IP Library Granted Patent US 11,932,735
Granted Patent B2
US 11,932,735 · App. 17/346,737 · Granted Mar 19, 2024

Graphene oxide-doped polyvinylidene fluoride particles with enhanced beta-phase crystallinity

Inventors: Valerie M. Farrugia (Oakville, CA); Robert Claridge (Kitchener, CA); Hojjat Seyed Jamali (Mississauga, CA)
Assignee: Xerox Corporation
C08J3/2056C08F14/22C08K3/042C09D11/037C09D11/101C09D11/106C08K2201/005C08K2201/011
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Quick Facts
Patent No.
US 11,932,735
App. No.
17/346,737
Granted
Mar 19, 2024
Kind
B2
Abstract

High spherical particles for use in piezoelectric applications may be produced mixing a mixture comprising a graphene oxide-polyvinylidene fluoride (GO-PVDF) composite, a carrier fluid that is immiscible with the PVDF, and optionally an emulsion stabilizer at a temperature equal to or greater than a melting point or softening temperature of the PVDF to disperse the GO-PVDF composite in the carrier fluid, wherein the GO-PVDF composite has a transmission FTIR minimum transmittance ratio of β-phase PVDF to α-phase PVDF of about 1 or less; cooling the mixture to below the melting point or softening temperature of the PVDF to form GO-PVDF particles; and separating the GO-PVDF particles from the carrier fluid, wherein the GO-PVDF particles comprise the graphene oxide dispersed in the PVDF, and wherein the GO-PVDF particles have a transmission FTIR minimum transmittance ratio of β-phase PVDF to α-phase PVDF of about 1 or less.

Claims (24)

1. A method of making graphene-oxide-polyvinylidene fluoride (GO-PVDF) particles, comprising:

providing a graphene oxide-polyvinylidene fluoride (GO-PVDF) composite comprising graphene oxide dispersed in polyvinylidene fluoride (PVDF), wherein the GO-PVDF composite has a transmission FTIR minimum transmittance ratio of β-phase PVDF to α-phase PVDF of about 1 or less;

mixing a mixture comprising a GO-PVDF composite, a carrier fluid that is immiscible with the PVDF, and optionally an emulsion stabilizer, at a temperature equal to or greater than a melting point or softening temperature of the PVDF to disperse the GO-PVDF composite in the carrier fluid;

cooling the mixture to below the melting point or softening temperature of the PVDF to form GO-PVDF particles; and

separating the GO-PVDF particles from the carrier fluid, wherein the GO-PVDF particles comprise the graphene oxide dispersed in the PVDF, and wherein the GO-PVDF particles have a transmission FTIR minimum transmittance ratio of β-phase PVDF to α-phase PVDF of about 1 or less.

2. The method of claim 1 further comprising:

producing a mixture comprising the graphene oxide, the PVDF, and a solvent; and

evaporating the solvent from the mixture to yield the GO-PVDF composite, the GO-PVDF composite comprising about 1 wt % or less of the solvent.

3. The method of claim 2 , wherein evaporating is at a temperature less than a boiling point+10° C. of the solvent (T BP+10C of the solvent).

4. The method of claim 2 , wherein evaporating comprises heating the mixture to a temperature less than a boiling point+10° C. of the solvent (T BP+10C of the solvent), and passing a gas over a surface of the mixture.

5. The method of claim 2 , wherein producing the mixture comprises dispersing the graphene oxide in the solvent, and dissolving the PVDF in the solvent having the graphene oxide dispersed therein.

6. The method of claim 1 , wherein the GO-PVDF particles have a D10 of about 0.1 μm to about 125 μm, a D50 of about 0.5 μm to about 200 μm, and a D90 of about 3 μm to about 300 μm, wherein D10<D50<D90.

7. The method of claim 1 , wherein the GO-PVDF particles have a diameter span of about 0.2 to about 10.

8. The method of claim 1 , wherein the GO-PVDF particles have a circularity of about 0.90 to about 1.0.

9. The method of claim 1 , wherein the mixture does not comprise an emulsion stabilizer.

10. A method of making a graphene oxide-polyvinylidene fluoride (GO-PVDF) composite, comprising:

producing a mixture comprising graphene oxide, PVDF, and a solvent; and

evaporating the solvent from the mixture to yield a GO-PVDF composite that comprises about 1 wt % or less of the solvent, wherein evaporating is at a temperature less than a boiling point+10° C. of the solvent (T BP+10C of the solvent), and wherein the GO-PVDF composite has a transmission FTIR minimum transmittance ratio of β-phase PVDF to α-phase PVDF of about 1 or less.

11. The method of claim 10 , wherein evaporating comprises heating the mixture to the temperature less than T BP+10C of the solvent, and passing a gas over a surface of the mixture.

12. The method of claim 10 , wherein producing the mixture comprises dispersing the graphene oxide in the solvent, and dissolving the PVDF in the solvent having the graphene oxide dispersed therein.

13. The method of claim 10 further comprising:

melt emulsifying the GO-PVDF composite to produce GO-PVDF particles, wherein the GO-PVDF particles have a β-phase retention from the GO-PVDF composite of about 0.1 to about 1.5.

14. The method of claim 13 , wherein an emulsion stabilizer is not present during the melt emulsifying.

15. The method of claim 10 , wherein the solvent is selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), triethyl phosphate (TEP), dimethyl sulfoxide (DMSO), acetone, hexamethylphosphoramide (HMPA), and any combination thereof.

Assignments (7)
SECOND LIEN NOTES PATENT SECURITY AGREEMENT Recorded Jul 2, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 071785/0550 →
FIRST LIEN NOTES PATENT SECURITY AGREEMENT Recorded Apr 11, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 070824/0001 →
SECURITY INTEREST Recorded Feb 13, 2024
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 066741/0001 →
SECURITY INTEREST Recorded Nov 20, 2023
From: XEROX CORPORATION
To: JEFFERIES FINANCE LLC, AS COLLATERAL AGENT
Reel/Frame 065628/0019 →
RELEASE OF SECURITY INTEREST IN PATENTS AT R/F 062740/0214 Recorded May 18, 2023
From: CITIBANK, N.A., AS AGENT
To: XEROX CORPORATION
Reel/Frame 063694/0122 →
SECURITY INTEREST Recorded Nov 10, 2022
From: XEROX CORPORATION
To: CITIBANK, N.A., AS AGENT
Reel/Frame 062740/0214 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 14, 2021
From: FARRUGIA, VALERIE M.; CLARIDGE, ROBERT; JAMALI, HOJJAT SEYED
To: XEROX CORPORATION
Reel/Frame 056533/0353 →
Continuity (1)
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