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

Patent metadata

Field	Value
Publication number	US-11932735-B2
Application number	US-202117346737-A
Country	US
Kind code	B2
Filing date	Jun 14, 2021
Priority date	Jun 14, 2021
Publication date	Mar 19, 2024
Grant date	Mar 19, 2024

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.

First claim

What is claimed:

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.

Assignees

• Xerox Corp

Inventors

• Farrugia Valerie M
• Claridge Robert
• Jamali Hojjat Seyed

Classifications

• C08J3/2056 Primary

  the polymer being pre-melted · CPC title

• C08F14/22

  Vinylidene fluoride · CPC title

• C08K3/042 Primary

  Graphene or derivatives, e.g. graphene oxides · CPC title

• C09D11/037

  characterised by the pigment · CPC title

• C09D11/101

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title