Manufacturing method of container floor with enhanced wear resistance

Abstract

The manufacturing method comprises the following steps that a basalt fiber / graphene modified epoxy resin base plate is prepared, a tungsten carbide reinforced titanium alloy honeycomb layer is formed through selective laser melting (SLM), the titanium alloy honeycomb layer is compounded to the surface of the base plate through vacuum diffusion welding, and the wear resistance of the container floor is enhanced. Gradient silicon nitride ceramic laser cladding is carried out on the surface of the composite substrate, and bionic micro-groove laser etching and diamond-like carbon (DLC) coating deposition are carried out on a cladding layer. According to the manufacturing method of the container floor with the enhanced wear resistance, compared with a traditional steel floor, the weight is reduced by 50% or above, meanwhile, the bending strength is improved to be larger than or equal to 320 MPa, through silane coupling agent pretreatment (KH-550) of basalt fibers and the nanometer enhancement effect of graphene, the impact resistance of the base plate is remarkably improved, and the harsh working condition requirements of high-frequency forklift loading and unloading are met.

Description

Technical Field

[0001] The present invention relates to the technical field of container floors, and specifically to a manufacturing method of a container floor with enhanced wear resistance. Background Art

[0002] The container floor is the core load-bearing structure inside the container, used to support and disperse the weight of goods to ensure transportation safety. Through anti-slip surface treatment, moisture-proof and corrosion-resistant materials (such as bamboo-wood composite boards, recycled plastics), and high-strength design, it effectively prevents goods from sliding, mildewing, and structural damage. At the same time, lightweight technologies (such as honeycomb sandwich) improve the loading efficiency, and green materials (bamboo, bio-based adhesives) reduce carbon emissions to meet environmental protection standards.

[0003] Traditional container floors mostly adopt wood composite boards or pure metal structures, and have the following defects: insufficient wear resistance, easy wear of wood materials, low friction coefficient of metal surfaces, resulting in forklift skidding; heavy weight, high density of all-metal structures, increasing transportation energy consumption; easy interface failure, low bonding strength of multi-layer composite materials, easy delamination under long-term impact; poor corrosion resistance, easy corrosion of metal honeycomb layers in salt spray environments, shortening service life. Existing technologies have tried to improve performance through ceramic coatings or fiber-reinforced resins, but there are the following problems: the thermal expansion coefficients of ceramic coatings and metal substrates do not match, easy to generate cracks, insufficient impact resistance of single fiber-reinforced resin substrates, and low bonding strength at the coating / substrate interface.

[0004] A manufacturing method of a container floor with enhanced wear resistance according to the present invention, through a multi-stage coupling design of a basalt fiber substrate, a gradient titanium alloy honeycomb, and an asymmetric micro-groove ceramic layer, synergistically realizes the core advantages of lightweight (≤3.2 g / cm³) and anti-multiple impacts (no penetration under the impact of a 5 kg steel hammer at 1 m). Summary of the Invention

[0005] The purpose of the present invention is to provide a manufacturing method of a container floor with enhanced wear resistance, so as to solve the problems in the traditional container floors on the current market, such as the mismatch of thermal expansion coefficients between ceramic coatings and metal substrates, easy generation of cracks, insufficient impact resistance of single fiber-reinforced resin substrates, and low bonding strength at the coating / substrate interface.

[0006] To achieve the above purpose, the present invention provides the following technical solution: A manufacturing method of a container floor with enhanced wear resistance, including the following steps: S1. Prepare a basalt fiber / graphene modified epoxy resin substrate, and the surface roughness Ra of the substrate is 6.3 ± 0.2 μm; S2. Use selective laser melting (SLM) to form a tungsten carbide reinforced titanium alloy honeycomb layer, and the porosity of the titanium alloy honeycomb layer is 65 ± 2%; S3. Composite the titanium alloy honeycomb layer to the surface of the substrate by vacuum diffusion welding, and preset an INcoNel 625 alloy transition layer at the diffusion welding interface; S4. Implement gradient silicon nitride ceramic laser cladding on the surface of the composite substrate, and the cladding layer contains ≥95% α-Si3N4 phase; S5. Carry out bionic micro-groove laser etching and diamond-like carbon (DLC) coating deposition on the cladding layer, and the sp 3 bonding content of the DLC coating is ≥40%; S6. Verify the mechanical properties of the finished substrate based on ASTM / DIN standards, including an interfacial bonding strength ≥45 MPa and a wet friction coefficient ≥0.45.

[0007] Furthermore, the substrate processing procedure of S1 includes mixing components, vacuum stirring, and stepwise curing: S11. The mixing components are, by mass, 100 parts of bisphenol A epoxy resin, 35 ± 1 parts of chopped basalt fiber yarn (3.0 ± 0.2 mm), 1.5 ± 0.1 parts of graphene nanosheets (≤5 layers), and 30 ± 0.5 parts of polyetheramine curing agent; S12. The vacuum stirring performs vacuum stirring on the mixed components. The conditions for the vacuum stirring are a temperature of 80 ± 2 °C, a time of 120 ± 5 minutes, and a vacuum degree ≤10 Pa. The rotation speed of the vacuum stirring is 300 ± 10 rpm, and the vacuum stirring uses a double planetary stirring paddle to alternate forward and reverse; S13. The stepwise curing cures the mixed components after vacuum stirring. The process of the stepwise curing is low-temperature curing at 60 ± 2 °C for 4 h followed by high-temperature curing at 120 ± 5 °C for 2 h. After the stepwise curing, hot pressing and shaping are performed on the substrate. The pressure for hot pressing and shaping is 10 ± 0.5 MPa, the temperature for hot pressing and shaping is 100 ± 2 °C, and the time for hot pressing and shaping is 30 minutes; S14. After hot pressing and shaping, the size of the substrate is 12.5 m × 2.4 m × 18 mm. The surface treatment of the substrate is carried out by sandblasting with 120 ± 20 mesh alumina sand, and after sandblasting, plasma cleaning is used. The cleaning power of the plasma cleaning is 5 kW, the argon flow rate of the plasma cleaning is 20 L / min, and the treatment time of the plasma cleaning is 10 ± 0.5 minutes.

[0008] Furthermore, the processing of the titanium alloy honeycomb layer in S2 is as follows: S21. The raw materials of the titanium alloy honeycomb layer are titanium alloy powder Ti-6Al-4V (particle size D50 = 30 μm) and tungsten carbide (WC) powder (accounting for 20 ± 0.5 wt% of the total addition amount of titanium alloy powder, particle size D50 = 8 ± 0.5 μm). The titanium alloy powder and tungsten carbide (WC) powder are mixed by a three-dimensional mixer for 120 ± 10 minutes, and the protective atmosphere during the mixing process is high-purity argon; S22. The uniformly mixed titanium alloy powder and tungsten carbide (WC) powder are formed by selective laser melting (SLM) technology. The parameters of SLM are laser power 300 ± 5 W, scanning speed 1000 ± 20 mm / s, and layer thickness 30 ± 2 μm; S23. The titanium alloy honeycomb layer formed by SLM technology has a regular hexagonal honeycomb structure with a pore diameter of 5.0 ± 0.2 mm, a wall thickness of 0.8 ± 0.02 mm, and a layer thickness of 3.5 ± 0.1 mm. A dense transition zone with a width of 5 mm is provided at the edge of the titanium alloy honeycomb layer, and the porosity of the titanium alloy honeycomb layer gradually decreases from 65% at the center to 50% at the edge.

[0009] Further, in S3, the titanium alloy honeycomb layer and the substrate are combined. The specific combination process is as follows: S31. Before the titanium alloy honeycomb layer and the substrate are combined, an alloy transition layer needs to be laid between the two. The thickness of the alloy foil of the alloy transition layer is 50 ± 5 μm, and the surface roughness Ra of the alloy foil after electron beam texturing process is 1.5 ± 0.1 μm; S32. With the assistance of the alloy transition layer, the titanium alloy honeycomb layer and the substrate are connected by diffusion welding process. The parameters of the diffusion welding process are vacuum degree ≤ 5 × 10⁻³ Pa, heat treatment 850 ± 10 °C / 60 min, and axial pressure 5.0 ± 0.3 MPa. During the cooling stage of the diffusion welding process, it is slowly cooled to 300 °C at a rate of ≤ 6 °C / min, and then air-cooled; S33. The porosity gradient within 5 mm from the edge of the honeycomb layer of the titanium alloy honeycomb layer is reduced to 50 ± 2%, the root fillet radius of the unit wall is R0.3 ± 0.02 mm, and the welding interface of the honeycomb layer is detected by X-ray flaw detection, and the defect rate ≤ 0.01%.

[0010] Further, the processing of the cladding layer in S4 is specifically as follows: S41. After the diffusion welding of the titanium alloy honeycomb layer and the substrate through the alloy transition layer, the preparation of the cladding layer is carried out. The cladding powder in the preparation of the cladding layer is 85±0.5% of Si3N4 (10 - 50μm) and 15±0.5% of INcoNel 625 (15 - 45μm). The pre-drying treatment of the cladding powder is at a temperature of 150±5°C, the pre-drying treatment time of the cladding powder is 2h, and the moisture content of the pre-dried cladding powder ≤0.05%. S42. The preparation of the cladding layer adopts a gradient cladding process. The gradient cladding includes a first layer, a transition layer, and a bonding layer: The first layer is 80±2% of Si3N4, with a layer thickness of 0.3±0.02mm, and contacts the alloy transition layer of the substrate; The transition layer is 50±1% of Si3N4, with a lap rate of 40±2% with the first layer; The bonding layer is pure INcoNel 625, with a lap rate of 60±2% with the transition layer; After the gradient cladding is completed, the cladding layer is subjected to laser remelting treatment after cladding. The power of the laser remelting treatment is 4±0.5kW and the scanning speed is 50mm / s to eliminate interlayer pores; S43. The cladding process of the cladding layer is a laser power of 6kW, a scanning speed of 20±0.5mm / s, the oxygen content of argon ≤50ppm, the surface residual stress of the cladding layer ≤200MPa, and the α-Si3N4 phase content of the cladding layer is detected by XRD.

[0011] Further, the processing of the micro-grooves and DLC coating in S5 is as follows: S51. On the basis of the titanium alloy honeycomb layer and the cladding layer, after being strengthened by the alloy transition layer, it enters the micro-groove etching. The etching process of the micro-grooves uses femtosecond laser to clean the surface. The energy density of the femtosecond laser is 2J / cm² and the pulse width is 500fs. The etching process of the micro-grooves uses a V-shaped asymmetric inclination angle (20° / 45°±0.5°), a depth of 80±2μm, a density of 200±20 strips / cm, and the etching direction forms an angle of 15±1° with the forklift direction; After the micro-groove etching is completed, the deposition of the DLC coating is carried out. The DLC coating is completed by magnetron sputtering deposition process. The thickness of the magnetron sputtering deposition is 2.0±0.1μm, the hardness ≥HV2500, and the deposition rate is 0.25μm / min. The DLC coating is subjected to argon ion etching cleaning before deposition. The bias voltage of the argon ion etching cleaning is -800V and the time is 30 minutes. The bonding force between the DLC coating and the substrate ≥50N (tested by scratch method).

[0012] Further, the mechanical property verification in S6 includes ASTM C633 test, ASTM G65 test, 5 kg steel hammer 1 m impact, DIN 51130, salt spray test and thermal cycle test. The ASTM C633 test combines strength, the ASTM G65 test, the 5 kg steel hammer 1 m impact test checks for cracks after impact, the DIN 51130 test measures the wet friction coefficient, the salt spray test checks for corrosion points on the surface, and the thermal cycle test checks for interface cracking.

[0013] Further, for the container floor prepared by the method, the container floor includes structure, interlayer bonding strength, surface Rockwell hardness, microgrooves, coefficient of linear expansion and chemical corrosion resistance: The total thickness of the structure is 20.0 ± 0.2 mm and the overall density is ≤ 3.2 g / cm³; The interlayer bonding strength is substrate-honeycomb layer ≥ 35 MPa and honeycomb-ceramic layer ≥ 40 MPa; The surface Rockwell hardness is ≥ HRA90 and the laser reflectivity (500 - 800 Nm) is ≤ 5%; The DLC coating in the microgrooves is continuously covered without visible cracks or spalling; The coefficient of linear expansion (25 - 150 °C) is ≤ 8×10⁻ 6 / K, and the test standard is ASTM E228; The chemical corrosion resistance is that after soaking in 5% NaCl + 3% H2O2 solution for 30 days, the mass loss is ≤ 0.01%.

[0014] Further, it also includes on-line monitoring of the production process: In step S2, high-speed photography is used to monitor the morphology of the molten pool in real time, and the fluctuation of the molten pool width is ≤ ±10 μm; In step S4, an infrared thermal imager is used to detect the cladding temperature field, and the temperature gradient is ≤ 50 °C / mm; In step S5, a white light interferometer is used to measure the three-dimensional morphology of the microgrooves, and the depth tolerance is ±1 μm Compared with the prior art, the beneficial effects of the present invention are: The manufacturing method of a container floor with enhanced wear resistance: (1) Lightweight and high-strength load-bearing: By synergistically modifying the epoxy resin substrate with basalt fiber (35 ± 1 parts) and graphene nanoplatelets (1.5 ± 0.1 parts), combined with vacuum stirring and step curing processes, the density of the substrate is ≤ 3.2 g / cm³, reducing the weight by more than 50% compared to traditional steel floors. At the same time, the bending strength is increased to ≥ 320 MPa. The silane coupling agent pretreatment (KH-550) of basalt fiber and the nano-enhancement effect of graphene significantly improve the impact resistance of the substrate. After a 5 kg steel hammer impacts from a height of 1 m, the crack is ≤ 0.5 mm, meeting the demanding working conditions of high-frequency forklift loading and unloading.

[0015] (2) Integrated structure of wear resistance and fatigue resistance: Using a tungsten carbide-reinforced titanium alloy honeycomb layer (porosity 65 ± 1%) formed by selective laser melting (SLM), combined with a gradient silicon nitride ceramic cladding layer (α-Si3N4 ≥ 95%), the surface hardness reaches HRA90, and the wear resistance is three times higher than that of traditional coatings (volume loss ≤ 3.0 ± 0.2 mm³ after 5000 revolutions in ASTM G65 test). The dense transition zone at the edge of the honeycomb layer (porosity 50 ± 2%) and the rounded corner design at the root of the cell wall (R0.3 ± 0.02 mm) effectively disperse stress, and the fatigue life reaches 10 7 cycles or more.

[0016] (3) High-reliability interface bonding: By pre-setting an INcoNel 625 alloy transition layer (50 ± 5 μm) through vacuum diffusion welding, combined with electron beam texturing treatment (Ra = 1.5 ± 0.1 μm), the interface bonding strength is ≥ 45 MPa (ASTM C633 test), which is 60% higher than that of conventional brazing processes. The slow cooling process of diffusion welding (≤ 5°C / min) and X-ray flaw detection (defect rate ≤ 0.01%) ensure that there are no micro-cracks at the interface, and there is no delamination phenomenon after thermal cycle testing (-40°C to 80°C, 100 times).

[0017] (4) Long-term anti-slip and corrosion resistance to the environment: The combination of I bionic micro-groove laser etching (V-shaped inclination angle 20° / 45° ± 0.5°, depth 80 ± 2 μm) and DLC coating (sp 3 bond content ≥ 40%, hardness ≥ HV2500), the wet friction coefficient ≥ 0.45 (DIN51130 standard), and the anti-slip performance is twice that of ordinary metal floors. The continuous coverage of the coating (no cracks / flakes) and chemical corrosion resistance (mass loss ≤ 0.01% after soaking in 5% NaCl + 3% H2O2 for 30 days) ensure the long-term stability of the floor in harsh environments such as the ocean and chemical industries.

[0018] (5) Precision-controlled intelligent manufacturing, which realizes closed-loop control of key process parameters by monitoring the SLM molten pool morphology in real time through high-speed cameras (fluctuation ≤ ±10 μm), detecting the cladding temperature gradient by an infrared thermal imager (≤50 °C / mm), and measuring the three-dimensional morphology of micro-grooves by a white light interferometer (depth tolerance ±1 μm). The qualified rate of finished products is ≥98%, and it is suitable for large-scale production of 12.5 m × 2.4 m large-size floors.

[0019] (6) Multi-functional adaptability expansion. The total thickness of the floor is 20.0 ± 0.2 mm, which can be adapted to the standard container sizes (20 ft / 40 ft). The linear expansion coefficient ≤ 8×10⁻ 6 / K (25 - 150 °C), avoiding deformation and cracking caused by temperature changes. The laser reflectivity ≤ 5% (500 - 800 Nm wavelength band), compatible with the automated operation scenario of laser-guided forklifts. The function has scalability. The honeycomb pore structure supports the embedding of fiber optic sensors to realize real-time monitoring of stress distribution and expand into an intelligent armor system. Description of the Drawings

[0020] Figure 1 It is a schematic flow chart of the manufacturing method of the present invention; Figure 2 It is a schematic flow chart of the substrate preparation of the present invention; Figure 3 It is a schematic flow chart of the honeycomb layer forming of the present invention; Figure 4 It is a schematic flow chart of the diffusion welding of the present invention; Figure 5 It is a schematic flow chart of the ceramic cladding of the present invention; Figure 6 It is a schematic flow chart of the surface treatment of the present invention; Figure 7 It is a schematic flow chart of the performance verification of the present invention. Specific Embodiments

[0021] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0022] According to the technical solutions of the patent claim, three implementation manners are provided as follows: Embodiment 1 is of the conventional parameter type: Step S1 is to prepare a basalt fiber / graphene modified epoxy resin substrate, including mixing components, vacuum stirring, stepwise curing and stepwise curing: First, accurately weigh the mixed components by mass: 100 parts of bisphenol A epoxy resin, 35 parts of 3.0 mm basalt fiber chopped strands, 1.5 parts of graphene nanosheets within 5 layers, and 30 parts of polyetheramine curing agent; Second, vacuum stirring: Place the mixed components in a double planetary mixer and stir at 80 °C and a vacuum degree of 10 Pa with forward and reverse rotation alternately at 300 rpm for 120 minutes to ensure uniform fiber dispersion; Then, stepwise curing of the mixed components after vacuum stirring: Inject the slurry into a mold and cure at 60 °C for 4 hours and then at 120 °C for 2 hours, and then hot press and shape at 100 °C and a pressure of 10 MPa for 30 minutes; Finally, surface treatment of the substrate: The substrate size is 12.5 m × 2.4 m × 18 mm. After sandblasting the surface of the substrate with 120 - mesh alumina sand, use 5 kW plasma cleaning (argon gas flow rate 20 L / min, treatment for 10 minutes), and finally Ra = 6.3 μm.

[0023] Step S2 is SLM forming of a tungsten carbide - reinforced titanium alloy honeycomb layer: First, mixing of the raw material powder for the titanium alloy honeycomb layer: Mix Ti - 6Al - 4V powder (D50 = 30 μm) with 20 wt% tungsten carbide (D50 = 8 μm) in a three - dimensional mixer under argon protection for 120 minutes; Then, form the above - mentioned uniformly mixed powder by laser melting (SLM) technology. The SLM parameters are laser power 300 W, scanning speed 1000 mm / s, layer thickness 30 μm, forming a regular hexagonal honeycomb structure (pore diameter 5.0 mm, wall thickness 0.8 mm, layer thickness 3.5 mm), and the porosity of the edge dense transition zone decreases from 65% to 50% in a gradient manner.

[0024] Step S3 is vacuum diffusion bonding and compounding: First, before bonding the titanium alloy honeycomb layer and the substrate, a transition layer needs to be laid between them. The transition layer is processed by pre - depositing a 50 - μm - thick INcoNel 625 alloy foil and subjecting it to electron beam texturing treatment to Ra = 1.5 μm; Then, with the assistance of the alloy transition layer, the titanium alloy honeycomb layer and the substrate are connected by a diffusion welding process. The diffusion welding process is carried out at a vacuum degree of 5×10⁻³ Pa, 850 °C, pressurized at 5 MPa and maintained for 60 minutes, control the cooling rate ≤ 5 °C / min until it reaches 300 °C and then air - cool. X - ray inspection confirms that the interface defect rate ≤ 0.01%.

[0025] Step S4 is gradient silicon nitride ceramic cladding: First, after the diffusion welding of the titanium alloy honeycomb layer and the substrate through the alloy transition layer, the preparation of the cladding layer is carried out. In the preparation of the cladding layer, the cladding powder is pre-dried with a mixed powder of Si3N4 (85%) and INcoNel 625 (15%) to a moisture content of 0.05%. Secondly, the gradient cladding process is used for the preparation of the cladding layer. The first layer of the gradient cladding is 80% Si3N4, with a layer thickness of 0.3 mm, a laser power of 4 kW, and a scanning speed of 20 mm / s. The transition layer of the gradient cladding is 50% Si3N4, with an overlapping rate of 40%. The bonding layer of the gradient cladding is pure INcoNel 625, with an overlapping rate of 60%. Finally, laser remelting (4 kW, 50 mm / s) is used to eliminate pores, and the XRD detection shows that the content of α-Si3N4 phase is ≥95%.

[0026] Step S5 is surface etching and DLC coating deposition: First, on the basis of the titanium alloy honeycomb layer and the cladding layer, after being strengthened by the alloy transition layer, micro-groove etching is carried out. After cleaning with femtosecond laser (2 J / cm², 500 fs), V-shaped grooves (depth 80 μm, density 200 grooves / cm, inclination angle 20° / 45°) are etched, and the etching direction forms an angle of 15° with the forklift direction. Then, after the micro-groove etching is completed, the deposition of the DLC coating is carried out. After argon ion etching, a 2.0 μm thick DLC coating (sp 3 bond content 40%) is deposited by magnetron sputtering, with a hardness of HV2500 and a bonding strength of ≥50 N.

[0027] Step S6 is mechanical property verification, including ASTM C633 test, ASTM G65 test, 1 m impact with a 5 kg steel hammer, DIN51130, salt spray test and thermal cycle test: First, the bonding strength of the ASTM C633 test is 45 MPa, the wear volume loss of the ASTM G65 test is 3.0 mm³, the wet friction coefficient of DIN51130 is 0.45, and the crack after a 1 m impact with a 5 kg steel hammer is ≤0.5 mm. Then, in the environmental test, the salt spray test passes without corrosion after 1000 hours of salt spray, and the thermal cycle test has no cracking after 100 thermal cycles from -40°C to 80°C.

[0028] Example 2 is a high-strength and wear-resistant optimization type: Step S1 is to prepare a basalt fiber / graphene modified epoxy resin substrate, including mixing components, vacuum stirring, step curing and step curing: First, the components are accurately weighed by mass: 100 parts of bisphenol A epoxy resin, 36 parts of 3.0 mm basalt fiber chopped yarn, 1.4 parts of graphene nanosheets within 5 layers, and 30 parts of polyetheramine curing agent. Secondly, vacuum stirring is carried out by placing the mixed components in a double planetary mixer and stirring them alternately forward and backward at 310 rpm for 120 minutes at 80 °C and a vacuum degree of 10 Pa to ensure uniform dispersion of the fibers; Then, the mixed components after vacuum stirring are subjected to stepwise curing by injecting the slurry into a mold, curing at 60 °C for 4 hours and at 120 °C for 2 hours in sequence, and then hot-pressing and shaping at 100 °C and a pressure of 10.5 MPa for 30 minutes; Finally, the substrate is surface-treated. The substrate size is 12.5 m × 2.4 m × 18 mm. After sandblasting the surface of the substrate with 120-mesh alumina sand, it is cleaned using 5 kW plasma (argon flow rate 20 L / min, treated for 10 minutes), and finally Ra = 6.3 μm.

[0029] Step S2 is to form a tungsten carbide-reinforced titanium alloy honeycomb layer by SLM: First, the raw material powders of the titanium alloy honeycomb layer are mixed. Ti-6Al-4V powder (D50 = 30 μm) and 20.2 wt% tungsten carbide (D50 = 8 μm) are three-dimensionally mixed for 120 minutes under argon protection; Then, the above-mentioned uniformly mixed powder is formed by laser melting (SLM) technology. The SLM parameters are a laser power of 305 W, a scanning speed of 1000 mm / s, a layer thickness of 30 μm, and a formed regular hexagonal honeycomb structure (pore diameter 4.8 mm, wall thickness 0.82 mm, layer thickness 3.5 mm). The porosity of the edge dense transition zone decreases from 65% to 50% in a gradient manner.

[0030] Step S3 is vacuum diffusion bonding and compounding: First, before the titanium alloy honeycomb layer and the substrate are combined, an intermediate layer needs to be laid between them. The intermediate layer is treated by pre-setting a 45-μm-thick INcoNel 625 alloy foil and subjecting it to electron beam texturing treatment to Ra = 1.5 μm; Then, with the assistance of the alloy intermediate layer, the titanium alloy honeycomb layer and the substrate are connected by a diffusion welding process. The diffusion welding process is carried out at a vacuum degree of 5 × 10⁻³ Pa and 840 °C, pressurized at 5 MPa and maintained for 60 minutes, the cooling rate is controlled ≤ 4 °C / min until 300 °C and then air-cooled, and X-ray inspection is used to confirm that the interface defect rate ≤ 0.01%.

[0031] Step S4 is gradient silicon nitride ceramic cladding: First, after the titanium alloy honeycomb layer and the substrate are diffusion-welded through the alloy intermediate layer, the preparation of the cladding layer is carried out. In the preparation of the cladding layer, the cladding powder is pre-dried to a water content of 0.05% for a mixed powder of Si3N4 (85%) and INcoNel 625 (15%); Secondly, the gradient cladding process is adopted for the preparation of the cladding layer. The first layer of the gradient cladding is 81% Si3N4, with a layer thickness of 0.32 mm, a laser power of 4.2 kW, and a scanning speed of 20 mm / s. The transition layer of the gradient cladding is 50% Si3N4, with an overlapping rate of 40%. The bonding layer of the gradient cladding is pure INcoNel 625, with an overlapping rate of 60%. Finally, laser remelting (4 kW, 50 mm / s) is carried out to eliminate pores, and the XRD detection shows that the content of α-Si3N4 phase is ≥95%.

[0032] Step S5 is surface etching and DLC coating deposition: Firstly, based on the titanium alloy honeycomb layer and the cladding layer, after being strengthened by the alloy transition layer, it enters the micro-groove etching. After being cleaned by femtosecond laser (2 J / cm², 500 fs), V-shaped grooves (depth 82 μm, density 200 grooves / cm, inclination angle 20° / 45°) are etched, forming an angle of 15° with the forklift direction. Then, after the micro-groove etching is completed, the DLC coating is deposited. After argon ion etching, the magnetron sputtering deposition rate is reduced to 0.23 μm / min, and a 2.0 μm thick DLC coating (sp 3 bonding content 42%) with a hardness of HV2500 and a bonding strength of ≥50 N.

[0033] Step S6 is mechanical property verification, including ASTM C633 test, ASTM G65 test, 1 m impact with a 5 kg steel hammer, DIN51130, salt spray test, and thermal cycle test: Firstly, the bonding strength in the ASTM C633 test is 45 MPa, and the wear volume loss in the ASTM G65 test is 2.8 mm³; the wet friction coefficient in DIN51130 is 0.45, and the crack after a 1 m impact with a 5 kg steel hammer is ≤0.5 mm; Then, in the environmental test, the salt spray test passes without corrosion after 1100 hours of salt spray, and the thermal cycle test has no cracking after 100 thermal cycles from -40°C to 80°C.

[0034] Example 3 is a low-cost and high-efficiency production type: Step S1 is to prepare a basalt fiber / graphene modified epoxy resin substrate, including mixing components, vacuum stirring, stepwise curing, and stepwise curing: Firstly, the mixing components are accurately weighed by mass: 100 parts of bisphenol A epoxy resin, 34 parts of 3.0 mm basalt fiber chopped yarn, 1.5 parts of graphene nanosheets within 5 layers, and 30 parts of polyetheramine curing agent. Secondly, vacuum stirring is carried out by placing the mixing components in a double planetary mixer and stirring alternately at 300 rpm in the forward and reverse directions at 80°C and a vacuum degree of 10 Pa for 120 minutes to ensure uniform dispersion of the fibers. Then, the mixed components after vacuum stirring are subjected to stepwise curing by injecting the slurry into a mold, curing at 60°C for 3.5 hours and then at 120°C for 1.5 hours in sequence, and subsequently hot-pressed and shaped at 100°C under a pressure of 10 MPa for 30 minutes; Finally, the substrate is surface-treated. The substrate size is 12.5 m × 2.4 m × 18 mm. After sandblasting with 100-mesh alumina sand, the substrate is subjected to 5-kW plasma cleaning (argon flow rate 20 L / min, treatment for 10 minutes), and finally Ra = 6.3 μm.

[0035] Step S2 is the SLM forming of the tungsten carbide-reinforced titanium alloy honeycomb layer: First, the raw material powders of the titanium alloy honeycomb layer are mixed. Ti-6Al-4V powder (D50 = 30 μm) and 20 wt% tungsten carbide (D50 = 8 μm) are three-dimensionally mixed for 120 minutes under argon protection; Then, the above-mentioned uniformly mixed powder is formed by laser melting (SLM) technology. The SLM parameters are a laser power of 295 W, a scanning speed of 1020 mm / s, a layer thickness of 30 μm, forming a regular hexagonal honeycomb structure (pore diameter 5.0 mm, wall thickness 0.8 mm, layer thickness 3.4 mm), and the porosity is maintained at 65%.

[0036] Step S3 is vacuum diffusion bonding composite: First, before the titanium alloy honeycomb layer and the substrate are bonded, an intermediate layer needs to be laid between them. The intermediate layer is treated by pre-depositing a 50-μm-thick INcoNel 625 alloy foil, and the roughness of the intermediate layer is Ra = 1.6 μm through mechanical polishing; Then, with the assistance of the alloy intermediate layer, the titanium alloy honeycomb layer and the substrate are connected by a diffusion welding process. The diffusion welding process is carried out at a vacuum degree of 5×10⁻³ Pa and 850°C, pressurized at 4.8 MPa and maintained for 50 minutes, controlling the cooling rate ≤ 5°C / min until 300°C and then air-cooling. X-ray inspection confirms that the interface defect rate ≤ 0.01%.

[0037] Step S4 is gradient silicon nitride ceramic cladding: First, after the diffusion welding of the titanium alloy honeycomb layer and the substrate through the alloy intermediate layer, the preparation of the cladding layer is carried out. In the preparation of the cladding layer, the cladding powder is pre-dried to mix Si3N4 (84.5%) and INcoNel 625 (15.5%) mixed powder to a moisture content of 0.05%; Secondly, the preparation of the cladding layer adopts a gradient cladding process. The first layer of the gradient cladding is 80% Si3N4, with a layer thickness of 0.3 mm, a laser power of 3.8 kW, and a scanning speed of 20 mm / s. The transition layer of the gradient cladding is 50% Si3N4, with a lap rate of 40%. The bonding layer of the gradient cladding is pure INcoNel 625, with a lap rate of 60%; Finally, laser remelting (4 kW, 50 mm / s) is carried out to eliminate pores, and the content of α-Si3N4 phase detected by XRD is ≥95%.

[0038] Step S5 is surface etching and DLC coating deposition: First, based on the titanium alloy honeycomb layer and the cladding layer, after being strengthened by the alloy transition layer, it enters micro-groove etching. After being cleaned by femtosecond laser (2 J / cm², 500 fs), V-shaped grooves (depth 80 μm, density 180 grooves / cm, inclination angle 20° / 45°) are etched, with an included angle of 15° with the forklift direction; Then, after the micro-groove etching is completed, the deposition of the DLC coating is carried out. After the DLC coating is etched by argon ions, the magnetron sputtering deposition rate is increased to 0.3 μm / min, and a 1.9-μm-thick DLC coating (sp 3 bond content 40%) with a hardness of HV2500 and a bonding force ≥50 N.

[0039] Step S6 is mechanical property verification, including ASTM C633 test, ASTM G65 test, 1 m impact with a 5 kg steel hammer, DIN51130, salt spray test, and thermal cycle test: First, the bonding strength in the ASTM C633 test is 44 MPa, the wear volume loss in the ASTM G65 test is 3.0 mm³, the wet friction coefficient in DIN51130 is 0.46, and the crack after a 1 m impact with a 5 kg steel hammer is ≤0.5 mm; Then, in the environmental test, the salt spray test passes without corrosion after 1000 hours of salt spray, and the thermal cycle test has no cracking after 100 thermal cycles from -40°C to 80°C.

[0040] It should also be noted that the term "including", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, commodity or equipment including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or elements inherent to such process, method, commodity or equipment. Without further limitations, an element defined by the statement "including one..." does not exclude the existence of another identical element in the process, method, commodity or equipment including the element.

[0041] Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for manufacturing a container floor with enhanced wear resistance, characterized in that: The following steps are involved: S1. Prepare a basalt fiber / graphene modified epoxy resin substrate, wherein the surface roughness of the substrate is Ra=6.3±0.2 μm; S2, forming a tungsten carbide reinforced titanium alloy honeycomb layer by selective laser melting (SLM), wherein the porosity of the titanium alloy honeycomb layer is 65±2%; S3, compounding the titanium alloy honeycomb layer onto the surface of the substrate by vacuum diffusion welding, and pre-setting an INcoNel 625 alloy transition layer on the diffusion welding interface; S4, performing gradient silicon nitride ceramic laser cladding on the surface of the composite substrate, wherein the cladding layer contains α-Si3N4 phase ≥ 95%; S5, performing bionic micro-groove laser etching and diamond-like carbon (DLC) coating deposition on the cladding layer, wherein the DLC coating sp 3 Bond content ≥40%; S6. Verify the mechanical properties of the finished substrate based on ASTM / DIN standards, including interface bonding strength ≥45MPa and wet friction coefficient ≥0.

45.

2. The method for manufacturing a container floor with enhanced wear resistance according to claim 1, characterized in that: The substrate processing steps in S1 include mixing components, vacuum stirring and step curing: S11, the mixed components are 100 parts by mass of bisphenol A epoxy resin, 35±1 parts of basalt fiber chopped yarn (3.0±0.2mm), 1.5±0.1 parts of graphene nanosheets (≤5 layers) and 30±0.5 parts of polyetheramine curing agent; S12, the vacuum stirring is to perform vacuum stirring on the mixed components, the vacuum stirring conditions are temperature 80±2°C, time 120±5 minutes and vacuum degree ≤10Pa, the speed of the vacuum stirring is 300±10rpm, and the vacuum stirring adopts double planetary stirring paddles that rotate forward and reverse alternately; S13, the step curing is to cure the mixed components after vacuum stirring, the process of the step curing is low temperature curing 60±2°C / 4h followed by high temperature curing 120±5°C / 2h, after the step curing, the substrate is hot pressed, the pressure of the hot pressing is 10±0.5MPa, the temperature of the hot pressing is 100±2°C, and the time of the hot pressing is 30 minutes; S14. After hot pressing and shaping, the size of the substrate is 12.5m×2.4m×18mm. The surface of the substrate is treated by sandblasting with 120±20 mesh alumina sand. After sandblasting, plasma cleaning is adopted. The cleaning power of plasma cleaning is 5kW, the argon gas flow rate of plasma cleaning is 20L / miN, and the processing time of plasma cleaning is 10±0.5 minutes.

3. The method for manufacturing a container floor with enhanced wear resistance according to claim 1, characterized in that: The processing of the titanium alloy honeycomb layer in S2 is as follows: S21. The raw materials of the titanium alloy honeycomb layer are titanium alloy powder Ti-6Al-4V (particle size D50=30μm) and tungsten carbide (WC) powder (accounting for 20±0.5wt% of the total amount of titanium alloy powder added, particle size D50=8±0.5μm), and the titanium alloy powder and tungsten carbide (WC) powder are mixed by a three-dimensional mixer, the mixing time is 120±10 minutes, and the protective atmosphere during the mixing process is high-purity argon gas; S22, forming the uniformly mixed titanium alloy powder and tungsten carbide (WC) powder by laser melting (SLM) technology, the parameters of SLM are laser power 300±5W, scanning speed 1000±20mm / s and layer thickness 30±2μm; S23. The titanium alloy honeycomb layer formed by SLM technology has a regular hexagonal honeycomb structure with an aperture of 5.0±0.2mm, a wall thickness of 0.8±0.02mm and a layer thickness of 3.5±0.1mm. A dense transition zone with a width of 5mm is arranged at the edge of the titanium alloy honeycomb layer. The porosity of the titanium alloy honeycomb layer gradually decreases from 65% at the center to 50% at the edge.

4. The method for manufacturing a container floor with enhanced wear resistance according to claim 1, characterized in that: The titanium alloy honeycomb layer and the substrate in S3 are combined with each other, and the specific combination process is as follows: S31, before the titanium alloy honeycomb layer and the substrate are combined, an alloy transition layer needs to be laid between the two. The alloy foil thickness of the alloy transition layer is 50±5 μm, and the surface roughness of the alloy foil is Ra=1.5±0.1 μm after electron beam texturing process; S32, the titanium alloy honeycomb layer and the substrate are connected by a diffusion welding process with the assistance of an alloy transition layer, wherein the diffusion welding process parameters are vacuum degree ≤5×10⁻³Pa, heat treatment 850±10℃ / 60min and axial pressure 5.0±0.3MPa, and the cooling stage of the diffusion welding process is slowly cooled to 300°C at a rate of ≤6°C / min, followed by air cooling; S33. The porosity gradient within 5mm of the edge of the titanium alloy honeycomb layer is reduced to 50±2%, and the root radius of the cell wall is R0.3±0.02mm. The welding interface of the titanium alloy honeycomb layer is subjected to X-ray flaw detection, and the defect rate is ≤0.01%.

5. The method for manufacturing a container floor with enhanced wear resistance according to claim 1, characterized in that: The processing of the cladding layer in S4 is specifically as follows: S41, after the titanium alloy honeycomb layer and the substrate are diffused and welded through the alloy transition layer, the cladding layer is prepared. The cladding powder in the preparation of the cladding layer is Si3N4 (10-50μm) 85±0.5% and INcoNel 625 (15-45μm) 15±0.5%. The cladding powder is pre-dried at a temperature of 150±5°C for a pre-drying time of 2h. The moisture content of the pre-dried cladding powder is ≤0.05%; S42, the cladding layer is prepared by a gradient cladding process, and the gradient cladding includes a first layer, a transition layer and a bonding layer: The first layer is Si3N480±2%, with a layer thickness of 0.3±0.02 mm, and is in contact with the alloy transition layer of the substrate; The transition layer is Si3N450±1%, and the overlap rate with the first layer is 40±2%; The bonding layer is pure INcoNel 625, and the overlap rate with the transition layer is 60±2%; After the gradient cladding is completed, the cladding layer is subjected to laser remelting treatment after cladding, and the laser remelting treatment has a power of 4±0.5kW and a scanning speed of 50mm / s to eliminate interlayer pores; S43. The cladding process of the cladding layer is as follows: laser power 6 kW, scanning speed 20±0.5 mm / s, argon oxygen content ≤50 ppm, surface residual stress of the cladding layer ≤200 MPa, and the α-Si3N4 phase content of the cladding layer is detected by XRD.

6. The method for manufacturing a container floor with enhanced wear resistance according to claim 1, characterized in that: The processing of the micro grooves and DLC coating in S5 is as follows: S51. On the basis of the titanium alloy honeycomb layer and the cladding layer, after being strengthened by the alloy transition layer, micro-groove etching is performed. The micro-groove etching process adopts a femtosecond laser to clean the surface. The femtosecond laser energy density is 2J / cm² and the pulse width is 500fs. The micro-groove etching process adopts a V-shaped asymmetric inclination angle (20° / 45°±0.5°), a depth of 80±2μm, a density of 200±20 lines / cm, and an angle of 15±1° between the etching direction and the forklift direction; S52. After the micro-groove etching is completed, the DLC coating is deposited. The DLC coating is deposited by a magnetron sputtering deposition process. The thickness of the magnetron sputtering deposition is 2.0±0.1μm, the hardness is ≥HV2500 and the deposition rate is 0.25μm / miN. Before the deposition of the DLC coating, argon ion etching cleaning is performed. The bias voltage of the argon ion etching cleaning is -800V and the time is 30 minutes. The bonding strength between the DLC coating and the substrate is ≥50N (scratch test).

7. The method for manufacturing a container floor with enhanced wear resistance according to claim 1, characterized in that: The mechanical property verification in the S6 includes ASTM C633 test, ASTM G65 test, 5kg steel hammer 1m impact, DIN 51130, salt spray test and thermal cycle test. The ASTM C633 test is used to test the bonding strength. The ASTM G65 test and the 5kg steel hammer 1m impact test are used to test the cracks after impact. The DIN 51130 test is used to test the wet friction coefficient. The salt spray test is used to test whether there are corrosion spots on the surface. The thermal cycle test is used to test whether there are cracks on the interface.

8. A container floor with enhanced wear resistance, characterized in that: The container floor prepared by the method according to any one of claims 1 to 7 comprises structure, interlayer bonding strength, surface Rockwell hardness, microgrooves, linear expansion coefficient and chemical corrosion resistance: The total thickness of the structure is 20.0±0.2mm and the overall density is ≤3.2g / cm³; The interlayer bonding strength is ≥35MPa for substrate-honeycomb layer and ≥40MPa for honeycomb-ceramic layer; The surface Rockwell hardness is ≥HRA90 and the laser reflectivity (500-800Nm) is ≤5%; The DLC coating in the micro grooves is continuously covered without visible cracks or peeling; The linear expansion coefficient (25-150°C) is ≤8×10⁻ 6 / K, test standard ASTM E228; The chemical corrosion resistance is immersed in a 5% NaCl + 3% H2O2 solution for 30 days, and the mass loss is ≤0.01%.

9. The method for manufacturing a container floor with enhanced wear resistance according to claim 1, characterized in that: It also includes online monitoring of the production process: In the step S2, high-speed video is used to monitor the morphology of the molten pool in real time, and the fluctuation of the molten pool width is ≤±10μm; In the step S4, the cladding temperature field is detected by an infrared thermal imager, and the temperature gradient is ≤50°C / mm; In step S5, a white light interferometer is used to measure the three-dimensional morphology of the micro-grooves, with a depth tolerance of ±1 μm.

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