CN101148541A - Method for enhancing nylon selectivity laser sintering forming element by inorganic nano particles - Google Patents
Method for enhancing nylon selectivity laser sintering forming element by inorganic nano particles Download PDFInfo
- Publication number
- CN101148541A CN101148541A CNA2007100536682A CN200710053668A CN101148541A CN 101148541 A CN101148541 A CN 101148541A CN A2007100536682 A CNA2007100536682 A CN A2007100536682A CN 200710053668 A CN200710053668 A CN 200710053668A CN 101148541 A CN101148541 A CN 101148541A
- Authority
- CN
- China
- Prior art keywords
- nylon
- nano
- inorganic nano
- particle
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention discloses process of preparing selectively laser sintered inorganic nanometer particle reinforced nylon part. The process includes the following steps: surface organizing treatment of inorganic nanometer particle and ultrasonic treatment to disperse the inorganic nanometer particle homogeneously in mixed solvent to form inorganic nanometer particle suspension; heating the mixture of inorganic nanometer particle suspension, nylon resin and antioxidant inside a sealed container to dissolve the nylon resin in the solvent; cooling, decompression distilling to recover solvent, vacuum drying, ball milling and sieving to obtain composite nylon/inorganic nanometer particle composite material; and final selectively laser sintering to form. The selectively laser sintered inorganic nanometer particle reinforced nylon part has raised strength and high toughness.
Description
Technical field
The invention belongs to the material field in the advanced manufacturing fast, be specifically related to a kind of method of enhancing nylon selectivity laser sintering forming element by inorganic nano particles.
Technical background
(selective laser sintering SLS) is a kind of Rapid Prototyping technique of coming the sintered powder material forming with laser as thermal source to selective laser sintering.The SLS technology adopts the principle that disperses, piles up moulding, by means of computer aided design (CAD) and manufacturing, is Three-dimensional Entity Components with the solid powder material direct forming.The SLS multiple material that can be shaped comprises polymer, metal and pottery etc.Because macromolecular material compares with metal and stupalith, have that mold temperature is low, the sintering laser power is little, the precision advantages of higher, becoming present application at most also is to use the most successful SLS material.
Nylon is a kind of semicrystalline polymeric, has good sintering character and lower melt viscosity, can be by SLS direct forming density height, mechanical property function part preferably, thereby become one of SLS shaped material that is most widely used at present.And determined the inside of nylon SLS drip molding also can have certain hole by the SLS shaping characteristic, and cause its mechanical property, especially toughness generally is lower than the injection molded goods.Thereby, the emphasis that how to strengthen, tenacity increased nylon SLS drip molding becomes present this area research.Enhancement Method commonly used at present is to add the mineral filler powder of particle diameter between 10～100 microns in nylon powder, as glass microballon, wollastonite, whisker, talcum powder, zinc oxide, lime carbonate etc., flexural strength, tensile strength and the Young's modulus of the SLS drip molding of this kind modified powder all increases to some extent, but shock strength and elongation at break have significantly reduction, though thereby the micron order mineral filler increases the intensity, rigidity of drip molding, damaged the toughness of SLS drip molding greatly.
The particle diameter of nanoparticle is between 1～100nm, because size of particles is little, surface non-matching electronics is many, big with polymkeric substance generation physics or chemically combined possibility, if can make its dispersion that in nylon matrix, reaches nanoscale, will have enhancing, toughness reinforcing dual function simultaneously to nylon SLS drip molding.
The preparation method of nylon/mineral filler composite powder that SLS is commonly used is: at first prepare nylon powder, again itself and mineral filler powder are carried out mechanically mixing.Document " the selective laser sintering preparation and the performance of composite nylon powder " (use by engineering plastics, the first phase in 2007) proposes to prepare pure nylon 12 powder by solvent precipitation earlier, purer nylon powder and mineral filler powder mechanically mixing are prepared SLS composite nylon powder.Because nanoparticle is very easily reunited, the method of this mechanically mixing obviously can not make nanoparticle be dispersed in the nylon powder, thereby nanoparticle can not disperse in the nylon matrix with nanoscale in its SLS drip molding, can not bring into play enhancing, the toughening effect of nanoparticle.
Summary of the invention
The object of the present invention is to provide a kind of method of enhancing nylon selectivity laser sintering forming element by inorganic nano particles, inorganic nano-particle is uniformly dispersed in the composite powder material of this method preparation, inorganic nano-particle is dispersed in the nylon matrix with nanoscale in the SLS drip molding, thereby nylon SLS drip molding is had enhancing, toughening effect simultaneously.
The method of enhancing nylon selectivity laser sintering forming element by inorganic nano particles provided by the invention, its step comprises:
(1) is to mix in 3: 1～4: 1 inorganic nano-particle and silane coupling agent alcohol-water solution by mass ratio, after the drying, through ball milling, sieve, obtains the inorganic nano-particle that surface organic is handled; Wherein, inorganic nano-particle is nano silicon, nano aluminium oxide, nano titanium oxide, nano-calcium carbonate or nano zine oxide; The silane coupling agent alcohol-water solution is formed and mass percent is: 90～95% ethanol, 1～2% silane coupling agent, all the other are distilled water; Described silane coupling agent is: γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane or N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan;
(2) under whipped state, will join in the mixed solvent, then this mixture is carried out ultrasonication, inorganic nano-particle is dispersed in the mixed solvent, form inorganic nano-particle suspension through the inorganic nano-particle that surface organic is handled; Again with this inorganic nano-particle suspension with join in the encloses container after nylon resin and antioxidant mix, vacuumize, logical protection of inert gas, wherein:
In per 100 gram nylon resins, the consumption of inorganic nano-particle is 1～10 gram; The consumption of mixed solvent is 500～1500 grams; The consumption of antioxidant is 0.1～0.5 gram;
The composition of mixed solvent and mass percent are: ethanol: 70～85%, and ethylene glycol: 0.1～20%, propylene glycol: 0.1～10%, surplus is a distilled water;
Antioxidant is made up of Hinered phenols antioxidant and phosphite ester kind antioxidant, and wherein the mass percent of Hinered phenols antioxidant is 60～80%, and all the other are phosphite ester kind antioxidant; Described Hinered phenols antioxidant is: 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2,6-di-t-butyl-4-methyl-phenol, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionic acid amide), 2,2 '-two (4-methyl-6-tert butyl-phenol) methane or 2,2 '-two (the 4-ethyl-6-tertiary butyl-phenol) methane; Described phosphite ester kind antioxidant is: 2, and 2 '-ethylenebis (4, the 6-di-tert-butyl-phenyl) fluorophosphite or four (2, the 4-di-tert-butyl-phenyl)-4,4 '-xenyl bis-phosphite;
(3) with the speed of 1～2 ℃/min, the said mixture material is warmed up to 150～165 ℃ gradually, makes nylon resin be dissolved in the solvent fully;
(4) under stirring fast, be cooled to room temperature gradually, carry out vacuum distillation recovered solvent simultaneously, obtain nylon/inorganic nano-particle composite powder aggregate with 2～4 ℃ of speed;
(5) powder aggregates that obtains is carried out vacuum-drying, carry out ball milling again and sieve, obtain nylon/inorganic nano-particle composite powder material;
(6) nylon/inorganic nano-particle composite powder material being carried out SLS is shaped.
The present invention at first just inorganic nano-particle carries out the surface organic processing, combines with the interface of matrix resin to strengthen nanoparticle.Adopt ultrasonication again, inorganic nano-particle is dispersed in the mixed solvent.Adopt solvent precipitation to prepare nylon/inorganic nano-particle composite powder material, in preparation composite powder process, nylon is the heterogeneous nucleation agent with the inorganic nano-particle, inorganic nano-particle is wrapped up in crystallization gradually, make inorganic nano-particle be dispersed in the composite powder material, inorganic nano-particle is dispersed in the nylon matrix with nanoscale in the SLS drip molding.
Embodiment
The present invention at first adopts coupling agent that inorganic nano-particle is carried out surface organic and handles, and by ultrasonication inorganic nano-particle is dispersed in the mixed solvent then, forms inorganic nano-particle suspension.In encloses container, this inorganic nano-particle suspension, nylon resin and antioxidant blends are heated, nylon resin is dissolved in the solvent, cooling gradually then, and vacuum distillation recovered solvent, obtain powder aggregates, through solvent recuperation, vacuum-drying, ball milling, sieve and promptly get nylon/inorganic nano-particle composite powder material, at last nylon/inorganic nano-particle composite powder material is carried out SLS and be shaped.
The preferable range of the nylon resin that the present invention uses is: nylon 6, nylon 46, nylon 66, NYLON610, nylon 612, nylon 1010, Ni Long11, nylon 12, nylon 1212, one or more in the nylon 1313, its further preferable range is that fusing point is lower than 200 ℃ nylon, preheating temperature when material melting point is hanged down laser sintering (SLS) requires also low, and sintering is controlled easily.
The present invention is further detailed explanation to enumerate example below, but the present invention is not limited thereto.Persons skilled in the art can adopt other raw material and processing parameter to realize the present invention according to content disclosed by the invention.
Embodiment 1:
(1) gets 1000 gram nano silicons, itself and 250 alcohol-water solution that restrain γ-An Bingjisanyiyangjiguiwans are mixed, at room temperature dry 2 days, again after under 65 ℃ dry 2 hours, ball milling, sieve, obtain the nano silicon that surface organic is handled.
The composition of the alcohol-water solution of γ-An Bingjisanyiyangjiguiwan and mass percent are: 95% ethanol, 3% distilled water, 2% γ-An Bingjisanyiyangjiguiwan.
(2) nano silicon that 10 gram surface organics are handled joins in the 5000 gram mixed solvents, and carries out ultrasonic dispersing and handle, and makes nano silicon suspension.
(3) the nano silicon suspension in (2), nylon 12 resins 1000 grams, composite antioxidant 2 grams are dropped in the 50L stainless steel cauldron of strap clamp cover,, vacuumize logical N with the reactor sealing
2Gas shiled.The proportioning of mixed solvent (massfraction) is: 85% ethanol, 1% distilled water, 10% ethylene glycol, 4% propylene glycol.The proportioning of composite antioxidant (massfraction) is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is 80%, 2,2 '-ethylenebis (4, the 6-di-tert-butyl-phenyl) fluorophosphite is 20%.
(3) with the speed of 1 ℃/min, be warmed up to 150 ℃ gradually, make nylon 12 be dissolved in the solvent heat-insulation pressure keeping 2h fully.
(4) under stirring fast, be cooled to room temperature gradually, carry out vacuum distillation recovered solvent simultaneously, obtain nylon/nano silicon composite powder aggregate with 2 ℃ of speed.
(5) powder aggregates that obtains is carried out vacuum-drying, carry out ball milling again and sieve, promptly get nylon/nano silicon composite powder material.
(6) nylon/nano silicon composite powder material that on the SLS former, is shaped, preparation technology parameter is: laser power 10W; Sweep velocity 2000mm/s; Sintering spacing 0.1mm; Sintered layer thickness 0.1mm; 160 ℃ of preheating temperatures.The SLS drip molding is carried out sem observation, and nano surface silicon-dioxide is dispersed in the nylon matrix with nanoscale as a result, and the part mechanical property of SLS drip molding sees Table 1.
Embodiment 2～3:
With embodiment 1, wherein the nanometer titanium dioxide silicone content is respectively 20g, 30g in Pei Zhi the nano silicon suspension, the part mechanical property of SLS drip molding sees Table 1, and the mechanical property of the pure nylon 12 powder SLS drip moldings of nano-silica-containing is not also listed in the table 1 as a comparison.
Embodiment 4:
(1) gets 1000 gram nano-aluminium oxides, itself and 250 alcohol-water solution that restrain γ-An Bingjisanyiyangjiguiwans are mixed, at room temperature dry 2 days, again after under 65 ℃ dry 2 hours, ball milling, sieve, obtain the nano-aluminium oxide that surface organic is handled.
The composition of the alcohol-water solution of γ-An Bingjisanyiyangjiguiwan and mass percent are: 95% ethanol, 3% distilled water, 2% γ-An Bingjisanyiyangjiguiwan.
(2) nano-aluminium oxide that 30 gram surface organics are handled joins in the 5000 gram mixed solvents, and carries out ultrasonic dispersing and handle, and makes nano-aluminium oxide suspension.
(3) the nano-aluminium oxide suspension in (2), Ni Long11 resin 1000 grams, composite antioxidant 2 grams are dropped in the 50L stainless steel cauldron of strap clamp cover,, vacuumize logical N with the reactor sealing
2Gas shiled.The proportioning of mixed solvent (massfraction) is: 85% ethanol, 1% distilled water, 10% ethylene glycol, 4% propylene glycol.The proportioning of composite antioxidant (massfraction) is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is 80%, 2,2 '-ethylenebis (4, the 6-di-tert-butyl-phenyl) fluorophosphite is 20%.
(3) with the speed of 2 ℃/min, be warmed up to 160 ℃ gradually, make Ni Long11 be dissolved in the solvent heat-insulation pressure keeping 2h fully.
(4) under stirring fast, be cooled to room temperature gradually, carry out vacuum distillation recovered solvent simultaneously, obtain nylon/nano-aluminium oxide composite powder aggregate with 2 ℃ of speed.
(5) powder aggregates that obtains is carried out vacuum-drying, carry out ball milling again and sieve, promptly get nylon/nano-aluminium oxide composite powder material.
(6) nylon/nano-aluminium oxide composite powder material that on the SLS former, is shaped, preparation technology parameter is: laser power 10W; Sweep velocity 2000mm/s; Sintering spacing 0.1mm; Sintered layer thickness 0.1mm; 160 ℃ of preheating temperatures.The SLS drip molding is carried out sem observation, and the nano surface aluminium sesquioxide is dispersed in the nylon matrix with nanoscale as a result, and the part mechanical property of SLS drip molding sees Table 2.
Embodiment 5～6:
With embodiment 4, wherein nano-aluminium oxide content is respectively 40g, 50g in Pei Zhi the nano-aluminium oxide suspension, the part mechanical property of SLS drip molding sees Table 2, and the mechanical property that does not contain the pure Ni Long11 powder SLS drip molding of nano-aluminium oxide is also listed in the table 2 as a comparison.
Embodiment 7:
(1) gets 1000 gram nano-calcium carbonates, itself and 250 alcohol-water solution that restrain N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwans are mixed, at room temperature dry 2 days, again after under 65 ℃ dry 2 hours, ball milling, sieve, obtain the nano-calcium carbonate that surface organic is handled.
The composition and the mass percent of the alcohol-water solution of N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan are: 95% ethanol, 3% distilled water, 2%N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan.
(2) nano-calcium carbonate that 20 gram surface organics are handled joins in the 5000 gram mixed solvents, and carries out ultrasonic dispersing and handle, and makes nano-calcium carbonate suspension.
(3) the nano-calcium carbonate suspension in (2), nylon 12 resins 1000 grams, composite antioxidant 2 grams are dropped in the 50L stainless steel cauldron of strap clamp cover,, vacuumize logical N with the reactor sealing
2Gas shiled.The proportioning of mixed solvent (massfraction) is: 85% ethanol, 1% distilled water, 10% ethylene glycol, 4% propylene glycol.The proportioning of composite antioxidant (massfraction) is: 1,3, and 5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene is 80%, 2,2 '-ethylenebis (4, the 6-di-tert-butyl-phenyl) fluorophosphite is 20%.
(3) with the speed of 1 ℃/min, be warmed up to 150 ℃ gradually, make nylon 12 be dissolved in the solvent heat-insulation pressure keeping 2h fully.
(4) under stirring fast, be cooled to room temperature gradually, carry out vacuum distillation recovered solvent simultaneously, obtain nylon/nano-calcium carbonate composite powder aggregate with 2 ℃ of speed.
(5) powder aggregates that obtains is carried out vacuum-drying, carry out ball milling again and sieve, promptly get nylon/nano-calcium carbonate composite powder material.
(6) nylon/nano-calcium carbonate composite powder material that on the SLS former, is shaped, preparation technology parameter is: laser power 12W; Sweep velocity 2000mm/s; Sintering spacing 0.1mm; Sintered layer thickness 0.08mm; 160 ℃ of preheating temperatures.The SLS drip molding is carried out sem observation, and nano surface lime carbonate is dispersed in the nylon matrix with nanoscale as a result, and the part mechanical property of SLS drip molding sees Table 3.
Embodiment 8～9:
With embodiment 7, wherein the nano-calcium carbonate calcium contents is respectively 30g, 40g in Pei Zhi the nano-calcium carbonate suspension, the part mechanical property of SLS drip molding sees Table 3, and the mechanical property that does not contain the pure nylon 12 powder SLS drip moldings of nano-calcium carbonate is also listed in the table 3 as a comparison.
Table 1
| Embodiment | Nanometer titanium dioxide silicone content/g | Flexural strength/MPa | Modulus in flexure/GPa | Shock strength/(KJ/m 2) | Tensile strength/MPa |
| - 1 2 3 | 0 10 20 30 | 50.8 58.6 60.5 63.1 | 1.36 1.52 1.60 1.71 | 37.2 39.5 39.2 39.0 | 44.0 51.2 55.4 56.1 |
Table 2
| Embodiment | Nano-aluminium oxide content/g | Flexural strength/MPa | Modulus in flexure/GPa | Shock strength/(KJ/m 2) | Tensile strength/MPa |
| - 4 5 6 | 0 30 40 50 | 51.8 58.5 60.2 62.1 | 1.40 1.50 1.62 1.70 | 36.7 38.5 38.3 38.0 | 45.2 51.0 54.1 55.9 |
Table 3
| Embodiment | Nano-calcium carbonate calcium contents/g | Flexural strength/MPa | Modulus in flexure/GPa | Shock strength/(KJ/m 2) | Tensile strength/MPa |
| - 7 8 9 | 0 20 30 40 | 50.8 54.5 58.5 61.1 | 1.36 1.49 1.58 1.70 | 37.2 38.5 39.0 38.1 | 44.0 50.2 53.1 55.2 |
Claims (3)
1. the method for an enhancing nylon selectivity laser sintering forming element by inorganic nano particles, its step comprises:
(1) is to mix in 3: 1～4: 1 inorganic nano-particle and silane coupling agent alcohol-water solution by mass ratio, after the drying, through ball milling, sieve, obtains the inorganic nano-particle that surface organic is handled; Wherein, inorganic nano-particle is nano silicon, nano aluminium oxide, nano titanium oxide, nano-calcium carbonate or nano zine oxide; The silane coupling agent alcohol-water solution is formed and mass percent is: 90～95% ethanol, 1～2% silane coupling agent, all the other are distilled water; Described silane coupling agent is: γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane or N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan;
(2) under whipped state, will join in the mixed solvent, then this mixture is carried out ultrasonication, inorganic nano-particle is dispersed in the mixed solvent through the inorganic nano-particle that surface organic is handled; Again with this inorganic nano-particle suspension with join in the encloses container after nylon resin and antioxidant mix, vacuumize, logical protection of inert gas, wherein:
In per 100 gram nylon resins, the consumption of inorganic nano-particle is 1～10 gram; The consumption of mixed solvent is 500～1500 grams; The consumption of antioxidant is 0.1～0.5 gram;
The composition of mixed solvent and mass percent are: ethanol: 70～85%, and ethylene glycol: 0.1～20%, propylene glycol: 0.1～10%, surplus is a distilled water;
Antioxidant is made up of Hinered phenols antioxidant and phosphite ester kind antioxidant, and wherein the mass percent of Hinered phenols antioxidant is 60～80%, and all the other are phosphite ester kind antioxidant; Described Hinered phenols antioxidant is: 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2,6-di-t-butyl-4-methyl-phenol, N, N '-two (3,5-di-tert-butyl-hydroxy phenyl propionic acid amide), 2,2 '-two (4-methyl-6-tert butyl-phenol) methane or 2,2 '-two (the 4-ethyl-6-tertiary butyl-phenol) methane; Described phosphite ester kind antioxidant is: 2, and 2 '-ethylenebis (4, the 6-di-tert-butyl-phenyl) fluorophosphite or four (2, the 4-di-tert-butyl-phenyl)-4,4 '-xenyl bis-phosphite;
(3) with the speed of 1～2 ℃/min, the said mixture material is warmed up to 150～165 ℃ gradually, makes nylon resin be dissolved in the solvent fully;
(4) under stirring fast, be cooled to room temperature gradually, carry out vacuum distillation recovered solvent simultaneously, obtain nylon/inorganic nano-particle composite powder aggregate with 2～4 ℃ of speed;
(5) powder aggregates that obtains is carried out vacuum-drying, carry out ball milling again and sieve, obtain nylon/inorganic nano-particle composite powder material;
(6) nylon/inorganic nano-particle composite powder material is carried out selective laser sintering (SLS).
2. preparation method according to claim 1 is characterized in that: nylon resin is: nylon 6, nylon 46, nylon 66, NYLON610, nylon 612, nylon 1010, Ni Long11, nylon 12, the mixing of one or more in nylon 1212 or the nylon 1313.
3. preparation method according to claim 1 and 2 is characterized in that: nylon resin is a fusing point smaller or equal to 200 ℃ nylon resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710053668A CN100587007C (en) | 2007-10-26 | 2007-10-26 | Method for enhancing nylon selectivity laser sintering forming element by inorganic nano particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710053668A CN100587007C (en) | 2007-10-26 | 2007-10-26 | Method for enhancing nylon selectivity laser sintering forming element by inorganic nano particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101148541A true CN101148541A (en) | 2008-03-26 |
| CN100587007C CN100587007C (en) | 2010-02-03 |
Family
ID=39249247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710053668A Active CN100587007C (en) | 2007-10-26 | 2007-10-26 | Method for enhancing nylon selectivity laser sintering forming element by inorganic nano particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100587007C (en) |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011124588A1 (en) * | 2010-04-09 | 2011-10-13 | Evonik Degussa Gmbh | Polyamide-based polymer powder, use thereof in a molding method, and molded articles made from said polymer powder |
| WO2011124278A1 (en) * | 2010-04-09 | 2011-10-13 | Evonik Degussa Gmbh | Polyamide-based polymer powder, use thereof in a molding method, and molded articles made from said polymer powder |
| CN102311637A (en) * | 2010-07-01 | 2012-01-11 | 湖南华曙高科技有限责任公司 | Nylon composite material used for selective laser sintering and preparation method thereof |
| CN102337021A (en) * | 2010-07-29 | 2012-02-01 | 湖南华曙高科技有限责任公司 | Nylon composite powder material for selective laser sintering |
| CN101445616B (en) * | 2008-12-19 | 2012-11-07 | 东华大学 | Method for preparing porous nylon-titanium dioxide nanometer composite particles |
| CN102146190B (en) * | 2010-02-08 | 2013-03-13 | 南京工业大学 | Preparation method of organic-inorganic composite |
| CN103881371A (en) * | 2014-04-11 | 2014-06-25 | 东北林业大学 | Stone-plastic composite powder for laser sintering 3D manufacturing technology and preparation method of stone-plastic composite powder |
| CN104140668A (en) * | 2014-07-28 | 2014-11-12 | 中国科学院重庆绿色智能技术研究院 | High-fluidity powder material for selective laser sintering |
| CN104250435A (en) * | 2013-06-26 | 2014-12-31 | 合肥杰事杰新材料股份有限公司 | Medical stone modified nylon microsphere material, its preparation method and its application in 3D printing |
| CN104744049A (en) * | 2015-03-23 | 2015-07-01 | 济南大学 | Preparation method of laser sintering 3D printing rapid prototyping silicon nitride powder material |
| CN104910616A (en) * | 2015-06-30 | 2015-09-16 | 广东银禧科技股份有限公司 | Low-temperature nylon powder material for selective laser sintering and preparation method thereof |
| CN104910613A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | 3D printing weather-resistant nylon powder composite material and preparation method thereof |
| CN105038212A (en) * | 2015-07-28 | 2015-11-11 | 湖南航天磁电有限责任公司 | Oxidized graphene-reinforced nylon material as well as preparation method and application thereof |
| CN105238007A (en) * | 2015-09-25 | 2016-01-13 | 四川大学 | Flexible polymer conductor, and preparation method and applications thereof |
| CN105462244A (en) * | 2014-09-10 | 2016-04-06 | 中国科学院理化技术研究所 | Preparation method of carbon fiber reinforced nylon composite micro-powder for selective laser sintering |
| CN105860514A (en) * | 2016-05-11 | 2016-08-17 | 广东银禧科技股份有限公司 | Toughening material for SLS and preparation method of toughening material |
| CN105985632A (en) * | 2015-10-28 | 2016-10-05 | 合肥学院 | Powder material for selective laser sintering and preparation method thereof |
| CN106147220A (en) * | 2016-09-27 | 2016-11-23 | 广东银禧科技股份有限公司 | Long-chain nylon and nylon66 fiber alloy powder material preparation method for SLS |
| CN106243705A (en) * | 2016-09-27 | 2016-12-21 | 广东银禧科技股份有限公司 | Long-chain nylon and the alloy powder material preparation method of nylon 6 for SLS |
| CN106317863A (en) * | 2016-08-22 | 2017-01-11 | 广东银禧科技股份有限公司 | Nylon/carbon nano-tube composite material and preparation method thereof |
| CN108047687A (en) * | 2017-12-14 | 2018-05-18 | 中国科学院宁波材料技术与工程研究所 | A kind of nylon/attapulgite composite granule, its preparation method and application |
| CN108373590A (en) * | 2018-02-02 | 2018-08-07 | 湖南华曙高科技有限责任公司 | The laser sintered preparation method with polyamide compoiste material |
| CN108587135A (en) * | 2018-05-14 | 2018-09-28 | 合肥学院 | A method of preparing photocatalysis sheet material using 3D forming techniques |
| US10106651B2 (en) | 2015-09-02 | 2018-10-23 | Guangdong Silver Age Sci & Tech Co., Ltd | PEEK/NANO-HA composites for SLS and preparation methods thereof |
| CN105754333B (en) * | 2016-03-03 | 2019-01-18 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering nylon powder and preparation method thereof |
| CN110240800A (en) * | 2019-06-28 | 2019-09-17 | 华南理工大学 | A kind of nylon cladding tungsten radiation shield composite material and preparation method |
| CN110283452A (en) * | 2019-06-19 | 2019-09-27 | 徐州腾飞工程塑料有限公司 | A kind of 3D printing stretchy nylon composite material and preparation method |
| CN110475658A (en) * | 2017-01-24 | 2019-11-19 | 捷普有限公司 | Three dimensional printing is melted using more jet streams of nylon 5 |
| CN110467812A (en) * | 2019-08-28 | 2019-11-19 | 贵州省冶金化工研究所 | A kind of manufacturing method of laser 3D printing composite modified nylon 12 |
| CN111218109A (en) * | 2020-03-03 | 2020-06-02 | 贵州森远增材制造科技有限公司 | Glass fiber reinforced nylon powder material for selective laser sintering and manufacturing method thereof |
| CN111356733A (en) * | 2017-10-16 | 2020-06-30 | Eos有限公司电镀光纤*** | Composition for use in an additive manufacturing process |
| CN112745461A (en) * | 2020-12-31 | 2021-05-04 | 河北科技大学 | High-molecular composite powder for selective laser sintering and preparation method thereof |
| CN113733567A (en) * | 2021-08-30 | 2021-12-03 | 华中科技大学 | Nanoparticle/high polymer material composite functional device, preparation and application thereof |
-
2007
- 2007-10-26 CN CN200710053668A patent/CN100587007C/en active Active
Cited By (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445616B (en) * | 2008-12-19 | 2012-11-07 | 东华大学 | Method for preparing porous nylon-titanium dioxide nanometer composite particles |
| CN102146190B (en) * | 2010-02-08 | 2013-03-13 | 南京工业大学 | Preparation method of organic-inorganic composite |
| WO2011124278A1 (en) * | 2010-04-09 | 2011-10-13 | Evonik Degussa Gmbh | Polyamide-based polymer powder, use thereof in a molding method, and molded articles made from said polymer powder |
| WO2011124588A1 (en) * | 2010-04-09 | 2011-10-13 | Evonik Degussa Gmbh | Polyamide-based polymer powder, use thereof in a molding method, and molded articles made from said polymer powder |
| US10406745B2 (en) | 2010-04-09 | 2019-09-10 | Evonik Degussa Gmbh | Polyamide-based polymer powder, use thereof in a molding method, and molded articles made from said polymer powder |
| CN102311637B (en) * | 2010-07-01 | 2016-01-06 | 湖南华曙高科技有限责任公司 | A kind of nylon composite materials for selective laser sintering and preparation method thereof |
| CN102311637A (en) * | 2010-07-01 | 2012-01-11 | 湖南华曙高科技有限责任公司 | Nylon composite material used for selective laser sintering and preparation method thereof |
| CN102337021A (en) * | 2010-07-29 | 2012-02-01 | 湖南华曙高科技有限责任公司 | Nylon composite powder material for selective laser sintering |
| CN102337021B (en) * | 2010-07-29 | 2016-01-06 | 湖南华曙高科技有限责任公司 | A kind of nylon composite powder material for selective laser sintering |
| CN104250435A (en) * | 2013-06-26 | 2014-12-31 | 合肥杰事杰新材料股份有限公司 | Medical stone modified nylon microsphere material, its preparation method and its application in 3D printing |
| CN103881371A (en) * | 2014-04-11 | 2014-06-25 | 东北林业大学 | Stone-plastic composite powder for laser sintering 3D manufacturing technology and preparation method of stone-plastic composite powder |
| CN103881371B (en) * | 2014-04-11 | 2016-08-03 | 东北林业大学 | Laser sintered 3D manufacturing technology stone plastic composite powder end and preparation method thereof |
| CN104140668A (en) * | 2014-07-28 | 2014-11-12 | 中国科学院重庆绿色智能技术研究院 | High-fluidity powder material for selective laser sintering |
| CN105462244B (en) * | 2014-09-10 | 2018-07-06 | 中国科学院理化技术研究所 | A kind of preparation method of selective laser sintering carbon fiber reinforced nylon composite micro-powder |
| CN105462244A (en) * | 2014-09-10 | 2016-04-06 | 中国科学院理化技术研究所 | Preparation method of carbon fiber reinforced nylon composite micro-powder for selective laser sintering |
| CN104744049B (en) * | 2015-03-23 | 2016-10-19 | 济南大学 | A kind of laser sintered 3D prints the preparation of rapid shaping silicon nitride powder powder material |
| CN104744049A (en) * | 2015-03-23 | 2015-07-01 | 济南大学 | Preparation method of laser sintering 3D printing rapid prototyping silicon nitride powder material |
| CN104910613A (en) * | 2015-06-23 | 2015-09-16 | 青岛科技大学 | 3D printing weather-resistant nylon powder composite material and preparation method thereof |
| CN104910616B (en) * | 2015-06-30 | 2017-07-21 | 广东银禧科技股份有限公司 | It is a kind of for low temperature nylon powder material of selective laser sintering and preparation method thereof |
| CN104910616A (en) * | 2015-06-30 | 2015-09-16 | 广东银禧科技股份有限公司 | Low-temperature nylon powder material for selective laser sintering and preparation method thereof |
| WO2017000923A1 (en) * | 2015-06-30 | 2017-01-05 | 广东银禧科技股份有限公司 | Low-temperature nylon powder material for selective laser sintering and preparation method therefor |
| CN105038212A (en) * | 2015-07-28 | 2015-11-11 | 湖南航天磁电有限责任公司 | Oxidized graphene-reinforced nylon material as well as preparation method and application thereof |
| DE112015006691B4 (en) | 2015-09-02 | 2020-06-25 | Guangdong Silver Age Sci & Tech Co., Ltd. | Polyetheretherketone / nano-hydroxyapatite composite material for the SLS technique and its manufacturing process |
| US10106651B2 (en) | 2015-09-02 | 2018-10-23 | Guangdong Silver Age Sci & Tech Co., Ltd | PEEK/NANO-HA composites for SLS and preparation methods thereof |
| CN105238007B (en) * | 2015-09-25 | 2018-12-25 | 四川大学 | A kind of flexible polymer conductor and its preparation method and application |
| CN105238007A (en) * | 2015-09-25 | 2016-01-13 | 四川大学 | Flexible polymer conductor, and preparation method and applications thereof |
| CN105985632A (en) * | 2015-10-28 | 2016-10-05 | 合肥学院 | Powder material for selective laser sintering and preparation method thereof |
| CN105754333B (en) * | 2016-03-03 | 2019-01-18 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering nylon powder and preparation method thereof |
| CN105860514A (en) * | 2016-05-11 | 2016-08-17 | 广东银禧科技股份有限公司 | Toughening material for SLS and preparation method of toughening material |
| CN106317863A (en) * | 2016-08-22 | 2017-01-11 | 广东银禧科技股份有限公司 | Nylon/carbon nano-tube composite material and preparation method thereof |
| CN106317863B (en) * | 2016-08-22 | 2019-04-02 | 广东银禧科技股份有限公司 | A kind of Studies of Polyamide/Carbon Nanotubes Composites and preparation method thereof |
| CN106147220A (en) * | 2016-09-27 | 2016-11-23 | 广东银禧科技股份有限公司 | Long-chain nylon and nylon66 fiber alloy powder material preparation method for SLS |
| CN106147220B (en) * | 2016-09-27 | 2018-06-19 | 广东银禧科技股份有限公司 | For the long-chain nylon of SLS and nylon66 fiber alloy powder material preparation method |
| CN106243705A (en) * | 2016-09-27 | 2016-12-21 | 广东银禧科技股份有限公司 | Long-chain nylon and the alloy powder material preparation method of nylon 6 for SLS |
| CN110475658A (en) * | 2017-01-24 | 2019-11-19 | 捷普有限公司 | Three dimensional printing is melted using more jet streams of nylon 5 |
| US11674013B2 (en) | 2017-10-16 | 2023-06-13 | Eos Gmbh Electro Optical Systems | Composition for use in additive manufacturing processes |
| CN111356733A (en) * | 2017-10-16 | 2020-06-30 | Eos有限公司电镀光纤*** | Composition for use in an additive manufacturing process |
| CN108047687A (en) * | 2017-12-14 | 2018-05-18 | 中国科学院宁波材料技术与工程研究所 | A kind of nylon/attapulgite composite granule, its preparation method and application |
| CN108373590A (en) * | 2018-02-02 | 2018-08-07 | 湖南华曙高科技有限责任公司 | The laser sintered preparation method with polyamide compoiste material |
| CN108587135A (en) * | 2018-05-14 | 2018-09-28 | 合肥学院 | A method of preparing photocatalysis sheet material using 3D forming techniques |
| CN108587135B (en) * | 2018-05-14 | 2021-01-15 | 合肥学院 | Method for preparing photocatalytic sheet by using 3D (three-dimensional) forming technology |
| CN110283452A (en) * | 2019-06-19 | 2019-09-27 | 徐州腾飞工程塑料有限公司 | A kind of 3D printing stretchy nylon composite material and preparation method |
| CN110240800A (en) * | 2019-06-28 | 2019-09-17 | 华南理工大学 | A kind of nylon cladding tungsten radiation shield composite material and preparation method |
| CN110467812A (en) * | 2019-08-28 | 2019-11-19 | 贵州省冶金化工研究所 | A kind of manufacturing method of laser 3D printing composite modified nylon 12 |
| CN110467812B (en) * | 2019-08-28 | 2022-02-11 | 贵州省冶金化工研究所 | Manufacturing method of composite modified nylon 12 for laser 3D printing |
| CN111218109A (en) * | 2020-03-03 | 2020-06-02 | 贵州森远增材制造科技有限公司 | Glass fiber reinforced nylon powder material for selective laser sintering and manufacturing method thereof |
| CN112745461A (en) * | 2020-12-31 | 2021-05-04 | 河北科技大学 | High-molecular composite powder for selective laser sintering and preparation method thereof |
| CN112745461B (en) * | 2020-12-31 | 2022-07-29 | 河北科技大学 | High-molecular composite powder for selective laser sintering and preparation method thereof |
| CN113733567A (en) * | 2021-08-30 | 2021-12-03 | 华中科技大学 | Nanoparticle/high polymer material composite functional device, preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100587007C (en) | 2010-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100587007C (en) | Method for enhancing nylon selectivity laser sintering forming element by inorganic nano particles | |
| CN101148540B (en) | Method for enhancing nylon selectivity laser sintering forming element by clay | |
| CN101418070B (en) | Epoxy resin combination, composite material and preparation method thereof | |
| Chunze et al. | A nanosilica/nylon-12 composite powder for selective laser sintering | |
| CN102786815B (en) | Method for modifying surface of BN (boron nitride) powder, modified BN and polymer composite material | |
| CN100432019C (en) | Manufacture method for nylon tectorial membrane ceramics powder material | |
| CN106380630A (en) | Preparation method and application of chemical-bonded thermally-conductive insulation composite filling material | |
| KR101191590B1 (en) | Aluminous-fiber mass, process for producing the same, and use | |
| CN105985632A (en) | Powder material for selective laser sintering and preparation method thereof | |
| CN104592620B (en) | Resin/graphene conductive plastic master batch as well as preparation method and use thereof | |
| CN111454067B (en) | Transparent ceramic orthodontic bracket and preparation method thereof | |
| CN106243503B (en) | A kind of Aluminum Powder/PP Composite and preparation method thereof | |
| CN109880231A (en) | A kind of preparation method of polypropylene flame redardant plate | |
| CN105111703A (en) | Preparation method of conductive polylactic acid composite for thermal fusion 3D printing | |
| CN107815170A (en) | A kind of graphene coating masterbatch and preparation method | |
| CN105778464A (en) | Graphene/glass fibre reinforced polycarbonate composite material and preparation method thereof | |
| CN100480323C (en) | Bi-maleimide self-lubricating nano-composite material and preparing method thereof | |
| CN101735509B (en) | Micron-nano silicon carbide/polypropylene composite and preparation method thereof | |
| CN103665527A (en) | Special polyolefin resin modified composition for rotational molded products and preparation method thereof | |
| CN106147220B (en) | For the long-chain nylon of SLS and nylon66 fiber alloy powder material preparation method | |
| CN115466486B (en) | Epoxy resin composition and preparation method thereof | |
| CN108299819A (en) | A kind of good counter body material of intensity high-termal conductivity and preparation method thereof | |
| CN101457020B (en) | Nano silicon nitride/epoxy silicone hydride/cyanate ester resin composite material and preparation method thereof | |
| CN104672770A (en) | Heat-resistant carbon fiber-reinforced polyformaldehyde composite material and preparation method thereof | |
| CN109467806A (en) | A kind of preparation method of compound micro-foaming material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |