Continuous liquid interphase printing

• US 9,205,601 B2
• Filed: 12/12/2014
• Issued: 12/08/2015
• Est. Priority Date: 02/12/2013
• Status: Active Grant

• Current Assignee: Carbon, Inc.
• Original Assignee: Carbon3D, Inc.
• Inventors: DeSimone, Joseph M., Ermoshkin, Alexander, Ermoshkin, Nikita, Samulski, Edward T.
• Primary Examiner(s): Tentoni, Leo B
• Application Number:
  US14/569,202
• Publication Number:
  US 20150097315A1
• Time in Patent Office: 361 Days
• Field of Search: 264/40.1, 264/338, 264/401, 264/497
• US Class Current: 1/1
• CPC Class Codes: A61F 2/82 Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents stent-grafts for tubular structures of the body other than blood vessels A61F2/04; stent-grafts for blood vessels A61F2/07; instruments specially adapted for placement or removal of stents or stent-grafts A61F2/95; for closing wounds, or holding wounds closed A61B17/04 - A61B17/115; dilators A61M29/00
• CPC Class Codes: A61F 2240/001 Designing or manufacturing processes
• CPC Class Codes: A61M 37/0015 by using microneedles
• CPC Class Codes: B29C 2033/0005 with transparent parts, e.g. permitting visual inspection of the interior of the cavity
• CPC Class Codes: B29C 2035/0827 using UV radiation
• CPC Class Codes: B29C 33/0061 characterised by the configuration of the material feeding channel sprue channels for injection moulding B29C45/27
• CPC Class Codes: B29C 35/0888 using transparant moulds
• CPC Class Codes: B29C 64/124 using layers of liquid which are selectively solidified
• CPC Class Codes: B29C 64/129 characterised by the energy source therefor, e.g. by global irradiation combined with a mask
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29C 64/393 for controlling or regulating additive manufacturing processes
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: B29K 2067/00 Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2071/02 Polyalkylene oxides, e.g. PEO, i.e. polyethylene oxide, or derivatives thereof
• CPC Class Codes: B29K 2105/0005 containing compounding ingredients releasing, lubricating or separating agents B29C33/56, fibers B29K2105/08, B29K2105/12; fillers B29K2105/16, recycled material B29K2105/26
• CPC Class Codes: B29K 2105/0058 Liquid or visquous
• CPC Class Codes: B29K 2827/12 containing fluorine
• CPC Class Codes: B29K 2883/005 LSR, i.e. liquid silicone rubbers, or derivatives thereof
• CPC Class Codes: B29K 2995/0026 Transparent
• CPC Class Codes: B29K 2995/006 Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
• CPC Class Codes: B29K 2995/0065 : Permeability to gases
• CPC Class Codes: B29L 2031/753 : Medical equipment; Accessories therefor bloodbags, medical bags B29L2031/7148; artificial eyes B29L2011/0008
• CPC Class Codes: B29L 2031/7534 : Cardiovascular protheses
• CPC Class Codes: B33Y 10/00 : Processes of additive manufacturing
• CPC Class Codes: B33Y 30/00 : Apparatus for additive manufacturing; Details thereof or accessories therefor
• CPC Class Codes: B33Y 50/02 : for controlling or regulating additive manufacturing processes
• CPC Class Codes: B33Y 80/00 : Products made by additive manufacturing
• CPC Class Codes: G03F 7/0037 : Production of three-dimensional images
• CPC Class Codes: G05B 2219/00 : Program-control systems
• CPC Class Codes: G05B 2219/49016 : Desktop manufacturing [DTM]; Solid freeform machining [SFM]; Solid freeform fabrication [SFF]

Abstract

A method of forming a three-dimensional object, comprises providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; filling the build region with a polymerizable liquid; irradiating the build region through the optically transparent member to form a solid polymer from the polymerizable liquid while concurrently advancing the carrier away from the build surface to form the three-dimensional object from the solid polymer, while also concurrently: (i) continuously maintaining a dead zone of polymerizable liquid in contact with the build surface, and (ii) continuously maintaining a gradient of polymerization zone between the dead zone and the solid polymer and in contact with each thereof, the gradient of polymerization zone comprising the polymerizable liquid in partially cured form. Apparatus for carrying out the method is also described.

Claims

1. A method of forming a three-dimensional object, comprising:

providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;

filling said build region with a polymerizable liquid;

irradiating said build region through said optically transparent member to form a solid polymer from said polymerizable liquid while concurrently advancing said carrier away from said build surface to form said three-dimensional object from said solid polymer, while also concurrently;

(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and

(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid polymer and in contact with each thereof, said gradient of polymerization zone comprising said polymerizable liquid in partially cured form.

2. The method of claim 1, wherein said optically transparent member comprises a semipermeable member, and said continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through said optically transparent member, thereby creating a gradient of inhibitor in said dead zone and optionally in at least a portion of said gradient of polymerization zone.

4. The method of claim 1, wherein said irradiating step is carried out by maskless photolithography.

5. The method claim 1, wherein said gradient of polymerization zone and said dead zone together have a thickness of from 1 to 1000 microns.

6. The method of claim 1, wherein said gradient of polymerization zone is maintained for a time of at least 5 seconds.

7. The method of claim 1, further comprising the step of disrupting said gradient of polymerization zone for a time sufficient to form a cleavage line in said three-dimensional object.

8. The method of claim 1, further comprising the step of heating said polymerizable liquid to reduce a viscosity thereof in said build region.

9. The method of claim 1, wherein said carrier has at least one channel formed therein, and said filling step is carried out by passing or forcing said polymerizable liquid into said build region through said at least one channel.

10. The method of claim 1, wherein said irradiating step is carried out with actinic radiation.

11. The method of claim 1, wherein said concurrently advancing is carried out at a cumulative rate of at least 10 microns per second.

12. The method of claim 1, wherein:

a total surface area of the build region occupies at least seventy percent of a total surface area of the build surface; and

/or

wherein lateral movement of the carrier and object in any direction is not more than thirty percent of a width of said build region in the corresponding direction.

13. The method of claim 2, wherein (a) said polymerizable liquid comprises a free radical polymerizable liquid and said inhibitor comprises oxygen, or (b) said polymerizable liquid comprises an acid-catalyzed or cationically polymerizable liquid, and said inhibitor comprises a base.

22. The method of claim 2, wherein said semipermeable member comprises a fluoropolymer film.

3. A method of forming a three-dimensional object, comprising:

providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;

filling said build region with a polymerizable liquid;

irradiating said build region through said optically transparent member to form a solid polymer from said polymerizable liquid while concurrently advancing said carrier away from said build surface to form said three-dimensional object from said solid polymer, while also concurrently;

(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and

(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid polymer and in contact with each thereof, said gradient of polymerization zone comprising said polymerizable liquid in partially cured form;

wherein said optically transparent member is comprised of a semipermeable fluoropolymer, a rigid gas-permeable polymer, porous glass, or a combination thereof.

23. The method of claim 3, wherein said optically transparent member comprises a semipermeable member, and said continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through said optically transparent member, thereby creating a gradient of inhibitor in said dead zone and optionally in at least a portion of said gradient of polymerization zone.

14. A method of forming a three-dimensional object, comprising:

providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;

filling said build region with a polymerizable liquid;

irradiating said build region with actinic radiation through said optically transparent member to form a solid polymer from said polymerizable liquid while concurrently advancing said carrier away from said build surface to form said three-dimensional object from said solid polymer, while also concurrently;

(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and

(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid polymer and in contact with each thereof, said gradient of polymerization zone comprising said polymerizable liquid in partially cured form;

wherein said gradient of polymerization zone and said dead zone together have a thickness of from 1 to 1000 microns;

wherein said gradient of polymerization zone is maintained for a time of at least 5 seconds.

15. The method of claim 14, wherein:

said optically transparent member comprises a semipermeable member, and said continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through said optically transparent member, thereby creating a gradient of inhibitor in said dead zone and optionally in at least a portion of said gradient of polymerization zone; and

said semipermeable member is comprised of a semipermeable fluoropolymer, a rigid gas-permeable polymer, porous glass, or a combination thereof.

16. The method of claim 15, wherein said optically transparent member is stationary.

17. The method of claim 16, wherein said semipermeable member comprises a flexible polymer film, there further being provided a tensioning member connected to said polymer film to fix and rigidify the film.

18. The method of claim 17, wherein said flexible polymer film comprises a fluoropolymer film.

21. The method of claim 15, and wherein (i) said polymerizable liquid comprises a free radical polymerizable liquid and said inhibitor comprises oxygen, or (ii) said polymerizable liquid comprises an acid-catalyzed or cationically polymerizable liquid, and said inhibitor comprises a base.

24. The method of claim 15, wherein said semipermeable member comprises a fluoropolymer film.

19. A method of forming a three-dimensional object, comprising:

providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;

filling said build region with a polymerizable liquid;

irradiating said build region through said optically transparent member to form a solid polymer from said polymerizable liquid while concurrently advancing said carrier away from said build surface to form said three-dimensional object from said solid polymer, while also concurrently;

(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and

(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid polymer and in contact with each thereof, said gradient of polymerization zone comprising said polymerizable liquid in partially cured form;

further comprising the steps of;

monitoring or detecting at least one process parameter and/or providing at least one known or predetermined process parameter; and

then

altering at least one process condition in response to said monitored process parameter or known or predetermined process parameter.

20. The method of claim 19, wherein:

said process parameter is expected consumption of polymerizable liquid; and

said process condition is a rate of supply of polymerizable liquid.

25. The method of claim 19, wherein said optically transparent member comprises a semipermeable member, and said continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through said optically transparent member, thereby creating a gradient of inhibitor in said dead zone and optionally in at least a portion of said gradient of polymerization zone.

26. The method of claim 25, wherein said semipermeable member comprises a fluoropolymer film.