Method of making fiber with gradient properties

Patent metadata

Field	Value
Publication number	US-10246798-B2
Application number	US-201715441181-A
Country	US
Kind code	B2
Filing date	Feb 23, 2017
Priority date	Dec 10, 2011
Publication date	Apr 2, 2019
Grant date	Apr 2, 2019

Abstract

There is provided a method of making a fiber having improved resistance to microfracture formation at a fiber-matrix interface. The method includes mixing a plurality of nanostructures and one or more first polymers in a first solvent to form an inner-volume portion mixture, mixing one or more second polymers in a second solvent to form an outer-volume portion mixture, spinning the inner-volume portion mixture and the outer-volume portion mixture to form a precursor fiber, heating the precursor fiber to oxidize the precursor fiber and to change a molecular-bond structure of the precursor fiber, and obtaining a fiber. The fiber has an inner-volume portion with a first outer diameter, the nanostructures, and with the one or more first polymers, and has an outer-volume portion with a second outer diameter and the one or more second polymers, the outer-volume portion being in contact with and completely encompassing the inner-volume portion.

First claim

What is claimed is:

1. A method of making a fiber having improved resistance to microfracture formation at a fiber-matrix interface, the method comprising:
mixing a plurality of nanostructures and one or more first polymers in a first solvent to form an inner-volume portion mixture;
mixing one or more second polymers in a second solvent to form an outer-volume portion mixture;
spinning the inner-volume portion mixture and the outer-volume portion mixture to form a precursor fiber;
heating the precursor fiber to oxidize the precursor fiber and to change a molecular-bond structure of the precursor fiber; and
obtaining the fiber comprising an inner-volume portion with a first outer diameter, the nanostructures, and with the one or more first polymers being oriented in a direction parallel to a longitudinal axis of the fiber, the fiber further comprising an outer-volume portion with a second outer diameter and the one or more second polymers, the outer-volume portion being in contact with and completely encompassing the inner-volume portion,
wherein the inner-volume portion has at least one of a tensile modulus and a strength that are higher than at least one of a tensile modulus and a strength of the outer-volume portion, resulting in the fiber having improved resistance to microfracture formation at the fiber-matrix interface.

2. The method of claim 1 further comprising curing a resin matrix to a plurality of the fibers to form a composite part.

3. The method of claim 1 wherein the one or more first polymers and the one or more second polymers each comprise an identical polymer.

4. The method of claim 1 wherein the one or more first polymers and the one or more second polymers each comprise a different polymer from a same polymer family.

5. The method of claim 1 wherein the one or more first polymers and the one or more second polymers each comprise a polymer comprising polyacrylonitrile (PAN), pitch, polyphenylene sulfide (PPS), viscose, cellulose, polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), or combinations thereof.

6. The method of claim 1 wherein the first solvent and the second solvent each comprise a solvent comprising dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethyl sulfone (DMSO 2 ), ethylene carbonate, propylene carbonate (PPC), chloroacetonitrile, dimethyl phosphate (DDVP), or acetic anhydride (Ac 2 O).

7. The method of claim 1 wherein the fiber comprises a carbon fiber or a carbon-based fiber.

8. The method of claim 1 wherein the nanostructures comprise carbon nanostructures, nanotubes, carbon nanotubes, halloysite nanotubes, or boron nitride nanotubes.

9. The method of claim 1 wherein the spinning comprises solution spinning, gel spinning, wet spinning, electrospinning, dry spinning, or combinations there.

10. A method of making a continuous-filament finished fiber having improved resistance to microfracture formation at a fiber-matrix interface, the method comprising:
forming an inner-volume portion mixture comprising:
a first solvent;
a plurality of nanostructures selected from the group consisting of nanotubes, carbon nanotubes, halloysite nanotubes, and boron nitride nanotubes; and
a first polymer selected from the group consisting of polyacrylonitrile (PAN), pitch, polyphenylene sulfide (PPS), viscose, cellulose, polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), and combinations thereof;

forming an outer-volume portion mixture comprising:
a second solvent; and
a second polymer selected from the group consisting of polyacrylonitrile (PAN), pitch, polyphenylene sulfide (PPS), viscose, cellulose, polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), and combinations thereof;

forming a precursor fiber by spinning the inner-volume portion mixture and the outer-volume portion mixture;
heating the precursor fiber to oxidize the precursor fiber and to change a molecular-bond structure of the precursor fiber; and
obtaining the continuous-filament finished fiber comprising:
an inner-volume portion having a first outer diameter, and having the plurality of nanostructures, and the first polymer, the plurality of nanostructures substantially aligned along a longitudinal axis of the continuous-filament finished fiber and polymer chains of the first polymer oriented in a direction parallel to the longitudinal axis of the continuous-filament finished fiber; and
an outer-volume portion having a second outer diameter, and having the second polymer,
wherein the inner-volume portion of the continuous-filament finished fiber has a greater tensile modulus and/or tensile strength than the outer-volume portion of the continuous-filament finished fiber, resulting in the continuous-filament finished fiber having improved resistance to microstructure formation at the fiber-matrix interface.

11. The method of claim 10 wherein forming the inner-volume portion mixture and forming the outer-volume portion mixture further comprise using the same first polymer and second polymer in the inner-volume portion mixture and the outer-volume portion mixture, respectively.

12. The method of claim 11 wherein forming the inner-volume portion mixture and forming the outer-volume portion mixture further comprise using the same first polymer and the second polymer, each comprising a solution spinnable polyacrylonitrile (PAN).

13. The method of claim 10 further comprising curing a resin matrix to a plurality of the continuous-filament finished fibers to form a composite part.

14. The method of claim 10 wherein forming the inner-volume portion mixture and forming the outer-volume portion mixture further comprise using the first solvent and the second solvent each comprising dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethyl sulfone (DMSO 2 ), ethylene carbonate, propylene carbonate (PPC), chloroacetonitrile, dimethyl phosphate (DDVP), or acetic anhydride (Ac 2 O).

15. The method of claim 10 wherein forming the inner-volume portion mixture comprises using the plurality of nanostructures comprising carbon nanotubes.

16. The method of claim 10 wherein forming the precursor fiber further comprises using spinning comprising solution spinning, gel spinning, wet spinning, electrospinning, dry spinning, or combinations thereof.

17. A method of making a continuous-filament finished carbon fiber, the method comprising:
forming an inner-volume portion mixture comprising:
a first solvent;
a plurality of carbon nanotubes; and
a first polymer selected from the group consisting of polyacrylonitrile (PAN), pitch, polyphenylene sulfide (PPS), viscose, cellulose, polyvinylidene chloride (PVDC), and polyvinyl alcohol (PVA);

forming an outer-volume portion mixture comprising:
a second solvent; and
a second polymer selected from the group consisting of polyacrylonitrile (PAN), pitch, polyphenylene sulfide (PPS), viscose, cellulose, polyvinylidene chloride (PVDC), and polyvinyl alcohol (PVA);

forming a precursor fiber by spinning the inner-volume portion mixture and the outer-volume portion mixture;
heating the precursor fiber to oxidize the precursor fiber and to change a molecular-bond structure of the precursor fiber; and
obtaining the continuous-filament finished carbon fiber comprising:
an inner-volume portion having a first outer diameter, and having the plurality of carbon nanotubes and the first polymer, the plurality of carbon nanotubes substantially aligned along a longitudinal axis of the continuous-filament finished carbon fiber and polymer chains of the first polymer oriented in

Assignees

• Boeing Co

Inventors

• Tsotsis Thomas Karl

Classifications

• Y10T428/2916

  including boron or compound thereof [not as steel] · CPC title

• D01F9/145

  from pitch or distillation residues · CPC title

• Y10T428/24994

  Fiber embedded in or on the surface of a polymeric matrix · CPC title

• Y10T428/2929

  Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type] · CPC title

• D01F1/10 Primary

  Other agents for modifying properties · CPC title