Method of making flexible ceramic fibers and polymer composite

Abstract

The present application discloses and claims a method to make a flexible ceramic fibers (Flexiramics™) and polymer composites. The resulting composite has an improved mechanical strength (tensile) when compared with the Flexiramics™ respective the nanofibers alone. Additionally a composite has better properties than the polymer alone such as lower fire retardancy, higher thermal conductivity and lower thermal expansion. Several different polymers can be used, both thermosets and thermoplastics. Flexiramics™ has unique physical characteristic and the composite materials can be used for numerous industrial and laboratory applications.

Claims

1. A process for making a flexible composite material comprising flexible ceramic nanofibers and a polymer, the process of making flexible ceramic nanofibers comprising the steps of: a) preparing a ceramic fiber precursor solution comprising (i) a dissolved metal precursor for ceramic selected from the group consisting of metallic ions and metal containing polymer and selected from the group consisting of Si.sup.4+, Zr.sup.4+, Ti.sup.4+, Y.sup.3+, Al.sup.3+, Zn.sup.2+, Mg.sup.2+, Pb.sup.4+, Ni.sup.2+, Sr.sup.2+, Ca.sup.2+, La.sup.3+; (ii) a polymer to increase the precursor solution viscosity, with the solid content of the precursor solution being above 5% by weight in order to obtain the required deposition, and (iii) solvent capable of providing the precursor solution a sufficiently high evaporation rate; b) allowing the dissolved metal precursors for ceramic to form a final ceramic metal oxide; c) maintaining the precursor solution viscosity between 0.01 and 1000 Pascal-second at a shear rate of 0.01 to 1 s.sup.−1 in order to spin usable fibers; d) blow spinning the precursor solution while setting the spinning parameters so that the spinning results in polymeric fibers and adapting the spinning parameters to the precursor solution; e) annealing the polymeric fibers comprising the metallic precursors comprising the metal precursors for ceramic obtained from the spinning process until all organic content is burned out and the metallic ion oxidizes to form a ceramic; f) tuning and calibrating annealing parameters comprising heating and cooling rates, annealing temperature and dwell time consistent with a trapezium shaped thermal profile so a crystallinity comprising a crystal size of 1 to 100 nm and a smoothness of 0.05 to 5 nm of root mean square roughness of the resulting 20 to 10000 nm thick fibers is obtained, the annealing parameters being distinct and specific with respect to material composition; g) setting the annealing temperature above a crystallization point of the ceramic fiber to form ceramic material; and h) rendering the composite dense with no porosity by the steps of either a′) casting non-diluted or little diluted polymeric solution on the ceramic nanofibers on flat and rigid surfaces with thickness between 0.1 to 5.0 millimeters; b′) depositing the ceramic nanofiber on top of the cast solution thus allowing the solution to permeate through the entire sample via capillary forces; and c′) thermally curing the resulting solution permeated sample by placing the sample into an oven at temperatures between 20° C. and 300° C. over a pre-determined curing time, and the cured sample comprising a polymer layer on one or on both sides of the composite with a thickness ranging from 1 μm to 5 mm; or a″) melting the polymer on top or bottom of the ceramic nanofibers; b″) applying pressure and/or temperature for better infiltration of the polymer in the ceramic nanofiber matrix, and c″) decreasing the temperature to solidify the polymer.

2. The process for making the flexible composite material of claim 1, further comprising the step of: selecting the composition of the flexible ceramic nanofiber from the group consisting of yttria-stabilized zirconia, zirconia, titania, alumina, zinc oxide, silica, magnesium oxide and pervoskites.

3. The process for making the flexible composite material of claim 1, wherein the polymer is selected from the group consisting of polydimethylsiloxane, polyimide, polypropylene, polyethylene, polyether ether ketone, polyethylenimine, polyurethanes, cyanate esters, epoxy resins, polyesters, vinyl esters, urea-formaldehyde, allylics, polyphthalamide and polyphenylene sulfide, polytetrafluoroethylene, polybenzimidazole and the ceramic content is between 0.1 to 99.9% of ceramic/total weight resulting in a composite that retains a flexibility of nearly 0° bending radius.

4. The process for making the flexible composite material of claim 1, wherein the resulting flexible ceramic nanofibers comprises a fiber diameter that ranges between 20 and 10000 nanometers thus allowing bendability of the ceramic nanofibers, a fiber length being measurable up to at least 4 centimeters, a crystal size ranging from 1 to 100 nanometers, a fiber smoothness ranging from 0.05 to 5 nanometers root mean square roughness and the fibers being disposed in a non-woven mat form in which the fibers are not physically attached to each other thus allowing the fibers to freely move and be bendable at a macroscopic scale.

5. The process for making the flexible composite material of claim 1, wherein the resulting composite material comprises more than 0% and less than 100% of ceramic/total weight by embedding the flexible ceramic nanofiber with polymeric solution of viscosity between 50 to 150 000 mPa s, with the coating step selected from the group consisting of casting a polymeric solution over a flat substrate by allowing impregnation by capillarity and/or gravity.

6. The process for making the flexible composite material of claim 1, wherein the resulting composite material comprises more than 0% and less than 100% of ceramic/total weight by casting a polymeric solution through a casting device selected from the group consisting of an extruder equipped with a slot die head, a casting knife, a spray coating gun and a doctor blade on top of the flexible ceramic filler thus allowing impregnation by capillarity.

7. The process for making the flexible composite material of claim 1, wherein the resulting composite material comprises more than 0% and less than 100% of ceramic/total weight by pressing and heating the solid polymer and the ceramic filler with typical pressures ranging between 1 and 10 kilo Newtons in a hot press melt.

8. The process for making the flexible composite material of claim 1, wherein the resulting composite material comprises more than 0% and less than 100% of ceramic/total weight by using thermosetting resin requiring curing temperatures ranging from 20 to 500° C. and thermoplastics requiring melting temperatures up to 700° C.

9. The process for making the flexible composite material of claim 1, wherein the resulting composite material is used to replace flexible printed circuit board substrates made using polyimide or polyimide with low ceramic fillers.

10. The process for making the flexible composite material of claim 1, wherein the resulting composite material is used to replace polymeric protective layers used for cable insulation.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

(1) The accompanying drawings, which are incorporated into and form a part of the specification, illustrate an embodiment of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating a preferred embodiment of the invention and are not to be construed as limiting the invention. The scope of the invention can only be limited by specific limitations contained in the appended claims.

(2) Simple sketches that allow one not necessarily familiar with the technical area to which this application pertains to gain a visual understanding of the invention.

(3) FIG. 1: A photographic depiction of Flexiramics® embedded in polyimide having a thick layer on one side (top) and a thin layer on the other side (bottom).

(4) FIG. 2: A graphic showing the ceramic nanofibers 3 point bending fatigue test measured in force versus time.

(5) FIG. 3: A typical thermal profile which displays parameters of the annealing process comprising heating/cooling rate, annealing temperature and dwell time.

(6) FIG. 4: A graphical depiction illustrating the dependency of the crystal size of YSZ (12% yttria-stabilized zirconia) nanofibers on the annealing step. The annealing vary from convection oven to microwave (MW). The heating and cooling rate range from 1° C./min to thermal shock (RTA).

(7) FIG. 5: A microphotograph of the formed flexible YSZ nonwoven fiber mat.

(8) FIG. 6A to 6D: Photographic depictions of the resulting flexible ceramic YSZ material (Flexiramics®) clearly showing the material's bendability and its pure ceramic nature by being not flammable.

(9) FIG. 7: A graph illustrating the dependence of the roughness of YSZ nanofibers on the annealing step. The annealing vary from convection oven to microwave (MW). The heating and cooling rate range from 1° C./min to thermal shock (RTA).