CN104385608B - A kind of laser sintered polyamide powder and preparation method thereof - Google Patents
A kind of laser sintered polyamide powder and preparation method thereof Download PDFInfo
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- CN104385608B CN104385608B CN201410519283.0A CN201410519283A CN104385608B CN 104385608 B CN104385608 B CN 104385608B CN 201410519283 A CN201410519283 A CN 201410519283A CN 104385608 B CN104385608 B CN 104385608B
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Abstract
A kind of laser sintered polyamide powder and preparation method thereof, it is characterised in that by polyamide solution fast cooling to less than its crystal Precipitation Temperature 15 ~ 20 DEG C, then raise temperature to its crystal Precipitation Temperature, then slow cooling separates out to polyamide powder.Polyamide powder incipient melting temperature Tmo and the difference of FCTA temprature Tco prepared by employing the method increase, powder diameter narrowly distributing, and good fluidity is especially suitable for selective laser sintering.
Description
Technical field
The present invention relates to a kind of polyamide powder and preparation method thereof, the polyamide powder using the method to prepare is the suitableeest
For Selective Laser Sintering.
Background technology
Selective laser sintering is a kind of method manufacturing three-dimensional body by optionally fusing multiple powder bed, should
Method allows not use tool processes only need to pass through the multiple heavy of laser sintering powder according to the 3-D view of object to be produced
Lamination, obtains 3D solid.The method mainly uses thermoplastic polymer to complete.Patent US6136948 and WO9606881
The method that this use polymer powder manufactures three-dimensional body is described in detail.
Silon powder material may be used for Selective Laser Sintering to manufacture three-dimensional body.To polyamide powder
When carrying out selective laser sintering, often polyamide powder is preheating to its FCTA temprature (Tco) and incipient melting temperature
(Tmo) temperature between, this temperature section is referred to as " sintering window ".It is generally acknowledged that the sintering window of powder is big as far as possible,
So can avoid that deformation (or curling) phenomenon occurs during sintering workpiece.It is true that after laser beam effect, sintering
The sample temperature at position is higher than the FCTA temprature Tco of powder, but the colder powder adding last layer new can cause sample portion
Temperature at part is reduced to below Tco, and causes deformation.It addition, the particle diameter distribution of powder particle and mobile performance are to laser
Sintering also has very important impact, centralized particle diameter, and the powder of good fluidity tends to improve laser sintering process
Effect.
Polyamide powder typically uses solvent precipitation to prepare, and will be dissolved in suitable solvent by polyamide, is heated to
Uniform temperature makes material fully dissolve, and then cools down precipitation.In order to obtain, sintering window is bigger, particle diameter distribution is greater concentration of poly-
Amide powder particle, people obtain often through improving sedimentation process.Patent CN1077582C is mentioned and being sunk higher than polyamide
Nucleating step, the then available narrow particle diameter distribution of isothermal precipitation and the Silon of low-porosity is carried out during shallow lake temperature 2 to 20 DEG C
End；Patent WO20130901174 is mentioned by thermoplastic is carried out heat treatment in the temperature close to its fusing point, can improve
Sintering window；Patent CN102399371 refer to a kind of cool-down method by two stages and obtains centralized particle diameter
Polyamide precipitates powder, and its first stage is cooled to higher than Precipitation Temperature 5 ~ 25 DEG C, and second stage is cooled to precipitation temperature again.This
A little methods can preferably improve some laser sintered performance of polyamide powder, but still can not reach the effect making us being satisfied with very much
Really.
Summary of the invention
Therefore the invention provides a kind of polyamide powder and preparation method thereof, use polyamide powder prepared by the method
Fusing point Tm and incipient melting temperature Tmo obtained effective raising, Tmo increases with FCTA temprature Tco difference, powder simultaneously
The narrow diameter distribution at end, good fluidity, it is especially suitable for selective laser sintering.
The present invention can realize by the following method: first dissolves polyamide, then by fast for polyamide solution prompt drop
Temperature, to less than its crystal Precipitation Temperature 15 ~ 20 DEG C, then raises temperature to the temperature that its crystal separates out, then slow cooling is to Silon
End separates out.
During solution fast cooling described in the present invention, polymer segment mobility in polyamide solution can be made
Decrease fast, thus quickly form crystal, control amount of crystals.Subsequently solution is warming up to crystal Precipitation Temperature, can make fast
Crystallizing the most perfect crystal during prompt drop temperature again to dissolve, having crystallized perfect crystal then can become during slow cooling
Nucleus, makes the high polymer not forming crystal grow with it for nucleator, such that it is able to control quantity and the crystalline substance of crystal
Body size.Slow cooling process now ensure that the trend of crystallization, and the mobility of high polymer is relatively strong simultaneously, and crystal can fill
Mitogenetic length and regular array, final precipitation obtains envisioned polyamide powder.
The rate of temperature fall of heretofore described quick cooling stage preferably employs-1.5 DEG C/min ~-2.5 DEG C/min, slow
The rate of temperature fall of slow temperature-fall period preferably employs-0.05 DEG C/min ~-0.15 DEG C/min.
When with laser to polyamide powder selective sintering, it is considered that size is suitable, the grain of narrow distribution range
Footpath is ideal, preferable particle size meansigma methods be the powder of 40 ~ 60 μm as sintered material, according to the polyamide powder of the present invention
Particle diameter is less than 110 μm, and mean particle size is 50 ~ 60 μm.
Polyamide powder incipient melting temperature (Tmo) according to the present invention improves 10 ~ 15 DEG C, and its FCTA temprature is basic
Constant, both differences (sintering window) increase.
Additionally, angle of repose is the important indicator weighing powder flowbility.The flowing angle of repose of polyamide powder in the present invention
All can carry out the most laser sintered when less than 40 °, and according to the polyamide powder of the present invention flow angle of repose be 35 ° ~
38°。
Described polyamide is selected from PA6, PA11, PA12, PA66, PA610, PA612, PA1010, PA1012, PA1212
In one or more.
Cooling involved in the present invention can use the common methods such as cooling water temperature, Precipitation process can use existing side
Method is monitored.
After temperature-fall period of the present invention terminates, by system temperature fast cooling to room temperature, taking-up material carries out solid-liquid and divides
From, pressed powder is dried process, this is the common method of this area dusty material post processing.
The polyamide powder precipitating preparation method simple process that the present invention provides is feasible, uses polyamide prepared by the method
Powder diameter distribution is concentrated, powder good sphericity, and powder flowbility is good, and thermal property is excellent, is particularly suitable for selectivity and swashs
Light sinters.
Accompanying drawing explanation
Fig. 1 is the powder DSC comparison diagram before enforcement 1 and process modification；
Fig. 2 is the powder DSC comparison diagram before enforcement 2 and process modification；
Fig. 3 is the powder DSC comparison diagram before enforcement 3 and process modification；
Fig. 4 is the powder DSC comparison diagram before enforcement 4 and process modification；
Fig. 5 is the powder DSC comparison diagram before enforcement 5 and process modification.
Detailed description of the invention
In following example, particle diameter distribution tests measures according to DIN ISO 3310-1, and thermal performance test uses DSC(poor
Show scanning calorimetry) to test, fluidity testing uses funnel method to measure according to DIN ISO 4324.
Embodiment 1
In 30L magnetic agitation reactor, add PA1212 pellet 3kg, ethanol 24kg, be passed through high pure nitrogen to pressure
0.3MPa, opens stirring；Make temperature in the kettle be increased to 145 DEG C with the speed of 1.5 DEG C/min, be incubated 1h at this temperature；Constant temperature
After end, use cooling water temperature, make temperature in the kettle be down to 90 DEG C with the cooldown rate of 2.0 DEG C/min, reheat in making still and rise
Temperature, to 110 DEG C, then makes temperature in the kettle be down to 90 DEG C with the speed of 0.15 DEG C/min, terminates to precipitation；Strengthen cooling water flow
Make temperature in the kettle be down to room temperature, take out material, centrifugation, powder solid vacuum drying 8h.Gained pressed powder performance is shown in Table 1
And Fig. 1.
This embodiment Sieving and casing is distributed as:
< 32 μm: 0.6%(weight)
< 38 μm: 1.8%(weight)
< 45 μm: 3.9%(weight)
< 53 μm: 22.1%(weight)
< 63 μm: 55.5%(weight)
< 75 μm: 75.8%(weight)
< 90 μm: 92.5%(weight)
< 106 μm: 98.6%(weight)
< 110 μm: 100%(weight)
Powder flowbility is:
Angle of repose: 35.56 °
Collapse angle: 30.12 °
Declinate: 5.44 °
Powder hot property:
Incipient melting temperature Tmo:182.36 DEG C
Melting point onset Tm:190.06 DEG C
Embodiment 2
In 30L magnetic agitation reactor, add PA1212 pellet 3kg, ethanol 24kg, be passed through high pure nitrogen to pressure
0.3MPa, opens stirring；Make temperature in the kettle be increased to 145 DEG C with the speed of 1.5 DEG C/min, be incubated 1h at this temperature；Constant temperature
After end, use cooling water temperature, make temperature in the kettle be down to 90 DEG C with the speed of 2.0 DEG C/min, reheat in making still and be warming up to
108 DEG C, then making temperature in the kettle be down to 90 DEG C with the speed of 0.12 DEG C/min, precipitation terminates；In increasing cooling water flow makes still
Temperature is down to room temperature, takes out material, centrifugation, powder solid vacuum drying 8h.Gained pressed powder performance is shown in Table 1 and Fig. 2.
Embodiment 3
In 30L magnetic agitation reactor, add PA1212 pellet 3kg, ethanol 24kg, be passed through high pure nitrogen to pressure
0.3MPa, opens stirring；Make temperature in the kettle be increased to 145 DEG C with the speed of 1.5 DEG C/min, be incubated 1h at this temperature；Constant temperature
After end, use cooling water temperature, make temperature in the kettle be down to 90 DEG C with the speed of 2.0 DEG C/min, reheat in making still and be warming up to
106 DEG C, then making temperature in the kettle be down to 90 DEG C with the speed of 0.09 DEG C/min, precipitation terminates；In increasing cooling water flow makes still
Temperature is down to room temperature, takes out material, centrifugation, powder solid vacuum drying 8h.Gained pressed powder performance is shown in Table 1 and Fig. 3.
Embodiment 4
In 30L magnetic agitation reactor, add PA6 pellet 3kg, ethanol 24kg, be passed through high pure nitrogen to pressure
0.3MPa, opens stirring；Make temperature in the kettle be increased to 145 DEG C with the speed of 1.5 DEG C/min, be incubated 1h at this temperature；Constant temperature
After end, use cooling water temperature, make temperature in the kettle be down to 90 DEG C with the speed of 2.0 DEG C/min, reheat in making still and be warming up to
106 DEG C, then making temperature in the kettle be down to 90 DEG C with the speed of 0.03 DEG C/min, precipitation terminates；In increasing cooling water flow makes still
Temperature is down to room temperature, takes out material, centrifugation, powder solid vacuum drying 8h.Gained pressed powder performance is shown in Table 1 and Fig. 4.
Embodiment 5
In 30L magnetic agitation reactor, add PA6 pellet 3kg, ethanol 24kg, be passed through high pure nitrogen to pressure
0.3MPa, opens stirring；Make temperature in the kettle be increased to 145 DEG C with the speed of 1.5 DEG C/min, be incubated 1h at this temperature；Constant temperature
After end, use cooling water temperature, make temperature in the kettle be down to 90 DEG C with the speed of 2.0 DEG C/min, reheat in making still and be warming up to
105 DEG C, then making temperature in the kettle be down to 90 DEG C with the speed of 0.01 DEG C/min, precipitation terminates；In increasing cooling water flow makes still
Temperature is down to room temperature, takes out material, centrifugation, powder solid vacuum drying 8h.Gained pressed powder performance is shown in Table 1 and Fig. 5.
Table 1 embodiment 1～5 relevant parameter and powder property
Claims (2)
1. the preparation method of a laser sintered polyamide powder, it is characterised in that by polyamide solution fast cooling to low
In its crystal Precipitation Temperature 15～20 DEG C, then raise temperature to its crystal Precipitation Temperature, then slow cooling separate out to polyamide powder,
The rate of temperature fall in described fast cooling stage is-1.5 DEG C/min～-2.5 DEG C/min, the cooling speed in described slow cooling stage
Rate is-0.05 DEG C/min～-0.15 DEG C/min.
Method the most according to claim 1, it is characterised in that described polyamide be selected from PA6, PA11, PA12, PA66,
One or more in PA610, PA612, PA1010, PA1012, PA1212.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106700529B (en) * | 2015-08-05 | 2019-10-01 | 湖南华曙高科技有限责任公司 | A kind of laser sintered polyamide powder preparation method |
| JP6907224B2 (en) * | 2016-02-19 | 2021-07-21 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | Polyamide composition containing polyamide and additives |
| CN105778128B (en) * | 2016-05-11 | 2017-05-24 | 广东银禧科技股份有限公司 | Method for improving Tf-Tc difference value of polyamide material and polyamide material |
| CN105860105B (en) * | 2016-06-03 | 2021-07-02 | 湖南华曙高科技有限责任公司 | Preparation method of polyamide 6 powder for laser sintering |
| CN108203542B (en) * | 2016-12-16 | 2021-01-05 | 中国石油化工股份有限公司 | Preparation method of nylon powder for selective laser sintering |
| CN107236295B (en) * | 2017-05-19 | 2020-06-30 | 湖南华曙高科技有限责任公司 | Polyamide 610 powder material for selective laser sintering and preparation method thereof |
| CN110951074B (en) * | 2019-11-04 | 2022-02-22 | 江门市德众泰工程塑胶科技有限公司 | Preparation method of polyamide with high crystallization temperature and low gas |
| CN114276566B (en) * | 2021-12-23 | 2023-11-28 | 广东聚石科技研究有限公司 | Nylon powder and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197082A (en) * | 1997-03-05 | 1998-10-28 | 希尔斯股份公司 | Preparation of precipitated polymide powders of narrow particle size distribution and low porosity |
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| JP2008303304A (en) * | 2007-06-07 | 2008-12-18 | Metal Color:Kk | Method for producing crystalline polyamide fine particle |
| CN102399371B (en) * | 2011-10-17 | 2015-11-04 | 湖南华曙高科技有限责任公司 | A kind of polyamide powder preparation method for selective laser sintering |
| DE102012205908A1 (en) * | 2012-04-11 | 2013-10-17 | Evonik Industries Ag | Polymer powder with adapted melting behavior |
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| CN1197082A (en) * | 1997-03-05 | 1998-10-28 | 希尔斯股份公司 | Preparation of precipitated polymide powders of narrow particle size distribution and low porosity |
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Address after: No. 181, Linyu Road, national high tech Industrial Development Zone, Changsha City, Hunan Province, 410205 Patentee after: Hunan Huashu High Tech Co.,Ltd. Address before: No. 181, Linyu Road, national high tech Industrial Development Zone, Changsha City, Hunan Province, 410205 Patentee before: HUNAN FARSOON HIGH-TECH Co.,Ltd. |
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