Weather-resistant and corrosion-resistant composite material for automobiles and preparation method thereof

Abstract

The application discloses a weather-resistant and corrosion-resistant composite material for automobiles and a preparation method thereof, and belongs to the field of high polymer materials. The weather-resistant and corrosion-resistant composite material for automobiles is prepared through the following steps: 1, modified functional filler powder is prepared; 1-a, lanthanum filled and smashed plant carbon source is prepared; 1-b, modified carbon composite particles are prepared; 2, functional filler powder is prepared; and 3, the weather-resistant and corrosion-resistant composite material for automobiles is prepared. According to the scheme, the weather resistance of the weather-resistant and corrosion-resistant composite material for automobiles is improved by modifying porous nano carbon particles with lanthanum; and the wear resistance of the weather-resistant and corrosion-resistant composite material for automobiles is improved by modifying nano carbon fibers with silicon and combining a rolling process.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a weather-resistant and corrosion-resistant composite material for automobiles and its preparation method. Background Technology

[0002] Improving the weather resistance, corrosion resistance, and wear resistance of structural materials is a perennial theme in structural material applications. While automotive composite materials currently exhibit good weather resistance, corrosion resistance, and wear resistance, exterior injection molded plastics often develop cracks, pitting, and even spalling during long-term use. These are signs of insufficient weather resistance and corrosion resistance, likely due to surface micropores and low wear resistance. Improving the radiation absorption capacity of structural materials through fillers, as well as enhancing material smoothness and wear resistance, is a viable approach.

[0003] In the prior art, CN117887175A discloses a high weather-resistant and anti-yellowing PP / PS alloy material for automotive interiors, comprising the following formulation by weight percentage: 30-70% polypropylene, 10-30% compatibilizer, 30-60% polystyrene, 0.2-2% anti-yellowing agent, 0.2-2% scratch resistant agent, 0.2-2% antioxidant, 0.2-2% light stabilizer, and 0-3% other additives. The high weather-resistant and anti-yellowing PP / PS alloy material obtained using the above technical solution possesses high weather resistance and anti-yellowing properties, while also exhibiting comprehensive mechanical properties, light resistance, and scratch resistance.

[0004] CN105482378A relates to a PBT composite material for automotive exterior trim, comprising the following components by weight: 100 parts PBT resin, 20-30 parts glass fiber, 5-10 parts polyimide fiber, 1-5 parts coupling agent, 0.5-2 parts compatibilizer, 1-5 parts heat resistant agent, 2-6 parts toughening agent, and 0.5-2 parts antistatic agent. The reinforcing material is a composite of glass fiber and polyimide fiber. The resulting PBT composite material retains the excellent properties of PBT composites, such as high heat resistance, high tensile strength, weather resistance, and chemical corrosion resistance, while effectively improving the impact resistance of the PBT composite material. The use of polyimide fiber particularly improves the impact resistance of the PBT composite material at low temperatures. The higher proportion of glass fiber and lower proportion of polyimide fiber allows for the economical and efficient preparation of PBT composite materials with excellent comprehensive performance, meeting the needs of long-term use of automotive exterior trim in cold regions. The above technologies can all achieve good weather resistance, but for long-term use, the wear resistance of the material is positively correlated with improving its weather resistance, which is not mentioned in the above solutions. Summary of the Invention

[0005] To solve the above problems, the application provides a weather-resistant and corrosion-resistant composite material for automobiles and a preparation method thereof, and the formed part has less surface pores, good weather resistance, corrosion resistance and wear resistance.

[0006] To achieve the above-mentioned purposes, the technical scheme of the application is:

[0007] The application provides a preparation method of the weather-resistant and corrosion-resistant composite material for automobiles, which comprises the following steps:

[0008] Step 1: preparing modified functional filler powder

[0009] 1-a: according to weight parts, crushing plant carbon source and sieving through a 20-50 mesh sieve to obtain crushed plant carbon source, taking 1 part of the crushed plant carbon source, adding to 1-1.5 parts of a lanthanum acetate solution with a mass concentration of 0.3%-0.5%, soaking for 2-3 hours, filtering, and dehydrating to obtain lanthanum-filled crushed plant carbon source;

[0010] 1-b: according to weight parts, mixing 1 part of bamboo fiber, 0.3-0.5 parts of lanthanum-filled crushed plant carbon source, 0.5-1 parts of silica sol and 0.5-1 parts of ethanol, ball milling for 3-5 hours, discharging, evaporating the solvent under vacuum conditions to obtain a mixture, calcining the mixture at 600-800 DEG C under anaerobic conditions for 2-3 hours, increasing the temperature to 1000-1100 DEG C, and calcining under anaerobic conditions for 0.5-1 hours to obtain modified carbon composite particles;

[0011] Step 2: preparing functional filler powder: according to weight parts, mixing 1 part of modified carbon composite particles, 0.05-0.15 parts of silicone oil, 1-2 parts of filler, 0.05-0.1 parts of leveling agent and 1-1.5 parts of water into a ball mill, ball milling for 1-2 hours, mixing and grinding at a speed of 800-1000 r / s for 1-2 hours, discharging, dehydrating and drying under anaerobic conditions to obtain functional filler powder;

[0012] Step 3: preparing the weather-resistant and corrosion-resistant composite material for automobiles: according to weight parts, heating 1 part of polyamide to 240-300 DEG C, adding 0.2-0.3 parts of functional filler powder, 0.01-0.05 parts of dispersant and 0.02-0.05 parts of weathering aid under stirring, stirring for 30-60 minutes, cooling to 180-220 DEG C, introducing into a pressure roller machine and rolling 2-3 times, cutting and granulating, cooling and drying to obtain the weather-resistant and corrosion-resistant composite material for automobiles.

[0013] The weather-resistant and corrosion-resistant composite material for automobiles prepared by the application has the following characteristics:

[0014] 1. Preparation of modified carbon composite particles. The modified carbon composite particles include two parts, one part is lanthanum modified porous nanocarbon particles, which mainly functions to improve weather resistance. The silicon-lanthanum modified porous nanocarbon particles can be obtained under the ball milling and calcination conditions of step 1-b, and the generated lanthanum oxide nanoparticles and silicon dioxide nanoparticles can be attached to the surface of the porous nanocarbon particles. In the further heating process, the lanthanum oxide nanoparticles and silicon dioxide nanoparticles can undergo a hometown reaction to form a heterojunction structure, change the surface potential of the porous nanocarbon particles, improve the microwave absorption capacity of the porous nanocarbon particles, and thus improve the weather resistance. The other part is silicon modified nanocarbon fiber, which mainly strengthens the mechanical properties through carbon fiber, and the generated nanosilica is adsorbed on the surface of the carbon fiber to improve the compatibility with the silicon oil of step 2 and further improve the compatibility with the polyamide.

[0015] 2. Improved compatibility between components. In order to obtain better component uniformity, in addition to the silicon oil modification ball milling of the filler component, the present scheme also proposes adding the remaining components to the molten polyamide, and at the same time improving the component uniformity through temperature control and rolling process. The present scheme first heats the polyamide to 240-300℃ to obtain molten polyamide, which is mainly to enable the remaining components to have sufficient fluidity when added, which is conducive to full dispersion. Secondly, after cooling to 180-220℃, the fluidity of the polyamide becomes poor, becoming a kind of high-elastic fluid, which can further strengthen the compatibility between components through multiple rolling, achieving more sufficient mixing. More importantly, the rolling process gives a mechanical force orientation, which can improve the arrangement regularity of the carbon fiber.

[0016] 3. Step 1-b is divided into two calcination stages, 600-800℃ stage is to volatilize organic matter, carbonize the plant carbon source and bamboo fiber, and at the same time decompose lanthanum acetate and silica sol into nanometer lanthanum oxide and nanometer silicon dioxide, which are attached to the carbonized surface; 1000-1100℃ stage is to promote the hometown reaction, so that the nanometer lanthanum oxide and nanometer silicon dioxide form a heterojunction structure, and thus change the surface state of the porous nanocarbon particles, so that they have better radiation absorption capacity, especially short-wave absorption capacity, i.e. improved weather resistance.

[0017] The leveling agent is used to improve the surface flatness of the weather-resistant and corrosion-resistant composite material after forming, and thus improve the corrosion resistance.

[0018] As a preferred, the plant carbon source in step 1-a is one or more combinations of dry grass leaves, dry sawdust, dry leaves, and straw. Sieving is mainly to increase the contact area, and selecting dry plant carbon source is mainly to enable the lanthanum acetate solution to be fully absorbed.

[0019] As a preferred, the water content of the lanthanum-filled and crushed plant carbon source in step 1-a is less than 10%.

[0020] As preferred, the silica sol in step 1-b is one of aqueous silica sol or organic silica sol; the silicone oil is resin type aqueous silicone oil.

[0021] As preferred, the anaerobic condition in step 1-b is one of vacuum anaerobic, nitrogen atmosphere anaerobic, inert gas anaerobic; the anaerobic condition in step 2 is one of vacuum anaerobic, nitrogen atmosphere anaerobic, inert gas anaerobic.

[0022] The anaerobic condition in step 1-b is mainly to prevent oxidation of plant carbon source or bamboo fiber; the anaerobic condition in step 2 is mainly to prevent oxidation of modified carbon composite particles.

[0023] As preferred, the drying temperature after dehydration in step 2 is 60-90℃ under anaerobic condition; the dispersion condition is high-speed pulverizer dispersion.

[0024] As preferred, the leveling agent in step 2 is one of silicone leveling agent, acrylate leveling agent or fluorocarbon compound leveling agent.

[0025] As preferred, the dispersant in step 3 is one or more of calcium stearate, zinc stearate and copolyamide wax.

[0026] As preferred, the weathering aid in step 3 is carbon black; the stirring condition in step 3 is 800-1000r / min.

[0027] As preferred, the filler in step 2 is one or more of zinc oxide powder, magnesium oxide powder, aluminum oxide powder, titanium dioxide powder and silicon dioxide powder. The filler functions to enhance wear resistance and strength.

[0028] The scheme also provides an automobile weather-resistant and corrosion-resistant composite material prepared by the preparation method of the automobile weather-resistant and corrosion-resistant composite material.

[0029] Compared with the prior art, the present application has the following advantages:

[0030] 1. The modified carbon composite particles, including lanthanum modified porous nano carbon particles and silicon modified nano carbon fibers, are introduced to improve the weather resistance of the automobile weather-resistant and corrosion-resistant composite material through the lanthanum modified porous nano carbon particles; and the strength of the automobile weather-resistant and corrosion-resistant composite material is improved through the silicon modified nano carbon fibers combined with the rolling process.

[0031] 2. The scheme is to improve the dispersibility by mixing the modified carbon composite particles, silicone oil, filler and leveling agent for ball milling, and the surface of each component is modified to obtain functional filler powder; and then the functional filler powder is added into the molten polyamide, and the dispersibility of each component is improved through temperature control, stirring and rolling processes. Detailed Implementation

[0032] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1

[0034] A weather-resistant and corrosion-resistant composite material for automobiles is prepared through the following steps:

[0035] Step 1, Preparation of modified functional filler powder:

[0036] 1-a By weight, the straw was crushed and passed through a 50-mesh sieve to obtain crushed plant carbon source. One part of the crushed plant carbon source was added to one part of a 0.5% lanthanum acetate solution, soaked for 2 hours, filtered, and dehydrated by pressure filtration to obtain lanthanum-filled crushed plant carbon source with a water content of 5%.

[0037] 1-b By weight, 1 part bamboo fiber, 0.5 part lanthanum-filled pulverized plant carbon source, 0.5 part aqueous silica sol and 1 part ethanol were mixed and ball-milled for 4 hours, unloaded, and the solvent was evaporated under vacuum to obtain a mixture. The mixture was calcined at 700℃ under nitrogen for 2 hours, then heated to 1000℃ and calcined under nitrogen for 0.5 hours to obtain modified carbon composite particles; the aqueous silica sol was LUDOX™-40.

[0038] Step 2, Preparation of functional filler powder: By weight, 1 part modified carbon composite particles, 0.1 part resin-based waterborne silicone oil, 1 part calcium carbonate, 0.2 parts magnesium oxide, 0.1 part zinc oxide, 0.08 parts organosilicon leveling agent, and 1 part water are mixed and added to a ball mill. After mixing and ball milling for 1 hour and grinding for 2 hours, the mixture is discharged, filtered and dehydrated, and dried at 80°C under nitrogen. The functional filler powder is then dispersed by a high-speed pulverizer. The resin-based waterborne silicone oil is polyether-modified silicone oil.

[0039] Step 3, Preparation of weather-resistant and corrosion-resistant composite material for automobiles: By weight, 1 part of polyamide is heated to 270°C, and 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black are added under stirring. After stirring at 900 r / s for 60 min, the mixture is cooled to 180°C and then rolled three times in a roller press. After chopping and granulating, the mixture is cooled and dried to obtain the weather-resistant and corrosion-resistant composite material for automobiles.

[0040] Example 2

[0041] A weather-resistant and corrosion-resistant composite material for automobiles is prepared by the following steps:

[0042] Step 1, preparation of modified functional filler powder:

[0043] 1-a, by weight parts, dry sawdust is crushed and sieved through a 50-mesh sieve to obtain a crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1.2 parts of a lanthanum acetate solution with a mass concentration of 0.4%. After soaking for 2 hours, filter and dehydrate by pressure filtration to obtain lanthanum-filled crushed plant carbon source with a water content of 7% by weight;

[0044] 1-b, by weight parts, mix 1 part of bamboo fiber, 0.5 parts of lanthanum-filled crushed plant carbon source, 0.5 parts of water-based silica sol, and 0.8 parts of ethanol, and ball mill for 4 hours. After discharging, the solvent is evaporated under vacuum conditions to obtain a mixture. After calcining the mixture at 750°C under nitrogen conditions for 2 hours and then increasing the temperature to 1050°C under nitrogen conditions for 1 hour, modified carbon composite particles are obtained. The water-based silica sol is LUDOXTM-40;

[0045] Step 2, preparation of functional filler powder: by weight parts, mix 1 part of modified carbon composite particles, 0.08 parts of resin-type water-based silicone oil, 1 part of calcium carbonate, 0.3 parts of titanium dioxide, and 0.1 parts of silicon dioxide, 0.12 parts of silicone-based leveling agent, and 1 part of water into a ball mill. After mixing and ball milling for 1 hour and mixing and grinding for 2 hours, discharge, dehydrate by pressure filtration, and dry at 80°C under nitrogen conditions. The functional filler powder is obtained by dispersing it through a high-speed pulverizer. The resin-type water-based silicone oil is a polyether-modified silicone oil.

[0046] Step 3, preparation of a weather-resistant and corrosion-resistant composite material for automobiles: by weight parts, heat 1 part of polyamide to 290°C, and under stirring conditions, add 0.28 parts of functional filler powder, 0.03 parts of zinc stearate, and 0.03 parts of carbon black. After stirring at a speed of 900 r / s for 60 minutes, cool to 200°C, and introduce into a press roller machine for rolling 3 times. After cutting and granulating, cool and dry to obtain a weather-resistant and corrosion-resistant composite material for automobiles.

[0047] Example 3

[0048] A weather-resistant and corrosion-resistant composite material for automobiles is prepared by the following steps:

[0049] Step 1, preparation of modified functional filler powder:

[0050] 1-a, by weight parts, dry sawdust is crushed and sieved through a 20-mesh sieve to obtain a crushed plant carbon source. Take 1 part of the crushed plant carbon source and add it to 1.2 parts of a lanthanum acetate solution with a mass concentration of 0.3%. After soaking for 2 hours, filter and dehydrate by pressure filtration to obtain lanthanum-filled crushed plant carbon source with a water content of 4% by weight;

[0051] 1-b, by weight parts, 1 part of bamboo fiber, 0.5 parts of lanthanum filled crushed plant carbon source, 0.7 parts of aqueous silica sol and 1 part of ethanol, mixed ball milling for 4h, unloaded, after evaporating the solvent under vacuum conditions to obtain the mixture, the mixture was calcined at 650℃ under nitrogen condition for 2h, then the temperature was increased to 1050℃, and calcined under nitrogen condition for 1h to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40;

[0052] Step 2, preparation of functional filler powder: by weight parts, 1 part of modified carbon composite particles, 0.12 parts of resin type aqueous silicone oil, 1 part of calcium carbonate, 0.3 parts of titanium dioxide and 0.1 parts of silicon dioxide, 0.12 parts of silicone leveling agent and 1 part of water were mixed and added into a ball mill, mixed ball milling for 1h, mixed grinding for 2h, then unloaded, dewatered by pressure filtration and dried at 80℃ under nitrogen condition, and then dispersed by a high-speed pulverizer to obtain the functional filler powder; the resin type aqueous silicone oil is polyether modified silicone oil;

[0053] Step 3, preparation of automobile weather-resistant corrosion-resistant composite material: by weight parts, 1 part of polyamide was heated to 250℃, 0.21 parts of functional filler powder, 0.03 parts of calcium stearate and 0.03 parts of carbon black were added under stirring condition, stirred at a speed of 980r / s for 60min, then cooled to 220℃, introduced into a pressure roller machine and rolled for 3 times, cut and granulated, cooled and dried to obtain the automobile weather-resistant corrosion-resistant composite material.

[0054] Comparative Example 1

[0055] An automobile weather-resistant corrosion-resistant composite material was prepared by the following steps:

[0056] Step 1, preparation of modified functional filler powder:

[0057] by weight parts, 1 part of bamboo fiber, 0.5 parts of lanthanum filled crushed plant carbon source, 0.5 parts of aqueous silica sol and 1 part of ethanol, mixed ball milling for 4h, unloaded, after evaporating the solvent under vacuum conditions to obtain the mixture, the mixture was calcined at 650℃ under nitrogen condition for 2h, then the temperature was increased to 1050℃, and calcined under nitrogen condition for 1h to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40;

[0058] Step 2, preparation of functional filler powder: by weight parts, 1 part of modified carbon composite particles, 0.1 parts of resin type aqueous silicone oil, 1 part of calcium carbonate, 0.2 parts of magnesium oxide and 0.1 parts of zinc oxide, 0.08 parts of silicone leveling agent and 1 part of water were mixed and added into a ball mill, mixed ball milling for 1h, mixed grinding for 2h, then unloaded, dewatered by pressure filtration and dried at 80℃ under nitrogen condition, and then dispersed by a high-speed pulverizer to obtain the functional filler powder; the resin type aqueous silicone oil is polyether modified silicone oil;

[0059] Step 3, preparation of weather-resistant and corrosion-resistant composite material for automobile: 1 part of polyamide is heated to 270℃, 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black are added under stirring conditions, stirring is carried out at a speed of 900r / s for 60min, then the temperature is lowered to 180℃, and then it is introduced into a roller machine for rolling 3 times, cutting and granulation, cooling, drying to obtain a weather-resistant and corrosion-resistant composite material for automobile.

[0060] Comparative Example 2

[0061] A weather-resistant and corrosion-resistant composite material for automobile is prepared by the following steps:

[0062] Step 1, preparation of modified functional filler powder:

[0063] The crushed plant carbon source is obtained by crushing the straw and passing it through a 50-mesh sieve. 1 part of the crushed plant carbon source is added to a 0.5% lanthanum acetate solution, soaked for 2h, filtered, and dehydrated by pressure filtration to obtain a lanthanum-filled crushed plant carbon source with a water content of 5%. The modified carbon composite particles are obtained by calcining under nitrogen for 2h, then increasing the temperature to 1000℃ and calcining under nitrogen for 0.5h. The aqueous silica sol is LUDOX TM-40;

[0064] Step 2, preparation of functional filler powder: 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of silicone leveling agent and 1 part of water are mixed and added to a ball mill, mixed and ball milled for 1h, mixed and ground for 2h, then unloaded, dehydrated by pressure filtration and dried at 80℃ under nitrogen, then dispersed by a high-speed pulverizer to obtain functional filler powder. The resin-type aqueous silicone oil is a polyether-modified silicone oil.

[0065] Step 3, preparation of weather-resistant and corrosion-resistant composite material for automobile: 1 part of polyamide is heated to 270℃, 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black are added under stirring conditions, stirring is carried out at a speed of 900r / s for 60min, then the temperature is lowered to 180℃, and then it is introduced into a roller machine for rolling 3 times, cutting and granulation, cooling, drying to obtain a weather-resistant and corrosion-resistant composite material for automobile.

[0066] Comparative Example 3

[0067] A weather-resistant and corrosion-resistant composite material for automobile is prepared by the following steps:

[0068] Step 1, preparation of modified functional filler powder:

[0069] 1-a, by weight parts, the straw is crushed and passed through a 50 mesh sieve to obtain a crushed plant carbon source, 1 part of the crushed plant carbon source is taken and added to 1 part of a lanthanum acetate solution with a mass concentration of 0.5%, soaked for 2 hours and then filtered, and dehydrated by pressure filtration to obtain lanthanum-filled crushed plant carbon source with a water content of 5% by volume;

[0070] 1-b, by weight parts, 1 part of bamboo fiber, 0.5 parts of lanthanum-filled crushed plant carbon source, 0.5 parts of aqueous silica sol and 1 part of ethanol are mixed, the solvent is evaporated under vacuum to obtain a mixture, the mixture is calcined at 700°C under nitrogen for 2 hours, then the temperature is raised to 1000°C and calcined under nitrogen for 0.5 hours to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40;

[0071] Step 2, preparation of functional filler powder: by weight parts, 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of silicone leveling agent and 1 part of water are mixed and added to a ball mill, mixed and ball milled for 1 hour, mixed and ground for 2 hours, then unloaded, dehydrated by pressure filtration and dried at 80°C under nitrogen, and dispersed by a high-speed pulverizer to obtain functional filler powder; the resin-type aqueous silicone oil is a polyether-modified silicone oil;

[0072] Step 3, preparation of automobile weather-resistant and corrosion-resistant composite material: by weight parts, 1 part of polyamide is heated to 270°C, 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black are added under stirring, stirred at a speed of 900 r / s for 60 minutes, then cooled to 180°C, introduced into a pressure roller machine and rolled 3 times, cut and granulated, cooled and dried to obtain an automobile weather-resistant and corrosion-resistant composite material.

[0073] Comparative Example 4

[0074] An automobile weather-resistant and corrosion-resistant composite material is prepared by the following steps:

[0075] Step 1, preparation of modified functional filler powder:

[0076] 1-a, by weight parts, the straw is crushed and passed through a 50 mesh sieve to obtain a crushed plant carbon source;

[0077] 1-b, by weight parts, 1 part of bamboo fiber, 0.5 parts of lanthanum-filled crushed plant carbon source, 0.5 parts of aqueous silica sol and 1 part of ethanol are mixed, the solvent is evaporated under vacuum to obtain a mixture, the mixture is calcined at 700°C under nitrogen for 2 hours, then the temperature is raised to 1000°C and calcined under nitrogen for 0.5 hours to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40;

[0078] Step 2, preparation of functional filler powder: 1 part of modified carbon composite particles, 0.1 part of resin type water-based silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of silicone leveling agent and 1 part of water were mixed into a ball mill, mixed ball milling for 1 h, after mixed grinding for 2 h, the material was unloaded, dewatered by pressure filtration, and then dried at 80°C under nitrogen atmosphere. The functional filler powder was obtained by dispersion with a high-speed pulverizer; the resin type water-based silicone oil was a polyether modified silicone oil;

[0079] Step 3, preparation of automobile weather-resistant corrosion-resistant composite material: 1 part of polyamide was heated to 270°C, and 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black were added under stirring at a speed of 900 r / s for 60 min. After cooling to 180°C, the material was introduced into a press roller machine and rolled 3 times, then cut, granulated, cooled and dried to obtain an automobile weather-resistant corrosion-resistant composite material.

[0080] Comparative Example 5

[0081] An automobile weather-resistant corrosion-resistant composite material was prepared by the following steps:

[0082] Step 1, preparation of modified functional filler powder:

[0083] 1-a, by weight, the crushed straw was sieved through a 50 mesh sieve to obtain a crushed plant carbon source. 1 part of the crushed plant carbon source was added to a 0.5% lanthanum acetate solution, soaked for 2 h, filtered, and dewatered by pressure filtration to obtain lanthanum-filled crushed plant carbon source with a water content of 5%;

[0084] 1-b, by weight, 1 part of bamboo fiber, 0.5 part of lanthanum-filled crushed plant carbon source and 1 part of ethanol were mixed and ball milled for 4 h. After the solvent was evaporated under vacuum, the mixture was obtained. The mixture was calcined at 700°C under nitrogen atmosphere for 2 h, and then the temperature was increased to 1000°C and calcined under nitrogen atmosphere for 0.5 h to obtain modified carbon composite particles; the water-based silica sol was LUDOX TM-40;

[0085] Step 2, preparation of functional filler powder: 1 part of modified carbon composite particles, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of silicone leveling agent and 1 part of water were mixed into a ball mill, mixed ball milling for 1 h, after mixed grinding for 2 h, the material was unloaded, dewatered by pressure filtration, and then dried at 80°C under nitrogen atmosphere. The functional filler powder was obtained by dispersion with a high-speed pulverizer; the resin type water-based silicone oil was a polyether modified silicone oil;

[0086] Step 3, preparation of weather-resistant and corrosion-resistant composite material for automobile: 1 part of polyamide is heated to 270℃, 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black are added under stirring conditions, stirring is carried out at a speed of 900r / s for 60min, then the temperature is lowered to 180℃, and then it is introduced into a pressure roller machine for rolling 3 times, cut into granules, cooled, dried to obtain a weather-resistant and corrosion-resistant composite material for automobile.

[0087] Comparative Example 6

[0088] A weather-resistant and corrosion-resistant composite material for automobile is prepared by the following steps:

[0089] Step 1, preparation of modified functional filler powder:

[0090] 1-a According to parts by weight, the straw is crushed and passed through a 50 mesh sieve to obtain a crushed plant carbon source, 1 part of the crushed plant carbon source is added to a 0.5% lanthanum acetate solution, soaked for 2h, filtered, and dehydrated by pressure filtration to obtain lanthanum-filled crushed plant carbon source with a water content of 5%;

[0091] 1-b According to parts by weight, 1 part of bamboo fiber, 0.5 parts of lanthanum-filled crushed plant carbon source, 0.5 parts of water-based silica sol and 1 part of ethanol are mixed and ball milled for 4h, then the mixture is obtained after the solvent is evaporated under vacuum conditions, and then the mixture is calcined at 700℃ under nitrogen conditions for 2h, and then the temperature is raised to 1000℃ and calcined under nitrogen conditions for 0.5h to obtain modified carbon composite particles; the water-based silica sol is LUDOXTM-40;

[0092] Step 2, preparation of functional filler powder: 1 part of modified carbon composite particles, 0.1 part of resin-type water-based silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide and 1 part of water are mixed and added to a ball mill, mixed and ball milled for 1h, mixed and ground for 2h, then the mixture is dehydrated by pressure filtration and dried at 80℃ under nitrogen conditions, and then the functional filler powder is obtained by dispersion with a high-speed pulverizer; the resin-type water-based silicone oil is a polyether-modified silicone oil;

[0093] Step 3, preparation of weather-resistant and corrosion-resistant composite material for automobile: 1 part of polyamide is heated to 270℃, 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black are added under stirring conditions, stirring is carried out at a speed of 900r / s for 60min, then the temperature is lowered to 180℃, and then it is introduced into a pressure roller machine for rolling 3 times, cut into granules, cooled, dried to obtain a weather-resistant and corrosion-resistant composite material for automobile.

[0094] Comparative Example 7

[0095] A weather-resistant and corrosion-resistant composite material for automobile is prepared by the following steps:

[0096] Step 1, preparation of modified functional filler powder:

[0097] 1-a by weight parts, after the straw is crushed and passed through a 50 mesh sieve, a crushed plant carbon source is obtained, take 1 part of the crushed plant carbon source, add to 1 part of lanthanum acetate solution with a mass concentration of 0.5%, soak for 2h, then filter and dewater by pressure filtration, to obtain lanthanum-filled crushed plant carbon source with a water content of 5% by weight;

[0098] 1-b by weight parts, mix 1 part of bamboo fiber, 0.5 parts of lanthanum-filled crushed plant carbon source, 0.5 parts of aqueous silica sol and 1 part of ethanol, ball mill for 4h, unload, evaporate the solvent under vacuum conditions to obtain a mixture, calcine the mixture at 1200℃ under nitrogen conditions for 0.5h to obtain modified carbon composite particles; the aqueous silica sol is LUDOX TM-40;

[0099] Step 2, preparation of functional filler powder: by weight parts, mix 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of silicone leveling agent and 1 part of water into a ball mill, ball mill for 1h, unload after mixing and grinding for 2h, dewater by pressure filtration, and dry at 80℃ under nitrogen conditions, then disperse by a high-speed pulverizer to obtain functional filler powder; the resin-type aqueous silicone oil is a polyether-modified silicone oil;

[0100] Step 3, preparation of automobile weather-resistant and corrosion-resistant composite material: by weight parts, heat 1 part of polyamide to 270℃, under stirring conditions, add 0.25 parts of functional filler powder, 0.02 parts of calcium stearate and 0.03 parts of carbon black, stir at a speed of 900r / s for 60min, then cool to 180℃, introduce into a press roller machine and roll 3 times, cut and granulate, cool and dry to obtain an automobile weather-resistant and corrosion-resistant composite material.

[0101] Comparative Example 8

[0102] An automobile weather-resistant and corrosion-resistant composite material is prepared by the following steps:

[0103] Step 1, preparation of modified functional filler powder:

[0104] 1-a by weight parts, after the straw is crushed and passed through a 50 mesh sieve, a crushed plant carbon source is obtained, take 1 part of the crushed plant carbon source, add to 1 part of lanthanum acetate solution with a mass concentration of 0.5%, soak for 2h, then filter and dewater by pressure filtration, to obtain lanthanum-filled crushed plant carbon source with a water content of 5% by weight;

[0105] 1-b: 1 part of bamboo fiber, 0.5 part of lanthanum filler, 0.5 part of aqueous silica sol and 1 part of ethanol were mixed and ball-milled for 4 h, and then the mixture was obtained by evaporating the solvent under vacuum. The mixture was calcined at 700°C for 2 h under nitrogen, and then the temperature was increased to 1000°C and calcined for 0.5 h under nitrogen to obtain modified carbon composite particles. The aqueous silica sol was LUDOXTM-40;

[0106] Step 2: Preparation of functional filler powder: 1 part of modified carbon composite particles, 0.1 part of resin-type aqueous silicone oil, 1 part of calcium carbonate, 0.2 part of magnesium oxide and 0.1 part of zinc oxide, 0.08 part of silicone leveling agent and 1 part of water were mixed and added to a ball mill, and then ball-milled for 1 h. After mixing and grinding for 2 h, the mixture was unloaded, dewatered by pressure filtration and dried at 80°C under nitrogen. The functional filler powder was obtained by dispersion with a high-speed pulverizer.

[0107] Step 3: Preparation of weather-resistant and corrosion-resistant composite material for automobiles: 1 part of polyamide was heated to 270°C, and then 0.25 part of functional filler powder, 0.02 part of calcium stearate and 0.03 part of carbon black were added under stirring at a speed of 900 r / s for 60 min. After extrusion granulation, cooling and drying, the weather-resistant and corrosion-resistant composite material for automobiles was obtained.

[0108] Test method:

[0109] Antibacterial test: The test sample was tested for whether it was easy to be attached by mold according to the standard method of GB / T31402, and the test strains were black mold.

[0110] Weather resistance test: The special standard for automobile exterior parts of SAE J2527 was referred to.

[0111] Surface detection: A sample plate of 60 mm x 60 mm x 3.2 mm was prepared, and a section was cut off. The surface pore condition was observed with a 500x optical microscope, and the number of pores in the field of view was recorded.

[0112] Wear resistance test: The sample was prepared according to ASTM D3702, and the test conditions were: pressure: 100 N, speed: 0.5 m / s, wear time: 2 h, and wear rate = wear mass / initial mass*100%.

[0113] Environmental use effect detection: A sample plate of 60 mm x 60 mm x 3.2 mm was prepared, and the surface state was observed after being placed in the same outdoor environment for 100 weeks.

[0114] Table 1

[0115] No. Gloss (60°) Black mold Gloss after aging (60°, 2000h) Color difference value after aging (2000h) Wear rate Surface state after standing outdoors for 100 weeks Number of pores Example 1 73 92.2 62 2.2 19 Few scratches, no significant change None Example 2 76 92.3 62 2.1 21 Few scratches, no significant change None Example 3 74 92.4 61 2.0 20 Few scratches, no significant change None Comparative Example 1 68 91.6 48 1.7 28 Yellowing, with cracks 3 Comparative Example 2 71 91.2 59 1.8 47 With cracks 4 Comparative Example 3 70 91.6 54 1.3 38 With cracks 12 Comparative Example 4 69 90.4 41 1.0 27 Yellowing 4 Comparative Example 5 70 90.3 53 1.1 46 With pits and cracks 17 Comparative Example 6 67 86.3 38 1.3 23 With pits and cracks 35 Comparative Example 7 72 91.0 45 1.9 29 Yellowing 2 Comparative Example 8 66 90.2 58 1.8 33 With obvious scratches, with a small number of pits 8

[0116] The results show that the products of Examples 1-3 are better than those of Comparative Examples 1-8, which is due to the combination of the formula and the process.

[0117] The main difference between Comparative Example 1 and Example 1 is that the lanthanum-filled crushed plant carbon source is not prepared in Comparative Example 1. Therefore, Comparative Example 1 cannot form a lanthanum oxide-silicon dioxide heterojunction structure, and the absorption of radiation and weather resistance are poor. Comparative Example 4 differs from Example 1 in that the plant carbon source is not soaked in a lanthanum acetate solution, and the weather resistance is also low.

[0118] The main difference between Comparative Example 2 and Example 1 is that the bamboo fiber is not calcined into carbon fiber in Comparative Example 2. Comparative Example 2 cannot obtain the enhancement of carbon fiber, and thus the wear resistance is poor.

[0119] The difference between Comparative Example 3 and Example 1 is that ball milling is not performed in step 1-b, which leads to poor mixing uniformity, uneven attachment of silica sol on the surface of bamboo fiber particles and crushed plant carbon source particles, and finally more surface pores and poor performance.

[0120] The difference between Comparative Example 5 and Example 1 is that no silica sol is added in step 1-b, and no silicon oil is added in step 2. This leads to poor compatibility of the prepared functional filler with polyamide, easy occurrence of microcracks on the contact surface, and thus affects the weather resistance and wear resistance, and there are more surface pores. Therefore, the test results of Comparative Example 5 in wear resistance and weather resistance are not satisfactory.

[0121] The difference between Comparative Example 6 and Example 1 is that no leveling agent is added. This leads to uneven surface of the prepared automobile weather-resistant and corrosion-resistant composite material after molding, more pores, easy attachment of bacteria and mold, and easy formation of corrosion sources. As can be seen from the data, the prepared product has little difference in wear resistance from Example 1, but has more pores, pits and cracks after being left outdoors for 100 weeks, indicating that the leveling agent has a strong promoting effect on the automobile weather-resistant and corrosion-resistant composite material described in the scheme.

[0122] The difference between Comparative Example 7 and Example 1 is that step 1-b is not divided into stages, and the temperature is too high, which leads to excessive solid-phase reaction, formation of coarse heterojunction grains, and reduction of the pore structure of the porous nano-carbon particles, and finally affects the absorption capacity of radiation and makes the weather resistance poor.

[0123] The difference between Comparative Example 8 and Example 1 is that a conventional extrusion granulation is used in step 3, which does not further enhance the combination between the components, reduces the mixing uniformity, and more importantly, affects the mechanical force orientation of the nano-carbon fiber, and thus affects the wear resistance and weather resistance.

[0124] The above merely describes preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art, according to the technical solution and inventive concept of the present application, makes equivalent replacement or change within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A method for preparing a weather resistant corrosion resistant composite material for automotive applications, characterized in that, The method comprises the following steps: Step 1, preparation of modified functional filler powder: 1-a, by weight, the plant carbon source is crushed and passed through a 20-50 mesh screen, and 1 part of the crushed plant carbon source is taken and added to 1-1.5 parts of a lanthanum acetate solution with a mass concentration of 0.3%-0.5%, soaked for 2-3 hours, filtered, and dehydrated to obtain lanthanum-filled crushed plant carbon source; 1-b, by weight, 1 part of bamboo fiber, 0.3-0.5 parts of lanthanum-filled crushed plant carbon source, 0.5-1 parts of silica sol, and 0.5-1 parts of ethanol are mixed and ball milled for 3-5 hours, unloaded, and the solvent is evaporated under vacuum conditions to obtain a mixture. The mixture is calcined at 600-800°C under anaerobic conditions for 2-3 hours, then the temperature is increased to 1000-1100°C, and calcined under anaerobic conditions for 0.5-1 hour to obtain modified carbon composite particles; Step 2, preparation of functional filler powder: by weight, 1 part of modified carbon composite particles, 0.05-0.15 parts of silicone oil, 1-2 parts of filler, 0.05-0.1 parts of leveling agent, and 1-1.5 parts of water are mixed and added to a ball mill, mixed and ball milled for 1-2 hours, then mixed and ground at a speed of 800-1000 r / s for 1-2 hours, unloaded, dehydrated, and dried under anaerobic conditions to obtain functional filler powder; Step 3, preparation of automobile weather-resistant and corrosion-resistant composite material: by weight, 1 part of polyamide is heated to 240-300°C, 0.2-0.3 parts of functional filler powder, 0.01-0.05 parts of dispersant, and 0.02-0.05 parts of weather-resistant additive are added under stirring conditions, stirred for 30-60 minutes, then cooled to 180-220°C, introduced into a press roller machine, rolled 2-3 times, cut and granulated, cooled, and dried to obtain an automobile weather-resistant and corrosion-resistant composite material.

2. The preparation method of the weather-resistant and corrosion-resistant composite material for automobiles as described in claim 1, characterized in that, The plant carbon source in step 1-a is one or a combination of dry grass leaves, dry sawdust, dry tree leaves, and straw.

3. The method for preparing a weather-resistant and corrosion-resistant composite material for automobiles as described in claim 1, characterized in that, The lanthanum-filled crushed plant carbon source in step 1-a has a water content of less than 10%.

4. The method for preparing a weather-resistant and corrosion-resistant composite material for automobiles as described in claim 1, characterized in that, The silica sol in step 1-b is one of aqueous silica sol or organic silica sol; the silicone oil is a resin-type aqueous silicone oil.

5. The method for preparing a weather-resistant and corrosion-resistant composite material for automobiles as described in claim 1, characterized in that, The anaerobic condition in step 1-b is one of vacuum anaerobic, nitrogen atmosphere anaerobic, or inert gas anaerobic; the anaerobic condition in step 2 is one of vacuum anaerobic, nitrogen atmosphere anaerobic, or inert gas anaerobic.

6. The method for preparing a weather-resistant and corrosion-resistant composite material for automobiles as described in claim 1, characterized in that, The dehydration temperature under anaerobic conditions in step 2 is 60-90°C, and the dispersion condition is high-speed pulverizer dispersion.

7. The method for preparing a weather-resistant and corrosion-resistant composite material for automobiles as described in claim 1, characterized in that, The leveling agent in step 2 is one of silicone leveling agent, acrylate leveling agent, or fluorocarbon compound leveling agent; the filler in step 2 is one or a combination of zinc oxide powder, magnesium oxide powder, aluminum oxide powder, titanium dioxide powder, and silica powder.

8. The method for preparing a weather-resistant and corrosion-resistant composite material for automobiles as described in claim 1, characterized in that, The dispersant in step 3 is one or a combination of calcium stearate, zinc stearate, and copolyamide wax.

9. The method of claim 1, wherein the weatherable corrosion resistant composite material is used for an automobile. The weather-resistant additive in step 3 is carbon black; the stirring condition in step 3 is 800-1000 r / min.

10. A weather resistant and corrosion resistant composite material for automobile prepared according to the method of any one of claims 1-9.