Semi-crystalline build materials

Patent metadata

Field	Value
Publication number	US-10023739-B2
Application number	US-201514723333-A
Country	US
Kind code	B2
Filing date	May 27, 2015
Priority date	Nov 21, 2012
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

A polymeric material includes a semi-crystalline polymer and a secondary material wherein when the secondary material is combined with the semi-crystalline polymer to form a blend having an enthalpy that is between about 2 J/g heat of fusion and about 80% of the heat of fusion of the neat semi-crystalline material, as measured by differential scanning calorimetry (DSC) when cooling from a melting temperature to a hot crystalline temperature at a rate of 10° C./min.

First claim

The invention claimed is:

1. A polymeric-based material configured for use as a feedstock in a layer-wise extrusion-based additive manufacturing system, the material comprising:
a polymeric matrix comprising a semi-crystalline polymer; and
a secondary material or materials combined with the semi-crystalline polymer, the polymeric matrix having a heat of fusion that is between about 2 J/g and about 80% of the heat of fusion of the neat semi-crystalline polymer, as measured by differential scanning calorimetry (DSC) when cooling from a melting temperature to hot crystallization temperature at a rate of 10° C./min, wherein the crystallization kinetics of the polymeric matrix are retarded relative to that of the neat semi-crystalline polymer such that the time required to reach full crystallization of the polymeric matrix is slowed by at least an order of magnitude relative to the neat semi-crystalline polymer wherein when the polymeric matrix resides between a hot crystallization temperature and a cold crystallization temperature for about one second after being melted, the polymeric matrix forms about 1-3% of the fully-achievable crystallinity, such that the solidified material is translucent in appearance.

2. The polymeric-based material of claim 1 , wherein the secondary material or materials comprises an amorphous polymer that is substantially miscible with the semi-crystalline polymer.

3. The polymeric-based material of claim 1 , wherein the secondary material or materials comprises an irregular monomer configured to breakup the regularity of repeating units of the semi-crystalline polymer, hindering the formation of crystallites.

4. The polymeric-based material of claim 1 , wherein the semi-crystalline material comprises one or more semi-crystalline polyesters and the secondary material comprises glycol modified polyethylene terephthalates.

5. The polymeric-based material of claim 4 , wherein the one or more semi-crystalline polyesters comprises between about 50 wt. % and about 99 wt. % and the glycol modified polyethylene terephthalates comprises between about 1 wt. % and about 50 wt. % of the polymeric matrix.

6. The polymeric-based material of claim 4 , wherein the one or more semi-crystalline polyesters comprises between about 55 wt. % and about 95 wt. % and the glycol modified polyethylene terephthalates comprises between about 2 wt. % and about 45 wt. % of the polymeric matrix.

7. The polymeric-based material of claim 4 , wherein the one or more semi-crystalline polyesters comprises between about 75 wt. % and about 85 wt. % and the glycol modified polyethylene terephthalates comprises between about 15 wt. % and about 25 wt. % of the polymeric matrix.

8. The polymeric-based material of claim 4 , further comprising a reinforcing material wherein the one or more semi-crystalline polyesters comprises between about 75 wt. % and about 85 wt. % and the glycol modified polyethylene terephthalates comprises between about 15 wt. % and about 25 wt. % and the reinforcing material comprises between about 10 wt. % and about 50 wt. %.

9. The polymeric-based material of claim 1 , further comprising reinforcing agents comprising between about 10 wt. % and about 50 wt. % of the material.

10. A polymeric-based material configured for use as a feedstock in a layer-wise extrusion-based additive manufacturing system, the material comprising:
a polymeric matrix comprising one or more semi-crystalline polyester materials; and
a glycol modified polyethylene terephthalates material combined with the semi-crystalline polyester material to form the polymeric matrix, the glycol modified polyethylene terephthalates composition comprises between about 1 wt. % and about 50 wt. % of the polymeric matrix, the polymeric matrix having heat of fusion that is between about 2 J/g and about 80% of the heat of fusion of the neat semi-crystalline polyester materials, as measured by differential scanning calorimetry (DSC) when cooling from a melting temperature to hot crystallization temperature at a rate of 10° C./min, wherein the crystallization kinetics of the polymeric matrix are retarded relative to that of the neat semi-crystalline polyester polymer such that the time required to reach full crystallization of the polymeric matrix is slowed by at least an order of magnitude relative to the neat semi-crystalline polymer wherein when the polymeric matrix resides between a hot crystallization temperature and a cold crystallization temperature for about one second after being melted, the polymeric matrix forms about 1-3% of the fully-achievable crystallinity, such that the solidified material is translucent in appearance.

11. The polymeric-based material of claim 10 , wherein the one or more semi-crystalline polyester materials comprises between about 50 wt. % and about 99 wt. %.

12. The polymeric-based material of claim 10 , wherein the one or more semi-crystalline polyester materials comprises between about 55 wt. % and about 95 wt. % and the glycol modified polyethylene terephthalates comprises between about 2 wt. % and about 45 wt. % of the polymeric matrix.

13. The polymeric-based material of claim 10 , wherein the one or more semi-crystalline polyester materials comprises between about 75 wt. % and about 85 wt. % and the glycol modified polyethylene terephthalates comprises between about 15 wt. % and about 25 wt. % of the build material.

14. The polymeric-based material of claim 10 , further comprising a reinforcing material wherein the one or more semi-crystalline polyester materials comprises between about 75 wt. % and about 85 wt. % and the glycol modified polyethylene terephthalates comprises between about 15 wt. % and about 25 wt. % and the reinforcing material comprises between about 10 wt. % and about 50 wt. %.

15. The polymeric-based material of claim 14 , wherein the reinforcing material comprises glass fiber or carbon fiber.

16. The polymeric-based material of claim 10 , further comprising reinforcing material comprising between about 10 wt. % and about 50 wt. % of the material.

17. The polymeric-based material of claim 15 , wherein the reinforcing material comprises glass fiber or carbon fiber.

18. The polymeric-based material of claim 9 , wherein the reinforcing agent comprises glass fiber or carbon fiber.

19. The polymeric-based material of claim 1 , wherein the matrix is translucent after extrusion into a layer.

20. The polymeric-based material of claim 10 , wherein the matrix is translucent after extrusion into a layer.

Assignees

• Stratasys Inc

Inventors

• Rodgers Luke M B
• Jaker Vittorio L

Classifications

• B33Y10/00

  Processes of additive manufacturing · CPC title

• C08L61/02

  Condensation polymers of aldehydes or ketones only · CPC title

• B29K2105/0002

  monomers or prepolymers · CPC title

• B29K2071/00

  Use of polyethers {, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof}, as moulding material · CPC title

• B29C71/0063

  for changing crystallisation · CPC title