CN111269563A - Nylon composite Sn-Bi material for 3D laser printing and manufacturing method thereof - Google Patents
Nylon composite Sn-Bi material for 3D laser printing and manufacturing method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a nylon composite Sn-Bi material for 3D laser printing and a manufacturing method thereof, wherein each polymer group of reinforced nylon is composed of a three-layer structure of a kernel, a modified layer and a surface layer, and the kernel is a tin-bismuth alloy with the particle size of 20-40 mu m and the melting point of 150-190 ℃; the modified layer is a 0.3-0.5 mu m mild micro-arc oxidation layer, and then polycarbonate and polylactic acid are mixed according to the mass ratio of about 3: 10, mixing, melting and coating the mixture on the surface of the micro-arc oxidation layer, and finally melting the mixture at a high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; the surface layer is nylon 12 of hindered phenol antioxidant and phosphite antioxidant. The invention has the advantages of eutectic precipitation, approximate melting point of the core and nylon, good combination of the metal core and the nylon, shock resistance, stable structure and good sintering performance during 3D printing.
Description
Technical Field
The invention relates to the technical field of chemical composite materials, in particular to a nylon composite Sn-Bi material for 3D laser printing and a manufacturing method thereof.
Background
Nylon 12, polydodecalactam, also known as polylaurolactam. The relative density of nylon 12 was 1.02g/cm3Is the lower of nylon products; the water absorption was 0.25% due to the low amide group content, which is also lower in nylon. The thermal decomposition temperature of the nylon 12 is more than 350 ℃, the long-term use temperature is 80-90 ℃, and the heat resistance is good. The nylon 12 membrane has good air tightness and water vapor transmission rate of only 9g/m2And simultaneously, the paint is resistant to alkali, oil, yeast and inorganic diluted acid, aromatic hydrocarbon and the like, so that the paint has a very good application prospect.
The metal reinforced nylon material is a novel nylon alloy which takes nylon 12 resin as a base material and metal as a core.
However, the metal reinforced nylon materials on the market at present are almost all simple nucleation structures which directly use fine-grained metal as a high-melting-point nucleating agent, but when the structures are applied to the technical field of 3D laser printing, the structures have two major defects which cannot be overcome: firstly, the surface polarity of metal and nylon is not similar, and the material can be modified by a coupling agent (the coupling agent is a substance with an amphoteric structure, can be combined with resin and inorganic substances, the coupling agent and glass fiber are easy to combine because of silicon-oxygen bonds, and metal is not easy to form because of metal bonds) unlike the existing glass fiber reinforced nylon, and the metal core cannot be modified by simply adding the coupling agent, so the material has poor self-bonding force; secondly, because the melting point of the core is high, the core is not melted during sintering, thus constituting the displacement obstacle in the microstructure of the fluid nylon in the overheating zone during sintering, not only influencing the fluid flow in the sintering zone, but also being easy to become the initiation point of defects (air holes, original tearing and the like).
Therefore, a nylon composite Sn-Bi material for 3D laser printing, which has the advantages of eutectic precipitation, approximate melting point of a core and nylon, good combination of a metal core and nylon, shock resistance, stable structure and good sintering performance during 3D printing, and a manufacturing method thereof are urgently needed in the market.
Disclosure of Invention
The invention aims to provide a nylon composite Sn-Bi material for 3D laser printing, which has the advantages of eutectic precipitation, approximate melting point of a core and nylon, good combination of a metal core and nylon, shock resistance, stable structure and good sintering performance during 3D printing, and a manufacturing method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a manufacturing method of a nylon composite Sn-Bi material for 3D laser printing is characterized by comprising the following steps:
1) raw material preparation
① raw material preparation, which is to prepare 10 parts of mixed material of metal tin and metal bismuth, 0.12-0.15 part of hindered phenol antioxidant, 0.05-0.10 part of phosphite antioxidant, 0.1-0.12 part of polycarbonate, 0.33-0.4 part of polylactic acid and 40-45 parts of nylon 12 powder according to the weight ratio of tin to bismuth corresponding to the melting point of 150-190 ℃ shown in the Sn-Bi phase diagram;
② preparing adjuvant materials by preparing enough ethanol;
2) low melting metal core preparation
①, uniformly mixing the metal tin and the metal bismuth prepared in the step ① in the stage 1), and then melting and casting the mixture into an alloy ingot;
②, ball-milling the alloy ingot obtained in step ① and sieving the alloy ingot to obtain metal cores with the particle size of 20-40 μm;
③, performing mild surface micro-arc oxidation treatment on the metal core obtained in the step ② to obtain a mild oxidation layer with the surface thickness of 0.3-0.5 μm, and performing surface modification on the obtained metal core with the mild oxidation layer by heating and melting the polycarbonate and polylactic acid prepared in the step ① in the stage 1) and then coating the surface to obtain a modified metal core;
3) precipitation forming of solution
①, soaking the nylon 12 powder prepared in the step ① in the stage 1) into ethanol which is 5-8 times of the total weight of the nylon 12 powder, and then adding the modified metal core obtained in the step ③ in the stage 2), the hindered phenol antioxidant prepared in the step ① in the stage 1) and the phosphite antioxidant into the ethanol to prepare a solution to be reacted;
② placing the liquid to be reacted obtained in step ① under the protection of nitrogen with the air pressure of 1.8MPa-2MPa, slowly heating to 185-190 ℃, and keeping the temperature and pressure for 2.5-3 h to obtain a molten pool;
③ stirring the molten pool obtained in step ② at 800-1000 rpm/min, and gradually releasing pressure and cooling to room temperature at a cooling rate of 2-4 ℃/min to obtain an enhanced nylon powder suspension;
④ distilling under reduced pressure the suspension of reinforced nylon powder obtained in step ③ to obtain powder agglomerate;
⑤ grinding the powder obtained in step ④ into powder particles with diameter of 30-90 μm, which is the required nylon composite Sn-Bi material for 3D laser printing.
In the above manufacturing method of the nylon composite Sn-Bi material for 3D laser printing, in the step 1), step ①, 10 parts by weight of a mixed material of metallic tin and metallic bismuth, specifically 3 to 5 parts by weight of metallic tin and 5 to 7 parts by weight of metallic bismuth, is prepared according to the weight ratio of tin to bismuth corresponding to the melting point region of 175 to 190 ℃ shown in the Sn-Bi phase diagram.
In the above manufacturing method of the nylon composite Sn-Bi material for 3D laser printing, in the step 1), step ①, 10 parts by weight of a mixed material of metallic tin and metallic bismuth, specifically 6 to 7.5 parts by weight of metallic tin and 2.5 to 4 parts by weight of metallic bismuth, is prepared according to the weight ratio of tin to bismuth corresponding to the melting point region of 180 to 190 ℃ shown in the Sn-Bi phase diagram.
A nylon composite Sn-Bi material for 3D laser printing is characterized in that each polymer group of the reinforced nylon is composed of a three-layer structure of a kernel, a modification layer and a surface layer, wherein the kernel is a tin-bismuth alloy with the particle size of 20-40 mu m and the melting point of 175-190 ℃; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio (0.1-0.12): (0.33-0.4) mixing, melting and coating on the surface of the micro-arc oxidation layer, and finally melting at the high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; the surface layer is nylon 12 of hindered phenol antioxidant and phosphite antioxidant.
Compared with the prior art, the invention has the following advantages: (1) different from the prior art that nylon is completely solidified by polymerization reaction between nylons during 3D printing, the melting point of the core is similar to that of nylon, and the two materials are both crystal materials or have crystal properties, so that when 3D laser printing is performed, after the instantaneous temperature of a printing area exceeds the melting points of the two materials, along with temperature reduction, the two materials have the technical characteristics of eutectic precipitation besides solidification performance caused by simultaneous condensation of the two eutectic materials, and the two materials are combined more tightly after 3D printing is completed. (2) Different from the problem that the surface polarity of metal and nylon is not similar in the metal reinforced nylon in the prior art, so that the self-bonding force of the material is poor, the invention obtains the metal surface modification base by carrying out slight micro-arc oxidation on the surface of the alloy, and then constructs a particle structure with rough surface and high bonding force by combining polycarbonate with tin oxide, bismuth oxide and nylon 12, which has good bonding force and high melting point (melting point is 220-230 ℃, and is inevitably remained on the surface of the oxidation layer) with the tin oxide, bismuth oxide, polycarbonate and nylon 12, and low melting point (molecular surface groups are still easy to polymerize with the polycarbonate after melting), so as to facilitate nucleation and improve the self-bonding force. (3) According to the polymer cluster structure obtained by the invention, the internal bonding weak points of the dry blocks formed after precipitation and drying are inevitably distributed at the nylon 12 interface at the intersection of each polymer cluster, so that the surfaces of the material particles obtained by ball milling are inevitably provided with a large proportion of separated pure nylon 12 surfaces, and the sintering interface only needs to consider the process parameters required by sintering nylon 12 and nylon 12 during sintering, thereby having small variable and easily controlled process. (4) The melting point of the core (the melting point is 180-190 ℃) and the melting point of the nylon 12 is 183 ℃ in the same area basically, so that the core and the nylon 12 are synchronously melted during sintering, the problem that the displacement of the microstructure of a hot area of the fluid nylon during sintering is obstructed and the sintering performance is influenced during 3D laser printing and sintering of the existing metal reinforced nylon is avoided, meanwhile, due to the synchronous melting of the metal, the sintered self-bonding force is obtained through condensation polymerization of the nylon 12, metal welding bonding is also increased, and the internal self-bonding force of the invention is superior to that of the prior art due to the diversification of the bonding forms. (4) As the core and the shell are made of anti-seismic and structurally stable materials, compared with the existing metal reinforced nylon, the composite material also has the advantages of better anti-seismic and structurally stable. Therefore, the invention has the characteristics of eutectic precipitation, approximate melting point of the core and nylon, good combination of the metal core and the nylon, shock resistance, stable structure and good sintering performance during 3D printing.
Detailed Description
Example 1:
a nylon composite Sn-Bi material for 3D laser printing is characterized in that each polymer group of the reinforced nylon is composed of a three-layer structure of a kernel, a modified layer and a surface layer, wherein the kernel is a tin-bismuth alloy with the particle size of 20-40 mu m and the melting point of 170-185 ℃; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio of 3: 10, mixing, melting and coating the mixture on the surface of the micro-arc oxidation layer, and finally melting the mixture at a high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; nylon 12 with hindered phenol antioxidant and phosphite antioxidant as surface layer;
the manufacturing method of the reinforced nylon comprises the following steps:
1) raw material preparation
① raw material preparation, preparing 3.6kg of metallic tin, 6.4kg of metallic bismuth, 0.13kg of hindered phenol antioxidant, 0.08kg of phosphite antioxidant, 0.12kg of polycarbonate, 0.4kg of polylactic acid and 42kg of nylon 12 powder according to parts by weight;
② preparing adjuvant materials by preparing enough ethanol;
2) low melting metal core preparation
①, uniformly mixing the metal tin and the metal bismuth prepared in the step ① in the stage 1), and then melting and casting the mixture into an alloy ingot;
②, ball-milling the alloy ingot obtained in step ① and sieving the alloy ingot to obtain metal cores with the particle size of 20-40 μm;
③, performing mild surface micro-arc oxidation treatment on the metal core obtained in the step ② to obtain a mild oxidation layer with the surface thickness of 0.3-0.5 μm, and performing surface modification on the obtained metal core with the mild oxidation layer by heating and melting the polycarbonate and polylactic acid prepared in the step ① in the stage 1) and then coating the surface to obtain a modified metal core;
3) precipitation forming of solution
①, soaking the nylon 12 powder prepared in the step ① in the stage 1) into ethanol which is 5-8 times of the total weight of the nylon 12 powder, and then adding the modified metal core obtained in the step ③ in the stage 2), the hindered phenol antioxidant prepared in the step ① in the stage 1) and the phosphite antioxidant into the ethanol to prepare a solution to be reacted;
② placing the liquid to be reacted obtained in step ① under the protection of nitrogen with the air pressure of 1.8MPa-2MPa, slowly heating to 185-190 ℃, and keeping the temperature and pressure for 2.5-3 h to obtain a molten pool;
③ stirring the molten pool obtained in step ② at 800-1000 rpm/min, and gradually releasing pressure and cooling to room temperature at a cooling rate of 2-4 ℃/min to obtain an enhanced nylon powder suspension;
④ distilling under reduced pressure the suspension of reinforced nylon powder obtained in step ③ to obtain powder agglomerate;
⑤ grinding the powder obtained in step ④ into powder particles with diameter of 30-90 μm, which is the required nylon composite Sn-Bi material for 3D laser printing.
Example 2:
the whole is in accordance with example 1, with the difference that:
a nylon composite Sn-Bi material for 3D laser printing is characterized in that each polymer group of the reinforced nylon is composed of a three-layer structure of a kernel, a modification layer and a surface layer, wherein the kernel is a composite Sn-Bi material which has a particle size of 20-40 mu m, a melting point of 180-190 ℃ and is prepared by mixing the following components in percentage by mass: 3 parts of bismuth: 7, a tin bismuth alloy; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio of 1: 4, mixing, melting and coating the mixture on the surface of the micro-arc oxidation layer, and finally melting the mixture at the high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; nylon 12 with hindered phenol antioxidant and phosphite antioxidant as surface layer;
the manufacturing method of the reinforced nylon comprises the following steps:
1) raw material preparation
① raw material preparation, which comprises preparing 3kg of metallic tin, 7kg of metallic bismuth, 0.12kg of hindered phenol antioxidant, 0.05kg of phosphite antioxidant, 0.1kg of polycarbonate, 0.4kg of polylactic acid and 45kg of nylon 12 powder according to parts by weight;
example 3:
the whole is in accordance with example 1, with the difference that:
a nylon composite Sn-Bi material for 3D laser printing is provided, each polymer group of the reinforced nylon is composed of a three-layer structure of a kernel, a modification layer and a surface layer, the kernel is 20-40 μm in particle size, 150-170 ℃ in melting point and is specifically tin in mass ratio: 1-bismuth: 1, a tin-bismuth alloy; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio of 0.12: 0.33, melting and coating the mixture on the surface of the micro-arc oxidation layer, and finally melting the mixture at the high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; nylon 12 with hindered phenol antioxidant and phosphite antioxidant as surface layer;
the manufacturing method of the reinforced nylon comprises the following steps:
1) raw material preparation
① preparing raw materials, namely preparing 5kg of metallic tin, 5kg of metallic bismuth, 0.15kg of hindered phenol antioxidant, 0.1kg of phosphite antioxidant, 0.12kg of polycarbonate, 0.33kg of polylactic acid and 40kg of nylon 12 powder according to parts by weight;
example 4
The metal reinforced nylon for 3D laser printing is characterized in that each polymer group of the reinforced nylon is specifically composed of three layers of a core, a modification layer and a surface layer, wherein the core is 20-40 mu m in particle size, 170-185 ℃ in melting point and specifically comprises tin: 7 parts of bismuth: 3, a tin-bismuth alloy; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio of 3: 10, mixing, melting and coating the mixture on the surface of the micro-arc oxidation layer, and finally melting the mixture at a high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; nylon 12 with hindered phenol antioxidant and phosphite antioxidant as surface layer;
the manufacturing method of the reinforced nylon comprises the following steps:
1) raw material preparation
① raw material preparation, 7kg of metallic tin, 3kg of metallic bismuth, 0.13kg of hindered phenol antioxidant, 0.08kg of phosphite antioxidant, 0.12kg of polycarbonate, 0.4kg of polylactic acid and 42kg of nylon 12 powder are prepared according to the parts by weight;
② preparing adjuvant materials by preparing enough ethanol;
2) low melting metal core preparation
①, uniformly mixing the metal tin and the metal bismuth prepared in the step ① in the stage 1), and then melting and casting the mixture into an alloy ingot;
②, ball-milling the alloy ingot obtained in step ① and sieving the alloy ingot to obtain metal cores with the particle size of 20-40 μm;
③, performing mild surface micro-arc oxidation treatment on the metal core obtained in the step ② to obtain a mild oxidation layer with the surface thickness of 0.3-0.5 μm, and performing surface modification on the obtained metal core with the mild oxidation layer by heating and melting the polycarbonate and polylactic acid prepared in the step ① in the stage 1) and then coating the surface to obtain a modified metal core;
3) precipitation forming of solution
①, soaking the nylon 12 powder prepared in the step ① in the stage 1) into ethanol which is 5-8 times of the total weight of the nylon 12 powder, and then adding the modified metal core obtained in the step ③ in the stage 2), the hindered phenol antioxidant prepared in the step ① in the stage 1) and the phosphite antioxidant into the ethanol to prepare a solution to be reacted;
② placing the liquid to be reacted obtained in step ① under the protection of nitrogen with the air pressure of 1.8MPa-2MPa, slowly heating to 185-190 ℃, and keeping the temperature and pressure for 2.5-3 h to obtain a molten pool;
③ stirring the molten pool obtained in step ② at 800-1000 rpm/min, and gradually releasing pressure and cooling to room temperature at a cooling rate of 2-4 ℃/min to obtain an enhanced nylon powder suspension;
④ distilling under reduced pressure the suspension of reinforced nylon powder obtained in step ③ to obtain powder agglomerate;
⑤ grinding the powder obtained in step ④ into powder particles with diameter of 30-90 μm, which is the metal reinforced nylon for 3D laser printing.
Example 5:
the whole is in accordance with example 4, with the difference that:
the metal reinforced nylon for 3D laser printing is characterized in that each polymer group of the reinforced nylon is specifically composed of three layers of a core, a modification layer and a surface layer, wherein the core is a metal material with the particle size of 20-40 mu m, the melting point of 150-170 ℃ and the mass ratio of tin: bismuth 6: 4, a tin-bismuth alloy; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio of 3: 10, mixing, melting and coating the mixture on the surface of the micro-arc oxidation layer, and finally melting the mixture at a high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; nylon 12 with hindered phenol antioxidant and phosphite antioxidant as surface layer;
the manufacturing method of the reinforced nylon comprises the following steps:
1) raw material preparation
① preparing raw materials, namely preparing 6kg of metallic tin, 4kg of metallic bismuth, 0.13kg of hindered phenol antioxidant, 0.08kg of phosphite antioxidant, 0.12kg of polycarbonate, 0.4kg of polylactic acid and 42kg of nylon 12 powder according to parts by weight;
example 6:
the whole is in accordance with example 4, with the difference that:
the metal reinforced nylon for 3D laser printing is characterized in that each polymer group of the reinforced nylon is specifically composed of three layers of a core, a modification layer and a surface layer, wherein the core is 20-40 mu m in particle size, 180-190 ℃ in melting point and specifically comprises tin in mass ratio: 3 parts of bismuth: 1, a tin-bismuth alloy; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio of 3: 10, mixing, melting and coating the mixture on the surface of the micro-arc oxidation layer, and finally melting the mixture at a high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; nylon 12 with hindered phenol antioxidant and phosphite antioxidant as surface layer;
the manufacturing method of the reinforced nylon comprises the following steps:
1) raw material preparation
① preparing raw materials, namely preparing 7.5kg of metallic tin, 2.5kg of metallic bismuth, 0.13kg of hindered phenol antioxidant, 0.08kg of phosphite antioxidant, 0.12kg of polycarbonate, 0.4kg of polylactic acid and 42kg of nylon 12 powder according to parts by weight;
the previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A manufacturing method of a nylon composite Sn-Bi material for 3D laser printing is characterized by comprising the following steps:
1) raw material preparation
① raw material preparation, which is to prepare 10 parts of mixed material of metal tin and metal bismuth, 0.12-0.15 part of hindered phenol antioxidant, 0.05-0.10 part of phosphite antioxidant, 0.1-0.12 part of polycarbonate, 0.33-0.4 part of polylactic acid and 40-45 parts of nylon 12 powder according to the weight ratio of tin to bismuth corresponding to the melting point of 150-190 ℃ shown in the Sn-Bi phase diagram;
② preparing adjuvant materials by preparing enough ethanol;
2) low melting metal core preparation
①, uniformly mixing the metal tin and the metal bismuth prepared in the step ① in the stage 1), and then melting and casting the mixture into an alloy ingot;
②, ball-milling the alloy ingot obtained in step ① and sieving the alloy ingot to obtain metal cores with the particle size of 20-40 μm;
③, performing mild surface micro-arc oxidation treatment on the metal core obtained in the step ② to obtain a mild oxidation layer with the surface thickness of 0.3-0.5 μm, and performing surface modification on the obtained metal core with the mild oxidation layer by heating and melting the polycarbonate and polylactic acid prepared in the step ① in the stage 1) and then coating the surface to obtain a modified metal core;
3) precipitation forming of solution
①, soaking the nylon 12 powder prepared in the step ① in the stage 1) into ethanol which is 5-8 times of the total weight of the nylon 12 powder, and then adding the modified metal core obtained in the step ③ in the stage 2), the hindered phenol antioxidant prepared in the step ① in the stage 1) and the phosphite antioxidant into the ethanol to prepare a solution to be reacted;
② placing the liquid to be reacted obtained in step ① under the protection of nitrogen with the air pressure of 1.8MPa-2MPa, slowly heating to 185-190 ℃, and keeping the temperature and pressure for 2.5-3 h to obtain a molten pool;
③ stirring the molten pool obtained in step ② at 800-1000 rpm/min, and gradually releasing pressure and cooling to room temperature at a cooling rate of 2-4 ℃/min to obtain an enhanced nylon powder suspension;
④ distilling under reduced pressure the suspension of reinforced nylon powder obtained in step ③ to obtain powder agglomerate;
⑤ grinding the powder obtained in step ④ into powder particles with diameter of 30-90 μm, which is the required nylon composite Sn-Bi material for 3D laser printing.
2. The method for manufacturing a nylon composite Sn-Bi material for 3D laser printing according to claim 1, wherein 10 parts by weight of the mixed material of metallic tin and metallic bismuth, specifically 3 to 5 parts by weight of metallic tin and 5 to 7 parts by weight of metallic bismuth, is prepared according to the weight ratio of tin to bismuth corresponding to the melting point region of 175 to 190 ℃ shown in the Sn-Bi phase diagram in the step 1) and ①.
3. The method for manufacturing a nylon composite Sn-Bi material for 3D laser printing according to claim 1, wherein 10 parts by weight of the mixed material of metallic tin and metallic bismuth, specifically 6 to 7.5 parts by weight of metallic tin and 2.5 to 4 parts by weight of metallic bismuth, is prepared according to the weight ratio of tin to bismuth in the region of the melting point of 180 to 185 ℃ shown in the Sn-Bi phase diagram in the step 1) and ①.
4. The nylon composite Sn-Bi material for 3D laser printing is characterized in that: each polymer group of the reinforced nylon is specifically composed of three layers of structures, namely a core, a modified layer and a surface layer, wherein the core is a tin-bismuth alloy with the particle size of 20-40 mu m and the melting point of 150-190 ℃; the modified layer is a slight micro-arc oxidation layer with the diameter of 0.3-0.5 mu m obtained after micro-arc oxidation treatment by taking the inner core as a base, and then polycarbonate and polylactic acid are mixed according to the mass ratio (0.1-0.12): (0.33-0.4) mixing, melting and coating on the surface of the micro-arc oxidation layer, and finally melting at the high temperature of 185-190 ℃ to form a composite structure layer with two combined structures which are still remained on the surface of the micro-arc oxidation layer; the surface layer is nylon 12 of hindered phenol antioxidant and phosphite antioxidant.
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2020
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| CN101036944A (en) * | 2007-04-04 | 2007-09-19 | 华中科技大学 | Method for preparing nylon coating film metal powder material |
| CN110343283A (en) * | 2019-07-20 | 2019-10-18 | 福建师范大学 | A kind of light of 3D printing skeleton@stannic oxide/wolframic acid tin urges the preparation method of device |
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