosion-proof and bullet-proof performance. In view of the penetration of fragments and the action time and load pressure amplitude of the explosion shock wave load, the required protective material / structure should have a high unit mass transient specific strength and specific toughness. When the bullet hits the coating, the hardness increases rapidly to consume most of the energy. The mesh molecular structure can hold the bullet on the back surface to prevent the bullet from penetrating; explosion-proof polyurea is a super tough skin-like coating with a strong energy absorption and conversion function. When encountering an explosion shock wave, its glass transition temperature changes rapidly, and the hardness increases dozens of times instantly. It can withstand huge explosion shocks without being damaged, and can be used to enhance the explosion-proof capabilities of various military substrates.

[0003] However, most of the polyurea materials currently used in explosion-proof and bullet-proof protection fields have poor coating tear strength. If polyurethane coatings other than polyurea elastic coatings are used on explosion-proof materials, only polyurea elastic coatings are used to form the coatings. However, the polyurea elastic coatings have insufficient coating capacity and adhesion properties, making it impossible to effectively cover the surface of the material, resulting in low explosion-proof performance of the overall material, which cannot meet the demand for high-strength explosion-proof performance.

[0004] A Chinese patent with announcement number CN119178362B discloses an explosion-proof and bullet-proof coating material and a preparation method thereof, wherein epoxy resin and chain extender are used as modified layers, and a filler layer is a carbon fiber mesh, which is coated on both sides of the substrate layer in an alternating manner of modified layer-filler layer-elastomer layer-filler layer. However, in this scheme, the bonding degree between the coatings is not high, and the bonding performance is insufficient, resulting in low explosion-proof performance. Summary of the invention

[0005] The object of the present invention is to provide an explosion-proof and bullet-proof coating material and a preparation method thereof, comprising a substrate layer and a composite layer, wherein the composite layer is coated on both sides of the substrate layer, and the composite layer comprises an elastic layer, a nano-needle composite carbon fiber layer and a composite ceramic microsphere layer, and is arranged alternately in the order of "composite ceramic microsphere layer-nano-needle composite carbon fiber layer-elastic layer"; a nano zinc oxide microneedle structure and carbon fiber are interlaced with each other as a second layer, thereby effectively bearing transverse shear stress, preventing the expansion of transverse microcracks between composite material layers, and the surface roughness structure can significantly increase the bonding force between the coatings.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing an explosion-proof and bullet-proof coating material, comprising the following steps:

[0008] Step 1: Add nanoneedle composite carbon fiber, acrylic acid, N,N-dimethylformamide and deionized water into a reactor, introduce nitrogen protection, stir the reaction at 95-100°C and 500-600r / min for 1-2h, cool to 55-65°C, add sodium sulfite as an initiator and hydroxymethyl acrylamide as a cross-linking agent into the reactor, continue stirring for 3-4h, filter, wash the filter cake with deionized water and anhydrous ethanol for 2-3 times respectively, and vacuum dry at 60-80°C for 1-2h to obtain a nanoneedle composite carbon fiber layer.

[0009] Step 2: Use the composite ceramic microsphere layer as a spraying material, perform supersonic flame spraying at a powder feeding rate of 50-60g / min, and spray it on the substrate layer to obtain the first layer; spray the nanoneedle composite carbon fiber layer on the first layer at 60-70°C and 12-14MPa to obtain the second layer; spray the elastic layer on the second layer under the same conditions to obtain an explosion-proof and bulletproof coating material.

[0010] Furthermore, in step one, the dosage ratio of the nanoneedle composite carbon fiber, acrylic acid, N,N-dimethylformamide, deionized water, sodium sulfite and hydroxymethyl acrylamide is 20-30g: 30-40mL: 70-80mL: 100-200mL: 1-2g: 1-2g.

[0011] Furthermore, the composite ceramic microsphere layer in step 2 is prepared by the following steps:

[0012] The hydrated zirconium oxynitrate and deionized water are added into a reaction kettle, stirred for 30-40 minutes at 90-100° C. and 500-600 r / min, cooled naturally, and then hexamethylenetetramine as a gelling agent and urea as a chelating agent are added, stirred for 30-40 minutes at 90-100° C. and 500-600 r / min, cooled naturally, and then amino carbon fiber is added, ultrasonically dispersed for 40-60 minutes to obtain a pre-treated glue solution; the pre-treated glue solution is gradually dripped into hot silicone oil at a temperature of 90-100° C. to form microspheres under the action of surface tension, aged for 30-40 minutes after the dripping is completed, filtered, and the filter cake is washed with deionized water and anhydrous ethanol for 2-3 times respectively, vacuum dried and transferred to a graphite crucible, kept warm at 1000-1100° C. for 4-6 hours under a nitrogen atmosphere, cooled naturally, and a composite ceramic microsphere layer is obtained.

[0013] Furthermore, the usage ratio of hydrated zirconium oxynitrate, deionized water, hexamethylenetetramine, urea and amino carbon fiber is 20-30 g: 200-300 mL: 3-4 g: 1-2 g: 20-30 g.

[0014] Furthermore, the dosage ratio of the pretreatment glue solution and the hot silicone oil is 40-50mL:100-200mL.

[0015] Furthermore, in step 1, the nanoneedle composite carbon fiber is prepared by the following steps:

[0016] Add zinc acetate dihydrate powder and anhydrous ethanol into a reaction kettle, stir for 1-2 hours at 20-25°C and 500-600r / min, then add amino carbon fiber, hexamethylenetetramine and deionized water, heat to 90-95°C, stir for 15-17 hours at 500-600r / min, filter, wash the filter cake with deionized water 2-3 times, and vacuum dry at 60-80°C for 1-2 hours to obtain nanoneedle composite carbon fiber.

[0017] Furthermore, the dosage ratio of zinc acetate dihydrate powder, anhydrous ethanol, amino carbon fiber, hexamethylenetetramine and deionized water is 10-15 g: 100-200 mL: 20-30 g: 2-3 g: 200-300 mL.

[0018] Further, the amination carbon fiber is prepared by the following steps:

[0019] Add carbon fiber with a length of 1-2 mm and an ethanol solution with a mass fraction of 50-60% into a reactor, stir for 20-30 min at 70-80°C and 500-600 r / min, add γ-aminopropyltriethoxysilane, and continue stirring for 1-2 h. After the reaction is completed, let it stand at 20-25°C for 24-26 h, filter, wash the filter cake with deionized water until the last washing liquid is neutral, and vacuum dry at 60-80°C for 1-2 h to obtain amino carbon fiber.

[0020] Furthermore, the usage ratio of carbon fiber, ethanol solution and γ-aminopropyltriethoxysilane is 30-40 g: 100-120 mL: 1-2 g.

[0021] Furthermore, in step 2, the elastic layer is prepared by the following steps:

[0022] Add polytetramethylene glycol to a reaction kettle, dehydrate under reduced pressure at 100-110°C, evacuate, and then add diisocyanate under nitrogen protection. Stir for 20-30 minutes at 20-25°C and 500-600r / min, then add 3,5-diethyltoluenediamine, heat to 70-80°C and continue to react for 2-3 hours, and cool naturally to obtain an elastic layer.

[0023] Furthermore, the usage ratio of polytetramethylene glycol, diisocyanate and 3,5-diethyltoluenediamine is 40-50 mL: 30-40 mL: 1-2 mL.

[0024] Beneficial effects of the present invention:

[0025] 1. The explosion-proof and bullet-proof coating material prepared by the present invention has excellent explosion-proof, bullet-proof and crack-proof capabilities. The microneedle structure is interlaced with each other as the second layer, thereby effectively bearing the transverse shear stress, preventing the expansion of transverse microcracks between composite material layers, and increasing the bonding force between each coating.

[0026] 2. The nanoneedle composite carbon fiber layer of the present invention, through the structural interlocking between the zinc oxide nanoneedles and the carbon fibers, and the resin is infiltrated into the pores in the interlaced structure, so that the connection between the carbon fibers is tighter, thereby improving the overall anti-ballistic performance; the growth of nano zinc oxide increases the surface roughness and friction coefficient between the fibers, which helps to better disperse and absorb energy when impacted, thereby improving the bulletproof effect; constructing a zinc oxide nano coating on the fiber surface can improve the bonding effect between the fiber and the resin, and the amino group on the surface of the nanoneedle composite carbon fiber is bonded to the carboxyl group of acrylic acid, thereby improving the interface performance of the fiber-reinforced composite material, and the enhancement of this interface performance helps to maintain the integrity of the composite material when impacted, thereby improving its anti-ballistic performance.

[0027] 3. The composite ceramic microsphere layer of the present invention is filled with carbon fiber into the ceramic microsphere. The carbon fiber has excellent high-temperature stability and corrosion resistance. Adding it to the ceramic microsphere can further improve the high-temperature resistance and corrosion resistance of the composite material, so that the composite material can still maintain stable performance under high temperature and acid-base environment; and through the supersonic flame spraying technology, a high-density coating with low porosity can be formed. The supersonic flame sprayed coating has high bonding strength with the substrate, ensuring that the coating is not easy to fall off, thereby improving the stability and durability of the coating; the second layer is a nano-needle composite carbon fiber layer by layer, and the nano-microneedle structure enables the second layer to be interlaced with each other when used as an intermediate layer, so that the coating is tightly bonded in time; and the microneedle structure is interlaced with each other, thereby effectively bearing the transverse shear stress and preventing the expansion of transverse microcracks between the composite material layers. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of 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.

[0029] Example 1: A method for preparing an explosion-proof and bullet-proof coating material, prepared by the following steps:

[0030] S1: Add 40mL of polytetramethylene glycol to a reaction kettle, dehydrate under reduced pressure at 100°C, evacuate, and then add 30mL of diisocyanate under nitrogen protection. Stir for 20min at 20°C and 500r / min, then add 1mL of 3,5-diethyltoluenediamine, heat to 70°C and continue to react for 2h, and cool naturally to obtain an elastic layer.

[0031] S2: Add 30g of carbon fiber with a length of 1-2mm and 100mL of 50% ethanol solution into the reactor, stir at 70℃ and 500r / min for 20min, add 1g of γ-aminopropyltriethoxysilane, continue stirring for 1h. After the reaction is completed, let it stand at 20℃ for 24h, filter, wash the filter cake with deionized water until the last washing liquid is neutral, and vacuum dry at 60℃ for 1h to obtain amino carbon fiber.

[0032] S3: 10 g zinc acetate dihydrate powder and 100 mL anhydrous ethanol were added to a reactor, stirred at 20 ° C and 500 r / min for 1 h, and then 20 g amino carbon fiber, 2 g hexamethylenetetramine and 200 mL deionized water were added, heated to 90 ° C, stirred at 500 r / min for 15 h, filtered, and the filter cake was washed with deionized water twice, and vacuum dried at 60 ° C for 1 h to obtain nanoneedle composite carbon fiber;

[0033] 20 g of nanoneedle composite carbon fiber, 30 mL of acrylic acid, 70 mL of N,N-dimethylformamide and 100 mL of deionized water were added to a reactor, and nitrogen was introduced for protection. The reaction was stirred at 95°C and 500 r / min for 1 hour, and then cooled to 55°C. 1 g of sodium sulfite as an initiator and 1 g of hydroxymethyl acrylamide as a cross-linking agent were added to the reactor, and stirring was continued for 3 hours. The filter cake was washed twice with deionized water and anhydrous ethanol respectively, and vacuum dried at 60°C for 1 hour to obtain a nanoneedle composite carbon fiber layer.

[0034] Zinc oxide nanoneedles can increase the structural interlocking between fibers, making the connection between fibers tighter, thereby improving the overall ballistic protection performance; the growth of nano zinc oxide increases the surface roughness and friction coefficient between fibers, which helps to better disperse and absorb energy when impacted, thereby improving the bulletproof effect; constructing a zinc oxide nano coating on the fiber surface can improve the bonding between the fiber and the resin, and the amino group on the surface of the nanoneedle composite carbon fiber bonds with the carboxyl group of acrylic acid, thereby improving the interfacial properties of the fiber-reinforced composite material. The enhancement of this interfacial performance helps to maintain the integrity of the composite material when impacted, thereby improving its ballistic protection performance.

[0035] S4: Add 20g of hydrated zirconium oxynitrate and 200mL of deionized water into a reactor, stir for 30min at 90℃ and 500r / min, cool naturally, add 3g of hexamethylenetetramine as a gelling agent and 1g of urea as a chelating agent, stir for 30min at 90℃ and 500r / min, cool naturally, add 20g of amino carbon fiber, ultrasonically disperse for 40min to obtain a pretreated glue solution; gradually drop 40mL of the pretreated glue solution into 100mL of hot silicone oil at 90℃ to form microspheres under the action of surface tension. After the dropwise addition is completed, age for 30min, filter, wash the filter cake twice with deionized water and anhydrous ethanol respectively, transfer it to a graphite crucible after vacuum drying, keep it at 1000℃ for 4h under a nitrogen atmosphere, cool naturally to obtain a composite ceramic microsphere layer.

[0036] Carbon fiber has excellent high-temperature stability and corrosion resistance. Adding it to ceramic microspheres can further enhance the high-temperature resistance and corrosion resistance of the composite material, which enables the composite material to maintain stable performance in high temperature and acid-base environments.

[0037] S5: The composite ceramic microsphere layer is used as a spraying material, and supersonic flame spraying is performed at a powder feeding rate of 50g / min, and sprayed on the substrate layer to obtain the first layer; the nanoneedle composite carbon fiber layer is sprayed on the first layer at 60°C and 12MPa to obtain the second layer; the elastic layer is sprayed on the second layer under the same conditions to obtain an explosion-proof and bulletproof coating material.

[0038] Supersonic flame spraying technology can form a high-density coating with low porosity. The supersonic flame sprayed coating has a high bonding strength with the substrate, ensuring that the coating is not easy to fall off, thereby improving the stability and durability of the coating; the second layer is a nanoneedle composite carbon fiber layer by layer, with a nano-microneedle structure, so that when the second layer is used as an intermediate layer, it can be interlaced with each other so that the coating is tightly bonded in time; and the microneedle structure is interlaced with each other, thereby effectively bearing the transverse shear stress and preventing the expansion of transverse microcracks between composite material layers.

[0039] Example 2: A method for preparing an explosion-proof and bullet-proof coating material, prepared by the following steps:

[0040] S1: Add 45mL of polytetramethylene glycol to the reaction kettle, dehydrate under reduced pressure at 105°C, evacuate, and then add 35mL of diisocyanate under nitrogen protection. Stir for 25min at 23°C and 550r / min, then add 1.2mL of 3,5-diethyltoluenediamine, heat to 75°C and continue to react for 2.3h, and cool naturally to obtain an elastic layer.

[0041] S2: Add 35g of carbon fiber with a length of 1-2mm and 110mL of 55% ethanol solution into the reactor, stir at 75℃ and 550r / min for 25min, add 1.2g of γ-aminopropyltriethoxysilane, and continue stirring for 1.2h. After the reaction is completed, let it stand at 23℃ for 25h, filter, wash the filter cake with deionized water until the last washing liquid is neutral, and vacuum dry at 70℃ for 1.5h to obtain amino carbon fiber.

[0042] S3: 13 g zinc acetate dihydrate powder and 150 mL anhydrous ethanol were added to the reactor, stirred at 23 ° C and 550 r / min for 1.2 h, and then 25 g amino carbon fiber, 2.3 g hexamethylenetetramine and 250 mL deionized water were added, heated to 93 ° C, stirred at 550 r / min for 16 h, filtered, and the filter cake was washed with deionized water twice, and vacuum dried at 70 ° C for 1.2 h to obtain nanoneedle composite carbon fiber;

[0043] 25 g of nanoneedle composite carbon fiber, 35 mL of acrylic acid, 75 mL of N,N-dimethylformamide and 150 mL of deionized water were added to a reactor, and nitrogen was introduced for protection. The reaction was stirred at 98°C and 550 r / min for 1.2 h, cooled to 60°C, and 1.2 g of sodium sulfite as an initiator and 1.2 g of hydroxymethyl acrylamide as a cross-linking agent were added to the reactor. The stirring was continued for 3.4 h, and the filter cake was washed twice with deionized water and anhydrous ethanol respectively, and vacuum dried at 70°C for 1.2 h to obtain a nanoneedle composite carbon fiber layer.

[0044] S4: Add 25g of hydrated zirconium oxynitrate and 250mL of deionized water into a reactor, stir for 35min at 95°C and 550r / min, cool naturally, add 3.4g of hexamethylenetetramine as a gelling agent and 1.2g of urea as a chelating agent, stir for 35min at 95°C and 550r / min, cool naturally, add 25g of amino carbon fiber, and ultrasonically disperse for 45min to obtain a pretreated glue solution; gradually drop 45mL of the pretreated glue solution into 150mL of hot silicone oil at 95°C to form microspheres under the action of surface tension. After the dropwise addition is completed, age for 35min, filter, wash the filter cake twice with deionized water and anhydrous ethanol respectively, transfer it to a graphite crucible after vacuum drying, keep it warm at 1050°C for 5h under a nitrogen atmosphere, cool naturally, and obtain a composite ceramic microsphere layer.

[0045] S5: The composite ceramic microsphere layer is used as a spraying material, and supersonic flame spraying is performed at a powder feeding rate of 55g / min, and sprayed on the substrate layer to obtain the first layer; the nanoneedle composite carbon fiber layer is sprayed on the first layer at 65°C and 13MPa to obtain the second layer; the elastic layer is sprayed on the second layer under the same conditions to obtain an explosion-proof and bulletproof coating material.

[0046] Example 3: A method for preparing an explosion-proof and bullet-proof coating material, prepared by the following steps:

[0047] S1: Add 50mL of polytetramethylene glycol to a reaction kettle, dehydrate under reduced pressure at 110°C, evacuate, and then add 40mL of diisocyanate under nitrogen protection. Stir for 30min at 25°C and 600r / min, then add 2mL of 3,5-diethyltoluenediamine, heat to 80°C and continue to react for 3h, and cool naturally to obtain an elastic layer.

[0048] S2: Add 40g of carbon fiber with a length of 1-2mm and 120mL of 60% ethanol solution into the reactor, stir at 80℃ and 600r / min for 30min, add 2g of γ-aminopropyltriethoxysilane, continue stirring for 2h. After the reaction is completed, let it stand at 25℃ for 26h, filter, wash the filter cake with deionized water until the last washing liquid is neutral, and vacuum dry at 80℃ for 2h to obtain amino carbon fiber.

[0049] S3: 15 g zinc acetate dihydrate powder and 200 mL anhydrous ethanol were added to a reactor, stirred at 25 ° C and 600 r / min for 2 h, and then 30 g amino carbon fiber, 3 g hexamethylenetetramine and 300 mL deionized water were added, heated to 95 ° C, stirred at 600 r / min for 17 h, filtered, and the filter cake was washed with deionized water for 3 times, and vacuum dried at 80 ° C for 2 h to obtain nanoneedle composite carbon fiber;

[0050] 30 g of nanoneedle composite carbon fiber, 40 mL of acrylic acid, 80 mL of N,N-dimethylformamide and 200 mL of deionized water were added to a reactor, and nitrogen was introduced for protection. The reaction was stirred at 100°C and 600 r / min for 2 hours, and then cooled to 65°C. 2 g of sodium sulfite as an initiator and 2 g of hydroxymethyl acrylamide as a cross-linking agent were added to the reactor, and stirring was continued for 4 hours. The filter cake was washed three times with deionized water and anhydrous ethanol respectively, and vacuum dried at 80°C for 2 hours to obtain a nanoneedle composite carbon fiber layer.

[0051] S4: Add 30g of hydrated zirconium oxynitrate and 300mL of deionized water into a reactor, stir for 40min at 100℃ and 600r / min, cool naturally, add 4g of hexamethylenetetramine as a gelling agent and 2g of urea as a chelating agent, stir for 40min at 100℃ and 600r / min, cool naturally, add 30g of amino carbon fiber, ultrasonically disperse for 60min to obtain a pretreated glue solution; gradually drop 50mL of the pretreated glue solution into 200mL of hot silicone oil at 100℃ to form microspheres under the action of surface tension. After the dropwise addition is completed, age for 40min, filter, wash the filter cake with deionized water and anhydrous ethanol for 3 times respectively, transfer to a graphite crucible after vacuum drying, keep warm at 1100℃ for 6h under a nitrogen atmosphere, cool naturally to obtain a composite ceramic microsphere layer.

[0052] S5: The composite ceramic microsphere layer is used as a spraying material, and supersonic flame spraying is performed at a powder feeding rate of 60g / min, and sprayed on the substrate layer to obtain the first layer; the nanoneedle composite carbon fiber layer is sprayed on the first layer at 70°C and 14MPa to obtain the second layer; the elastic layer is sprayed on the second layer under the same conditions to obtain an explosion-proof and bulletproof coating material.

[0053] Comparative Example 1: On the basis of Example 3, the nanoneedle composite carbon fiber in step S3 is replaced by the carbon fiber in step S2, and the other steps remain unchanged to prepare an explosion-proof and bulletproof coating material.

[0054] Comparative Example 2: On the basis of Example 3, the amino-treated carbon fiber in step S4 is omitted, and the other steps remain unchanged to prepare an explosion-proof and bullet-proof coating material.

[0055] Comparative Example 3: Based on Example 3, the composite ceramic microsphere layer in step S5 is used as a spraying material and sprayed on the substrate layer at 70° C. and 14 MPa, and the remaining steps remain unchanged to prepare an explosion-proof and bullet-proof coating material.

[0056] The performance test of the explosion-proof and bullet-proof coating materials obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was performed: All the above coating materials were subjected to performance tests according to the standard of GB9278, and the test results are shown in Table 1. In addition, all coating materials were prepared into 3 mm thick coatings, and 1.5 kg TNT explosives were used for explosion impact to detect the damage of the coatings.

[0057] The results are shown in Table 1:

[0058] Table 1 Performance test table of explosion-proof and bullet-proof coating materials

[0059]

[0060] It can be seen from Table 1 that the tensile strength, tear strength, bonding strength and explosion-proof performance of the explosion-proof and bullet-proof coating materials obtained in Examples 1 to 3 are significantly better than those in the comparative example, indicating that the explosion-proof and bullet-proof coating materials prepared by the present invention have excellent explosion-proof, bullet-proof and crack-proof capabilities.

[0061] In Comparative Example 1, the nanoneedle composite carbon fiber is replaced with carbon fiber. The nanoneedle composite carbon fiber is obtained by structural interlocking between zinc oxide nanoneedles and carbon fibers, and resin is infiltrated into the pores in the interlaced structure. This interlaced structure can make the connection between the carbon fibers tighter, thereby improving the overall ballistic performance. The growth of nano zinc oxide increases the surface roughness and friction coefficient between the fibers, which helps to better disperse and absorb energy when impacted, thereby improving the bulletproof effect.

[0062] In Comparative Example 2, the amino-treated carbon fiber is omitted. In the composite ceramic microsphere layer, the carbon fiber as a reinforcing phase can increase the high temperature stability and corrosion resistance of the composite ceramic microsphere material, and can transform the fracture mode of the ceramic from brittle fracture to non-brittle fracture, thereby significantly improving the fracture toughness of the ceramic.

[0063] In Comparative Example 3, the composite ceramic microsphere layer is used as a spraying material and sprayed on the substrate layer at 70°C and 14MPa. By supersonic flame spraying, a high-density coating with low porosity and high bonding strength can be formed on the substrate layer, thereby avoiding the problem of insufficient bonding between the smooth ceramic surface and the substrate layer.

[0064] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0065] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an explosion-proof and bullet-proof coating material, characterized in that: Prepared by the following steps: Step 1: Add nanoneedle composite carbon fiber, acrylic acid, N,N-dimethylformamide and deionized water into a reactor, introduce nitrogen protection, stir and react for 1-2 hours at 95-100°C and 500-600r / min, cool to 55-65°C, add sodium sulfite and hydroxymethyl acrylamide into the reactor, continue stirring for 3-4 hours, filter, wash the filter cake with deionized water and anhydrous ethanol for 2-3 times respectively, and vacuum dry to obtain a nanoneedle composite carbon fiber layer; Step 2: Use the composite ceramic microsphere layer as a spraying material, perform supersonic flame spraying at a powder feeding rate of 50-60g / min, and spray it on the substrate layer to obtain the first layer; spray the nanoneedle composite carbon fiber layer on the first layer at 60-70°C and 12-14MPa to obtain the second layer; spray the elastic layer on the second layer under the same conditions to obtain an explosion-proof and bulletproof coating material.

2. The method for preparing an explosion-proof and bullet-proof coating material according to claim 1, characterized in that: The dosage ratio of the nanoneedle composite carbon fiber, acrylic acid, N,N-dimethylformamide, deionized water, sodium sulfite and hydroxymethyl acrylamide in step 1 is 20-30g: 30-40mL: 70-80mL: 100-200mL: 1-2g: 1-2g.

3. The method for preparing an explosion-proof and bullet-proof coating material according to claim 1, characterized in that: The composite ceramic microsphere layer in step 2 is prepared by the following steps: Add hydrated zirconium oxynitrate and deionized water into a reaction kettle, stir at 90-100° C. and 500-600 r / min for 30-40 min, cool naturally, add hexamethylenetetramine and urea, stir at 90-100° C. and 500-600 r / min for 30-40 min, cool naturally, add amino carbon fiber, and ultrasonically disperse for 40-60 min to obtain a pretreated glue solution; The pretreated glue solution is gradually dripped into hot silicone oil at a temperature of 90-100°C. After the addition is completed, it is aged for 30-40 minutes, filtered, and the filter cake is washed with deionized water and anhydrous ethanol for 2-3 times respectively. After vacuum drying, it is transferred to a graphite crucible and kept at 1000-1100°C for 4-6 hours under a nitrogen atmosphere. It is naturally cooled to obtain a composite ceramic microsphere layer.

4. The method for preparing an explosion-proof and bullet-proof coating material according to claim 3, characterized in that: The usage ratio of the hydrated zirconium oxynitrate, deionized water, hexamethylenetetramine, urea and amino carbon fiber is 20-30 g: 200-300 mL: 3-4 g: 1-2 g: 20-30 g.

5. The method for preparing an explosion-proof and bullet-proof coating material according to claim 3, characterized in that: The usage ratio of the pre-treated glue solution and the hot silicone oil is 40-50 mL: 100-200 mL.

6. The method for preparing an explosion-proof and bullet-proof coating material according to claim 1, characterized in that: The nanoneedle composite carbon fiber described in step 1 is prepared by the following steps: Add zinc acetate dihydrate powder and anhydrous ethanol into a reaction kettle, stir for 1-2 hours at 20-25°C and 500-600r / min, then add amino carbon fiber, hexamethylenetetraamine and deionized water, heat to 90-95°C, stir at 500-600r / min for 15-17 hours, filter, wash the filter cake with deionized water 2-3 times, and vacuum dry to obtain nanoneedle composite carbon fiber.

7. The method for preparing an explosion-proof and bullet-proof coating material according to claim 6, characterized in that: The usage ratio of the zinc acetate dihydrate powder, anhydrous ethanol, amino carbon fiber, hexamethylenetetramine and deionized water is 10-15g: 100-200mL: 20-30g: 2-3g: 200-300mL.

8. The method for preparing an explosion-proof and bullet-proof coating material according to claim 3, characterized in that: The amination carbon fiber is prepared by the following steps: Add carbon fibers with a length of 1-2 mm and a 50-60 wt% ethanol solution into a reactor, stir at 70-80° C. and 500-600 r / min for 20-30 min, add γ-aminopropyltriethoxysilane, continue stirring for 1-2 h, and after the reaction is completed, stand at 20-25° C. for 24-26 h, filter, wash the filter cake with deionized water until the last washing liquid is neutral, and vacuum dry to obtain amino carbon fibers; The usage ratio of the carbon fiber, the ethanol solution and the gamma-aminopropyltriethoxysilane is 30-40 g: 100-120 mL: 1-2 g.

9. The method for preparing an explosion-proof and bullet-proof coating material according to claim 1, characterized in that: The elastic layer in step 2 is prepared by the following steps: Add polytetramethylene glycol to a reaction kettle, dehydrate under reduced pressure at 100-110°C, evacuate, and then add diisocyanate under nitrogen protection, stir at 20-25°C and 500-600r / min for 20-30min, then add 3,5-diethyltoluenediamine, heat to 70-80°C and continue to react for 2-3h, and cool naturally to obtain an elastic layer; The dosage ratio of the polytetramethylenetetrahydrofuran ether polyol, diisocyanate and 3,5-diethyltoluenediamine is 40-50 mL: 30-40 mL: 1-2 mL.

10. An explosion-proof and bullet-proof coating material, characterized in that: Prepared by the preparation method described in any one of claims 1 to 9.

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