	US 12,049,427 B2
	Formulations with active functional additives for 3D printing of preceramic polymers, and methods of 3D-printing the formulations
Zak C. Eckel, Thousand Oaks, CA (US); Tobias A. Schaedler, Oak Park, CA (US); John H. Martin, Oxnard, CA (US); and Kenneth Cante, La Puente, CA (US)
Assigned to HRL Laboratories, LLC, Malibu, CA (US)
Filed by HRL Laboratories, LLC, Malibu, CA (US)
Filed on Feb. 28, 2022, as Appl. No. 17/682,337.
Application 17/682,337 is a continuation of application No. 15/822,203, filed on Nov. 26, 2017, granted, now 11,299,430.
Claims priority of provisional application 62/556,388, filed on Sep. 9, 2017.
Claims priority of provisional application 62/428,207, filed on Nov. 30, 2016.
Claims priority of provisional application 62/428,203, filed on Nov. 30, 2016.
Claims priority of provisional application 62/428,213, filed on Nov. 30, 2016.
Prior Publication US 2022/0177373 A1, Jun. 9, 2022
This patent is subject to a terminal disclaimer.
Int. Cl. B33Y 80/00 (2015.01); B28B 1/00 (2006.01); B29C 64/10 (2017.01); B29C 64/379 (2017.01); B33Y 40/10 (2020.01); B33Y 40/20 (2020.01); B33Y 70/10 (2020.01); C04B 35/117 (2006.01); C04B 35/14 (2006.01); C04B 35/44 (2006.01); C04B 35/46 (2006.01); C04B 35/488 (2006.01); C04B 35/515 (2006.01); C04B 35/532 (2006.01); C04B 35/56 (2006.01); C04B 35/563 (2006.01); C04B 35/565 (2006.01); C04B 35/571 (2006.01); C04B 35/58 (2006.01); C04B 35/581 (2006.01); C04B 35/589 (2006.01); C04B 35/597 (2006.01); C04B 35/622 (2006.01); C04B 35/628 (2006.01); C04B 35/634 (2006.01); C04B 35/64 (2006.01); C04B 35/80 (2006.01); C08L 83/08 (2006.01); C09D 5/33 (2006.01); C09D 7/40 (2018.01); C09D 7/61 (2018.01); C09D 7/62 (2018.01); C09D 11/03 (2014.01); C09D 11/037 (2014.01); C09D 11/101 (2014.01); C09D 11/102 (2014.01); B29C 35/08 (2006.01); B29C 64/129 (2017.01); B29C 71/02 (2006.01); B29K 83/00 (2006.01); B29K 105/00 (2006.01); B29K 509/04 (2006.01); B33Y 10/00 (2015.01); C08G 77/18 (2006.01); C08G 77/20 (2006.01); C08G 77/28 (2006.01); C08K 3/34 (2006.01); C08K 7/00 (2006.01); C08K 7/10 (2006.01); C08K 9/04 (2006.01)

CPC C04B 35/5603 (2013.01) [B28B 1/001 (2013.01); B29C 64/10 (2017.08); B29C 64/379 (2017.08); B33Y 40/10 (2020.01); B33Y 40/20 (2020.01); B33Y 70/10 (2020.01); B33Y 80/00 (2014.12); C04B 35/117 (2013.01); C04B 35/14 (2013.01); C04B 35/44 (2013.01); C04B 35/46 (2013.01); C04B 35/488 (2013.01); C04B 35/515 (2013.01); C04B 35/532 (2013.01); C04B 35/5611 (2013.01); C04B 35/5622 (2013.01); C04B 35/563 (2013.01); C04B 35/565 (2013.01); C04B 35/571 (2013.01); C04B 35/58 (2013.01); C04B 35/58014 (2013.01); C04B 35/58028 (2013.01); C04B 35/581 (2013.01); C04B 35/589 (2013.01); C04B 35/597 (2013.01); C04B 35/62218 (2013.01); C04B 35/62836 (2013.01); C04B 35/62839 (2013.01); C04B 35/63448 (2013.01); C04B 35/64 (2013.01); C04B 35/80 (2013.01); C08L 83/08 (2013.01); C09D 5/004 (2013.01); C09D 7/61 (2018.01); C09D 7/62 (2018.01); C09D 7/67 (2018.01); C09D 7/68 (2018.01); C09D 7/69 (2018.01); C09D 7/70 (2018.01); C09D 11/03 (2013.01); C09D 11/037 (2013.01); C09D 11/101 (2013.01); C09D 11/102 (2013.01); B29C 2035/0827 (2013.01); B29C 2035/0838 (2013.01); B29C 64/129 (2017.08); B29C 71/02 (2013.01); B29K 2083/00 (2013.01); B29K 2105/0002 (2013.01); B29K 2509/04 (2013.01); B29K 2995/0026 (2013.01); B29K 2995/003 (2013.01); B33Y 10/00 (2014.12); C04B 2235/3826 (2013.01); C04B 2235/3895 (2013.01); C04B 2235/483 (2013.01); C04B 2235/5216 (2013.01); C04B 2235/5436 (2013.01); C04B 2235/6026 (2013.01); C04B 2235/6562 (2013.01); C04B 2235/6565 (2013.01); C04B 2235/77 (2013.01); C04B 2235/96 (2013.01); C08G 77/18 (2013.01); C08G 77/20 (2013.01); C08G 77/28 (2013.01); C08K 3/34 (2013.01); C08K 7/00 (2013.01); C08K 7/10 (2013.01); C08K 9/04 (2013.01); C08K 2201/005 (2013.01)]

14 Claims

1. A 3D-printing composition comprising:

(a) from about 10 vol % to about 99 vol % of one or more preceramic, UV-curable monomers;

(b) from about 1 vol % to about 70 vol % of solid-phase functional additives, wherein said functional additives have an average effective diameter from about 5 nanometers to about 1000 nanometers, wherein said functional additives actively improve a final ceramic structure through one or more changes induced by said functional additives during pyrolysis of a polymerized form of said one or more preceramic, UV-curable monomers, and wherein said functional additives are characterized by the property that at a temperature of 1300° C., said functional additives catalyze nucleation and/or crystallization associated with conversion of a polymerized form of said one or more said one or more preceramic, UV-curable monomers into a solid ceramic phase;

(d) a 3D-printing resolution agent,

wherein said functional additives are selected from silicon carbide, silicon oxycarbide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, silicon carbonitride, silicon boronitride, silicon boron carbonitride, or combinations thereof; and

wherein said functional additives contain a surface treatment that increases the compatibility, solubility, and/or bonding reactivity of said functional additives with said preceramic, UV-curable monomers.