Laser melting resin doped with CdSnBiKC alloy powder and preparation method thereof

Abstract

The invention discloses laser melting resin doped with CdSnBiKC alloy powder and a preparation method of the laser melting resin, and belongs to the technical field of organic resin.The Cd, Sn, Bi, K and C nanoparticles are doped in a resin matrix, so that the characteristic that traditional light-cured resin is easy to operate is reserved, the bending resistance, the tensile property, the impact resistance and the hardness of photosensitive resin are greatly improved, and the service life of the photosensitive resin is prolonged. The prepared laser melting resin doped with the metal particles has stable chemical properties, thermal stability and heat and humidity resistance. According to the invention, the technical problems of high brittleness, poor mechanical strength and temperature resistance and low molding precision of the molded part caused by the existing photosensitive resin molding method are effectively solved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic resins, and particularly relates to a laser-fused resin doped with CdSnBiKC alloy powder and a preparation method thereof. Background Art

[0002] Traditional photosensitive resin, commonly known as ultraviolet curable invisible glue, or UV resin or resin glue, is mainly composed of polymer monomers and prepolymers, and a photoinitiator, or photosensitizer, is added thereto. Under the irradiation of ultraviolet light with a certain wavelength of 250 nm to 300 nm, a polymerization reaction will be immediately induced to complete the solidification conversion. The photosensitive resin refers to a liquid photosensitive resin used for stereolithography, or liquid photosensitive resin, which is mainly composed of oligomers, photoinitiators, and diluents. In the past two years, photosensitive resin has been used in the emerging 3D printing industry and has been favored and valued by the industry because of its excellent properties.

[0003] The existing photosensitive resin has advantages such as good surface quality, convenient grinding and coloring, and can be vacuum electroplated and baked. However, the formed parts prepared from the photosensitive resin have insufficient toughness, poor strength, stress concentration, and are prone to deformation. Summary of the Invention

[0004] In view of the above problems, the present invention provides a laser-fused resin doped with metal particles and a preparation method thereof, effectively solving the technical problems that the formed parts of the existing photosensitive resin have insufficient toughness, poor strength, stress concentration, and are prone to deformation. The present invention dopes Cd, Sn, Bi, K, and C nanoparticles in the resin matrix, not only retaining the easy operation characteristics of the traditional photocurable resin, but also greatly improving the bending resistance, tensile resistance, impact resistance, and hardness of the photosensitive resin. The laser-fused resin doped with CdSnBiKC alloy powder prepared by the present invention has stable chemical properties, thermal stability, and moisture and heat resistance.

[0005] The first object of the present invention is to provide a preparation method of a laser-fused resin doped with CdSnBiKC alloy powder, comprising the following steps: Under vacuum, the wire material and the powder material are laser scanned and cured in an inert atmosphere to obtain a laser-fused resin doped with CdSnBiKC alloy powder; The wire material is composed of the following components mixed in mass percentages: 34% to 60% acrylate, 12% to 34% isocyanate, 14% to 28% epoxy silane, 9% to 13% photoinitiator, and 5% to 7% epoxy resin diluent, totaling 100%; The powder material is composed of the following components mixed in mass percentages: 20% to 32% cadmium, 16% to 26% tin, 9% to 19% bismuth, 15% to 27% potassium, and 20% carbon, totaling 100%; The mass ratio of the wire material to the powder material is 2.0 - 2.5:1.

[0006] As a preferred embodiment, the wire feeding speed of the wire material is 60 g / min - 170 g / min, and the powder feeding speed of the powder material is 30 g / min - 70 g / min.

[0007] As a preferred embodiment, the parameters of the laser are: the laser power is 120 W - 500 W, the laser scanning speed is 220 mm / min - 440 mm / min, and the spot diameter is 1 mm - 3 mm.

[0008] As a preferred embodiment, the inert gas is helium, and the helium flow rate is 3 L / min - 18 L / min.

[0009] As a preferred embodiment, the parameters of the vacuum are 450 Torr - 600 Torr.

[0010] As a preferred embodiment, the epoxy resin diluent is styrene, vinyl pyrrolidone, vinyl acetate, butyl acrylate, isooctyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate or trimethylolpropane triacrylate.

[0011] As a preferred embodiment, the photoinitiator is BPO photoinitiator, benzoin dimethyl ether, benzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate or photoinitiator 819.

[0012] As a preferred embodiment, the acrylate is phenoxyethyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate.

[0013] The second object of the present invention is to provide a laser-fused resin doped with CdSnBiKC alloy powder prepared by the preparation method of the laser-fused resin doped with CdSnBiKC alloy powder described above.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a laser-melted resin doped with CdSnBiKC alloy powder and a preparation method thereof. Copolymerizing epoxy silane with acrylate and isocyanate not only improves the adhesion and durability of the resin containing metal powder, but also further improves the toughness of the resin material, endowing the molded resin with good thermal stability and resistance to humidity and heat. The photoinitiator undergoes a photolysis reaction under light irradiation to generate free ions, which serve as the starting point for the copolymerization reaction, initiating the polymerization reactions of isocyanate with epoxy silane and epoxy silane with acrylate. The photoinitiator has high photosensitivity and a long lifespan, improving the corrosion resistance of the molded resin. The epoxy resin diluent contains reactive groups in its molecule, releasing no harmful gases during the resin molding process and also playing a toughening role. Mixing cadmium, tin, bismuth, and potassium metal powders with carbon powder, the nano-cadmium tin bismuth potassium is evenly distributed in the network structure of the carbon powder, forming an alloy with a low melting point below 90 °C. Doping the alloy powder of Cd, Sn, Bi, K, and C in the resin matrix, during the subsequent curing process, under the protection of an inert gas, cadmium, tin, bismuth, potassium, and carbon are melted with the wire under the action of a laser to form a resin with high strength. In an anhydrous environment, cadmium, tin, bismuth, and potassium do not react with water and do not form alkali compounds, and cadmium, tin, bismuth, and potassium will not form Cd 3+ 、Bi 3+ 、Sn 2+ 、K + ions and will not undergo an explosion reaction. The alloy powder will further enhance the overall rigidity of the resin during the laser melting process, significantly improving the mechanical properties such as the anti-bending property, anti-tensile property, and anti-impact property of the model, and greatly increasing the hardness of the material.

[0015] In the present invention, no acidic substances are generated during the copolymerization reaction of inorganic substances, avoiding the release and migration of cadmium under acidic conditions, thus posing a threat to the environment and human health.

[0016] In the present invention, the metal powder and the non-metallic resin matrix are melted into an alloy under a laser scanner. The alloy has stable chemical properties, and the mechanical properties such as the anti-bending property, anti-tensile property, and anti-impact property of the model are significantly improved, and the hardness of the material is greatly increased, enabling it to be applied in more complex environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a schematic structural diagram of the processing equipment for preparing a photosensitive resin containing metal particles by laser scanning curing according to the present invention.

[0018] Description of the reference numerals: 1. Control system and laser instrument, 2. Cured finished product, 3. Workbench, 4. Resin powder injector, 5. Metal wire injector. DETAILED DESCRIPTION OF THE INVENTION

[0019] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the exemplified embodiments shall not be construed as limiting the present invention. The following test methods and detection methods are all conventional methods unless otherwise specified; the reagents and raw materials are all commercially available unless otherwise specified.

[0020] Aiming at the technical problems of the existing photosensitive resin molded parts with insufficient toughness, poor strength, stress concentration and easy deformation, the present invention provides a laser melting resin doped with CdSnBiKC alloy powder and a preparation method thereof.

[0021] The technical solution of the present invention will be described in detail below.

[0022] The present invention first provides a preparation method of a laser melting resin doped with CdSnBiKC alloy powder, comprising the following steps: Under vacuum, the wire material and the powder material are subjected to laser scanning curing in an inert atmosphere to obtain a laser melting resin doped with CdSnBiKC alloy powder; The wire material is composed of the following components mixed by mass percentage: 34% - 60% acrylate, 12% - 34% isocyanate, 14% - 28% epoxy group silane, 9% - 13% photoinitiator and 5% - 7% epoxy resin diluent, totaling 100%; The powder material is composed of the following components mixed by mass percentage: 20% - 32% cadmium, 16% - 26% tin, 9% - 19% bismuth, 15% - 27% potassium and 20% carbon, totaling 100%; The mass ratio of the wire material to the powder material is 2.0 - 2.5:1.

[0023] Acrylate is the matrix component of the resin, and its content directly affects the mechanical properties and curing characteristics of the resin. Too low content may lead to insufficient mechanical properties of the resin, while too high content may lead to increased brittleness and decreased flexibility of the resin; insufficient isocyanate content may result in insufficient cross-linking of the resin, affecting its hardness and wear resistance; too high content may lead to the resin being too hard and lacking necessary toughness; epoxy group silane helps to improve the adhesion performance and weather resistance of the resin. Too low content may weaken the adhesion strength and environmental resistance of the resin; too high content may affect the processing performance of the resin and increase the cost; insufficient photoinitiator content may lead to incomplete curing of the resin, affecting its final performance; too high content may lead to excessive bubbles generated during the curing process of the resin, affecting its transparency and mechanical properties; the diluent is used to adjust the viscosity of the resin and improve its processing performance. Too low content may make the resin too viscous and not conducive to processing; too high content may lead to a decrease in the mechanical properties of the resin and poor chemical resistance.

[0024] The melting point of the alloy powder is lower than that of its constituent elements. This proportion of alloy powder will melt below 100°C; exceeding or falling below this proportion will cause the melting temperature to exceed 100°C.

[0025] In the above technical solution, Cd, Sn, Bi, K, and C nanoparticles are doped in the resin matrix, which greatly improves the bending resistance, tensile resistance, impact resistance, and hardness of the photosensitive resin while retaining the easy operation characteristics of traditional photocurable resins. The laser-melted resin doped with metal particles prepared by the present invention has stable chemical properties, thermal stability, and moisture and heat resistance.

[0026] It should be emphasized that the mass ratio of the wire material to the powder material is 2.0 - 2.5:1. If the mass ratio of the wire material is lower than 2.0, excessive alloy powder will lead to a decline in the mechanical properties of the finished product because the bonding force of the resin is not sufficient to effectively bond the excessive powder; if the mass ratio of the wire material is higher than 2.5, insufficient alloy powder proportion may lead to a decline in the mechanical properties of the composite material, such as strength, hardness, and toughness may not reach the expected effect.

[0027] As a preferred embodiment, the wire feeding speed of the wire material is 60 g / min - 170 g / min, and the powder feeding speed of the powder material is 30 g / min - 70 g / min; if the speed is too fast, it may cause the cladding layer to be uneven, with voids or lack of fusion; if the speed is too slow, it may lead to excessive melting, affecting the density and uniformity of the cladding layer.

[0028] As a preferred embodiment, the parameters of the laser are: the laser power is 120 W - 500 W. Too low power will cause poor formation of the cladding layer or weld, affecting the bonding strength; too high power may cause excessive melting, resulting in pores or cracks. The laser scanning speed is 220 mm / min - 440 mm / min. Too slow speed may cause the cladding layer to be too thick, increasing the porosity; too fast speed may cause the cladding layer to be discontinuous or lack of fusion. The spot diameter is 1 mm - 3 mm. Too large a spot diameter may cause energy dispersion, reducing the quality of the cladding layer; too small a spot diameter may limit the deposition rate of the cladding material, affecting production efficiency.

[0029] As a preferred embodiment, the inert gas is helium, and the helium flow rate is 3 L / min - 18 L / min. If the flow rate is lower than 3 L / min, the molten pool cannot be effectively protected, while if the flow rate is too high, higher than 18 L / min, it will cause the molten pool to cool too quickly, affecting the formation and performance of the joint.

[0030] As a preferred embodiment, the parameters of the vacuum are 450 Torr - 600 Torr. An appropriate vacuum degree helps to remove bubbles during the resin flow process, reduce porosity, thereby improving the integrity and strength of the product.

[0031] In the present invention, the epoxy resin diluent is styrene (St), vinyl pyrrolidone (NVP), vinyl acetate (VA), butyl acrylate (BA), isooctyl acrylate (EHA), 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 1,6 - hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), neopentyl glycol diacrylate (NPGDA) or trimethylolpropane triacrylate (TMPTA).

[0032] It should be noted that in the subsequent embodiments of the present invention, styrene is selected as the epoxy resin diluent, which has good formability, can easily form products with complex shapes, can enhance the surface gloss of the resin, improve the hardness and rigidity of the resin, and has good chemical corrosion resistance and good thermal stability.

[0033] In the present invention, the photoinitiator is BPO photoinitiator, benzoin dimethyl ether (BDK), benzophenone (BP), 4 - chlorobenzophenone (CBP), methyl o - benzoylbenzoate (OMBB) or photoinitiator 819.

[0034] It should be noted that the BPO photoinitiator selected in the subsequent embodiments of the present invention has a relatively high activation energy, can effectively initiate free - radical polymerization reactions, the generated free - radical reaction speed is fast, and has a good initiation effect. The maximum light absorption wavelength range of BPO photolysis is 235nm - 275nm, which enables it to efficiently absorb ultraviolet light and initiate polymerization reactions during the photocuring process.

[0035] It should be noted that the acrylate is phenoxyethyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, 2 - hydroxyethyl methacrylate or 2 - hydroxypropyl methacrylate.

[0036] It should be noted that in the subsequent embodiments of the present invention, phenoxyethyl acrylate is selected as the acrylate. Phenoxyethyl acrylate is a monomer with a low shrinkage rate, which can adjust the viscosity of the resin and participate in the photocuring process, thereby affecting the photocuring speed of the system and various properties of the cured film.

[0037] The content of the present invention will be specifically described below through the following examples and comparative examples.

[0038] Example 1 A laser - melted resin doped with CdSnBiKC alloy powder, comprising a resin matrix and alloy powder.

[0039] The resin matrix is composed of the following raw materials by mass percentage: 34% phenoxyethyl acrylate, 21% isocyanate, 27% epoxy silane, 13% BPO photoinitiator and 5% styrene, totaling 100%.

[0040] The alloy powder is composed of raw materials with the following mass percentages: 20% cadmium, 26% tin, 19% bismuth, 15% potassium, and 20% carbon, totaling 100%.

[0041] The method for preparing the laser-fused resin doped with CdSnBiKC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly, and obtain a wire.

[0042] Weigh the raw materials of the alloy powder, mix them evenly, and obtain a powder.

[0043] Under a vacuum condition of 450 Torr, in a helium atmosphere with a flow rate of 5 L / min, according to a mass ratio of 2.0:1, put the wire and the powder into the wire feeding mechanism and the powder feeding mechanism respectively. The wire is fed at a rate of 60 g / min, and the powder is fed at a speed of 30 g / min. With a laser power of 120 W and a laser scanning speed of 220 mm / min, control the spot diameter to be 1 mm, and use Figure 1 the shown processing equipment for laser scanning and curing to obtain the laser-fused resin doped with CdSnBiKC alloy powder.

[0044] Example 2 A laser-fused resin doped with CdSnBiKC alloy powder includes a resin matrix and an alloy powder.

[0045] The resin matrix is composed of raw materials with the following mass percentages: 36% phenoxyethyl acrylate, 23% isocyanate, 22% epoxy silane, 12% BPO photoinitiator, and 7% styrene, totaling 100%.

[0046] The alloy powder is composed of raw materials with the following mass percentages: 24% cadmium, 24% tin, 15% bismuth, 17% potassium, and 20% carbon, totaling 100%.

[0047] The method for preparing the laser-fused resin doped with CdSnBiKC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly, and obtain a wire.

[0048] Weigh the raw materials of the alloy powder, mix them evenly, and obtain a powder.

[0049] Under a vacuum condition of 500 Torr, in a helium atmosphere with a flow rate of 8 L / min, according to a mass ratio of 2.2:1, the wire material and powder material are respectively placed into a wire feeding mechanism and a powder feeding mechanism. The wire material is fed at a rate of 80 g / min, and the powder material is fed at a speed of 40 g / min. At a laser power of 150 W and a laser scanning speed of 250 mm / min, controlling the spot diameter to be 1 mm, using Figure 1 the processing equipment shown in

[0050] Example 3 A laser-melted resin doped with CdSnBiKC alloy powder, comprising a resin matrix and alloy powder.

[0051] The resin matrix is composed of the following raw materials by mass percentage: 43% phenoxyethyl acrylate, 26% isocyanate, 16% epoxy silane, 9% BPO photoinitiator, and 6% styrene, totaling 100%.

[0052] The alloy powder is composed of the following raw materials by mass percentage: 26% cadmium, 21% tin, 14% bismuth, 19% potassium, and 20% carbon, totaling 100%.

[0053] The preparation method of the above laser-melted resin doped with CdSnBiKC alloy powder comprises the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire material.

[0054] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0055] Under a vacuum condition of 530 Torr, in a helium atmosphere with a flow rate of 10 L / min, according to a mass ratio of 2.3:1, the wire material and powder material are respectively placed into a wire feeding mechanism and a powder feeding mechanism. The wire material is fed at a rate of 100 g / min, and the powder material is fed at a speed of 45 g / min. At a laser power of 200 W and a laser scanning speed of 280 mm / min, controlling the spot diameter to be 2 mm, using Figure 1 the processing equipment shown in

[0056] Example 4 A laser-melted resin doped with CdSnBiKC alloy powder, comprising a resin matrix and alloy powder.

[0057] The resin matrix is composed of the following raw materials by mass percentage: 60% phenoxyethyl acrylate, 12% isocyanate, 14% epoxy silane, 9% BPO photoinitiator, and 5% styrene, totaling 100%.

[0058] The alloy powder consists of raw materials in the following mass percentages: 29% cadmium, 20% tin, 10% bismuth, 21% potassium, and 20% carbon, totaling 100%.

[0059] The method for preparing the laser-melted resin doped with CdSnBiKC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0060] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0061] Under a vacuum condition of 560 Torr and in a helium atmosphere with a flow rate of 12 L / min, according to a mass ratio of 2.33:1, put the wire and the powder into the wire feeding mechanism and the powder feeding mechanism respectively. The wire is fed at a rate of 110 g / min, and the powder is fed at a speed of 50 g / min. With a laser power of 220 W and a laser scanning speed of 300 mm / min, control the spot diameter to be 3 mm, and use Figure 1 the shown processing equipment for laser scanning and curing to obtain the laser-melted resin doped with CdSnBiKC alloy powder.

[0062] Example 5 A laser-melted resin doped with CdSnBiKC alloy powder includes a resin matrix and an alloy powder.

[0063] The resin matrix consists of raw materials in the following mass percentages: 35% phenoxyethyl acrylate, 34% isocyanate, 17% epoxy silane, 9% BPO photoinitiator, and 5% styrene, totaling 100%.

[0064] The alloy powder consists of raw materials in the following mass percentages: 30% cadmium, 18% tin, 10% bismuth, 22% potassium, and 20% carbon, totaling 100%.

[0065] The method for preparing the laser-melted resin doped with CdSnBiKC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0066] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0067] Under a vacuum condition of 570 Torr, in a helium atmosphere with a flow rate of 15 L / min, according to a mass ratio of 2.4:1, the wire material and the powder material are respectively placed into a wire feeding mechanism and a powder feeding mechanism. The wire material is fed at a rate of 130 g / min, and the powder material is fed at a speed of 55 g / min. At a laser power of 300 W and a laser scanning speed of 340 mm / min, the spot diameter is controlled to be 2 mm, and Figure 1 the laser scanning and curing are carried out using the processing equipment shown to obtain a laser-melted resin doped with CdSnBiKC alloy powder.

[0068] Example 6 A laser-melted resin doped with CdSnBiKC alloy powder, comprising a resin matrix and alloy powder.

[0069] The resin matrix is composed of raw materials in the following mass percentages: 38% phenoxyethyl acrylate, 18% isocyanate, 28% epoxy silane, 10% BPO photoinitiator, and 6% styrene, totaling 100%.

[0070] The alloy powder is composed of raw materials in the following mass percentages: 32% cadmium, 12% tin, 9% bismuth, 27% potassium, and 20% carbon, totaling 100%.

[0071] The preparation method of the above laser-melted resin doped with CdSnBiKC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire material.

[0072] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0073] Under a vacuum condition of 600 Torr, in a helium atmosphere with a flow rate of 18 L / min, according to a mass ratio of 2.5:1, the wire material and the powder material are respectively placed into a wire feeding mechanism and a powder feeding mechanism. The wire material is fed at a rate of 170 g / min, and the powder material is fed at a speed of 70 g / min. At a laser power of 400 W and a laser scanning speed of 440 mm / min, the spot diameter is controlled to be 3 mm, and Figure 1 the laser scanning and curing are carried out using the processing equipment shown to obtain a laser-melted resin doped with CdSnBiKC alloy powder.

[0074] To further illustrate the effects of the present invention, the present invention also sets a comparative example. Based on previous experimental studies, the dosage of each element has an impact on the melting temperature, and among them, the K element has the greatest impact on the melting temperature. Therefore, the following comparative examples are set for the change in the dosage of the K element, specifically as follows: Comparative Example 1 Compared with Example 1, the difference lies in that the K element is removed and the dosage of the C element is increased.

[0075] The alloy powder is composed of the following raw materials by mass percentage: 20% cadmium, 26% tin, 19% bismuth, and 35% carbon, totaling 100%.

[0076] A laser-fused resin doped with CdSnBiC alloy powder, comprising a resin matrix and alloy powder.

[0077] The resin matrix is composed of the following raw materials by mass percentage: 34% phenoxyethyl acrylate, 21% isocyanate, 27% epoxy silane, 13% BPO photoinitiator, and 5% styrene, totaling 100%.

[0078] The alloy powder is composed of the following raw materials by mass percentage: 20% cadmium, 26% tin, 19% bismuth, and 35% carbon, totaling 100%.

[0079] The preparation method of the above laser-fused resin doped with CdSnBiC alloy powder comprises the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0080] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0081] Under a vacuum condition of 450 Torr, in a helium gas atmosphere with a flow rate of 5 L / min, according to a mass ratio of 2.0:1, put the wire and the powder into a wire feeding mechanism and a powder feeding mechanism respectively. The wire is fed at a rate of 60 g / min, and the powder is fed at a speed of 30 g / min. At a laser power of 120 W and a laser scanning speed of 220 mm / min, control the spot diameter to be 1 mm, and use Figure 1 the shown processing equipment for laser scanning and curing to obtain a laser-fused resin doped with CdSnBiC alloy powder.

[0082] Comparative Example 2 Compared with Example 2, the difference lies in that the K element is removed and the dosage of the C element is increased.

[0083] The alloy powder is composed of the following raw materials by mass percentage: 24% cadmium, 24% tin, 15% bismuth, and 37% carbon, totaling 100%.

[0084] A laser-fused resin doped with CdSnBiC alloy powder, comprising a resin matrix and alloy powder.

[0085] The resin matrix is composed of raw materials in the following mass percentages: 36% phenoxyethyl acrylate, 23% isocyanate, 22% epoxy group silane, 12% BPO photoinitiator, and 7% styrene, totaling 100%.

[0086] The alloy powder is composed of raw materials in the following mass percentages: 24% cadmium, 24% tin, 15% bismuth, and 37% carbon, totaling 100%.

[0087] The method for preparing the laser-melted resin doped with CdSnBiC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0088] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0089] Under a vacuum condition of 500 Torr, in a helium atmosphere with a flow rate of 8 L / min, according to a mass ratio of 2.2:1, put the wire and the powder into a wire feeding mechanism and a powder feeding mechanism respectively. The wire is fed at a rate of 80 g / min, and the powder is fed at a speed of 40 g / min. At a laser power of 150 W and a laser scanning speed of 250 mm / min, control the spot diameter to be 1 mm, and use Figure 1 the shown processing equipment for laser scanning and curing to obtain the laser-melted resin doped with CdSnBiC alloy powder.

[0090] Comparative Example 3 Compared with Example 3, the difference is that the mass percentage of K element is reduced from 19% to 13%, and at the same time, the mass percentage of Bi element is increased from 14% to 20%.

[0091] The alloy powder is composed of raw materials in the following mass percentages: 26% cadmium, 21% tin, 20% bismuth, 13% potassium, and 20% carbon, totaling 100%.

[0092] A laser-melted resin doped with CdSnBiKC alloy powder, including a resin matrix and an alloy powder.

[0093] The resin matrix is composed of raw materials in the following mass percentages: 43% phenoxyethyl acrylate, 26% isocyanate, 16% epoxy group silane, 9% BPO photoinitiator, and 6% styrene, totaling 100%.

[0094] The alloy powder is composed of raw materials in the following mass percentages: 26% cadmium, 21% tin, 20% bismuth, 13% potassium, and 20% carbon, totaling 100%.

[0095] The method for preparing the laser-melted resin doped with CdSnBiKC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire material.

[0096] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0097] Under a vacuum condition of 530 Torr and in a helium atmosphere with a flow rate of 10 L / min, according to a mass ratio of 2.3:1, put the wire material and the powder material into the wire feeding mechanism and the powder feeding mechanism respectively. The wire material is fed at a rate of 100 g / min, and the powder material is fed at a speed of 45 g / min. With a laser power of 200 W and a laser scanning speed of 280 mm / min, control the spot diameter to be 2 mm, and use the Figure 1 shown processing equipment for laser scanning curing to obtain a laser-melted resin doped with CdSnBiKC alloy powder.

[0098] Comparative Example 4 Compared with Example 4, the difference is that the mass percentage of K element is reduced from 21% to 10%, at the same time, the mass percentage of Cd element is increased from 29% to 34%, and the mass percentage of Bi element is increased from 10% to 16%.

[0099] The alloy powder is composed of the following raw materials by mass percentage: 34% cadmium, 20% tin, 16% bismuth, 10% potassium, and 20% carbon, totaling 100%.

[0100] A laser-melted resin doped with CdSnBiKC alloy powder, comprising a resin matrix and an alloy powder.

[0101] The resin matrix is composed of the following raw materials by mass percentage: 60% phenoxyethyl acrylate, 12% isocyanate, 14% epoxy silane, 9% BPO photoinitiator, and 5% styrene, totaling 100%.

[0102] The alloy powder is composed of the following raw materials by mass percentage: 34% cadmium, 20% tin, 16% bismuth, 10% potassium, and 20% carbon, totaling 100%.

[0103] The preparation method of the above-mentioned laser-melted resin doped with CdSnBiKC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire material.

[0104] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0105] Under a vacuum condition of 560 Torr, in a helium atmosphere with a flow rate of 12 L / min, according to a mass ratio of 2.33:1, the wire material and powder material are respectively placed into a wire feeding mechanism and a powder feeding mechanism. The wire material is fed at a rate of 110 g / min, and the powder material is fed at a rate of 50 g / min. With a laser power of 220 W and a laser scanning speed of 300 mm / min, controlling the spot diameter to be 3 mm, using Figure 1 the processing equipment shown in

[0106] Comparative Example 5 Compared with Example 5, the difference is that the mass percentage of element K is reduced from 22% to 8%, and at the same time, the mass percentage of element Cd is increased from 30% to 36%, and the mass percentage of element Bi is increased from 10% to 18%.

[0107] The alloy powder is composed of raw materials with the following mass percentages: 36% cadmium, 18% tin, 18% bismuth, 8% potassium, and 20% carbon, totaling 100%.

[0108] A laser - melted resin doped with CdSnBiKC alloy powder, comprising a resin matrix and an alloy powder.

[0109] The resin matrix is composed of raw materials with the following mass percentages: 35% phenoxyethyl acrylate, 34% isocyanate, 17% epoxy silane, 9% BPO photoinitiator, and 5% styrene, totaling 100%.

[0110] The alloy powder is composed of raw materials with the following mass percentages: 36% cadmium, 18% tin, 18% bismuth, 8% potassium, and 20% carbon, totaling 100%.

[0111] The preparation method of the above - mentioned laser - melted resin doped with CdSnBiKC alloy powder comprises the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire material.

[0112] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0113] Under a vacuum condition of 570 Torr, in a helium atmosphere with a flow rate of 15 L / min, according to a mass ratio of 2.4:1, the wire material and powder material are respectively placed into a wire feeding mechanism and a powder feeding mechanism. The wire material is fed at a rate of 130 g / min, and the powder material is fed at a rate of 55 g / min. With a laser power of 300 W and a laser scanning speed of 340 mm / min, controlling the spot diameter to be 2 mm, using Figure 1The processing equipment shown is used for laser scanning curing to obtain a laser-melted resin doped with CdSnBiKC alloy powder.

[0114] Comparative Example 6 Compared with Example 6, the difference is that the mass percentage of K element is reduced from 27% to 12%, while the mass percentage of Sn element is increased from 12% to 15%, and the mass percentage of Bi element is increased from 9% to 21%.

[0115] The alloy powder is composed of raw materials with the following mass percentages: 32% cadmium, 15% tin, 21% bismuth, 12% potassium, and 20% carbon, totaling 100%.

[0116] A laser-melted resin doped with CdSnBiKC alloy powder, comprising a resin matrix and alloy powder.

[0117] The resin matrix is composed of raw materials with the following mass percentages: 38% phenoxyethyl acrylate, 18% isocyanate, 28% epoxy silane, 10% BPO photoinitiator, and 6% styrene, totaling 100%.

[0118] The alloy powder is composed of raw materials with the following mass percentages: 32% cadmium, 15% tin, 21% bismuth, 12% potassium, and 20% carbon, totaling 100%.

[0119] The preparation method of the above-mentioned laser-melted resin doped with CdSnBiKC alloy powder comprises the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0120] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0121] Under a vacuum condition of 600 Torr, in a helium gas atmosphere with a flow rate of 18 L / min, according to a mass ratio of 2.5:1, put the wire and the powder into the wire feeding mechanism and the powder feeding mechanism respectively. The wire is fed at a rate of 170 g / min, and the powder is fed at a speed of 70 g / min. At a laser power of 400 W and a laser scanning speed of 440 mm / min, control the spot diameter to be 3 mm, and use Figure 1 The processing equipment shown is used for laser scanning curing to obtain a laser-melted resin doped with CdSnBiKC alloy powder.

[0122] The properties of the laser-melted resins doped with CdSnBiKC alloy powder provided in Examples 1 to 6 and Comparative Examples 3 to 6 above, and the laser-melted resins doped with CdSnBiC alloy powder provided in Comparative Examples 1 to 2 are respectively detected, and the results are shown in Table 1.

[0123] Table 1 Performance Detection Table of Laser-Melted Resins in Embodiments and Comparative Examples of the Present Invention

[0124] As can be seen from Table 1, the laser-melted resin prepared with the doped CdSnBiKC alloy powder of the present invention has excellent wear resistance, corrosion resistance, and high-temperature oxidation resistance. The flexural modulus of the laser-melted resin of the doped CdSnBiKC alloy powder in Embodiments 1 to 6 of the present invention reaches 5.0 MPa, the tensile modulus is as high as 7.2 MPa, the impact strength can reach 78 MPa, and the hardness reaches 172 D. After adjusting the components and mass percentages of the alloy powder in Comparative Examples 1 to 6 respectively, K element is missing in Comparative Examples 1 to 2, and the proportion of K element is increased or decreased in Comparative Examples 3 to 6. The performance of the obtained laser-melted resin is not ideal.

[0125] The mechanical properties of the laser-melted resins obtained in the above Comparative Examples 1 to 6 are poor, and the main reasons are as follows: In Comparative Example 1, the K element is missing and the amount of C element is increased. The K element affects the thermal stability of the material, and the C element reduces the hardness and strength of the material. The change in the alloy powder ratio causes a change in the macroscopic mechanical properties between elements, reducing the comprehensive performance of the finished product.

[0126] In Comparative Example 2, the K element is removed, the C element is increased, Cd is increased, and the Sn element and Bi element are reduced. Although the C element is increased compared with Comparative Example 1, the change in the ratio of other elements affects the mechanical properties of the finished product. The reduction in the content of Sn and Bi elements leads to a decrease in the stability of the alloy, ultimately resulting in a decrease in mechanical properties.

[0127] In Comparative Example 3, the proportion of the K element is reduced and the proportion of the Bi element is increased. The reduction of the K element reduces the thermal stability, and the increase of the Bi element reduces the strength of the material, resulting in a decrease in the physical properties of the material.

[0128] In Comparative Example 4, the proportion of the K element is further reduced, the thermal stability of the material is reduced, and the increase of the Cd element reduces the overall strength of the material, resulting in a further decrease in the mechanical properties of the finished product.

[0129] In Comparative Example 5, the reduction of the K element and the increase of the Bi element lead to excessive refinement of the grains between alloy elements, reducing the macroscopic properties of the material, and finally resulting in a decrease in the mechanical properties of the finished product.

[0130] In Comparative Example 6, the proportion of Sn is increased and the proportion of Bi is increased, resulting in grain coarsening, affecting the migration of grain boundaries, and reducing the strength and toughness of the material.

[0131] In summary, the present invention dopes Cd, Sn, Bi, K, and C nanoparticles in a resin matrix, which not only retains the easy operation characteristics of traditional photocurable resins but also greatly improves the flexural resistance, tensile properties, impact resistance, and hardness of the photosensitive resin. The laser melting resin doped with metal particles prepared by the present invention has stable chemical properties, thermal stability, and moisture and heat resistance.

[0132] Obviously, those skilled in the art can make various modifications and variations to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.

Claims

1. A preparation method of a laser-melted resin doped with CdSnBiKC alloy powder, characterized in that, It includes the following steps: Under vacuum, the wire material and powder material are laser scanned and solidified in an inert atmosphere to obtain a laser melted resin doped with CdSnBiKC alloy powder; The wire material is composed of the following components mixed by mass percentage: 34% - 60% acrylate, 12% - 34% isocyanate, 14% - 28% epoxy group silane, 9% - 13% photoinitiator and 5% - 7% epoxy resin diluent, totaling 100%; The powder material is composed of the following components mixed by mass percentage: 20% - 32% cadmium, 16% - 26% tin, 9% - 19% bismuth, 15% - 27% potassium and 20% carbon, totaling 100%; The mass ratio of the wire material to the powder material is 2.0 - 2.5:

1.

2. The preparation method of the laser-fused resin doped with CdSnBiKC alloy powder according to claim 1, characterized in that, The wire feeding speed of the wire material is 60g / min - 170g / min, and the powder feeding speed of the powder material is 30g / min - 70g / min.

3. The preparation method of the laser-fused resin doped with CdSnBiKC alloy powder according to claim 1, characterized in that, The parameters of the laser are: laser power is 120W - 500W, laser scanning speed is 220mm / min - 440mm / min, and spot diameter is 1mm - 3mm.

4. The preparation method of the laser-melted resin doped with CdSnBiKC alloy powder according to claim 1, wherein, The inert gas is helium, and the helium flow rate is 3L / min - 18L / min.

5. The preparation method of the laser-melted resin doped with CdSnBiKC alloy powder according to claim 1, wherein The parameters of the vacuum are 450Torr - 600Torr.

6. The preparation method of the laser-melted resin doped with CdSnBiKC alloy powder according to claim 1, characterized in that, The epoxy resin diluent is styrene, vinyl pyrrolidone, vinyl acetate, butyl acrylate, isooctyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1,6 - hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate or trimethylolpropane triacrylate.

7. The preparation method of the laser-melted resin doped with CdSnBiKC alloy powder according to claim 1, characterized in that The photoinitiator is BPO photoinitiator, benzoin dimethyl ether, benzophenone, 4 - chlorobenzophenone, methyl o - benzoylbenzoate or photoinitiator 819.

8. The preparation method of the laser-melted resin doped with CdSnBiKC alloy powder according to claim 1, characterized in that, The acrylate is phenoxyethyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isooctyl acrylate, 2 - hydroxyethyl methacrylate or 2 - hydroxypropyl methacrylate.

9. A laser melted resin doped with CdSnBiKC alloy powder prepared by the preparation method of the laser melted resin doped with CdSnBiKC alloy powder according to any one of claims 1 - 8.

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