Wear-resistant PE composite material, water supply pipe and preparation method of water supply pipe

Abstract

The invention discloses a wear-resistant PE composite material, a water supply pipe and a preparation method of the wear-resistant PE composite material, and belongs to the technical field of PE composites.The preparation method comprises the steps that firstly, flower-shaped aluminum oxide is obtained through hydrothermal reaction and calcination, then a porous coating is formed on the surface of the flower-shaped aluminum oxide through tannic acid, cerium ions are loaded, calcination is conducted, and cerium dioxide loaded flower-shaped aluminum oxide is obtained; the preparation method comprises the following steps: taking cerium dioxide loaded flower-shaped aluminum oxide as a template, taking mesoporous silicon dioxide as a template, etching by ammonia water to form air and doping zirconium and zinc to obtain zirconium-zinc doped hollow mesoporous silicon dioxide spheres, mixing polyethylene PE100, cerium dioxide loaded flower-shaped aluminum oxide, the zirconium-zinc doped hollow mesoporous silicon dioxide spheres, an antioxidant 1010 and polyethylene wax, melting, extruding and granulating to obtain the wear-resistant PE composite material. Melting, plasticizing and extruding through a single-screw extruder, and carrying out vacuum sizing and cooling traction, so as to prepare the wear-resistant PE water supply pipe. The wear resistance, the toughness, the aging resistance and the antibacterial effect of the water supply pipe are further improved.

Description

Technical Field

[0001] This invention belongs to the field of PE composite material technology, specifically relating to a wear-resistant PE composite material, a water supply pipe, and its preparation method. Background Technology

[0002] With the continuous advancement of urbanization, the upgrading and renovation of municipal water supply networks, and the comprehensive rollout of rural drinking water safety projects, polyethylene (PE) water supply pipes, with their advantages of corrosion resistance, good flexibility, and convenient construction, have widely replaced traditional pipe materials such as cast iron pipes and galvanized steel pipes, becoming the mainstream pipeline material in urban and rural water supply, water conservancy transmission, and sponge city construction.

[0003] In long-term engineering applications, ordinary PE water supply pipes have gradually revealed significant shortcomings: under complex conditions such as transporting sandy raw water, trenchless laying in mountainous areas, and high-velocity water conveyance, the pipe walls are easily eroded by silt, subjected to sand and gravel friction, and scratched by external forces, leading to problems such as thinning of the inner wall, localized stress concentration, and decreased pressure resistance, seriously affecting the service life and operational safety of the pipeline. At the same time, with the increasing public awareness of health, the safety of drinking water quality in water supply networks is receiving increasing attention. PE material itself does not possess antibacterial properties, especially in scenarios with high risks of water retention, such as secondary water supply in high-rise buildings, where bacteria easily grow on the pipe walls, forming biofilms and causing secondary water pollution. Therefore, developing new PE water supply pipes that combine excellent wear resistance with highly efficient antibacterial functions has become an important direction for technological upgrading in the industry.

[0004] Chinese patent application CN117105256A discloses a cerium dioxide-based nanopowder. The prepared cerium dioxide nanopowder has a small particle size and a large specific surface area, exhibiting excellent antibacterial properties and enhancing the antibacterial performance of plastic products. Besides nano-cerium dioxide, other nanomaterials such as nano-silver, nano-zinc oxide, and quaternary ammonium salt-modified graphene also possess good antibacterial effects. However, nanomaterials tend to agglomerate in plastic materials, affecting the antibacterial effect and mechanical properties of products such as PE water pipes. Summary of the Invention

[0005] The purpose of this invention is to provide a wear-resistant PE composite material, a water supply pipe, and a method for preparing the same. A porous coating is formed by polymerizing tannic acid-formaldehyde on the surface of flower-shaped alumina under alkaline conditions. The coating utilizes the efficient coordination and capture ability of cerium ions by the phenolic hydroxyl groups to uniformly load cerium dioxide nanoparticles onto the flower-shaped alumina surface, effectively preventing the aggregation of cerium dioxide nanoparticles. Simultaneously, the invention, in conjunction with zirconium-zinc doped hollow mesoporous silica spheres, enhances the antibacterial and wear-resistant properties of the PE water supply pipe.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A wear-resistant PE composite material, comprising the following components by weight:

[0008] 800-1000 parts of polyethylene PE100, 10-15 parts of titanate coupling agent, 50-100 parts of cerium dioxide-supported flower-shaped alumina, 10-25 parts of zirconium zinc-doped hollow mesoporous silica spheres, 5-15 parts of antioxidant 1010, and 10-30 parts of polyethylene wax.

[0009] Furthermore, the specific preparation steps for cerium dioxide-supported flower-like alumina are as follows:

[0010] Flower-shaped alumina and anhydrous ethanol were added to deionized water and stirred for 30-40 min. Then, 2.55 wt% tannic acid solution was added and stirred evenly. Next, 25 wt% ammonia and 3.7 wt% formaldehyde solution were added and stirred at 60 °C for 12-14 h. Then, 0.118 wt% cerium nitrate hexahydrate solution was slowly added dropwise and stirred for another 12-14 h. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and hydrothermally reacted at 100-120 °C for 24-26 h. The precipitate was collected by centrifugation, washed, freeze-dried, and then placed in a muffle furnace and calcined at 500-600 °C for 2-4 h to obtain cerium dioxide-supported flower-shaped alumina.

[0011] Furthermore, the ratio of flower-shaped alumina, anhydrous ethanol, deionized water, 2.55wt% tannic acid solution, 25wt% ammonia water, 3.7wt% formaldehyde solution, and 0.118wt% cerium nitrate hexahydrate solution is 18-22g: 150-180mL: 650-850mL: 140-160mL: 5-8mL: 50-80mL: 18.75-22.4mL.

[0012] Furthermore, the specific preparation steps for flower-shaped alumina are as follows:

[0013] Potassium sulfate, urea, aluminum nitrate nonahydrate, and deionized water were added to a reaction vessel and stirred until the solid was completely dissolved. The reaction was carried out at 180-200℃ for 3-5 hours. After cooling to room temperature, the mixture was centrifuged and washed for 10-20 minutes. The precipitate was collected, dried, and transferred to a muffle furnace. The furnace was heated to 1100-1200℃ and calcined for 3-5 hours to obtain flower-shaped alumina.

[0014] Furthermore, the ratio of potassium sulfate, urea, aluminum nitrate nonahydrate, and deionized water is 224-256g: 38.4-42.2g: 240-260g: 12.8-14.2L.

[0015] Furthermore, the specific preparation steps for zirconium-zinc doped hollow mesoporous silica spheres are as follows:

[0016] Zirconium nitrate pentahydrate and zinc nitrate hexahydrate were dissolved in deionized water to obtain a mixed solution. Mesoporous silica nanospheres were added to the deionized water and stirred for 30-40 min. The mixed solution was then slowly added dropwise and magnetically stirred for 30-40 min. 25 wt% ammonia water was then added dropwise and transferred to a reaction vessel. The reaction was carried out at 160-180℃ for 24-26 h. After cooling to room temperature, the mixture was centrifuged for 10-20 min, the precipitate was collected, washed, and vacuum dried to constant weight to obtain zirconium-zinc doped hollow mesoporous silica nanospheres.

[0017] Furthermore, the ratio of zirconium nitrate pentahydrate, zinc nitrate hexahydrate, and deionized water is 21.5-24g: 14.85-16.2g: 2000-2500mL.

[0018] Furthermore, the ratio of mesoporous silica nanospheres, deionized water, mixed solution and 25wt% ammonia is 6.5-8.2g: 2000-2500mL: 2000-2500mL: 600-800mL.

[0019] Furthermore, the specific preparation steps for the wear-resistant PE composite material are as follows:

[0020] Polyethylene PE100, titanate coupling agent, cerium dioxide-supported flower-shaped alumina, zirconium zinc-doped hollow mesoporous silica spheres, antioxidant 1010 and polyethylene wax are added to a high-speed premixer and mixed at 500-800 rpm for 8-10 min. The mixture is then transferred to a twin-screw extruder for melt extrusion and granulation. After drying at 60-80℃ for 2-4 h, a wear-resistant PE composite material is obtained.

[0021] Furthermore, the temperature settings for the twin-screw extruder are: Zone 1 165-175℃, Zone 2 185-195℃, Zone 3 205-215℃, Zone 4 205-210℃, and Die head 200-210℃.

[0022] The present invention also provides a water supply pipe, which is prepared from the above-mentioned wear-resistant PE composite material.

[0023] The present invention also provides a method for preparing a water supply pipe, comprising the following steps:

[0024] Wear-resistant PE composite material is added to a single-screw extruder, melted, plasticized, and extruded. It is then transferred to a vacuum sizing box and adsorbed onto the sizing sleeve at a pressure of -0.06 to -0.09 MPa. The pipe is then placed into a spray-type cooling water tank and gradually cooled at a water temperature of 15-25℃. After cooling, the pipe is pulled at a constant speed by a traction machine and cut to a fixed length by a planetary cutter to obtain a wear-resistant PE water supply pipe.

[0025] Furthermore, the temperature settings for the single-screw extruder are: Zone 1 180-190℃, Zone 2 190-200℃, Zone 3 200-210℃, and Die Head 210-220℃.

[0026] The beneficial effects of this invention are:

[0027] 1. This invention prepares a wear-resistant PE composite material by melt blending and extrusion granulation of cerium dioxide-loaded flower-shaped alumina, zirconium-zinc doped hollow mesoporous silica spheres, and a polyethylene matrix. The flower-shaped alumina serves as a rigid skeleton with a high surface area, bearing the main responsibility for wear resistance. Cerium dioxide strengthens and improves wear resistance while providing efficient antibacterial, anti-aging, and improved interfacial compatibility. Combined with zirconium-zinc doped hollow mesoporous silica spheres to enhance antibacterial properties, the multiple synergistic effects of structural wear resistance enhancement, antibacterial supplementation, and synergistic migration of cerium dioxide-loaded flower-shaped alumina to the PE substrate surface, together endow the water supply pipe with excellent wear resistance, high tensile strength, good aging resistance, and excellent antibacterial effect.

[0028] 2. In this invention, cerium dioxide-loaded flower-shaped alumina is prepared by using potassium sulfate as a morphology guide and urea as a homogeneous precipitant. The self-assembly of nanosheets is induced by hydrothermal reaction and then calcined at high temperature to obtain flower-shaped alumina. Its high-hardness skeleton provides basic wear-resistant support for the composite material, while the high specific surface area provides conditions for loading cerium dioxide. Tannic acid-formaldehyde is polymerized on the surface of flower-shaped alumina under alkaline conditions to form a porous coating. The coating's phenolic hydroxyl groups have a high efficiency in coordinating and capturing cerium ions. After hydrothermal reaction and calcination, highly dispersed cerium dioxide nanoparticles are obtained and loaded on the surface of flower-shaped alumina. This not only endows the material with high-efficiency contact antibacterial activity, but also enhances the interfacial bonding force with the polyethylene matrix through nanoscale interface modification, and also plays a role in thermo-oxidative stabilization.

[0029] 2. In this invention, zirconium-zinc doped hollow mesoporous silica spheres are used as hard templates. The internal hollowing and zirconium-zinc metal doping are achieved simultaneously through ammonia water under high-temperature hydrothermal conditions. The zirconium doping significantly improves the shell strength of the hollow mesoporous silica spheres and enhances the mechanical interlocking effect with the polyethylene matrix. The zinc doping endows it with slow-release antibacterial function and forms a dual antibacterial mechanism with cerium dioxide. The chemical modification of the surface of the hollow mesoporous silica spheres by zirconium-zinc doping improves its interfacial compatibility with hydrophobic polyethylene. During the melt processing, shear-induced migration and surface energy drive promote the enrichment of cerium dioxide-loaded flower-shaped alumina onto the pipe surface, ensuring that the antibacterial components effectively contact bacteria. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments in the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] Example 1: A method for preparing a wear-resistant PE composite material and a water supply pipe, comprising the following steps:

[0032] S1: Add 224g potassium sulfate, 38.4g urea, 240g aluminum nitrate nonahydrate and 12.8L deionized water to a reaction vessel, stir until the solid is completely dissolved, react at 180℃ for 3h, cool to room temperature, centrifuge and wash at 8000rpm for 10min, collect the precipitate, dry it, transfer it to a muffle furnace, and calcine it at 1100℃ for 3h at a rate of 2℃ / min to obtain flower-shaped alumina with a particle size of 2μm.

[0033] Using urea as a homogeneous precipitant and potassium sulfate as a morphology guiding agent, nanosheets are induced to self-assemble into flower-like precursors through hydrothermal reaction. These precursors are then converted into high-hardness α-crystalline alumina through high-temperature calcination, ultimately yielding a micron-scale flower-like structure.

[0034] S2: Add 18g of flower-shaped alumina and 150mL of anhydrous ethanol to 650mL of deionized water and stir for 30min. Add 140mL of 2.55wt% tannic acid solution and stir evenly. Then add 5mL of 25wt% ammonia water and 50mL of 3.7wt% formaldehyde solution and stir at 60℃ for 12h. Slowly add 18.75mL of 0.118wt% cerium nitrate hexahydrate solution and continue stirring for 12h. Transfer to a polytetrafluoroethylene-lined reactor and hydrothermally react at 100℃ for 24h. Centrifuge to collect the precipitate and wash it three times with ethanol and deionized water. After freeze-drying, place it in a muffle furnace and calcine at 500℃ for 2h at a rate of 2℃ / min to obtain cerium dioxide-supported flower-shaped alumina.

[0035] Tannic acid polymerizes with formaldehyde under alkaline conditions to form a porous tannic acid coating. The phenolic hydroxyl groups on its surface can effectively coordinate and capture cerium ions. After high-temperature calcination, highly dispersed cerium dioxide is obtained and loaded onto flower-shaped alumina.

[0036] S3: Dissolve 21.5g zirconium nitrate pentahydrate and 14.85g zinc nitrate hexahydrate in 2000mL of deionized water to obtain a mixed solution; add 6.5g mesoporous silica nanospheres to 2000mL of deionized water and stir for 30min; slowly add 2000mL of the mixed solution dropwise and stir magnetically for 30min; then add 600mL of 25wt% ammonia water dropwise and transfer to a reaction vessel; react at 160℃ for 24h; cool to room temperature; centrifuge at 11000rpm for 10min; collect the precipitate; wash three times alternately with deionized water and anhydrous ethanol; and vacuum dry at 60℃ to constant weight to obtain zirconium-zinc doped hollow mesoporous silica nanospheres.

[0037] Hollow mesoporous silica microspheres with enhanced structure and antibacterial effects were prepared by using mesoporous silica as a hard template and simultaneously achieving internal etching and external doping with zirconium and zinc under high-temperature hydrothermal conditions.

[0038] S4: Add 80g of polyethylene PE100, 1g of titanate coupling agent, 5g of cerium dioxide-supported flower-shaped alumina, 1g of zirconium zinc-doped hollow mesoporous silica spheres, 0.5g of antioxidant 1010 and 1g of polyethylene wax to a high-speed premixer and mix at 500rpm for 8min. Transfer to a twin-screw extruder and melt extrude and granulate at 165℃ in zone 1, 185℃ in zone 2, 205℃ in zone 3, 205℃ in zone 4 and 200℃ at the die head. Dry at 60℃ for 2h to obtain abrasion-resistant PE composite material.

[0039] S5: The wear-resistant PE composite material is added to a single screw extruder and melted and plasticized at 180℃ in zone 1, 190℃ in zone 2, 200℃ in zone 3, and 210℃ at the die head. The material is then transferred to a vacuum sizing box and adsorbed onto the sizing sleeve at -0.06MPa. The pipe is then placed into a spray-type cooling water tank and gradually cooled at 15℃. After cooling, the pipe is pulled at a constant speed by a traction machine and cut to a fixed length by a planetary cutter to obtain a wear-resistant PE water supply pipe.

[0040] Example 2: A method for preparing a wear-resistant PE composite material and a water supply pipe, comprising the following steps:

[0041] S1: Add 240g potassium sulfate, 40.3g urea, 250g aluminum nitrate nonahydrate and 13.5L deionized water to a reaction vessel, stir until the solid is completely dissolved, react at 190℃ for 4h, cool to room temperature, centrifuge and wash at 8500rpm for 15min, collect the precipitate, dry it, transfer it to a muffle furnace, and calcine it at 1150℃ for 4h at a rate of 3℃ / min to obtain flower-shaped alumina with a particle size of 3μm.

[0042] S2: Add 20g of flower-shaped alumina and 165mL of anhydrous ethanol to 750mL of deionized water and stir for 35min. Add 150mL of 2.55wt% tannic acid solution and stir evenly. Then add 6.5mL of 25wt% ammonia water and 65mL of 3.7wt% formaldehyde solution and stir at 60℃ for 13h. Slowly add 20.575mL of 0.118wt% cerium nitrate hexahydrate solution and continue stirring for 13h. Transfer to a polytetrafluoroethylene-lined reactor and hydrothermally react at 110℃ for 25h. Centrifuge to collect the precipitate and wash it four times with ethanol and deionized water. After freeze-drying, place it in a muffle furnace and calcine at 550℃ for 3h at a rate of 3℃ / min to obtain cerium dioxide-supported flower-shaped alumina.

[0043] S3: Dissolve 22.75 g of zirconium nitrate pentahydrate and 15.525 g of zinc nitrate hexahydrate in 2250 mL of deionized water to obtain a mixed solution; add 7.35 g of mesoporous silica nanospheres to 2250 mL of deionized water and stir for 35 min; slowly add 2250 mL of the mixed solution dropwise and magnetically stir for 35 min; then add 700 mL of 25 wt% ammonia water dropwise and transfer to a reaction vessel; react at 170 °C for 25 h; cool to room temperature; centrifuge at 11500 rpm for 15 min; collect the precipitate; wash 4 times alternately with deionized water and anhydrous ethanol; and vacuum dry at 65 °C to constant weight to obtain zirconium-zinc doped hollow mesoporous silica nanospheres.

[0044] S4: Add 90g of polyethylene PE100, 1.25g of titanate coupling agent, 8g of cerium dioxide-supported flower-shaped alumina, 1.6g of zirconium zinc-doped hollow mesoporous silica spheres, 1g of antioxidant 1010 and 2g of polyethylene wax to a high-speed premixer and mix at 650rpm for 9min. Transfer to a twin-screw extruder and melt extrude and granulate at 170℃ in zone 1, 190℃ in zone 2, 210℃ in zone 3, 207.5℃ in zone 4 and 205℃ at the die head. Dry at 70℃ for 3h to obtain abrasion-resistant PE composite material.

[0045] S5: The wear-resistant PE composite material is added to a single screw extruder and melted and plasticized at 185℃ in zone 1, 195℃ in zone 2, 205℃ in zone 3, and 215℃ at the die head. The material is then transferred to a vacuum sizing box and adsorbed onto the sizing sleeve at -0.075MPa. The pipe is then placed into a spray-type cooling water tank and gradually cooled at 20℃. After cooling, the pipe is pulled at a constant speed by a traction machine and cut to a fixed length by a planetary cutter to obtain a wear-resistant PE water supply pipe.

[0046] Example 3: A method for preparing a wear-resistant PE composite material and a water supply pipe, comprising the following steps:

[0047] S1: Add 256g potassium sulfate, 42.2g urea, 260g aluminum nitrate nonahydrate and 14.2L deionized water to a reaction vessel, stir until the solid is completely dissolved, react at 200℃ for 5h, cool to room temperature, centrifuge and wash at 9000rpm for 20min, collect the precipitate, dry it, transfer it to a muffle furnace, and calcine it at 1200℃ for 5h at a rate of 4℃ / min to obtain flower-shaped alumina with a particle size of 4μm.

[0048] S2: Add 22g of flower-shaped alumina and 180mL of anhydrous ethanol to 850mL of deionized water and stir for 40min. Add 160mL of 2.55wt% tannic acid solution and stir evenly. Then add 8mL of 25wt% ammonia water and 80mL of 3.7wt% formaldehyde solution and stir at 60℃ for 14h. Slowly add 22.4mL of 0.118wt% cerium nitrate hexahydrate solution and continue stirring for 14h. Transfer to a polytetrafluoroethylene-lined reactor and hydrothermally react at 120℃ for 26h. Centrifuge to collect the precipitate and wash it five times with ethanol and deionized water. After freeze-drying, place it in a muffle furnace and calcine at 600℃ for 4h at a rate of 4℃ / min to obtain cerium dioxide-supported flower-shaped alumina.

[0049] S3: Dissolve 24g zirconium nitrate pentahydrate and 16.2g zinc nitrate hexahydrate in 2500mL deionized water to obtain a mixed solution; add 8.2g mesoporous silica nanospheres to 2500mL deionized water and stir for 40min; slowly add 2500mL of the mixed solution dropwise and stir magnetically for 40min; then add 800mL of 25wt% ammonia water dropwise and transfer to a reaction vessel; react at 180℃ for 26h; cool to room temperature; centrifuge at 12000rpm for 20min; collect the precipitate; wash 5 times alternately with deionized water and anhydrous ethanol; and vacuum dry at 70℃ to constant weight to obtain zirconium-zinc doped hollow mesoporous silica nanospheres.

[0050] S4: Add 100g of polyethylene PE100, 1.5g of titanate coupling agent, 10g of cerium dioxide-supported flower-shaped alumina, 2.5g of zirconium zinc-doped hollow mesoporous silica spheres, 1.5g of antioxidant 1010 and 3g of polyethylene wax to a high-speed premixer and mix at 800rpm for 10min. Transfer to a twin-screw extruder and melt extrude and granulate at 175℃ in zone 1, 195℃ in zone 2, 215℃ in zone 3, 210℃ in zone 4 and 210℃ at the die head. Dry at 80℃ for 4h to obtain abrasion-resistant PE composite material.

[0051] S5: The wear-resistant PE composite material is added to a single screw extruder and melted and plasticized at 190℃ in zone 1, 200℃ in zone 2, 210℃ in zone 3, and 220℃ at the die head. The material is then transferred to a vacuum sizing box and adsorbed onto the sizing sleeve at -0.09MPa. The pipe is then placed into a spray-type cooling water tank and gradually cooled at 25℃. After cooling, the pipe is pulled at a constant speed by a traction machine and cut to a fixed length by a planetary cutter to obtain a wear-resistant PE water supply pipe.

[0052] In the PE composite materials of Examples 1-3: potassium sulfate was selected from Jinan Huijinchuan Chemical Co., Ltd., CAS No.: 7778-80-5; urea was selected from Foshan Sanzhong Environmental Protection Technology Co., Ltd., CAS No.: 57-13-6; aluminum nitrate nonahydrate was selected from Jiangsu Bosite Chemical Technology Co., Ltd., CAS No.: 7784-27-2; tannic acid was selected from Hebei Jiuyu Biotechnology Co., Ltd., CAS No.: 1401-55-4; ammonia water was selected from Wuhan Jiyesheng Chemical Co., Ltd., CAS No.: 1336-21-6; formaldehyde solution was selected from Shandong Shengze Chemical Co., Ltd.; cerium nitrate hexahydrate was selected from Hubei Bohuer New Materials Co., Ltd., CAS No.: 10294-41-4; zirconium nitrate pentahydrate was selected from Kandis Chemical (Hubei) Co., Ltd., CAS No.: 13746-89-9; zinc nitrate hexahydrate was selected from Hubei Diehua New Materials Technology Co., Ltd., CAS No.: 90-15-3 10196-18-6; Mesoporous silica nanospheres were selected from Beijing Bailingwei Technology Co., Ltd., CAS No. 7631-86-9.

[0053] In the water supply pipes of Examples 1-3: Polyethylene PE100 was selected from Dongguan Hongyi Plastics Technology Co., Ltd., model HE3490DSH; Titanate coupling agent was selected from model 201, brand Rongzheng; Antioxidant 1010 was selected from Xi'an Lavia Biotechnology Co., Ltd., CAS number 6683-19-8; Polyethylene wax was selected from Guangzhou Yuantai New Materials Co., Ltd., model YY-613A; The remaining raw materials were all commercially available products.

[0054] Comparative Example 1: The difference from Example 1 is that step S1 is omitted, and the flower-shaped alumina in step S2 is replaced with commercially available ordinary alumina with a particle size of about 2 μm. The remaining steps remain unchanged, and a wear-resistant PE water supply pipe is prepared.

[0055] Comparative Example 2: The difference from Example 1 is that step S2 is omitted, and the cerium dioxide-loaded flower-shaped alumina in step S4 is replaced with the flower-shaped alumina prepared in step S1. The remaining steps remain unchanged, and a wear-resistant PE water supply pipe is prepared.

[0056] Comparative Example 3: The difference from Example 1 is that zirconium nitrate pentahydrate and zinc nitrate hexahydrate are not added in step S3. Instead, mesoporous silica nanospheres are used as templates and treated under the same hydrothermal conditions to obtain undoped hollow mesoporous silica nanospheres. The remaining steps remain unchanged, and wear-resistant PE water supply pipes are prepared.

[0057] The following performance tests were conducted on the wear-resistant PE water supply pipes prepared in Examples 1-3 and Comparative Examples 1-3:

[0058] Wear resistance: Referring to GB / T3960-2016 "Plastics Sliding Friction and Wear Test Method", the ring block wear test was adopted. The volume wear of the sample was tested at a friction sliding distance of 1.61km under a load of 196N and a speed of 200rpm. The smaller the wear, the better the wear resistance of the material.

[0059] Tensile properties: In accordance with GB / T1040.1-2018 "Determination of tensile properties of plastics - Part 1: General", a type 1A standard dumbbell-shaped specimen was prepared and tested at a tensile rate of 50 mm / min at room temperature to determine the tensile strength of the specimen; the higher the tensile strength, the better the mechanical properties of the material.

[0060] Bending strength: In accordance with GB / T9341-2008 "Determination of bending properties of plastics", a standard specimen of 80mm×10mm×4mm was prepared for a three-point bending test at a test speed of 2mm / min. The bending strength was measured. The higher the bending strength, the better the rigidity of the material and the stronger its ability to resist bending deformation.

[0061] Aging resistance: Referring to GB / T 7141-2016 "Test Method for Thermal Aging of Plastics", the standard sample was placed in a thermal aging test chamber, the aging temperature was set to 80℃, and the aging time was 168h. After aging, the tensile strength of the sample was tested again according to GB / T1040.1-2018, and the tensile strength retention rate was calculated. The calculation formula is: tensile strength retention rate = (tensile strength after aging / initial tensile strength) × 100%; the higher the retention rate, the better the heat aging resistance of the material.

[0062] Antibacterial properties: Referring to GB / T31402-2015 "Test Method for Antibacterial Properties of Plastic Surfaces", Escherichia coli (ATCC 29522) and Staphylococcus aureus (ATCC 6538) were selected as test strains. The antibacterial rate was calculated after cultivation using the film-coating method. The higher the antibacterial rate, the better the antibacterial effect of the material.

[0063] The results are shown in Table 1:

[0064] Table 1 Performance Test Results of Wear-Resistant PE Water Supply Pipes

[0065]

[0066] As can be seen from Table 1, the wear-resistant PE water supply pipes prepared in Examples 1-3 of the present invention are significantly better than those in Comparative Examples 1-3 in terms of wear amount, tensile strength, aging resistance (tensile strength retention rate) and antibacterial properties.

[0067] The significant increase in wear, marked decrease in tensile strength and aging resistance, and substantial reduction in antibacterial rate in Comparative Example 1 are likely due to the direct substitution of flower-shaped alumina with commercially available ordinary alumina. Ordinary alumina has a low specific surface area, few surface active sites, and a dense structure, which cannot provide a uniform and firm substrate for the porous tannic acid coating. This results in uneven coating of the subsequent tannic acid-formaldehyde polymer layer and a significant weakening of its coordination and trapping ability for cerium ions. Consequently, cerium dioxide cannot be loaded onto the alumina surface in the form of highly dispersed nanoparticles, but instead forms aggregates. During melt blending, the interfacial bonding between this load-failed filler and the polyethylene matrix is ​​weak, easily forming stress concentration points, which leads to a significant reduction in mechanical load-bearing capacity and wear resistance. At the same time, cerium dioxide loses its high catalytic activity at the nanoscale due to agglomeration. Although the antibacterial effect of zinc ions provided by zirconium-zinc doped hollow mesoporous silica spheres still exists in the system, the overall antibacterial performance is still significantly reduced due to the lack of cerium dioxide synergy and the limited release of zinc ions. In addition, poor dispersion of cerium dioxide also weakens its stabilizing effect on thermo-oxidative aging, resulting in a significant deterioration in aging resistance.

[0068] In Comparative Example 2, the wear rate increased, tensile strength and aging resistance decreased, and the antibacterial rate was significantly reduced, possibly due to the lack of tannic acid porous coating and cerium dioxide loading. The lack of uniform dispersion and interface modification of cerium dioxide nanoparticles on the flower-shaped alumina surface, while providing some mechanical reinforcement, resulted in limited reinforcement of the polyethylene matrix due to the absence of further optimization of the filler-matrix interface by cerium dioxide and its synergistic effect with zirconium-zinc doped hollow mesoporous silica spheres, leading to a relative decrease in tensile strength and wear resistance. Regarding antibacterial properties, the absence of cerium dioxide, a key antibacterial component, meant the material's antibacterial performance relied entirely on the slow-release effect of zinc ions from the zirconium-zinc doped hollow mesoporous silica spheres. However, embedded in the polyethylene matrix, the migration rate of zinc ions to the material surface was low, and the release concentration was insufficient, making it difficult to form an effective bactericidal concentration within the test period, resulting in a significant decrease in the antibacterial rate. Simultaneously, the absence of cerium dioxide also prevented its catalytic stabilizing effect on thermo-oxidative aging, leading to a decline in aging resistance.

[0069] In Comparative Example 3, the wear and tensile strength decreased significantly, the aging resistance was markedly reduced, and the antibacterial rate dropped sharply, possibly due to the absence of zirconium and zinc doping. The lack of zirconium doping resulted in insufficient shell structure strength of the hollow mesoporous silica spheres, weakening the mechanical interlocking effect with the polyethylene matrix and reducing its contribution to improving the overall rigidity and wear resistance of the composite material. The lack of zinc doping caused the hollow mesoporous silica spheres themselves to lose their antibacterial function. Crucially, although Comparative Example 3 retained the flower-like alumina and cerium dioxide loading, the antibacterial performance still dropped sharply. This indicates that the absence of zirconium-zinc doped hollow mesoporous silica spheres may indirectly lead to a reduced enrichment of cerium-loaded flower-like alumina on the pipe surface by affecting filler migration behavior during processing. This results in most of the antibacterial components being embedded inside the matrix, unable to effectively contact bacteria, thus causing a sharp loss of antibacterial performance. Simultaneously, the lack of zirconium and zinc doping also worsened the interfacial compatibility between the hollow mesoporous silica spheres and the matrix, further leading to a simultaneous decrease in tensile strength and aging resistance.

[0070] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. A wear-resistant PE composite material, characterized in that, The following components are included by mass: 800-1000 parts of polyethylene PE100, 10-15 parts of titanate coupling agent, 50-100 parts of cerium dioxide-supported flower-shaped alumina, 10-25 parts of zirconium zinc-doped hollow mesoporous silica spheres, 5-15 parts of antioxidant 1010 and 10-30 parts of polyethylene wax. The cerium dioxide-supported flower-shaped alumina is prepared by the following steps: Flower-shaped alumina and anhydrous ethanol were added to deionized water and stirred for 30-40 min. Then, 2.55 wt% tannic acid solution was added and stirred evenly. Next, 25 wt% ammonia and 3.7 wt% formaldehyde solution were added and stirred at 60 °C for 12-14 h. Then, 0.118 wt% cerium nitrate hexahydrate solution was slowly added dropwise and stirred for another 12-14 h. The mixture was then transferred to a polytetrafluoroethylene-lined reactor and hydrothermally reacted at 100-120 °C for 24-26 h. The precipitate was collected by centrifugation, washed, freeze-dried, and then placed in a muffle furnace and calcined at 500-600 °C for 2-4 h to obtain cerium dioxide-supported flower-shaped alumina.

2. The wear-resistant PE composite material according to claim 1, characterized in that, The ratio of the following components is as follows: flower-shaped alumina, anhydrous ethanol, deionized water, 2.55 wt% tannic acid solution, 25 wt% ammonia water, 3.7 wt% formaldehyde solution, and 0.118 wt% cerium nitrate hexahydrate solution. The ratio is 18-22 g: 150-180 mL: 650-850 mL: 140-160 mL: 5-8 mL: 50-80 mL: 18.75-22.4 mL.

3. The wear-resistant PE composite material according to claim 2, characterized in that, The specific preparation steps for the flower-shaped alumina are as follows: Potassium sulfate, urea, aluminum nitrate nonahydrate, and deionized water were added to a reaction vessel and stirred until the solid was completely dissolved. The reaction was carried out at 180-200℃ for 3-5 hours. After cooling to room temperature, the mixture was centrifuged and washed for 10-20 minutes. The precipitate was collected, dried, and transferred to a muffle furnace. The furnace was heated to 1100-1200℃ and calcined for 3-5 hours to obtain flower-shaped alumina.

4. The wear-resistant PE composite material according to claim 3, characterized in that, The ratio of potassium sulfate, urea, aluminum nitrate nonahydrate, and deionized water is 224-256g: 38.4-42.2g: 240-260g: 12.8-14.2L.

5. The wear-resistant PE composite material according to claim 1, characterized in that, The specific preparation steps for the zirconium-zinc doped hollow mesoporous silica spheres are as follows: Zirconium nitrate pentahydrate and zinc nitrate hexahydrate were dissolved in deionized water to obtain a mixed solution. Mesoporous silica nanospheres were added to the deionized water and stirred for 30-40 min. The mixed solution was then slowly added dropwise and magnetically stirred for 30-40 min. 25 wt% ammonia water was then added dropwise and transferred to a reaction vessel. The reaction was carried out at 160-180℃ for 24-26 h. After cooling to room temperature, the mixture was centrifuged for 10-20 min, the precipitate was collected, washed, and vacuum dried to constant weight to obtain zirconium-zinc doped hollow mesoporous silica nanospheres.

6. The wear-resistant PE composite material according to claim 5, characterized in that, The ratio of zirconium nitrate pentahydrate, zinc nitrate hexahydrate, and deionized water is 21.5-24 g: 14.85-16.2 g: 2000-2500 mL; The ratio of the mesoporous silica nanospheres, deionized water, mixed solution and 25wt% ammonia is 6.5-8.2g: 2000-2500mL: 2000-2500mL: 600-800mL.

7. The wear-resistant PE composite material according to claim 1, characterized in that, The wear-resistant PE composite material is prepared through the following steps: Polyethylene PE100, titanate coupling agent, cerium dioxide-supported flower-shaped alumina, zirconium zinc-doped hollow mesoporous silica spheres, antioxidant 1010 and polyethylene wax are added to a high-speed premixer and mixed at 500-800 rpm for 8-10 min. The mixture is then transferred to a twin-screw extruder for melt extrusion and granulation. Finally, it is dried at 60-80℃ for 2-4 h to obtain a wear-resistant PE composite material. The temperature settings of the twin-screw extruder are as follows: Zone 1: 165-175℃, Zone 2: 185-195℃, Zone 3: 205-215℃, Zone 4: 205-210℃, and Die head: 200-210℃.

8. A method for preparing a water supply pipe, characterized in that, Includes the following steps: The wear-resistant PE composite material as described in any one of claims 1-7 is added to a single screw extruder, melted and plasticized, extruded, and transferred to a vacuum sizing box. It is then adsorbed onto the sizing sleeve at a pressure of -0.06 to -0.09 MPa. The pipe is placed in a spray-type cooling water tank and gradually cooled at a water temperature of 15-25°C. After cooling, the pipe is pulled at a constant speed by a traction machine and cut to a fixed length by a planetary cutter to obtain a wear-resistant PE water supply pipe.

9. A method for preparing a water supply pipe according to claim 8, characterized in that, The temperature settings of the single screw extruder are 180-190℃ in zone 1, 190-200℃ in zone 2, 200-210℃ in zone 3, and 210-220℃ at the die head.

10. A water supply pipe, characterized in that, It is prepared by the method of any one of claims 8-9 for preparing the water supply pipe.

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