Sinterable semi-crystalline powder and near-fully dense article formed therewith

• US 5,342,919 A
• Filed: 11/23/1992
• Issued: 08/30/1994
• Est. Priority Date: 11/23/1992
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: DTM Corporation (3D Systems Corporation)
• Inventors: Ng, Hendra, Dickens, Elmer D. Jr., Lee, Biing Lin, Magistro, Angelo J., Taylor, Glenn A.
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): Mosley, T.
• Application Number:
  US07/980,004
• Time in Patent Office: 645 Days
• Field of Search: 528/310, 528/323, 156/62.2
• US Class Current: 528/323
• CPC Class Codes: B29C 2035/0838 using laser
• CPC Class Codes: B29C 41/003 characterised by the choice of material
• CPC Class Codes: B29C 64/153 using layers of powder being selectively joined, e.g. by selective laser sintering or melting
• CPC Class Codes: B29C 67/04 Sintering combined with compression B29C43/00
• CPC Class Codes: B29K 2023/00 Use of polyalkenes or derivatives thereof as moulding material
• CPC Class Codes: B29K 2023/06 PE, i.e. polyethylene
• CPC Class Codes: B29K 2023/12 PP, i.e. polypropylene
• CPC Class Codes: B29K 2059/00 Use of polyacetals , e.g. POM, i.e. polyoxymethylene or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2067/006 PBT, i.e. polybutylene terephthalate
• CPC Class Codes: B29K 2077/00 Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2079/00 Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain , not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
• CPC Class Codes: B29K 2995/0094 Geometrical properties
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08J 3/12 Powdering or granulating
• CPC Class Codes: C08J 9/24 by surface fusion and bonding of particles to form voids, e.g. sintering of expandable particles C08J9/232

Abstract

A laser-sinterable powder product has been prepared having unique properties which allow the powder to be sintered in a selective laser sintering (SLS) machine to form a sintered part which is near-fully dense. For most purposes, the sintered part is indistinguishable from another part having the same dimensions made by isotropically molding the powder. In addition to being freely flowable at a temperature near its softening temperature, the powder has a two-tier distribution in which substantially no primary particles has an average diameter greater than 180μm, provided further that the number average ratio of particles smaller than 53μm is greater than 80%, the remaining larger particles being in the size range from 53μm to 180μm. When the powder is a semicrystalline synthetic resin having a number average molecular weight in the range from about 30,000 to 500,000; a molecular weight distribution M_w /M_n in the range from 1 to 5; and, provides a window of sinterability in the temperature range from near the powder'"'"'s softening temperature T_s to its caking temperature T_c, it is sintered layer-upon layer to form a near-fully dense part of arbitrary shape.

Claims

1. A laser-sinterable powder product, adapted to be sintered in a selective laser sintering machine to form a sintered part, said powder consisting essentially of an unblended .polymer which provides signs of crystalline order under X-ray examination, and shows a crystalline melting point Tm as well as a glass transition temperature Tg, said polymer having a two-tier particle size distribution said powder having the following properties:

(a) freely-flowable semi-crystalline powder having a crystallinity in the range from 10-90% measured by [DSC] differential scanning calorimetry;

(b) a major portion by weight of the powder having a sphericity in the range from greater than 0.5 to 0.9, and a two-tier distribution in which substantially no primary particles has an average diameter greater than 180μ

m, provided further that the number average ratio of particles smaller than 53μ

m is greater than 80%, the remaining larger particles being in the size range from 53μ

m to 180μ

m;

a layer of said powder no more than 250μ

m deep absorbing essentially all infra-red energy beamed therethrough at a wavelength of 10.6μ

m, and a layer of said powder no more than 180μ

m thick absorbing more than 50% of said energy;

(c) a number average molecular weight in the range from about 30,000 to 500,000, and a molecular weight distribution M_w /M_n in the range from 1 to 5; and

, (d) a window of sinterability in the temperature range from near said powder'"'"'s softening temperature T_s to said powder'"'"'s caking temperature T_c ;

whereby when said powder is sintered layer-wise in said window of sinterability to form a slice, it will not curl.

2. The laser-sinterable powder product of claim 1, essentially all of which has a sphericity in the range from greater than 0.5 to 0.9, and is freely flowable near said softening temperature T_s ±

5°

C.;

said number average ratio of particles smaller than 53μ

m is greater than 90%, said crystallinity is in the range from 15% to 60%, said molecular weight distribution is in the range from 1.2 to 3, said window of sinterability is in the range from 2°

-25°

C., and, said powder'"'"'s storage modulus G'"'"' _c is in the range from 1×

10⁶ dynes/cm² to 3×

10⁶ dynes/cm² when the temperature of said powder being sintered exceeds T_c in less time than is required to melt contiguous large particles >

53μ

m.

3. The laser-sinterable powder of claim 2 wherein the mean primary particle diameter is in the range from 80μ

m-100μ

m.

4. The laser-sinterable powder of claim 3 wherein said powder is selected from the group consisting of Nylons 6, 11, 12, polybutylene terephthalate, and polyacetal and said window of sinterability is in the range from 5°

-20°

C.

15. The laser-sinterable powder product of claim 2 wherein said crystallinity is in the range from 15-60%.

5. A bed of a laser-sinterable powder in a selective laser sintering zone, said bed consisting essentially of particles of an unblended synthetic resinous material which provides signs Of crystalline order under X-ray examination, and shows a crystalline melting point Tm as well as a glass transition temperature Tg, said material in particulate form having a two-tier particle size distribution from which powder, a laser-sintered part is formed and removably embedded in said bed, said powder being a freely-flowable semi-crystalline powder having primary particles in the size range smaller than 180μ

m and a sphericity in the range from greater than 0.5 to 0.9, provided further that the number average ratio of particles smaller than 53μ

m is greater than 80%, the remaining larger particles being in the size range from 53μ

m to 180μ

m;

having a crystallinity measured by differential scanning calorimetry in the range from 10% to 90%, and when sufficiently heated, having a softening temperature T_s, and a caking temperature T_c from about 2°

-25°

C. above T_s , and, when sintered, has a melt viscosity in the range from 100-10⁴ poise (10-1000 Pa-sec) when said powder'"'"'s temperature as it is being sintered, exceeds T_c in less time than is required to melt contiguous large particles >

53μ

m;

said bed having a porosity in the range from 0.4 to 0.55, and providing, during operation, a temperature profile defined by sequential positive and negative temperature gradients in a vertical plane through upper and lower portions of said bed, respectively, when said bed'"'"'s uppermost layer, less than 25082 m thick, is in the range from near said T_s to said T_c ;

said bed maintaining said positive temperature gradient from said upper surface to a maximum temperature in a horizontal zone in which said sintered part lies, said upper temperature gradient being in the range 0.2°

C./cm (0.5°

C./in) to 2°

C./cm (5°

C./in); and

, said bed maintaining a negative temperature gradient from said maximum temperature to the bottom of said bed, said negative lower temperature gradient being in the range from 0.2°

C./cm (0.5°

C./in) to 2°

C./cm (5°

C./in).

6. A bed of a laser-sinterable powder in a selective laser sintering zone, said bed consisting essentially of finely divided particles of an unblended synthetic resinous material which provides signs of crystalline order under X-ray examination, and Shows a crystalline melting point Tm as well as a glass transition temperature Tg, said material in finely divided particulate form having a two-tier particle size distribution from which particles a laser-sintered part is formed, said powder being a freely-flowable semi-crystalline powder having a crystallinity measured by differential scanning calorimetry in the range from 10% to 90%, said powder having primary particles in the size range smaller than 180μ

m, having a sphericity in the range from greater than 0.5 to 0.9, provided further that the number average ratio of particles smaller than 53μ

m is greater than 80%, the remaining larger particles being in the size range from 53μ

m to 180μ

m;

said bed having a porosity in the range from 0.4 to 0.55 allowing a pressure drop of less than 6.89 kPa when cooling gas is flowed in a direction from top to bottom through said bed at a rate of 5 L/min and said bed is 30 cm deep.

7. The bed of powder of claim 6 wherein said powder is selected from the group consisting of Nylons 6, 11, 12, polybutylene terephthalate, and polyacetal and said window of sinterability is in the range from 7°

-17°

C.

8. The bed of powder of claim 7 wherein said powder is Nylon 11 having a number average molecular weight in the range from 75,000 to 80,000 and a molecular weight distribution in the range from 1.2-1.7.

16. The bed of powder of claim 7 wherein said crystallinity is in the range from 15-60%.

9. A laser-sintered article or `part` of arbitrary shape sintered in a selective laser sintering machine containing a laser-sinterable powder of a semi-crystalline synthetic resin, said part consisting essentially of a sintered mass of said powder, said part having a density in the range from 80% to 90% of the density of an isotropically molded part of said powder and fracture surfaces, when broken by bending, which are visually identical to fracture surfaces of said molded part but including a profusion of cavities having an average diameter in the range from 1μ

m-30μ

m randomly scattered throughout said part which has substantially the same flexural modulus and maximum stress at yield (psi) when fractured in bending, but substantially less ultimate elongation (%), and notched Izod impact (ftlb/in), than a compression molded article molded from a portion of said powder.

10. The laser-sintered article of claim 9 wherein said article is free from growth on its surfaces which are smooth to the touch.

11. The laser-sintered article of claim 10 wherein said powder consists essentially of an unblended polymer having a two-tier particle size distribution said powder having the following properties:

(a) freely-flowable semi-crystalline powder having a crystallinity in the range from 10-90% measured by differential scanning calorimetry;

(b) a major portion by weight of the powder having a sphericity in the range from greater than 0.5 to 0.9, and a two-tier distribution in which substantially no primary particles having an average diameter greater than 180μ

m, provided further that the number average ratio of particles smaller than 53μ

m is greater than 80%, the remaining larger particles being in the size range from 53μ

m to 180μ

m;

a layer of said powder no more than 250μ

m deep absorbing essentially all infra-red energy beamed therethrough at a wavelength of 10.6μ

m, and a layer of said powder no more than 180μ

m thick absorbing more than 50% of said energy; and

, (b) a number average molecular weight in the range from about 30,000 to 500,000, and a molecular weight distribution M_w /M_n in the range from 1 to 5;

(c) a window of sinterability in the temperature range from near said powder'"'"'s softening temperature T_s to said powder'"'"'s caking temperature T_c.

12. The laser-sintered article of claim 11 wherein said powder consists essentially of an unblended polymer having a two-tier particle size distribution said powder having the following properties:

(a) freely-flowable semi-crystalline powder having a crystallinity in the range from 10-90% measured by differential scanning calorimetry;

(b) a major portion by weight of the powder having a sphericity in the range from greater than 0.5 to 0.9, and a two-tier distribution in which substantially no primary particles having an average diameter greater than 180μ

m, provided further that the number average ratio of particles smaller than 53μ

m is greater than 80%, the remaining larger particles being in the size range from 53μ

m to 180μ

m;

a layer of said powder no more than 250μ

m deep absorbing essentially all infra-red energy beamed therethrough at a wavelength of 10.6μ

m, and a layer of said powder no more than 180μ

m thick absorbing more than 50% of said energy;

(b) a number average molecular weight in the range from about 30,00 to 500,000, and a molecular weight distribution M_w /M_n in the range from 1 to 5; and

, (c) a melt viscosity in the range from 100-10⁴ poise (10-1000 Pa-sec) when the powder being sintered exceeds T_c in less time than is required to melt contiguous large particles >

53μ

m.

13. The laser-sintered article of claim 12 wherein said article is essentially distortion-free having no linear dimension of a part and no dimension of a surface out of plane by more than ±

250μ

m (20 mils).

14. The laser-sinterable powder product of claim 13 wherein said crystallinity is in the range from 15-60%.