IP Library › Granted Patent US 12,234,368
Granted Patent B2
US 12,234,368 · App. 17/187,658 · Granted Feb 25, 2025

Dispersions comprising high surface area nanotubes and discrete carbon nanotubes

Inventors: Kurt W. Swogger (Austin, TX); Clive P. Bosnyak (Dripping Springs, TX); Malcolm Francis Finlayson (Houston, TX); Jerry Gazda (Austin, TX); Vinay Bhat (Austin, TX); Nancy Henderson (Austin, TX); Emily Barton Cole (Austin, TX)
C09D11/52B60C1/00B82Y30/00B82Y40/00C01B32/158C01B32/174C08C1/14C08J3/2053C09C1/44C09D5/24C09D7/45C09D7/62C09D11/03C09D11/033C09K23/002C01B2202/06C01B2202/20C01B2202/22C01B2202/36C01P2004/13C01P2004/54C08J2321/02C08K3/041C08K2201/011C08K2201/016C08L7/00C08L9/06C08L9/08Y10S977/734Y10S977/753Y10S977/842Y10S977/892Y10S977/932
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,234,368
App. No.
17/187,658
Granted
Feb 25, 2025
Kind
B2
Abstract

The present application pertains to dispersions comprising oxidized, discrete carbon nanotubes and high-surface area carbon nanotubes. The oxidized, discrete carbon nanotubes comprise an interior and exterior surface, each surface comprising an interior surface oxidized species content and an exterior surface oxidized species content. The interior surface oxidized species content differs from the exterior surface oxidized species content by at least 20%, and as high as 100%. The high-surface area nanotubes are generally single-wall nanotubes. The BET surface area of the high-surface area nanotubes is from about 550 m 2 /g to about 1500 m 2 /g according to ASTM D6556-16. The aspect ratio is at least about 500 up to about 6000. The dispersions comprise from about 0.1 to about 30% by weight nanotubes based on the total weight of the dispersion.

Claims (25)

1. A dispersion comprising:

oxidized, discrete carbon nanotubes wherein the discrete carbon nanotubes comprise an interior and exterior surface, each surface comprising an interior surface oxidized species content and an exterior surface oxidized species content, wherein the interior surface oxidized species content is in the range of from about 0.01 to about 3 weight percent relative to carbon nanotube weight, wherein the exterior surface oxidized content is from about 0.1 to about 65 weight percent relative to carbon nanotube weight and wherein the interior surface oxidized species content differs from the exterior surface oxidized species content by at least 20% in magnitude; and

high-surface area carbon nanotubes, wherein the high-surface area nanotubes are single-wall nanotubes, wherein the BET surface area of the high-surface area nanotubes is from about 550 m 2 /g to about 1500 m 2 /g according to ASTM D6556-16 and wherein the aspect ratio is at least about 500 up to about 6000;

wherein the sum of the weight of the oxidized, discrete carbon nanotubes and the high surface area carbon nanotubes is in the range of from about 0.1 to about 30% by weight based on the total weight of the dispersion.

2. The dispersion of claim 1 , wherein the interior surface oxidized species content of the oxidized, discrete carbon nanotubes is less than the exterior surface oxidized species content.

3. The dispersion of claim 1 , wherein the oxidized, discrete carbon nanotubes have an aspect ratio that is bimodal.

4. The dispersion of claim 1 , further comprising a diluent.

5. The dispersion of claim 1 , wherein the oxidized, discrete carbon nanotubes have an aspect ratio of 25 to 500.

6. The dispersion of claim 1 , further comprising at least one dispersant.

7. The dispersion of claim 6 , wherein the dispersant is selected from the group consisting of hydrophobic polymers, anionic polymers, non-ionic polymers, cationic polymers, ethylene oxide containing polymers, propylene oxide containing polymers, amphiphilic polymers, fatty acids, dihydrolevoglucosenone, and mixtures thereof.

8. The dispersion of claim 1 , wherein at least a portion of the oxidized, discrete carbon nanotubes comprise an oxidation species selected from carboxylic acid or a derivative carbonyl containing species wherein the derivative carbonyl species is selected from ketones, quaternary amines, amides, esters, acyl halogens, and metal salts.

9. The dispersion of claim 1 , wherein at least a portion of the oxidized, discrete carbon nanotubes comprise an oxidation species selected from hydroxyl or derived from hydroxyl containing species.

10. The dispersion of claim 1 , wherein at least a portion of the oxidized, discrete carbon nanotubes comprise multiwall carbon nanotubes.

11. A dispersion comprising:

oxidized, high-surface area carbon nanotubes, wherein the BET surface area of the high-surface area nanotubes comprises from about 550 m 2 /g to about 1500 m 2 /g according to ASTM D6556-16 and wherein the aspect ratio is at least about 500 up to about 6000 and wherein at least a portion of the high surface area carbon nanotubes are discrete and comprise about 0.1 to about 30% by weight based on the total weight of the dispersion.

12. The dispersion of claim 11 , wherein at least a portion of the high-surface area carbon nanotubes comprise single wall carbon nanotubes.

13. The dispersion of claim 1 , wherein a portion of high-surface area carbon nanotubes comprise an oxygen containing species.

14. The dispersion of claim 1 , further comprising at least one polymer.

15. The dispersion of claim 1 , wherein the polymer is selected from the group consisting of vinyl polymers, poly(styrene-butadiene), partially or fully hydrogenated poly(styrene butadiene) containing copolymers, functionalized poly(styrene butadiene) copolymers such as carboxylated poly(styrene butadiene), poly(styrene-isoprene), poly(methacrylic acid), poly(methylmethacrylate), poly(acrylic acid), poly(vinylalcohols), poly(vinylacetates), fluorinated polymers, polyvinylpyrrolidone, conductive polymers, polymers derived from natural sources, polyethers, polyesters, polyurethanes, and polyamides; homopolymers, graft, block or random co- or ter-polymers, and copolymers and mixtures thereof.

16. The dispersion of claim 1 , which further comprises a cellulose-based polymer or salt thereof.

17. The dispersion of claim 16 , wherein the cellulose-based polymer is carboxymethylcellulose or a salt thereof.

18. The dispersion of claim 1 , wherein the high-surface area carbon nanotubes have an impurity residue of less than about 25 weight percent.

19. The dispersion of claim 1 , wherein the high-surface area carbon nanotubes have an impurity residue of less than about 12 weight percent.

20. The dispersion of claim 1 , wherein the high-surface area carbon nanotubes have an impurity residue of less than about 1 weight percent.

21. The dispersion of claim 1 , wherein the BET surface area of the high-surface area carbon nanotubes is from about 1000 m 2 /g to about 1500 m 2 /g according to ASTM D6556-16.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 20, 2023
From: SWOGGER, KURT W.; BOSNYAK, CLIVE P.; FINLAYSON, MALCOLM FRANCIS; GAZDA, JERRY; BHAT, VINAY; HENDERSON, NANCY; COLE, EMILY BARTON
To: MOLECULAR REBAR DESIGN LLC
Reel/Frame 062440/0049 →
Continuity (10)
Continuation In Part 16012265 · Jun 19, 2018
Continuation In Part 15840174 · Dec 13, 2017
Continuation 15496721 · Apr 25, 2017
Continuation In Part 15288553 · Oct 7, 2016
Continuation In Part 15225215 · Aug 1, 2016
Continuation In Part 15166931 · May 27, 2016
Continuation 14924246 · Oct 27, 2015
Continuation 13993206
Provisional Application 61423033 · Dec 14, 2010
Related Publication 20210179880A1 · Jun 17, 2021
References Cited (74)
US 3471395A · Summer · 1969 [cited by applicant]
US 4421878A · Close · 1983 [cited by applicant]
US 4625761A · Uchida · 1986 [cited by applicant]
US 5079123A · Nanya · 1992 [cited by applicant]
US 5458681A · Hasegawa · 1995 [cited by applicant]
US 5750304A · Yamaguchi · 1998 [cited by applicant]
US 6544326B1 · Itou · 2003 [cited by applicant]
US 6569231B1 · Mathias · 2003 [cited by applicant]
US 6783746B1 · Zhang et al. · 2004 [cited by applicant]
US 7091120B2 · Buretea · 2006 [cited by applicant]
US 7163973B2 · Ahsan · 2007 [cited by applicant]
US 7601421B2 · Khabashesku et al. · 2009 [cited by applicant]
US 7749682B2 · Miyabe · 2010 [cited by applicant]
US 7763229B2 · Nikolaev et al. · 2010 [cited by applicant]
US 7807127B1 · Forohar · 2010 [cited by applicant]
US 7846998B2 · Akagi · 2010 [cited by applicant]
US 7959280B2 · Koike · 2011 [cited by applicant]
US 8282725B2 · Shimomura · 2012 [cited by applicant]
US 9327054B2 · Sundara · 2016 [cited by applicant]
US 9636649B2 · Bosnyak et al. · 2017 [cited by applicant]
US 10000653B2 · Swogger et al. · 2018 [cited by applicant]
US 20030049443A1 · Nishimura et al. · 2003 [cited by applicant]
US 20030213939A1 · Narayan · 2003 [cited by applicant]
US 20060014873A1 · Ikezawa · 2006 [cited by applicant]
US 20060124028A1 · Huang · 2006 [cited by applicant]
US 20070259994A1 · Tour · 2007 [cited by applicant]
US 20080315453A1 · Molitor · 2008 [cited by applicant]
US 20090168301A1 · Viswanathan · 2009 [cited by applicant]
US 20090200517A1 · El Bounia · 2009 [cited by applicant]
US 20100004468A1 · Wong et al. · 2010 [cited by applicant]
US 20100006152A1 · Hatton · 2010 [cited by applicant]
US 20100009165A1 · Patel · 2010 [cited by applicant]
US 20100016473A1 · Kaji · 2010 [cited by applicant]
US 20100122642A1 · Farrugia · 2010 [cited by examiner]
US 20100124713A1 · Farrugia · 2010 [cited by applicant]
US 20100197832A1 · Sun · 2010 [cited by applicant]
US 20100267883A1 · Bhatt · 2010 [cited by applicant]
US 20110183253A1 · Aga · 2011 [cited by applicant]
US 20110272856A1 · Rasmussen · 2011 [cited by applicant]
US 20120035309A1 · Zhu et al. · 2012 [cited by applicant]
US 20120058255A1 · Gan · 2012 [cited by applicant]
US 20120183770A1 · Bosnyak et al. · 2012 [cited by applicant]
US 20170050158A1 · Bosnyak et al. · 2017 [cited by applicant]
US 20180298221A1 · Swogger et al. · 2018 [cited by applicant]
US 20190161350A1 · Swogger et al. · 2019 [cited by applicant]
US 20200018535A1 · Leal et al. · 2020 [cited by applicant]
US 20200198973A1 · Swogger et al. · 2020 [cited by applicant]
US 20200369522A1 · Finlayson et al. · 2020 [cited by applicant]
US 20210179880A1 · Swogger et al. · 2021 [cited by applicant]
US 20210237509A1 · Bosnyak et al. · 2021 [cited by applicant]
CN 1402888A · 2003 [cited by applicant]
EP 2139630B1 · 2010 [cited by applicant]
JP 2009235650A · 2009 [cited by applicant]
KR 1020080111488 · 2008 [cited by applicant]
WO 200135473A1 · 2001 [cited by applicant]
WO 2008054845A2 · 2008 [cited by applicant]
WO 2008067137A2 · 2008 [cited by applicant]
WO 2011163129A2 · 2011 [cited by applicant]
Chaturvedi, Poornendu et al., “Carbon Nanotube-Purification and Sorting Protocols” Defence Science Journal, vol. 58, No. 5, Sep. 2008, pp. 591-599. [cited by applicant]
Kim, Dong Sik et al., Individualization of Single-walled Carbon Nanotubes: Is the Solvent Important? Small, 2005, 1, No. 11, pp. 1117-1124. [cited by applicant]
International Search Report and Written Opinion dated Aug. 2, 2022 issued in PCT/US2022/21737 filed on Mar. 24, 2022. [cited by applicant]
International Search Report and Written Opinion dated May 3, 2022 issued in International Application No. PCT/US2022/017992. [cited by applicant]
J. Mijovic, E. M. Pearce, and C.-C. Foun. “Fluoroelastomer Modified Thermoset Resins.” Advances in Chemistry; American Chemical Society 1984, 293-307. [cited by applicant]
P. C. Hiemenz, T.P. Lodge. “Polymer Chemistry, Second Edition.” CRC Press 2007. Chapters 2 and 10. [cited by applicant]
B.D. Cullity. “Elements of X-Ray Diffraction.” Addison-Wesley Publishing Company, Inc. 1978. p. 86-87. [cited by applicant]
J.E. Plevyak and L.A. Sobieski. “Improved RIM Processing with Silicone Internal Mold Release Technology.” Journal of Cellular Plastics 1984, 363-368. [cited by applicant]
N. Canter. “Mold-release agents and coatings.” Tribology & Lubrication Technology 2008, 31-38. [cited by applicant]
A. Hirsch. “Functionalization of Single-Walled Carbon Nanotubes” Angew. Chem. Int. Ed. 2002, 41, No. 11, 1853-1859. [cited by applicant]
“The IUPAC Rules for Naming Organic Molecules” Stanislaw Skonieczny. Journal of Chemical Education. vol. 83 No. 11, pp. 1633-1637 (2006) (“Skonieczny”). [cited by applicant]
“Characterization of Zirconium Phosphate/Polycation Thin Films Grown by Sequential Adsorption Reactions” Hyuk-Nyun Kim, Steven W. Keller, Thomas E. Mallouk, Johannes Schmitt, and Gero Decher. Chem. Mater., vol. 9, No. 6… [cited by applicant]
“Sonochemical Oxidation of Multiwalled Carbon Nanotubes.” Yangchuan Xing, Liang Li, Charles C. Chusuei, and Robert V. Hull. Langmuir 2005, 21, 4185-4190. [cited by applicant]
“Surface modified multi-walled carbon nanotubes in CNT/epoxycomposites.” Florian H. Gojny, Jacek Nastalczyk, Zbigniew Roslaniec, Karl Schulte. Chemical Physics Letters 370 (2003) 820-824. [cited by applicant]
Peddini S.K. et al., Nanocomposites from styrene-butadiene rubber (SBR) and multiwall carbon nanotubes (MWCNT) part 1: Morphology and rheology, Polymer 55 (2014) pp. 258-270. [cited by applicant]
Datsyuk V. et al., Chemical oxidation of multiwalled carbon nanotubes, Carbon 46 (2008) pp. 833-840. [cited by applicant]