CN109749442B - Polyimide powder material for selective laser sintering and preparation method and application thereof - Google Patents
Polyimide powder material for selective laser sintering and preparation method and application thereof Download PDFInfo
- Publication number
- CN109749442B CN109749442B CN201811545026.9A CN201811545026A CN109749442B CN 109749442 B CN109749442 B CN 109749442B CN 201811545026 A CN201811545026 A CN 201811545026A CN 109749442 B CN109749442 B CN 109749442B
- Authority
- CN
- China
- Prior art keywords
- laser sintering
- selective laser
- parts
- polyimide
- powder material
- 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.)
- Active
Links
Images
Abstract
The invention relates to a powder material for laser sintering rapid prototyping, a preparation method and application thereof, belongs to the field of rapid prototyping high polymer materials, and particularly relates to a polyimide powder material for selective laser sintering and a preparation method thereof. The material comprises the following raw material components in parts by weight: 70-100 parts of crystalline polyimide resin, 0-30 parts of nano inorganic filler, 0.1-5 parts of polyphenylene sulfide resin and 0.1-3 parts of antioxidant. The material is beneficial to layering in the printing process, and 3D products printed by the polyimide powder material for selective laser sintering can be continuously used at the highest temperature of 330-380 ℃.
Description
Technical Field
The invention relates to a powder material for laser sintering rapid prototyping, a preparation method and application thereof, belongs to the field of rapid prototyping high polymer materials, and particularly relates to a polyimide powder material for selective laser sintering and a preparation method thereof.
Background
Selective Laser Sintering (SLS) technology appeared in the last 80 th century, is a 3D printing technology based on additive manufacturing, can directly manufacture three-dimensional complex structures, and is known as a key technology of "third industrial revolution". Sintered materials are an important factor that limits the development of SLS technology. At present, among various types of laser sintering materials, a high polymer material has the characteristics of overcoming the spheroidizing effect during metal powder sintering and the like due to low forming temperature, low surface energy, higher melt viscosity and low laser power required by sintering, and becomes the SLS material which is most applied and is also the most successful.
At present, the high molecular materials used for SLS forming are mainly thermoplastic polymers and composites thereof. Thermoplastic polymers, in turn, can be divided into crystalline and non-crystalline polymers, which differ greatly in sintering behavior and in the properties of the sintered article. The amorphous polymer has high apparent viscosity and low sintering speed, and cannot form a compact sintered part, so that the mechanical property of the sintered part is poor, and the post-treatment is required. The laser sintering of the crystalline polymer is a melting-solidifying mechanism, the particles are completely melted in the laser irradiation area, the single particles disappear, a compact whole is formed, the density and the strength of an SLS product are similar to those of a molded product, and the SLS product can be directly used as a functional part. Therefore, the SLS technology requires that the polymer has excellent crystallization property and excellent melt crystallization ability, and the polymer should have a melting peak with narrow melting range and high melting enthalpy value during heating and a similar crystallization peak during cooling; the region between the melting peak onset point and the crystallization peak onset point is called the sintering window, and the wider the sintering window, the more beneficial the SLS formation.
Polyimide is a special engineering plastic with excellent comprehensive performance, can resist high temperature of more than 400 ℃, has a long-term use temperature range of 200-300 ℃, has excellent mechanical properties, dielectric properties and the like, and is widely applied to the fields of aviation, aerospace, automobiles, microelectronics and the like. In chinese patent application publication nos. CN 106380847A, CN 106432757a and CN 106433126a, polyimide materials are used in selective laser sintering molding, but these polyimide materials are amorphous and have no crystallinity. When they are sintered by laser, they can not be melted rapidly in a narrow temperature range, and the apparent viscosity is high, so that it is difficult to form compact sintered piece, and the higher porosity can make the mechanical property of sintered piece far lower than that of bulk material. The crystalline polyimide can be rapidly melted when heated to the melting point temperature, has a narrow melting range and lower melt viscosity, and can regulate and control a sintering window. The crystalline polyimide can maintain more excellent mechanical property, solvent resistance, heat stability and dimensional stability at high temperature, and becomes a potential SLS forming material.
In summary, in the prior art, the amorphous polyimide material is mostly used for selective laser sintering molding, the fixed melting temperature and the sintering window are not available, the melt viscosity is high, and the comprehensive performance of a sintered part is poor.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polyimide powder material for selective laser sintering, which has a wider sintering window.
The purpose of the invention can be realized by the following technical scheme: a polyimide powder material for selective laser sintering comprises the following raw material components in parts by weight:
70-100 parts of crystalline polyimide resin
0-30 parts of nano inorganic filler
0.1-5 parts of polyphenylene sulfide resin
0.1-3 parts of antioxidant.
The polyimide powder is a crystalline polymer, has a narrow melting range and a wide sintering window (25-40 ℃), and completely melts particles in the laser sintering process to form a compact whole used as a structural member; adding a proper amount of polyphenylene sulfide which also has crystallinity and extremely low melt viscosity into crystalline polyimide resin, wherein the polyphenylene sulfide resin is rapidly melted, and the addition of the polyphenylene sulfide resin can further reduce the melt viscosity of the whole material; meanwhile, the inorganic filler added in the invention can play a role in reinforcement, and after the crystalline polyimide material is reinforced, the use temperature reaches the melting point temperature of the polymer, which can be 330-380 ℃ at most, and is far higher than that of the amorphous material.
In the polyimide powder material for selective laser sintering, the sintering window of the polyimide powder material for selective laser sintering is 25 to 40 ℃.
In the polyimide powder material for selective laser sintering, the polyimide powder for selective laser sintering is spherical particles having a particle diameter of 20 to 100 micrometers.
In the polyimide powder material for selective laser sintering, the molecular weight of the crystalline polyimide resin is 15000-35000 g/mol; spherical powder solid with the grain diameter of 10-150 microns. The molecular weight of the polyimide resin can affect the sintering window of the polyimide powder for selective laser sintering: the molecular weight is too low, and the mechanical strength of the material cannot be maintained; the molecular weight is too high, the viscosity of the resin melt is too high, the apparent viscosity is high in the sintering process, and sintering molding is not facilitated.
In the above polyimide powder material for selective laser sintering, the crystalline polyimide resin is synthesized from an aromatic dianhydride monomer, an aromatic diamine monomer, and a capping agent. The mass ratio of the aromatic dianhydride monomer, the aromatic diamine monomer and the end capping agent is determined according to the molecular weight and the monomer structure.
Preferably, the aromatic dianhydride monomer is composed of 3,3',4,4' -triphendiether tetracid dianhydride blended with another dianhydride monomer.
More preferably, the molar ratio of 3,3',4,4' -triphendiethanetetracarboxylic dianhydride to another dianhydride is 10/90-99/1.
Further preferably, the another dianhydride is one or more of 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 4,4' -diphenyl ether dianhydride, pyromellitic dianhydride and 2,2',3,3' -triphenyl diether tetracarboxylic dianhydride.
Preferably, the aromatic diamine monomer is 1, 3-bis (4' -aminophenoxy) benzene, 1, 4-bis (4' -aminophenoxy) benzene, 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -biphenyldiamine, 4' -bis (4' -aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 2' -bis [4- (4-aminophenoxyphenyl) ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 1, 3-bis [4- (4-aminophenoxy) benzoyl ] benzene, toluene, xylene, or mixtures thereof, One or more of 1, 4-bis [4- (4-aminophenoxy) benzoyl ] benzene.
Preferably, the end-capping agent is monofunctional pyromellitic anhydride.
In the polyimide powder material for selective laser sintering, the nano inorganic filler is one or more of nano silicon dioxide, nano aluminum oxide, carbon nano tube, graphite, graphene and fullerene.
In the polyimide powder material for selective laser sintering, the polyphenylene sulfide resin is coating grade, and the melt index of the polyphenylene sulfide resin is more than 1500g/10min at 316 ℃ and 5 kg; the polyphenylene sulfide resin is spherical powder solid with the grain diameter of 10-150 microns.
In the polyimide powder material for selective laser sintering, the antioxidant is one or more of antioxidant 1010, antioxidant 1096, antioxidant 1330, antioxidant 168 and antioxidant 628.
The invention also provides a preparation method of the polyimide powder material for selective laser sintering, which comprises the following steps:
(1) cooling the crystalline polyimide resin to-200 to-100 ℃ in a liquid nitrogen tank, crushing by using an ultrafine crusher, and then carrying out constant temperature treatment at 200 to 300 ℃;
(2) cooling the polyphenylene sulfide resin to-50 to-100 ℃ in refrigeration equipment, and crushing by using a superfine crusher;
(3) weighing the crystalline polyimide resin prepared in the step (1), the polyphenylene sulfide resin prepared in the step (2), the nano inorganic filler and the antioxidant according to the weight parts of the raw material components as claimed in claim 1, and putting the raw material components into a high-speed mixer for uniformly mixing;
(4) and (4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering.
In the preparation of the polyimide powder material of the present invention, the crystalline polyimide resin and the polyphenylene sulfide resin are first cooled to a low temperature, because the resin can have a better pulverization effect after cooling, and a powder having a lower particle size can be obtained. The crystalline polyimide resin is cooled to-200 to-100 ℃ and then heated to 200 to 300 ℃ for constant temperature treatment, so that the crushing effect can be improved, and the crystalline polyimide powder can be completely crystallized, so that the crystalline polyimide resin can be rapidly melted in the heating and sintering process, and different thermal histories have great influence on the crystallization performance of a crystalline material.
In the preparation method of the polyimide powder material for selective laser sintering, spherical particles with the particle size of 20-100 microns are screened in the step (4). The powder with small and large particle size is sieved off. In the 3D printing process, the powder spreading process is adopted, and the spherical particles of 20-100 micrometers can enable the powder spreading to be more uniform.
The invention also provides a 3D product, and the 3D product is printed by the polyimide powder material for selective laser sintering. That is, the polyimide powder described above in the present invention is present in the form of a 3D printed article.
Preferably, the continuous use temperature of the 3D product is 330-380 ℃ at most.
Compared with the prior art, the invention has the following advantages:
(1) in the invention, a proper amount of polyphenylene sulfide which also has crystallinity and extremely low melt viscosity is added into crystalline polyimide resin, the polyphenylene sulfide resin is rapidly melted, and the addition of the polyphenylene sulfide resin can further reduce the melt viscosity of the whole material; meanwhile, the inorganic filler added in the invention can play a role in reinforcement, and after the crystalline polyimide material is reinforced, the use temperature reaches the melting point temperature of the polymer, which can be 330-380 ℃ at most, and is far higher than that of the amorphous material.
(2) After the crystalline polyimide resin is cooled and then heated for constant temperature treatment, the crystalline polyimide resin has a narrow melting range and a wide sintering window (25-40 ℃), and particles are completely melted in the laser sintering process to form a compact whole which can be used as a structural member; the resin is cooled and then crushed, and finally the resin is mixed and screened, and the particle size of the powder can meet the requirement of 20-100 microns.
(3) The polyimide powder material for selective laser sintering is beneficial to layering in the printing process, and 3D products printed by the polyimide powder material for selective laser sintering can be continuously used at the highest temperature of 330-380 ℃.
Drawings
FIG. 1 is a graph showing a sintering window of a polyimide powder for selective laser sintering in example 1 of the present invention.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the drawings, but the present invention is not limited to these embodiments.
Example 1
A polyimide powder material for selective laser sintering comprises the following components in parts by weight:
[ crystalline polyimide resin powder 100 parts (synthesized from aromatic dianhydride monomer 55 parts of 3,3',4,4' -triphendiether tetracarboxylic dianhydride, aromatic diamine 32 parts of 1, 4-bis (4 '-aminophenoxy) benzene and 3,4' -diaminodiphenyl ether 12 parts, end-capping agent 1 part of phthalic anhydride, resin number average molecular weight 25000g/mol)
② 0.3 portion of polyphenylene sulfide resin powder (coating grade, melt index (316 ℃/5kg) is 1700g/10min, particle size is 10 μm-150 μm spherical powder solid)
③ 0.5 portion of antioxidant (10100.3 portions and 1680.2 portions)
The preparation method of the polyimide powder material for selective laser sintering comprises the following steps:
(1) cooling the polyimide resin powder to-110 ℃ in a liquid nitrogen tank, then crushing by using an ultrafine crusher, and then processing for 1 hour at the constant temperature of 250 ℃;
(2) cooling polyphenylene sulfide resin powder to-60 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher;
(3) weighing the polyimide resin powder prepared in the step (1), the polyphenylene sulfide resin powder prepared in the step (2) and an antioxidant in parts by weight, and uniformly mixing in a high-speed mixer;
(4) and (4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering, wherein the powder is spherical particles with the particle size (D50) of 60 micrometers.
And (3) testing: testing a sintering window (shown in figure 1) by adopting a differential thermal scanner to obtain a sintering window of 39 ℃; the continuous use temperature of the 3D article is greater than 170 ℃.
Example 2:
a polyimide powder material for selective laser sintering comprises the following components in parts by weight:
crystalline polyimide resin powder 90 parts (synthesized from an aromatic dianhydride monomer of 56 parts of 3,3',4,4' -triphendiether tetracarboxylic dianhydride, an aromatic diamine monomer of 32 parts of 1, 3-bis (4 '-aminophenoxy) benzene and 10 parts of 3,4' -diaminodiphenyl ether, a capping agent of 2 parts of pyromellitic anhydride, and a resin having a number average molecular weight of 25000g/mol)
② 2 parts of polyphenylene sulfide resin powder (coating grade, melt index (316 ℃/5kg) is 1700g/10min, particle size is 10 μm-150 μm spherical powder solid)
③ 10 portions of nano silicon dioxide
0.5 part of antioxidant (10100.4 parts of antioxidant and 1680.1 parts of antioxidant)
The preparation method of the polyimide powder material for selective laser sintering comprises the following steps:
(1) cooling the polyimide resin powder to-130 ℃ in a liquid nitrogen tank, then crushing by using an ultrafine crusher, and then processing at the constant temperature of 260 ℃ for 1 hour;
(2) cooling polyphenylene sulfide resin powder to-60 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher;
(3) according to the parts by weight, putting the polyimide resin powder prepared in the step (1), the polyphenylene sulfide resin powder prepared in the step (2), nano silicon dioxide and an antioxidant into a high-speed mixer, and uniformly mixing;
(4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering, wherein the powder is spherical particles with the particle size (D50) of 65 micrometers;
and (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 29 ℃; the continuous use temperature of the 3D article is greater than 210 ℃.
Example 3:
a polyimide powder material for selective laser sintering comprises the following components in parts by weight:
crystalline polyimide resin powder 90 parts (synthesized from aromatic dianhydride monomer comprising a mixture of 8.5 parts of 3,3',4,4' -triphendiethanetetracarboxylic dianhydride and 35.5 parts of 3,3',4,4' -biphenyltetracarboxylic dianhydride, aromatic diamine monomer comprising 44.5 parts of 1, 3-bis (4' -aminophenoxy) benzene, end-capping agent comprising 1.5 parts of phthalic anhydride, and resin number-average molecular weight 20000g/mol)
② 2 parts of polyphenylene sulfide resin powder (coating grade, melt index (316 ℃/5kg) is 1700g/10min, particle size is 10 μm-150 μm spherical powder solid)
③ 10 portions of carbon nanotubes
0.5 part of antioxidant (10100.2 parts of antioxidant and 1680.3 parts of antioxidant)
The preparation method of the polyimide powder material for selective laser sintering comprises the following steps:
(1) cooling the polyimide resin powder to-120 ℃ in a liquid nitrogen tank, then crushing by using an ultrafine crusher, and then processing at the constant temperature of 300 ℃ for 1 hour;
(2) cooling polyphenylene sulfide resin powder to-60 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher;
(3) according to the parts by weight, putting the polyimide resin powder prepared in the step (1), the polyphenylene sulfide resin powder prepared in the step (2), the carbon nano tube and the antioxidant into a high-speed mixer, and uniformly mixing;
(4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering, wherein the powder is spherical particles with the particle size (D50) of 65 micrometers;
and (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 27 ℃; the continuous use temperature of the 3D article is greater than 210 ℃.
Example 4:
a polyimide powder material for selective laser sintering comprises the following components in parts by weight:
[ crystalline polyimide resin powder 95 parts (a mixture of 10 parts of 3,3',4,4' -triphendiethanetetracarboxylic dianhydride and 37 parts of 3,3',4,4' -biphenyltetracarboxylic dianhydride, synthesized from an aromatic dianhydride and a diamine, 46 parts of 1, 3-bis (4' -aminophenoxy) benzene, 2 parts of phthalic anhydride as a capping agent, and 20000g/mol as a resin number-average molecular weight)
② 1 part of polyphenylene sulfide resin powder [ coating grade, melt index (316 ℃/5kg) is 1700g/10min, particle size is 10 μm-150 μm spherical powder solid ]
(iii) graphene 5 parts
0.8 part of antioxidant (10100.4 parts of antioxidant and 1680.4 parts of antioxidant)
The preparation method of the polyimide powder material for selective laser sintering comprises the following steps:
(1) cooling the polyimide resin powder to-120 ℃ in a liquid nitrogen tank, then crushing by using an ultrafine crusher, and then processing at the constant temperature of 300 ℃ for 1 hour;
(2) cooling polyphenylene sulfide resin powder to-60 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher;
(3) according to the parts by weight, putting the polyimide resin powder prepared in the step (1), the polyphenylene sulfide resin powder prepared in the step (2), graphene and an antioxidant into a high-speed mixer, and uniformly mixing;
(4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering, wherein the powder is spherical particles with the particle size (D50) of 65 micrometers;
and (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 26 ℃; the continuous use temperature of the 3D article is greater than 170 ℃.
Example 5
A polyimide powder material for selective laser sintering comprises the following components in parts by weight:
crystalline polyimide resin powder 90 parts (synthesized from aromatic dianhydride monomer 8.5 parts of 3,3',4,4' -triphendiether tetracarboxylic dianhydride and 35.5 parts of 3,3',4,4' -biphenyltetracarboxylic dianhydride, aromatic diamine monomer 33.5 parts of 1, 4-bis (4 '-aminophenoxy) benzene and 11 parts of 3,4' -diaminodiphenyl ether, end-capping agent 1.5 parts of phthalic anhydride, resin number average molecular weight 25000g/mol, spherical powdery solid with particle size of 10-150 micrometers)
10 parts of nano silicon dioxide
③ 2 parts of polyphenylene sulfide resin powder (coating grade, melt index (316 ℃/5kg) is 1700g/10min, and particle size is 10 μm-150 μm spherical powder solid)
0.5 part of antioxidant (10100.1 parts of antioxidant and 1680.4 parts of antioxidant)
The preparation method of the polyimide powder material for selective laser sintering comprises the following steps:
(1) cooling the polyimide resin powder to-150 ℃ in a liquid nitrogen tank, then crushing by using an ultrafine crusher, and then processing for 1 hour at the constant temperature of 250 ℃;
(2) cooling polyphenylene sulfide resin powder to-80 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher;
(3) weighing the polyimide resin powder prepared in the step (1), the polyphenylene sulfide resin powder prepared in the step (2) and an antioxidant in parts by weight, and uniformly mixing in a high-speed mixer;
(4) and (4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering, wherein the powder is spherical particles with the particle size (D50) of 60 micrometers.
And (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 30 ℃; the continuous use temperature of the 3D article is greater than 210 ℃.
Example 6
The only difference from example 5 is that the composition of the polyimide powder material for selective laser sintering in this example (in parts by weight):
80 parts of crystalline polyimide resin powder (synthesized from 7.8 parts of 3,3',4,4' -triphendiethanetetracarboxylic dianhydride and 31.2 parts of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 27 parts of 1, 4-bis (4 '-aminophenoxy) benzene and 12 parts of 3,4' -diaminodiphenyl ether, an end-capping agent of 2502 parts of phthalic anhydride, and a resin number-average molecular weight of 00g/mol)
② 20 parts of carbon nano tube
③ 3 parts of polyphenylene sulfide resin powder (coating grade, melt index (316 ℃/5kg) is 1700g/10min, and particle size is 10 μm-150 μm spherical powder solid)
And 1 part of antioxidant (10100.5 parts of antioxidant and 1680.5 part of antioxidant).
The polyimide powder material for selective laser sintering in this example was prepared in accordance with the method in example 5.
And (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 30 ℃; the continuous use temperature of the 3D article is greater than 350 ℃.
Example 7
The only difference from example 5 is that the composition of the polyimide powder material for selective laser sintering in this example (in parts by weight):
70 parts of crystalline polyimide resin powder (synthesized from 7 parts of 3,3',4,4' -triphendiether tetracid dianhydride and 27 parts of pyromellitic dianhydride, 7 parts of 4,4 '-diaminodiphenyl ether and 7 parts of 4,4' -biphenyldiamine, 1.5 parts of phthalic anhydride as an end-capping agent, and 30000g/mol of resin number average molecular weight)
② 30 portions of nano alumina
③ 4 portions of polyphenylene sulfide resin powder (coating grade, melt index (316 ℃/5kg) is 1800g/10min, and the grain diameter is 10 mu m-150 mu m spherical powder solid)
And 2 parts of antioxidant (10101 parts of antioxidant and 1681 part of antioxidant).
The polyimide powder material for selective laser sintering in this example was prepared in accordance with the method in example 5.
And (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 25 ℃; the continuous use temperature of the 3D article is greater than 340 ℃.
Example 8
The only difference from example 5 is that the composition of the polyimide powder material for selective laser sintering in this example does not contain nano silica, and the polyimide powder material for selective laser sintering was prepared in the same manner as in example 1, and in the same manner as in example 5.
And (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 30 ℃; the continuous use temperature of the 3D article is greater than 170 ℃.
Example 9
The only difference from example 5 is that this example produced a polyimide powder material for selective laser sintering by the following method:
(1) cooling the polyimide resin powder to-180 ℃ in a liquid nitrogen tank, then crushing by using an ultrafine crusher, and then processing for 2 hours at the constant temperature of 280 ℃;
(2) cooling polyphenylene sulfide resin powder to-60 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher;
(3) weighing the polyimide resin powder prepared in the step (1), the polyphenylene sulfide resin powder prepared in the step (2) and an antioxidant in parts by weight, and uniformly mixing in a high-speed mixer;
(4) and (4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering, wherein the powder is spherical particles with the particle size (D50) of 65 micrometers.
And (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 30 ℃; the continuous use temperature of the 3D article is greater than 210 ℃.
Example 10
The only difference from example 5 is that in this example, in step (1), the polyimide resin powder was cooled to-100 ℃ in a liquid nitrogen tank, then pulverized using an ultra-fine pulverizer, and then treated at a constant temperature of 200 ℃ for 2 hours; cooling the polyphenylene sulfide resin powder to-50 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher; the rest is the same as in example 5.
And (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 30 ℃; the continuous use temperature of the 3D article is greater than 210 ℃.
Example 11
The only difference from example 5 is that in this example, in step (1), the polyimide resin powder was cooled to-200 ℃ in a liquid nitrogen tank, then pulverized using an ultra-fine pulverizer, and then treated at a constant temperature of 300 ℃ for 2 hours; cooling the polyphenylene sulfide resin powder to-100 ℃ in refrigeration equipment, and then crushing by using an ultrafine crusher; the rest is the same as in example 5.
And (3) testing: testing the sintering window by adopting a differential thermal scanner to obtain a sintering window of 30 ℃; the continuous use temperature of the 3D article is greater than 170 ℃.
In conclusion, in the invention, a proper amount of polyphenylene sulfide with crystallinity and extremely low melt viscosity is added into the crystalline polyimide resin, the crystalline polyimide resin is cooled and then heated for constant temperature treatment to prepare the polyimide powder material for selective laser sintering with a wider sintering window, the material is favorable for layering in the printing process, and 3D products printed by the polyimide powder material for selective laser sintering can be continuously used at the temperature of 330-380 ℃.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (8)
1. The polyimide powder material for selective laser sintering is characterized by comprising the following raw material components in parts by weight:
70-100 parts of crystalline polyimide resin
0-30 parts of nano inorganic filler
0.1-5 parts of polyphenylene sulfide resin
0.1-3 parts of an antioxidant;
the sintering window of the polyimide powder material for selective laser sintering is 25-40 ℃;
the preparation method of the polyimide powder material for selective laser sintering comprises the following steps:
(1) cooling the crystalline polyimide resin to-200 to-100 ℃ in a liquid nitrogen tank, crushing by using an ultrafine crusher, and then carrying out constant temperature treatment at 200 to 300 ℃;
(2) cooling the polyphenylene sulfide resin to-50 to-100 ℃ in refrigeration equipment, and crushing by using a superfine crusher;
(3) weighing the crystalline polyimide resin powder prepared in the step (1), the polyphenylene sulfide resin powder prepared in the step (2), nano inorganic filler and antioxidant according to the weight parts of the raw material components, and uniformly mixing the raw material components in a high-speed mixer;
(4) and (4) screening the mixed powder prepared in the step (3) in a mechanical vibration sieve to obtain the polyimide powder material for selective laser sintering.
2. The polyimide powder material for selective laser sintering according to claim 1, wherein the polyimide powder material for selective laser sintering is spherical particles having a particle size of 20 to 100 μm.
3. The polyimide powder material for selective laser sintering according to claim 1, wherein the crystalline polyimide resin has a molecular weight of 15000 to 35000 g/mol; the crystalline polyimide resin is spherical powder solid with the grain diameter of 10-150 microns.
4. The polyimide powder material for selective laser sintering according to claim 1 or 3, wherein the crystalline polyimide resin is synthesized from an aromatic dianhydride monomer, an aromatic diamine monomer, and a capping agent.
5. The polyimide powder material for selective laser sintering according to claim 1, wherein the nano inorganic filler is one or more of nano silica, nano alumina, carbon nanotube, graphite, graphene and fullerene.
6. The polyimide powder material for selective laser sintering according to claim 1, wherein the polyphenylene sulfide resin is coating grade, and the melt index of the polyphenylene sulfide resin is more than 1500g/10min at 316 ℃ and 5 kg; spherical powder solid with the grain diameter of 10-150 microns.
7. A 3D article, wherein the 3D article is printed from the polyimide powder material for selective laser sintering of claim 1.
8. The 3D article according to claim 7, wherein the 3D article has a continuous use temperature of up to 330-380 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811545026.9A CN109749442B (en) | 2018-12-17 | 2018-12-17 | Polyimide powder material for selective laser sintering and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811545026.9A CN109749442B (en) | 2018-12-17 | 2018-12-17 | Polyimide powder material for selective laser sintering and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109749442A CN109749442A (en) | 2019-05-14 |
| CN109749442B true CN109749442B (en) | 2021-07-23 |
Family
ID=66403865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811545026.9A Active CN109749442B (en) | 2018-12-17 | 2018-12-17 | Polyimide powder material for selective laser sintering and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109749442B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI721497B (en) * | 2019-07-17 | 2021-03-11 | 財團法人紡織產業綜合研究所 | Thermoplastic composition and method of preparing the same |
| CN110791096B (en) * | 2019-10-08 | 2022-05-27 | 苏州市新广益电子有限公司 | 5G PPS film and preparation method thereof |
| CN111334105A (en) * | 2020-04-26 | 2020-06-26 | 江苏科环新材料有限公司 | Salt-fog-resistant anticorrosive paint |
| US20220298303A1 (en) * | 2021-03-17 | 2022-09-22 | Zymergen Inc. | Powder composition comprising polyimide particles, three-dimensional polyimde-based body, and method of forming the body |
| CN114479454A (en) * | 2021-12-24 | 2022-05-13 | 长沙新材料产业研究院有限公司 | Polyimide composition and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN104031319A (en) * | 2014-06-30 | 2014-09-10 | 广东银禧科技股份有限公司 | Preparation and application methods of selective laser sintering polypropylene powdery material |
| CN104231626A (en) * | 2013-06-07 | 2014-12-24 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene sulfide powder material used for selective laser sintering, and preparation method thereof |
| CN104760296A (en) * | 2015-03-24 | 2015-07-08 | 浙江工业大学 | Selective laser sintering forming method of heat-conducting functional material |
| CN105985632A (en) * | 2015-10-28 | 2016-10-05 | 合肥学院 | Powder material for selective laser sintering and preparation method thereof |
| CN106380610A (en) * | 2016-09-23 | 2017-02-08 | 江西师范大学 | Method for preparing polyether sulfone powder consumable item for 3D printing of laser sintering and molding |
| CN106380847A (en) * | 2016-09-23 | 2017-02-08 | 江西师范大学 | Method for preparing laser sintering molded three-dimensional (3D) printing polyimide/polyether sulfone/nano carbon powder consumable |
| CN106433126A (en) * | 2016-09-23 | 2017-02-22 | 江西师范大学 | Preparation method of laser sintering and molding 3D (Three-dimensional) printing polyimide/carbon nano tube powder consumable material |
| WO2018122734A1 (en) * | 2016-12-27 | 2018-07-05 | Sabic Global Technologies B.V. | Compositions for use in selective laser sintering and other additive manufacturing processes |
-
2018
- 2018-12-17 CN CN201811545026.9A patent/CN109749442B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231626A (en) * | 2013-06-07 | 2014-12-24 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene sulfide powder material used for selective laser sintering, and preparation method thereof |
| CN103980489A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | Low-melt-viscosity thermoplastic polyimide material and 3D printing moulding method thereof |
| CN104031319A (en) * | 2014-06-30 | 2014-09-10 | 广东银禧科技股份有限公司 | Preparation and application methods of selective laser sintering polypropylene powdery material |
| CN104760296A (en) * | 2015-03-24 | 2015-07-08 | 浙江工业大学 | Selective laser sintering forming method of heat-conducting functional material |
| CN105985632A (en) * | 2015-10-28 | 2016-10-05 | 合肥学院 | Powder material for selective laser sintering and preparation method thereof |
| CN106380610A (en) * | 2016-09-23 | 2017-02-08 | 江西师范大学 | Method for preparing polyether sulfone powder consumable item for 3D printing of laser sintering and molding |
| CN106380847A (en) * | 2016-09-23 | 2017-02-08 | 江西师范大学 | Method for preparing laser sintering molded three-dimensional (3D) printing polyimide/polyether sulfone/nano carbon powder consumable |
| CN106433126A (en) * | 2016-09-23 | 2017-02-22 | 江西师范大学 | Preparation method of laser sintering and molding 3D (Three-dimensional) printing polyimide/carbon nano tube powder consumable material |
| WO2018122734A1 (en) * | 2016-12-27 | 2018-07-05 | Sabic Global Technologies B.V. | Compositions for use in selective laser sintering and other additive manufacturing processes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109749442A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109749442B (en) | Polyimide powder material for selective laser sintering and preparation method and application thereof | |
| TWI712642B (en) | Resin composition containing liquid crystal polymer particles, molded body using the same, and manufacturing method thereof | |
| Feng et al. | Microwave assisted sinter molding of polyetherimide/carbon nanotubes composites with segregated structure for high-performance EMI shielding applications | |
| CN107825621B (en) | Polymer-based micro/nano functional composite spherical powder and preparation method thereof | |
| Xia et al. | Preparation of polypropylene/carbon nanotube composite powder with a solid‐state mechanochemical pulverization process | |
| Kuang et al. | Coupled effect of self-assembled nucleating agent, Ni-CNTs and pressure-driven flow on the electrical, electromagnetic interference shielding and thermal conductive properties of poly (lactic acid) composite foams | |
| Yan et al. | An organically modified montmorillonite/nylon‐12 composite powder for selective laser sintering | |
| Yang et al. | Selective laser sintering of polyamide 12/potassium titanium whisker composites | |
| US20080093577A1 (en) | Metal-carbon nanotube composites for enhanced thermal conductivity for demanding or critical applications | |
| Yang et al. | Solid‐state shear milling method to prepare PA12/boron nitride thermal conductive composite powders and their selective laser sintering 3D‐printing | |
| Wieme et al. | The relevance of material and processing parameters on the thermal conductivity of thermoplastic composites | |
| Chaurasia et al. | Effect of hexagonal boron nitride nanoplatelet on crystal nucleation, mechanical behavior, and thermal stability of high‐density polyethylene‐based nanocomposites | |
| Jin et al. | Self-constructing thermal conductive filler network via reaction-induced phase separation in BNNSs/epoxy/polyetherimide composites | |
| Li et al. | Preparation and properties of polyimide/chopped carbon fiber composite foams | |
| KR102034425B1 (en) | Polymer powder and the preparing method for the same | |
| Hu et al. | Preparation of CNTs/PP@ Gr composites with a segregated structure and enhanced electrical and thermal conductive properties by the Pickering emulsion method | |
| Yudin et al. | Carbon plastics based on thermoplastic polyimide binders modified with nanoparticles | |
| US4942007A (en) | Continuous preparation of shaped long articles of polyimide | |
| Wu et al. | Development of PA6/GO microspheres with good processability for SLS 3D printing | |
| JPS62153349A (en) | Production of resin composition for fiber-reinforced prepreg | |
| Sun et al. | Rapid spheronization of irregular polymeric particles via microwave heating without stirring | |
| Liang et al. | Morphological and structural development of poly (ether ether ketone) during mechanical pulverization | |
| Hosur et al. | Rheology, flexure and thermomechanical characterization of epoxy/CNF nanocomposites: Effect of dispersion techniques | |
| JP2007197717A (en) | Polyarylene sulfide-based resin composition and resin composition for sliding | |
| CN107151363A (en) | A kind of scattered graphene for preparing of utilization electric field strengthens the method for masterbatch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220113 Address after: 315000 1503 (plant), building 1, Jinhai East Road, Shangqiao science and Technology Industrial Park, Xiwu Street Economic Development Zone, Fenghua District, Ningbo City, Zhejiang Province Patentee after: Ningbo Lingke New Material Technology Co.,Ltd. Address before: 315100, Qian 1, Yinzhou District, Ningbo, Zhejiang, Hunan Road Patentee before: Ningbo Institute of Technology, Zhejiang University |