CN105694068A - Polyamide powder and preparation method thereof - Google Patents
Polyamide powder and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The invention relates to the technical field of polyamide preparation, in particular to polyamide powder and a preparation method thereof. The preparation method comprises the following steps: dissolution and heat preservation, wherein polyamide is dissolved and added into a reaction kettle, heating is conducted, and the temperature is raised to be 25-80 DEG C higher than the polyamide precipitation temperature; cooling and powder making, wherein the temperature is lowered to be 14-16 DEG C higher than the polyamide powder precipitation temperature at the speed of 0.5-2.0 DEG C/min, then the temperature is lowered to the polyamide powder precipitation temperature at the speed of 0.1-0.4 DEG C/min, finally the temperature is lowered to the room temperature at the speed of 1-5 DEG C/min, precipitation is conducted, and polyamide precipitate is obtained; drying, wherein the polyamide precipitate is dried, and polyamide powder particles are obtained. The polyamide powder particles prepared through the preparation method are good in size concentration degree, simple and convenient in process and particularly applicable to SLS process requirements, and performance of products is excellent.
Description
Technical field
The present invention relates to polyamide preparing technical field, be specifically related to a kind of polyamide powder and preparation method thereof。
Background technology
Polyamide is also commonly called as nylon, and it is the general name of the high polymer in macromolecular main chain repetitive containing amide group。Nylon is as the engineering plastics of big consumption, it is widely used in the fields such as machinery, automobile, electrical equipment, textile equipment, chemical industry equipment, aviation, metallurgy, becoming indispensable structural material in every profession and trade, its main feature is as follows: 1, excellent mechanical property: the mechanical strength of nylon is high, good toughness；2, self-lubricity, rub resistance are good: nylon has good self-lubricity, and coefficient of friction is little, thus, as its long service life of drive disk assembly；3, excellent thermostability: the heat distortion temperature such as high crystalline nylon such as Stanyl (DSM). is significantly high, can at 150 DEG C the long-term phase use, PA66 is after glass fiber reinforcement, and its heat distortion temperature reaches more than 250 DEG C；4, excellent electrical insulation capability: the volume resistance of nylon is significantly high, breakdown voltage resistant height, is excellent electric, electrical apparatus insulation material；5, excellent against weather；6, water absorption: sucking nylon aqueous is big, and saturation water can reach more than 3%。In the dimensional stability that to a certain degree can also affect product。
Selective laser sintering (SLS) is to adopt infrared laser to make the energy, and the Modeling Material of use mostly is dusty material, is mainly used in working of plastics, casting wax-pattern, exemplar or model。SLS is a kind of 3D printing technique emerging recently。Polyamide is a kind of crystalline polymer, adopts the SLS product that polyamide prepares all to have more excellent performance in intensity, consistency etc., is a kind of macromolecular material being highly suitable for SLS technique。
Solvent precipitation is one of more method preparing nylon powder of using at present, is be dissolved in suitable solvent by nylon, makes material be uniformly distributed in a solvent by high degree of agitation and cools down the Powdered precipitation of precipitation。Nylon powder prepared by existing solvent precipitation is based on the purposes of Nylon powder coating and rotational moulding mostly, and pattern and the particle diameter of nylon powder are had higher requirement by SLS technology, if powder morphology is poor, selective laser sintering process causing, powder paving powder effect is poor, make paving powder out-of-flatness, crack, thus causing that the molding of sintering product is bad。Nylon powder prepared by existing method still suffers from many defects for SLS molding manufacture, as: powder particle shape irregular (such as various abnormity granules), powder diameter size differs, and powder diameter is distributed too wide and powdered heat-resistant difference etc.。Thus affecting the surface roughness of SLS molded article, compact dimensions precision, outside product, powder removes the paving powder effect etc. in the course of processing of easy degree and SLS。
Nylon powder prepared by existing method in order to be able to obtain the powder particle of centralized particle diameter in case be applicable to SLS sintering, generally require and powder is carried out sieve classification, the smaller particle (grain diameter is below 20 microns) in powder and larger particles (grain diameter is more than 80 microns) are removed。And the problem in order to make up the irregular poor fluidity caused of powder particle, it is necessary to add substantial amounts of flow promortor, to obtain paving powder effect good in SLS sintering process。Or in solvent method pulverizing process, add a certain amount of butanone, and so that powder particle regular appearance, there is good sphericity, but the interpolation of butanone can damage again the antioxidant effect of material, powder can be made to turn yellow, part performance is deteriorated。
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the preparation method that it is an object of the invention to provide a kind of polyamide powder, adopt the polyamide powder granule good sphericity that this preparation method obtains, powder particle size concentration degree is good, simple process, being particularly suited for the technological requirement of SLS, part performance is excellent。
Another goal of the invention of the present invention is in that to provide a kind of polyamide powder, and this polyamide powder granule good sphericity, powder particle size concentration degree is good, is particularly suited for the technological requirement of SLS, and part performance is excellent。
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of polyamide powder, comprises the following steps:
Dissolve insulation: dissolved by polyamide and join in reactor, be heated to higher 25-80 DEG C than polyamide temperature Precipitation Temperature；
Three sections of cooling powder process:
First stage: be cooled to the temperature than high 20-30 DEG C of polyamide powder Precipitation Temperature with the speed of 0.5-2.0 DEG C/min；
Second stage: be cooled to the Precipitation Temperature of polyamide powder with the speed of 0.1-0.4 DEG C/min；
Phase III: be finally cooled to room temperature with the speed of 1-5 DEG C/min, precipitate out polyamide precipitation。
The rate of temperature fall of three phases must be strict controlled in certain scope, and the sphericity of the polyamide powder obtained beyond this scope does not reach the effect of the present invention。
The Precipitation Temperature of polyamide powder can be measured by conventional method, then carries out triphasic cooling powder process further according to its Precipitation Temperature, and the powder diameter obtained is uniform, sphericity is high。
This processing step is related to the success of powder process, the dusty material prepared beyond this temperature process scope, is be difficult to use in the 3D SLS technique printed。
The present invention utilizes indirect cool-down method to reach a good powder particle sphericity and the particle size distribution relatively concentrated。If directly being lowered the temperature by inner chamber, it is difficult to have good sphericity and centralized particle diameter degree。
Dry: polyamide to be precipitated out precipitation and is dried and obtains polyamide powder granule, can also be centrifuged before dry filtering, obtain Silon, obtain powder particle after drying。
Wherein, having nitrogen protection in described dissolving incubation step in reactor, temperature retention time is 0.5-1.5 hour。Strand, in order to make material fully dissolve at high temperature under high pressure, is also had impact by the purpose of insulation simultaneously, improves the sphericity of polyamide powder。
Wherein, in described dissolving incubation step, the pressure in reactor is 0.8-1.2MPa, and the forming degree effect of polyamide powder is had a significant effect by pressure, and the Stress control technique in reactor is simple, very easily realizes。
Wherein, uniform stirring solution in reactor in described cooling pulverizing process, mixing speed is 100-1000r/min, it is preferred to 450-550r/min。Uniform stirring can make the temperature in reactor more uniform, and without influence on the Precipitation of polyamide。
Wherein, cooling milling step utilize the conduction oil temperature controlling reactor to reach temperature control purpose。Carrying out temperature control by controlling the conduction oil temperature of reactor, temperature in the kettle is more uniform, and in entirety cooling in temperature-fall period, the sphericity and the uniform concentration degree that obtain polyamide powder can be better。
Wherein, in described dissolving incubation step, polyamide utilizes organic solvent dissolution, and organic solvent is alcohols solvent or amide solvent, it is preferred to use Methanamide, dimethylformamide。The ratio mixed solvent of the mixed proportion of solvent and polyamide polyamide solvent method conventionally。
Wherein, described polyamide is any one in PA6, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, PA1212。
Wherein, described dissolving incubation step can also add nucleation-accelerant, contribute to the powder particle nucleating effect in powder precipitation process。
Wherein, described nucleation-accelerant is metal-oxide, the addition of nucleation-accelerant is the 0.1-2% of nylon addition, more preferably 0.5-1%, the addition of nucleation-accelerant can reduce the control requirement of rate of temperature fall technique in temperature-fall period, production technology is easy to control, and product yields is higher, it is preferred to use titanium dioxide, molybdenum oxide。
Wherein, it is also possible to add flow promortor, such as gas-phase silica, gaseous oxidation aluminum etc., it is preferred to use aerosil, making the material good fluidity in reactor, be heated evenly, Precipitation is more stable, and the polyamide sphericity obtained is high and the uniformity is concentrated more。Its addition is the 0.1-2%, more preferably 0.5-1% that polyamide powder adds quality。
A kind of polyamide powder utilizing said method to prepare, powder particle size is evenly distributed, and grain diameter is about 40-60 μm, and by laser particle size measurement, its D10 is more than 30 μm, and D50 is at 55-65 μm, and D75 is less than 80 μm。Finding in actual applications, identical nylon material, powder morphology is closer to spherical, powder particle size ratio is more uniform, particle size distribution is more concentrated, and its powder flowbility is more good, and bulk density is more big, and apparent density of powder is more high, good fluidity, then part performance is more good, and article surface is more smooth, product dimensional accuracy is more high, and the removal of article surface powder is more easy。Can the powder diameter distribution of the present invention be an important parameter of inspection dusty material performance, be directly connected to the global formation performance that be smoothed out processing and processing product。
By on the veneer of poly-phthalein amine powder horizontal plate in room, maintain certain temperature, according to the geometry corresponding to article, laser makes the powder particle agglomeration of the difference at powder bed, such as by means of computer, this computer has the shape of article in its memorizer and restores this shape with the form of thin slice。Then, make the value that this horizontal plate reduces corresponding to layer thickness, then deposit new powder bed, and this laser makes powder particle agglomeration according to the geometry of the new thin slice corresponding to these article。Repeat this process until prepared by whole article。
This chamber interior obtain by polyamide powder around article, it does not have therefore the part being agglomerated keeps powder type。Then this assembly is leniently cooled down, after cooling completely, by article from powder separation out, this powder can be used further to other operation, recycling rate of waterused is high, and the sphericity of polyamide powder is more good, the uniformity is more high, the product degree of accuracy obtained will be more high, the polyamide powder of the present invention can prepare various three-dimensional article by laser beam (i.e. selective laser sintering) agglomeration process, such as master mold and model, especially at automobile, boats and ships, aviation, space flight, medical science (artificial limb, auditory system, cell tissue etc.), fabric, clothes, fashionable dress, decoration, the shell of electronics, phone, home automation, in information technology and lighting field。
The beneficial effects of the present invention is: the method for a kind of powder morphology sphericity and powder particle size concentration degree for improving polyamide powder provided by the invention, it is with nylon pellet for raw material, adopt solvent method powder process, through dissolving, cooling, precipitation obtains sphericity height and the powder particle of grain size concentration。
The present invention utilizes indirect sublevel segmentation cool-down method, the polyamide powder pattern sphericity obtained is high, powder particle size is uniform, centralized particle diameter, and therefore powder flowbility is good, bulk density area is big, apparent density is high, and part performance is good, is particularly suited for SLS technique, the degree of accuracy of product is high, and after product, powder is easily removed and recycled and reused。
The present invention another advantage is that: the polyamide powder particle size distribution of the present invention is uniform, and grain diameter is 40-60 μm, and by laser particle size measurement, its D10 is more than 30 μm, and D50 is at 55-65 μm, and D75 is less than 80 μm。
The polyamide powder pattern of the present invention is close to spherical, and powder particle size is uniform, centralized particle diameter, and its powder flowbility is good, bulk density is big, good fluidity, and part performance is good, article surface is smooth, and product dimensional accuracy is high, and article surface powder is removed and is easy for。
Accompanying drawing explanation
Fig. 1 is the granule-morphology figure that the polyamide powder obtained by the embodiment of the present invention 1 amplifies 4 times under the microscope；
Fig. 2 is the granule-morphology figure that the polyamide powder obtained by comparative example of the present invention amplifies 4 times under the microscope。
Detailed description of the invention
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment and accompanying drawing 1-2, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention。
Embodiment 1
The preparation method of a kind of polyamide powder, comprises the following steps:
Dissolve insulation: joined by the Methanamide of PA12 and 10 parts by volume of 1 weight portion in the reactor of nitrogen protection; stir with the speed of 500r/min; heat the mixture to higher than PA12 powder Precipitation Temperature 40 DEG C insulation 1 little time, reactor pressure is 1.0MPa。
Cooling powder process: be cooled to 125 DEG C with the speed of 0.5 DEG C/min, be then cooled to PA12 Precipitation Temperature 100 DEG C with the speed of 0.18 DEG C/min, is finally cooled to room temperature with the speed of 2.8 DEG C/min, precipitates out and obtains PA12 precipitation。
Dry: polyamide to be precipitated out precipitation and is centrifuged, dry obtains PA12 powder particle。The polyamide powder material powder granule of gained is spherical particle, good sphericity, and granule is uniform, granularity is concentrated, and grain diameter is 40-60 μm, by laser particle size measurement, its D10 is 36.9 μm, and D25 is 48.7 μm, D50 is 65.3 μm, and D75 is 80 μm, and D90 is 98.2 μm。
Embodiment 2
The preparation method of a kind of polyamide powder, comprises the following steps:
Dissolve insulation: the titanium dioxide of PA6 pellet, 1% utilizes Methanamide dissolve in the reactor joining nitrogen protection; stir with the speed of 450r/min; heat the mixture to higher than PA6 powder Precipitation Temperature 40 DEG C insulation 0.5 little time, reactor pressure is 1.2MPa。
Cooling powder process: be cooled to the temperature than high 20 DEG C of PA6 powder Precipitation Temperature with the speed of 0.5 DEG C/min, be then cooled to the Precipitation Temperature of PA6 powder with the speed of 0.4 DEG C/min, is finally cooled to room temperature with the speed of 5 DEG C/min, precipitates out and obtains PA6 precipitation。
Dry: polyamide to be precipitated out precipitation and is centrifuged, dry obtains PA6 powder particle。The pattern powder particle of the Silon powder material of gained is spherical particle, good sphericity, and granule is uniform, granularity is concentrated, grain diameter is about 40-60 μm, and by laser particle size measurement, its D10 is 33.7 μm, D25 is 43.9 μm, D50 is 58.6 μm, and D75 is 77.2 μm, and D90 is 96.7 μm。
Embodiment 3
The preparation method of a kind of polyamide powder, comprises the following steps:
Dissolve insulation: utilize Methanamide to dissolve in the reactor joining nitrogen protection PA11 pellet, the titanium dioxide of 0.1%, the aerosil of 1%; stir with the speed of 500r/min; heat the mixture to higher than PA11 powder Precipitation Temperature 25 DEG C insulation 1.5 little time, reactor pressure is 0.8MPa。
Cooling powder process: be cooled to the temperature than high 20 DEG C of PA11 powder Precipitation Temperature with the speed of 2.0 DEG C/min, be then cooled to the Precipitation Temperature of PA11 powder with the speed of 0.1 DEG C/min, is finally cooled to room temperature with the speed of 1 DEG C/min, precipitates out and obtains PA11 precipitation。
Dry: polyamide to be precipitated out precipitation and is centrifuged, dry obtains PA11 powder particle。The visible powder particle of pattern of the Silon powder material of gained is spherical particle, good sphericity, and granule is uniform, granularity is concentrated, grain diameter is about 40-60 μm, and by laser particle size measurement, its D10 is 33.5 μm, D25 is 42.5 μm, D50 is 56.2 μm, and D75 is 73.8 μm, and D90 is 92.5 μm。
Embodiment 4
The preparation method of a kind of polyamide powder, comprises the following steps:
Dissolve insulation: the titanium dioxide of PA1012 pellet, 1% utilizes Methanamide dissolve and joins in the reactor of nitrogen protection, stir with the speed of 450r/min, heat the mixture to higher than PA1012 powder Precipitation Temperature 80 DEG C be incubated 0.5 little time。
Cooling powder process: be cooled to the temperature than high 30 DEG C of PA6 powder Precipitation Temperature with the speed of 0.5 DEG C/min, be then cooled to the Precipitation Temperature of PA1012 powder with the speed of 0.4 DEG C/min, is finally cooled to room temperature with the speed of 5 DEG C/min, precipitates out and obtains PA1012 precipitation。
Dry: polyamide to be precipitated out precipitation and is centrifuged, dry obtains PA1012 powder particle。The pattern of the Silon powder material of gained is shown in described in Fig. 2, in figure, visible powder particle is spherical particle, good sphericity, and granule is uniform, granularity is concentrated, grain diameter is 40-60 μm, pass through laser particle size measurement, its D10 is 35 μm, and D25 is 45 μm, and D50 is 57.1 μm, D75 is 77.2 μm, and D90 is 94.7 μm。
Embodiment 5
The preparation method of a kind of polyamide powder, comprises the following steps:
Dissolve insulation: the titanium dioxide of PA612 pellet, 1% utilizes Methanamide dissolve and joins in the reactor of nitrogen protection, stir with the speed of 480r/min, heat the mixture to higher than PA12 powder Precipitation Temperature 60 DEG C be incubated 0.8 little time。
Cooling powder process: be cooled to the temperature than high 25 DEG C of PA6 powder Precipitation Temperature with the speed of 1 DEG C/min, be then cooled to the Precipitation Temperature of PA612 powder with the speed of 0.2 DEG C/min, is finally cooled to room temperature with the speed of 2 DEG C/min, precipitates out and obtains PA612 precipitation。
Dry: polyamide to be precipitated out precipitation and is centrifuged, dry obtains PA612 powder particle。The pattern powder particle of the Silon powder material of gained is spherical particle, good sphericity, and granule is uniform, granularity is concentrated, grain diameter is about 40-60 μm, and by laser particle size measurement, its D10 is 34.1 μm, D25 is 42.9 μm, D50 is 56.8 μm, and D75 is 76.8 μm, and D90 is 94.6 μm。
Embodiment 6
The preparation method of a kind of polyamide powder, comprises the following steps:
Dissolve insulation: the titanium dioxide of PA6 pellet, 1% utilizes Methanamide dissolve and joins in the reactor of nitrogen protection, stir with the speed of 450r/min, heat the mixture to higher than PA6 powder Precipitation Temperature 50 DEG C be incubated 0.5 little time。
Cooling powder process: be cooled to the temperature than high 28 DEG C of PA6 powder Precipitation Temperature with the speed of 0.5 DEG C/min, be then cooled to the Precipitation Temperature of PA6 powder with the speed of 0.4 DEG C/min, is finally cooled to room temperature with the speed of 5 DEG C/min, precipitates out and obtains PA6 precipitation。
Dry: polyamide to be precipitated out precipitation and is centrifuged, dry obtains PA6 powder particle。The pattern powder particle of the Silon powder material of gained is spherical particle, good sphericity, and granule is uniform, granularity is concentrated, and grain diameter is 40-60 μm, by laser particle size measurement, its D10 is 35.8 μm, and D25 is 45.7 μm, D50 is 63.2 μm, and D75 is 79.3 μm, and D90 is 97.3 μm。
Comparative example 1
The Methanamide of PA12 and 10 parts by volume of 1 weight portion is dissolved in the reactor joining nitrogen protection, stirs with the speed of 450r/min, heat the mixture to 150 DEG C and be incubated 0.5 hour。
Cooling powder process: be cooled to 128 DEG C with the speed of 0.1 DEG C/min, be then cooled to 100 DEG C with the speed of 0.5 DEG C/min, is finally cooled to room temperature with the speed of 2.5 DEG C/min, precipitates out and obtains PA12 precipitation。
Dry: polyamide to be precipitated out precipitation and is centrifuged, dry obtains polyamide powder granule。The pattern powder of the Silon powder material of gained is shown in that in Fig. 2, figure, visible powder morphology is very poor, and powder particle is irregularly shaped, and grain edges is very coarse, and fractionlet granule is more。The particle size distribution simultaneously recorded through particle size distribution measuring instrument shows, its little granule and bulky grain are more, and its D10 is 11.9 μm, and D25 is 22.6 μm, and D50 is 28.9 μm, and D75 is 57.6 μm, and D90 is 106.5 μm。
By contrast, the polyamide granules powder prepared by the present invention is shown in Fig. 1, and the visible powder particle of pattern is spherical particle, good sphericity, and granule is uniform, granularity is concentrated, and grain diameter is 40-60 μm。
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise。
Claims (10)
1. the preparation method of a polyamide powder, it is characterised in that: comprise the following steps:
Dissolve insulation: dissolved by polyamide and join in reactor, be heated to higher 25-80 DEG C than polyamide temperature Precipitation Temperature；
Three sections of cooling powder process:
First stage: be cooled to the temperature than high 20-30 DEG C of polyamide powder Precipitation Temperature with the speed of 0.5-2.0 DEG C/min；
Second stage: be cooled to the Precipitation Temperature of polyamide powder with the speed of 0.1-0.4 DEG C/min；
Phase III: be finally cooled to room temperature with the speed of 1-5 DEG C/min, precipitate out polyamide precipitation；
Dry: polyamide to be precipitated out precipitation and is dried and obtains polyamide powder granule。
2. the preparation method of a kind of polyamide powder according to claim 1; it is characterized in that: described dissolving incubation step has nitrogen protection in reactor; temperature retention time is 0.5-1.5 hour, and in described dissolving incubation step, the pressure in reactor is 0.8-1.2MPa。
3. the preparation method of a kind of polyamide powder according to claim 1, it is characterised in that: uniform stirring solution in reactor in described cooling pulverizing process, mixing speed is 100-1000r/min。
4. the preparation method of a kind of polyamide powder according to claim 1, it is characterised in that: cooling milling step utilize the conduction oil temperature controlling reactor to reach temperature control purpose。
5. the preparation method of a kind of polyamide powder according to claim 1, it is characterised in that: in described dissolving incubation step, polyamide utilizes organic solvent dissolution, and consumption of organic solvent is 8-30 times of volume of polyamide weight。
6. the preparation method of a kind of polyamide powder according to claim 5, it is characterised in that: described organic solvent is alcohols solvent or amide solvent。
7. the preparation method of a kind of polyamide powder according to claim 1, it is characterised in that: described polyamide is any one in PA6, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, PA1212。
8. the preparation method of a kind of polyamide powder according to claim 1, it is characterised in that: can also adding auxiliary agent in described dissolving incubation step, the addition of auxiliary agent is the 0.1-2% that polyamide adds quality。
9. the preparation method of a kind of polyamide powder according to claim 7, it is characterised in that: described auxiliary agent is the combination of any one or two kinds of in nucleation-accelerant or flow promortor。
10. the polyamide powder that a method according to any one of claim 1-9 prepares, it is characterised in that: powder particle size is evenly distributed, and by laser particle size measurement, its D10 is more than 30 μm, and D50 is at 55-65 μm, and D75 is less than 80 μm。
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106671416A (en) * | 2016-12-28 | 2017-05-17 | 华中科技大学 | Distillation cooling device and method for nylon powder for SLS |
| CN107189087A (en) * | 2017-06-01 | 2017-09-22 | 深圳市业天科技有限公司 | A kind of preparation method and applications of PLA powder for selective laser sintering |
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| CN106671416A (en) * | 2016-12-28 | 2017-05-17 | 华中科技大学 | Distillation cooling device and method for nylon powder for SLS |
| JP2020506991A (en) * | 2017-02-01 | 2020-03-05 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing polyamide powder by precipitation |
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| CN107236295A (en) * | 2017-05-19 | 2017-10-10 | 湖南华曙高科技有限责任公司 | A kind of selective laser sintering polyamide 610 dusty material and preparation method |
| CN107189087A (en) * | 2017-06-01 | 2017-09-22 | 深圳市业天科技有限公司 | A kind of preparation method and applications of PLA powder for selective laser sintering |
| US10889694B2 (en) | 2018-07-06 | 2021-01-12 | Taiwan Green Point Enterprises Co., Ltd. | Method and composition for preparing polyamide powders |
| CN110684213A (en) * | 2018-07-06 | 2020-01-14 | 绿点高新科技股份有限公司 | Method for producing polyamide powder and composition for producing polyamide powder |
| CN109199651A (en) * | 2018-09-22 | 2019-01-15 | 广东兰湾智能科技有限公司 | Artificial limb socket of myoelectric hand |
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| CN110885456A (en) * | 2019-12-13 | 2020-03-17 | 万华化学集团股份有限公司 | Nylon powder with narrow particle size distribution, preparation method thereof and application thereof in 3D printing |
| CN110885456B (en) * | 2019-12-13 | 2022-07-12 | 万华化学集团股份有限公司 | Nylon powder with narrow particle size distribution, preparation method thereof and application thereof in 3D printing |
| CN111171345A (en) * | 2019-12-31 | 2020-05-19 | 广东聚石科技研究有限公司 | Preparation method of polyamide microspheres |
| CN114456409A (en) * | 2021-12-28 | 2022-05-10 | 常州增材制造研究院有限公司 | PA11 material for selective laser sintering 3D printing and preparation method thereof |
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