SYSTEM AND METHOD OF ACCELERATING POLYMER FIBER STABILIZATION VIA IRRADIATION TREATMENT
20220235516 · 2022-07-28
Assignee
Inventors
- Xiaodong Li (Charlottesville, VA)
- Zan Gao (Willimantic, CT, US)
- Jiadeng Zhu (Charlottesville, VA, US)
- Yellapu V. Murty (Charlottesville, VA, US)
- Kenneth Brown (Charlottesville, VA, US)
- Clifton Bumgardner (Charlottesville, VA, US)
Cpc classification
D06M11/28
TEXTILES; PAPER
D06M11/13
TEXTILES; PAPER
D06M10/001
TEXTILES; PAPER
International classification
D06M10/00
TEXTILES; PAPER
Abstract
A new technique for treating non-PAN-based pre-cursor polymeric fibers, tows, yarns, and films has been created for use in making stabilized pre-cursor polymers. By applying stepwise or non-stepwise microwave and/or ultraviolet radiation to the pre-cursor polymeric fibers, tows, yarn, or films prior to the stabilization thereof, a reduction in time for the costly stabilization process is achieved. Application of this technique extends to less-costly production of carbon fibers, for uses in industries such as automotive, aviation, trains, medical, military, sporting goods, orthopedics, and other industries. The pre-cursor polymeric fibers, tows, yarns, or films may be a multi-component polymer composite comprised of a non-PAN-based polymeric fiber, tow, yarn, or film and at least one or more constituent materials. Carbonization of such pre-cursor polymeric fibers, tows, yarns, or films results in less-costly carbon fibers that perform equally, if not better, than traditional costly PAN-based carbon fibers.
Claims
1. A method for treating pre-cursor polymeric fibers, tows, yarns, or films, said method comprising: irradiating the pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure to microwaves and/or ultraviolet light; and cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films.
2. The method of claim 1, further comprising: irradiating the irradiated pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure to microwaves and/or ultraviolet light; and cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films.
3. The method of claim 1, further comprising heating the cooled irradiated pre-cursor polymeric fibers, tows, yarns, or films to achieve stabilization of said pre-cursor polymeric fibers, tows, yarns, or films.
4. The method of claim 3, wherein the heating occurs at a temperature within one of the following ranges: about 150° C. to about 300° C.; about 200° C. to about 250° C.; about 250° C. to about 300° C.; or about 200° C. to about 215° C.
5. The method of claim 3, wherein the stabilization is provided over a duration of one of the following ranges: about 15 hours to about 25 hours; about 10 hours to about 15 hours; about 5 hours to about 10 hours; about 2 hours to about 5 hours; or about 1 hour to about 2 hours.
6. The method of claim 4, further comprising at least one or more additional heating occurrences to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
7. The method of claim 6, wherein said secondary thermochemical process may comprise: thermal carbonization or microwave-assisted plasma carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
8. The method of claim 7, wherein said additional heating includes increasing the heat at a ramp rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the ranges of about 1000° C. to about 1700° C. or of about 500° C. to about 3000° C. to achieve the carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
9. The method of claim 8, wherein the carbonization occurs over a duration of one of the following: a range of about 15 minutes to about 3 hours; a range of about 1 hour to about 2 hours; a range of about 30 minutes to about 60 minutes; or about 30 minutes.
10. The method of claim 1, wherein the specified duration of the irradiation has the duration of one of the following ranges: about 5 seconds to about 60 seconds; about 60 seconds to about 10 minutes; about 10 minutes to about 20 minutes; about 20 minutes to about 30 minutes; about 30 minutes to about 45 minutes; or about 45 minutes to about 60 minutes.
11. The method of claim 2, wherein said specified duration of the irradiation of claim 2 is a longer duration, shorter duration, or equal duration as that of the duration of the irradiation in claim 1.
12. The method of claim 2, wherein said specified duration of the irradiation of claim 2 is of one of the following ranges: about 5 seconds to about 120 minutes; about 5 seconds to about 60 seconds; about 60 seconds to about 10 minutes; about 10 minutes to about 20 minutes; about 20 minutes to about 30 minutes; about 30 minutes to about 45 minutes; about 45 minutes to about 60 minutes; or about 60 minutes to about 120 minutes.
13. The method of claim 2, wherein said irradiating and cooling of claim 2 are repeated a specified number of times of one of the following ranges: between 5 and 10 times; or between 1 and 4 times.
14. The method of claim 13, wherein said duration of the irradiation is sequentially longer.
15. The method of claim 1, wherein the irradiation of claim 1, is applied at one of the following: a power of a range between about 100 W and about 100 kW; a power of a range between about 100 W and about 1000 W; or a power of about 700 W.
16. The method of claim 13, further comprising heating the cooled irradiated pre-cursor polymeric fibers, tows, yarns, or films to achieve stabilization of said pre-cursor polymeric fibers, tows, yarns, or films.
17. The method of claim 13, wherein the heating occurs at a temperature within one of the following ranges: about 150° C. to about 300° C.; about 200° C. to about 250° C.; about 250° C. to about 300° C.; or about 200° C. to about 215° C.
18. The method of claim 16, wherein the stabilization is provided over a duration of one of the following ranges: about 15 hours to about 25 hours; about 10 hours to about 15 hours; about 5 hours to about 10 hours; about 2 hours to about 5 hours; or about 1 hour to about 2 hours.
19. The method of claim 16, further comprising at least one or more additional heating occurrences to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
20. The method of claim 19, wherein said secondary thermochemical process may comprise: carbonization or microwave-assisted plasma carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
21. The method of claim 20, wherein said additional heating includes increasing the heat at a ramp rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the ranges of about 1000° C. to about 1700° C. or of about 500° C. to about 3000° C. to achieve the carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
22. The method of claim 21, wherein the carbonization occurs over a duration of one of the following: a range of about 15 minutes to about 3 hours; a range of about 1 hour to about 2 hours; a range of about 30 minutes to about 60 minutes; or about 30 minutes.
23. The method of claim 1, wherein said exposure to microwaves comprises exposure to microwave frequencies in the range of about 300 GHz to about 300 MHz.
24. The method of claim 23, wherein said exposure to microwaves comprises exposure to microwave frequency of about 2.45 GHz.
25. The method of claim 1, wherein said exposure to ultraviolet light comprises exposure to ultraviolet light wavelengths in the range of about 10 nm to about 450 nm.
26. The method of claim 25, wherein said exposure to ultraviolet light comprises exposure to ultraviolet light wavelength of about 405 nm.
27. The method of claim 1, wherein said pre-cursor polymeric fiber, tow, yarn, or film is a multi-component polymer composite comprised of a polymeric fiber, tow, yarn, or film and at least one or more constituent materials.
28. The method of claim 27, wherein said at least one or more constituent materials defines a constituent content having a concentration comprising a range of one of the following: about 0.01% to about 1%; or about 0.05% to about 0.1%, of the multi-component polymer composite.
29. The method of claim 28, wherein said at least one or more constituent materials may comprise the following: graphene, borophene, boron carbide, carbon nanotubes, or other nanomaterials.
30. The method of claim 27, wherein the polymeric fiber, tow, yarn, or film comprises polyamide, polyethylene, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), other bio-sourced polymer, or a non-PAN-based polymer.
31. The method of claim 27, wherein the polymeric fiber, tow, yarn, or film comprises polyamide.
32. The method of claim 31, wherein the at least one or more constituent materials comprise graphene.
33. The method of claim 31, wherein the at least one or more constituent materials may further comprise one of the following metallic compounds: CuCl, CuCl.sub.2, or FeCl.sub.3.
34. The method of claim 1, wherein the treated pre-cursor polymeric fibers, tows, yarns, or films have a diameter in the range of about 5 μm to about 250 μm.
35. A carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite, comprising: a carbonized graphene-polymer hybrid fiber, tow, yarn, or film composed of carbonized pre-cursor polymeric fibers, tows, yarns, or films; and graphene.
36. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of claim 35, wherein the graphene is in the form of graphene sheets.
37. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of claim 36, wherein the graphene sheets are present on the interior and exterior of the composite.
38. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of claim 36, wherein the graphene is present in an amount ranging from one of the following: about 0.01% to about 1%; or about 0.05% to about 0.1%, by weight based on total weight of the composite.
39. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of claim 35, wherein said pre-cursor polymeric fibers, tows, yarns, or films comprise polyamide, polyethylene, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), other bio-sourced polymer, or a non-PAN-based polymer.
40. The carbonized graphene-polymer hybrid fiber composite of claim 35, wherein said pre-cursor polymeric fibers, tows, yarns, or films are polyamide.
41. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of claim 35, wherein said pre-cursor polymeric fibers, tows, yarns, or films are polyethylene.
42. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of claim 35, wherein the carbonized graphene-polymer hybrid fiber, tow, yarn, or film has the following properties: a strength in the range of one of the following: about 1.00 GPa to about 3.50 GPa; or about 1.86 GPa to about 2.06 GPa, an elastic modulus in the range of one of the following: about 100 GPa to about 350 GPa; or about 176 GPa to about 192 GPa, and a strain in the range of one of the following: about 0.6% to about 2.5%; or about 1.05% to about 1.17%.
43. A pre-cursor polymeric fiber, tow, yarn, or film that is a multi-component polymer composite comprised of a polymeric fiber, tow, yarn, or film and at least one or more constituent materials, wherein said fiber, tow, yarn, or film is irradiated and stabilized.
44. The pre-cursor polymeric fiber, tow, yarn, or film of claim 43, wherein said at least one or more constituent materials defines a constituent content having a concentration comprising a range of about 0.01% to about 1% of the multi-component polymer composite.
45. The pre-cursor polymeric fiber, tow, yarn, or film of claim 44, wherein said at least one or more constituent materials may comprise the following: graphene, borophene, boron carbide, carbon nanotubes, or other nanomaterials.
46. The pre-cursor polymeric fiber, tow, yarn, or film of claim 43, wherein the polymeric fiber, tow, yarn, or film comprises polyamide, polyethylene, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), other bio-sourced polymer, or a non-PAN-based polymer.
47. The pre-cursor polymeric fiber, tow, yarn, or film of claim 43, wherein the polymeric fiber, tow, yarn, or film comprises polyamide.
48. The pre-cursor polymeric fiber, tow, yarn, or film of claim 47, wherein the at least one or more constituent materials comprise graphene.
49. The pre-cursor polymeric fiber, tow, yarn, or film of claim 47, wherein the at least one or more constituent materials may further comprise one of the following metallic compounds: CuCl, CuCl.sub.2, or FeCl.sub.3.
50. The pre-cursor polymeric fiber, tow, yarn, or film of claim 43, where said pre-cursor polymeric fiber, tow, yarn, or film is carbonized.
51. The carbonized pre-cursor polymeric fiber, tow, yarn, or film composite of claim 50, wherein said carbonized pre-cursor polymeric fiber has the following properties: a strength in the range of one of the following: about 1.00 GPa to about 3.50 GPa; or about 1.86 GPa to about 2.06 GPa, an elastic modulus in the range of one of the following: about 100 GPa to about 350 GPa; or about 176 GPa to about 192 GPa, and a strain in the range of one of the following: about 0.6% to about 2.5%; or about 1.05% to about 1.17%.
52. A system for treating pre-cursor polymeric fibers, tows, yarns, or films, said system comprising: an irradiating means for irradiating the pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure; and a heating means for heating the irradiated pre-cursor polymeric fibers, tows, yarns, or films to achieve stabilization of said pre-cursor polymeric fibers, tows, yarns, or films.
53. The system of claim 52, wherein said irradiating means is further configured to apply a specified number of additional doses of irradiation to the irradiated pre-cursor polymeric fibers, tows, yarns, or films, said additional doses of irradiation having a specified duration.
54. The system of claim 52, wherein said irradiation means is configured to apply the irradiation to a continuous line of precursor fiber, tow, yarn, or film, such as a production line or off-line in batch application format.
55. The system of claim 52, wherein said irradiating means is configured to provide microwaves with frequencies in the range of about 300 GHz to about 300 MHz.
56. The system of claim 55, wherein said irradiating means is configured to provide microwaves with a frequency of about 2.45 GHz.
57. The system of claim 52, wherein said irradiating means is configured to provide ultraviolet light with wavelengths in the range of about 10 nm to about 450 nm.
58. The system of claim 57, wherein said irradiating means is configured to provide ultraviolet light with a wavelength of about 405 nm.
59. The system of claim 52, further comprising a cooling means for cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films.
60. The system of claim 59, wherein said cooling means is further configured to perform one of the following: cooling the pre-cursor polymeric fibers, tows, yarns, or films by convection of ambient or chilled air; cooling the pre-cursor polymeric fibers, tows, yarns, or films by exposure to the surrounding air; or cooling the pre-cursor polymeric fibers, tows, yarns, or films by washing them in a liquid bath.
61. The system of claim 53, further comprising a cooling means for cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films following each of one or more additional doses of irradiation.
62. The system of claim 61, wherein said cooling means is further configured to perform one of the following: cooling the pre-cursor polymeric fibers, tows, yarns, or films by convection of ambient or chilled air; cooling the pre-cursor polymeric fibers, tows, yarns, or films by exposure to the surrounding air; or cooling the pre-cursor polymeric fibers, tows, yarns, or films by washing them in a liquid bath.
63. The system of claim 52, wherein the heating means is configured to heat within the following range: about 150° C. to about 300° C.
64. The system of claim 63, wherein the heating means is further configured to provide stabilization over a duration of one of the following ranges: about 15 hours to about 25 hours; about 10 hours to about 15 hours; about 5 hours to about 10 hours; about 2 hours to about 5 hours; or about 1 hour to about 2 hours.
65. The system of claim 52, wherein the heating means is further configured to provide at least one or more additional heating occurrences to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
66. The system of claim 65, wherein said secondary thermochemical process may comprise: carbonization or microwave-assisted plasma carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
67. The system of claim 65, wherein the heating means is further configured to include increasing the heat at a ramp rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the ranges of about 1000° C. to about 1700° C. or of about 500° C. to about 3000° C. to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
68. The method of claim 1, wherein the pre-cursor polymeric fiber, tow, yarn, or film is already spun or otherwise prepared prior to the irradiation.
69. The pre-cursor polymeric fiber, tow, yarn, or film of claim 43, wherein the pre-cursor polymeric fiber, tow, yarn, or film is already spun or otherwise prepared prior to the irradiation.
70. The system of claim 52, wherein the pre-cursor polymeric fiber, tow, yarn, or film is already spun or otherwise prepared prior to the irradiation.
71. The method of claim 2, wherein the irradiation of claim 2, is applied at one of the following: a power of a range between about 100 W and about 100 kW; a power of a range between about 100 W and about 1000 W; or a power of about 700 W.
72. The method of claim 13, wherein the irradiation of claim 13, is applied at one of the following: a power of a range between about 100 W and about 100 kW; a power of a range between about 100 W and about 1000 W; or a power of about 700 W.
73. The method of claim 2, wherein the treated pre-cursor polymeric fibers, tows, yarns, or films have a diameter in the range of about 5 μm to about 250 μm.
74. The method of claim 13, wherein the treated pre-cursor polymeric fibers, tows, yarns, or films have a diameter in the range of about 5 μm to about 250 μm.
75. The system of claim 53, wherein the heating means is configured to heat within the following range: about 150° C. to about 300° C.
76. The system of claim 53, wherein the heating means is further configured to provide at least one or more additional heating occurrences to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] The foregoing and other objects, features and advantages of the present invention, as well as the invention itself, will be more fully understood from the following description of preferred embodiments, when read together with the accompanying drawings.
[0039] The accompanying drawings, which are incorporated into and form a part of the instant specification, illustrate several aspects and embodiments of the present invention and, together with the description herein, serve to explain the principles of the invention. The drawings are provided only for the purpose of illustrating select embodiments of the invention and are not to be construed as limiting the invention.
[0040]
[0041]
[0042]
[0043]
[0044]
[0045]
[0046]
[0047]
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
Method
[0048] An aspect of an embodiment of the present invention provides, but is not limited to, a method for treating pre-cursor polymeric fibers, tows, yarns, or films comprising: irradiating the pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure to microwaves and/or ultraviolet light; and cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films. In an embodiment, it should be understood that the pre-cursor polymeric fibers, tows, yarns, or films have already been spun (or otherwise prepared).
[0049] An aspect of an embodiment provides re-irradiating the irradiated pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure to microwaves and/or ultraviolet light; and cooling the re-irradiated pre-cursor polymeric fibers, tows, yarns, or films.
[0050] An aspect of an embodiment of the present invention provides, but not limited thereto, irradiating the pre-cursor polymeric fibers, tows, yarns, or films by exposing the pre-cursor polymeric fibers, tows, yarns, or films to microwave frequencies in the range of about 300 Hz to about 300 MHz. A further embodiment provides irradiating the pre-cursor polymeric fibers, tows, yarns, or films by exposing the pre-cursor polymeric fibers, tows, yarns, or films to microwave frequency of about 2.45 GHZ. An aspect of an embodiment of the present invention provides, but not limited thereto, irradiating the pre-cursor polymeric fibers, tows, yarns, or films by exposing the pre-cursor polymeric fibers, tows, yarns, or films to ultraviolet light wavelengths in the range of about 10 nm to about 405 nm. An aspect of an embodiment of the present invention provides, but not limited thereto, irradiating the pre-cursor polymeric fibers, tows, yarns, or films by exposing the pre-cursor polymeric fibers, tows, yarns, or films to ultraviolet light wavelength of about 405 nm. Other parameters for microwave frequency and ultraviolet light wavelength of the irradiation and re-irradiation are considered embodiments of the present invention, as such parameters can be adjusted for different compositions of pre-cursor polymeric fibers, tows, yarns, or films to be employed in the context of the various embodiments of the present invention disclosed herein.
[0051] An aspect of an embodiment of the present invention provides that each instance of the irradiation and re-irradiation of the pre-cursor polymeric fibers, tows, yarns, or films is applied at a power of a range between about 100 W and about 100 kW. A further embodiment provides that each instance of the irradiation and re-irradiation of the pre-cursor polymeric fibers, tows, yarns, or films is applied at a power of a range between about 100 W and about 1000 W. Another embodiment provides that each instance of the irradiation and re-irradiation of the precursor polymeric fibers, tows, yarns, or films is applied at a power of about 700 W. Other parameters for power at which irradiation and re-irradiation is applied to the pre-cursor polymeric fibers, tows, yarns, or films are considered embodiments of the present invention, as the power can be adjusted for different heating environments or machines (e.g.: different types of furnaces, ovens, or microwave devices) to be employed in the context of the various embodiments of the present invention disclosed herein.
[0052] An aspect of an embodiment of the present invention provides heating the cooled irradiated pre-cursor polymeric fibers, tows, yarns, or films to achieve stabilization of said pre-cursor polymeric fibers, tows, or yarns. Notably, performance of the stabilization can occur after one cycle of irradiation and cooling of the pre-cursor polymeric fibers, tows, yarns, or films according to various embodiments presented herein.
[0053] An aspect of an embodiment of the present invention provides, among other things, achieving a secondary thermochemical process to the irradiated, stabilized pre-cursor polymeric fibers, tows, yarns, or films via the application of at least one or more additional heating occurrences. An aspect of an embodiment provides that said secondary thermochemical process may comprise: thermal carbonization or microwave-assisted plasma carbonization of the pre-cursor polymeric fibers, tows, yarns, or films.
[0054]
[0055] An aspect of an embodiment provides carbonization of the irradiated, stabilized pre-cursor polymeric fibers, tows, yarns, or films, wherein said carbonization is achieved by applying additional heat at a rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the range of about 500° C. to about 3000° C. An embodiment provides the carbonization by applying additional heat at a rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the range of about 1000° C. to about 1700° C.
[0056] An aspect of an embodiment of the present invention provides carbonization of the irradiated, stabilized pre-cursor polymeric fibers, tows, yarns, or films wherein the carbonization occurs over a duration of about 15 minutes to about 3 hours. Another embodiment provides carbonization of the irradiated, stabilized pre-cursor polymeric fibers over a duration of about 1 hour to about 2 hours. In another preferred embodiment, the carbonization is provided over a duration of about 30 minutes to about 60 minutes. In yet another embodiment, the carbonization is provided over a duration of 30 minutes. Other parameters for temperature and duration of carbonization are considered embodiments of the present invention, as such parameters can be adjusted for different compositions of pre-cursor polymeric fibers, tows, yarns, or films to be employed in the context of the various embodiments of the present invention disclosed herein.
[0057] An aspect of an embodiment of the present invention provides, but not limited thereto, a pre-cursor polymeric fiber, tow, yarn, or film that is a multi-component polymer composite comprised of a polymeric fiber, tow, yarn or film and at least one or more constituent materials. An aspect of an embodiment provides that said at least one or more constituent materials defines a constituent content having a concentration comprising a range of about 0.01% to about 1% of the multi-component polymer composite. An aspect of an embodiment provides that said at least one or more constituent materials defines a constituent content having a concentration comprising about 0.05% to about 0.1% of the multi-component polymer composite. A further embodiment provides, among other things, that said at least one or more constituent materials of the multi-component polymer composite may comprise the following: graphene, borophene, boron carbide, carbon nanotubes, or other nanomaterials. A further embodiment provides that said at least one or more constituent materials of the multi-component polymer composite comprise graphene. Another embodiment provides, among other things, that said at least one or more constituent materials of the multi-component polymer composite may comprise one of the following metallic compounds: CuCl, CuCl.sub.2, or FeCl.sub.3. An aspect of an embodiment provides that said at least one or more constituent materials of the multi-component polymer composite comprise CuCl. A further aspect of an embodiment provides, but not limited thereto, that said at least one or more constituent materials of the multi-component polymer composite comprise FeCl.sub.3. An aspect of an embodiment provides that the polymeric fiber of the multi-component polymer composite comprises: polyamide, polyethylene, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), other bio-sourced polymer, or a non-PAN-based polymer. An aspect of an embodiment provides that the polymeric fiber of the multi-component polymer composite comprises polyamide. An aspect of an embodiment provides that the polymeric fiber of the multi-component polymer composite comprises polyethylene.
[0058] An aspect of an embodiment of the present invention provides, among other things, that the treated pre-cursor polymeric fibers, tows, yarns, or films have a diameter in the range of about 5 μm to about 250 μm.
Carbonized Graphene-Polymer Hybrid Fiber, Composite
[0059] An aspect of an embodiment of the present invention provides, among other things, a carbonized graphene-polymer hybrid fiber, tow, yarn or film composite and related method of treating and stabilizing the same. An aspect of an embodiment provides a carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite comprising: a carbonized graphene-polymer hybrid fiber, tow yarn, or film composed of carbonized pre-cursor polymeric fibers, tows, yarns, or films; and graphene.
[0060] An aspect of an embodiment provides, but not limited thereto, a carbonized graphene-polymer hybrid fiber, tow, yarn or film composite with varied values for strength, elastic modulus, and strain. An example of such an embodiment may possess strength in the range of about 1.00 GPa to about 3.50 GPa; an elastic modulus in the range of about 100 GPa to about 350 GPa; and strain in the range of about 0.6% to about 2.5% (such as shown, for example and not limited thereto in
[0061] An aspect of an embodiment of the present invention provides, among other things, a carbonized graphene-polyamide hybrid fiber and method of producing the same (such as shown, for example and not limited thereto in
[0062] An aspect of an embodiment of the present invention provides, among other things, a carbonized graphene-polyethylene hybrid fiber and method of producing the same.
Pre-Cursor Polymeric Fiber (Multi-Component Polymer Composite)
[0063] An aspect of an embodiment of the present invention provides, among other things, a pre-cursor polymeric fiber that is a multi-component polymer composite comprised of a polymeric fiber, tow, yarn, or film and at least one or more constituent materials, wherein said fiber, tow, yarn, or film is irradiated and stabilized. An aspect of an embodiment provides that said at least one or more constituent materials defines a constituent content have a concentration comprising a range of about 0.01% to about 1% of the multi-component polymer composite. An aspect of an embodiment provides that said at least one or more constituent materials comprise graphene, borophene, boron carbide, carbon nanotubes, or other nanomaterials. An aspect of an embodiment provides that the polymeric fiber component of the pre-cursor polymeric fiber, tow, yarn, or film comprises: polyamide, polyethylene, HDPE, UHMWPE, other bio-sourced polymer, or a non-PAN-based polymer; and at least one or more constituent materials. An embodiment of said multi-component polymer composite may comprise, among other things, polyamide and graphene (such as shown, for example and not limited thereto in
[0064] An aspect of an embodiment provides that the pre-cursor polymeric fiber, tow, yarn, or film (e.g.: the multi-component polymer composite) is carbonized. An aspect of an embodiment provides, but not limited thereto, a carbonized pre-cursor polymeric fiber, tow, yarn or film with varied values for strength, elastic modulus, and strain. An example of such an embodiment may possess strength in the range of about 1.00 GPa to about 3.50 GPa; an elastic modulus in the range of about 100 GPa to about 350 GPa; and strain in the range of about 0.6% to about 2.5% (such as shown, for example and not limited thereto in
System
[0065] An aspect of an embodiment of the present invention shall deploy a system to treat pre-cursor polymeric fibers, tows, tarns, or films as described in other embodiments, wherein the precursors are irradiated by an irradiating means and stabilized by a heating means (such as shown, for example and not limited thereto in
[0066] In an embodiment, the irradiating means 833 may comprise a means to provide microwave irradiation. In another embodiment, the irradiating means 833 may comprise a means to provide ultraviolet light irradiation. Such irradiation and stabilization will occur according to various embodiments of the invention method described herein.
[0067] An aspect of an embodiment of the system is configured to irradiate the pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure to radiation; and heat the irradiated precursor polymeric fibers, tows, yarns, or films to achieve stabilization thereof. Another embodiment of this system is configured to apply a specified number of additional doses of irradiation to the irradiated pre-cursor fibers, tows, yarns, or films, each additional dose having a specified duration. An embodiment of the irradiating means can be configured to provide microwaves with frequencies in the range of about 300 GHz to about 300 MHz. In an embodiment, the irradiating means is configured to provide microwaves with a frequency of about 2.45 GHz. Another embodiment of the irradiating means can be configured to provide ultraviolet light with wavelengths in the range of about 10 nm to 405 nm. In an embodiment, the irradiating means can be configured to provide ultraviolet light with a wavelength of about 405 nm.
[0068] An aspect of an embodiment of the present invention system provides a cooling means to actively cool the irradiated pre-cursor polymeric fibers, tows, yarns, or films according to above described embodiments of the method. Notably, as depicted schematically in
[0069] An aspect of an embodiment of the present invention system provides a heating means configured to heat within the following range: about 150° C. to about 300° C.
[0070] Another embodiment of the present invention system may be configured such that the heating means provides at least one or more additional heating occurrences to achieve a secondary thermochemical process to the stabilized pre-cursor polymeric fibers, tows, yarns, or films. In an embodiment, the secondary thermochemical process may comprise carbonization. In another embodiment, the secondary thermochemical process may comprise microwave-assisted plasma carbonization. An aspect of an embodiment provides carbonization of the irradiated, stabilized pre-cursor polymeric fibers, tows, yarns, or films, wherein said carbonization is achieved by configuring the heating means to apply additional heat at a range rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the ranges of about 1000° C. to about 1700° C. or of about 500° C. to about 3000° C. An embodiment of the system 831 as depicted in
[0071] It should also be appreciated that an embodiment of the invention system can be configured to apply irradiation to a continuous line of pre-cursor fiber, tow, yarn, or film. As a result, an embodiment of the invention system described may be configured for large-scale industrial use, or for small-scale use in laboratories.
Pre-Cursor Production (Spinning)
[0072] Additionally, it should be appreciated that any of the embodiments of pre-cursor polymeric fibers, tows, yarns, or films presented in this disclosure, or any variations thereof, may be produced by techniques including but not limited to: melt-spinning, wet-spinning, or other spinning techniques. Example embodiments of pre-cursor production are discussed below in Example and Experimental Results Sets No. 1 and No. 2. Variations of parameters including temperature and extrusion diameter for spinning of the pre-cursor polymeric fibers, tows, yarns, or films are considered embodiments of the present invention, as such parameters can be adjusted for different compositions and uses of pre-cursor polymeric fibers, tows, yarns, or films to be employed in the context of the various embodiments of the present invention disclosed herein.
EXAMPLES
[0073] Practice of an aspect of an embodiment (or embodiments) of the invention will be still more fully understood from the following examples and experimental results, which are presented herein for illustration only and should not be construed as limiting the invention in any way.
Example and Experimental Results Set No. 1
Faster Stabilization of Nylon 6/Graphene Composite Fiber Using Microwave Irradiation
[0074] Nylon 6 pellets (Sigma-Aldrich) were coated in graphene nanoparticles and melt-spun at 250° C. into fibers from a 200 μm nozzle. The precursor fibers were then soaked in a 1 wt % aqueous copper-chloride solution at 95° C. for 2 hours. Following the soaking process, the fibers were allowed to cool naturally in ambient air, washed with deionized water, and dried. The fibers were then exposed to 2.45 GHz microwaves at 700 W in a microwave device (EM720CWA-PMB, Rival) in a stepwise fashion. The initial treatment duration was 60 seconds, which was followed by a 2-minute exposure, 3-minute exposure, and 4-minute exposure in series. The irradiated fibers were then stabilized at 205° C. for 5 hours and subsequently carbonized with a temperature ramp rate of 5° C./min to 1000° C. for 30 min. The resultant fibers had a diameter of 10 μm and exhibited a yield strength of 2.06 GPa, elastic modulus of 176 GPa, and strain of 1.17%.
Example and Experimental Results Set No. 2
[0075] Faster Stabilization of Neat Nylon Fiber Using Microwave Irradiation Nylon 6 pellets (BASF) were melt spun into fibers with an average diameter of 25 μm from a 288-hole spinnerette with outlets of 350 μm diameter. A single tow of these fibers was immersed in a 5 wt % aqueous FeCl.sub.3 solution at 95° C. for 2 hours. After 2 hours elapsed, the bath with immersed fibers was irradiated with 2.45 GHz microwaves at 700 W in a microwave device (EM720CWA-PMB, Rival) for 10 minutes. The fibers were then allowed to cool naturally in ambient air, washed with deionized water, and dried. The irradiated fibers were stabilized at 200 ° C. for 5 hours and subsequently carbonized with a temperature ramp rate of 5° C./min to 1000° C. for 30 min. The resultant carbon fibers had an average diameter of 14 μm and exhibited a yield strength of 2.3 GPa, elastic modulus of 138 GPa, and strain at break of 1.7%.
Example and Experimental Result Set No. 3
[0076] In an embodiment, the method and system may be practiced for reducing the stabilization time for polymeric fibers. The method may include: irradiating polymeric fibers with short duration exposure to microwaves; allowing the fibers to cool; and applying a multiple additional doses of microwave and/or irradiation to the already irradiated fibers. In an embodiment, the polymeric fibers may or may not include additives or interstitial components comprising a composite polymeric fiber. In an embodiment, the treated fibers have a diameter in the range of about 5 μm to about 250 μm. Further, in an embodiment, the initial microwave irradiation duration is in a range of about 5 sec to about 60 sec. In another embodiment, additional doses of microwave or ultraviolet irradiation may or may not be applied and their duration is in a range of about 0 minutes to about 120 minutes. In an approach, fiber irradiation is applied to a continuous line of precursor fiber such as a production line or off-line in batch application format. In an embodiment, the irradiation power applied is between about 100 W and about 1000 W. An aspect of an embodiment may include an article of manufacture produced by any embodiment of the method or system as described herein.
Additional Examples
[0077] Example 1. A method for treating pre-cursor polymeric fibers, tows, yarns, or films, said method comprising:
[0078] irradiating the pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure to microwaves and/or ultraviolet light; and
[0079] cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films.
[0080] Example 2. The method of example 1, further comprising:
[0081] irradiating the irradiated pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure to microwaves and/or ultraviolet light; and
[0082] cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films.
[0083] Example 3. The method of example 1 (as well as subject matter in whole or in part of example 2), further comprising heating the cooled irradiated pre-cursor polymeric fibers, tows, yarns, or films to achieve stabilization of said pre-cursor polymeric fibers, tows, yarns, or films.
[0084] Example 4. The method of example 3 (as well as subject matter in whole or in part of example 2), wherein the heating occurs at a temperature within one of the following ranges:
[0085] about 150° C. to about 300° C.;
[0086] about 200° C. to about 250° C.;
[0087] about 250° C. to about 300° C.; or
[0088] about 200° C. to about 215° C.
[0089] Example 5. The method of example 3 (as well as subject matter of one or more of any combination of examples 2 or 4, in whole or in part), wherein the stabilization is provided over a duration of one of the following ranges:
[0090] about 15 hours to about 25 hours;
[0091] about 10 hours to about 15 hours;
[0092] about 5 hours to about 10 hours;
[0093] about 2 hours to about 5 hours; or
[0094] about 1 hour to about 2 hours.
[0095] Example 6. The method of example 4 (as well as subject matter of one or more of any combination of examples 2-3 and 5, in whole or in part), further comprising at least one or more additional heating occurrences to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
[0096] Example 7. The method of example 6 (as well as subject matter of one or more of any combination of examples 2-5, in whole or in part), wherein said secondary thermochemical process may comprise: thermal carbonization or microwave-assisted plasma carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
[0097] Example 8. The method of example 7, (as well as subject matter of one or more of any combination of examples 2-6, in whole or in part) wherein said additional heating includes increasing the heat at a ramp rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the ranges of about 1000° C. to about 1700° C. or of about 500° C. to about 3000° C. to achieve the carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
[0098] Example 9. The method of example 8 (as well as subject matter of one or more of any combination of examples 2-7, in whole or in part), wherein the carbonization occurs over a duration of one of the following:
[0099] a range of about 15 minutes to about 3 hours;
[0100] a range of about 1 hour to about 2 hours;
[0101] a range of about 30 minutes to about 60 minutes; or
[0102] about 30 minutes.
[0103] Example 10. The method of example 1 (as well as subject matter of one or more of any combination of examples 2-9, in whole or in part), wherein the specified duration of the irradiation has the duration of one of the following ranges:
[0104] about 5 seconds to about 60 seconds;
[0105] about 60 seconds to about 10 minutes;
[0106] about 10 minutes to about 20 minutes;
[0107] about 20 minutes to about 30 minutes;
[0108] about 30 minutes to about 45 minutes; or
[0109] about 45 minutes to about 60 minutes.
[0110] Example 11. The method of example 2 (as well as subject matter of one or more of any combination of examples 2-10, in whole or in part), wherein said specified duration of the irradiation of example 2 is a longer duration, shorter duration, or equal duration as that of the duration of the irradiation in example 1.
[0111] Example 12. The method of example 2 (as well as subject matter of one or more of any combination of examples 2-11, in whole or in part), wherein said specified duration of the irradiation of example 2 is of one of the following ranges:
[0112] about 5 seconds to about 120 minutes;
[0113] about 5 seconds to about 60 seconds;
[0114] about 60 seconds to about 10 minutes;
[0115] about 10 minutes to about 20 minutes;
[0116] about 20 minutes to about 30 minutes;
[0117] about 30 minutes to about 45 minutes;
[0118] about 45 minutes to about 60 minutes; or
[0119] about 60 minutes to about 120 minutes.
[0120] Example 13. The method of example 2 (as well as subject matter of one or more of any combination of examples 2-12, in whole or in part), wherein said irradiating and cooling of example 2 are repeated a specified number of times of one of the following ranges:
[0121] between 5 and 10 times; or
[0122] between 1 and 4 times.
[0123] Example 14. The method of example 13 (as well as subject matter of one or more of any combination of examples 2-12, in whole or in part), wherein said duration of the irradiation is sequentially longer.
[0124] Example 15. The method of any of examples 1, 2, or 13 (as well as subject matter of one or more of any combination of examples 3-12 or 14, in whole or in part), wherein the irradiation of examples 1, 2, or 13, respectively, is applied at one of the following:
[0125] a power of a range between about 100 W and about 100 kW;
[0126] a power of a range between about 100 W and about 1000 W; or
[0127] a power of about 700 W.
[0128] Example 16. The method of example 13 (as well as subject matter of one or more of any combination of examples 2-12 and 14-15, in whole or in part), further comprising heating the cooled irradiated pre-cursor polymeric fibers, tows, yarns, or films to achieve pre-cursor stabilization of said polymeric fibers, tows, yarns, or films.
[0129] Example 17. The method of example 13 (as well as subject matter of one or more of any combination of examples 2-12 and 14-16, in whole or in part), wherein the heating occurs at a temperature within one of the following ranges:
[0130] about 150° C. to about 300° C.;
[0131] about 200° C. to about 250° C.;
[0132] about 250° C. to about 300° C.; or
[0133] about 200° C. to about 215° C.
[0134] Example 18. The method of example 16 (as well as subject matter of one or more of any combination of examples 2-15 and 17, in whole or in part), wherein the stabilization is provided over a duration of one of the following ranges:
[0135] about 15 hours to about 25 hours;
[0136] about 10 hours to about 15 hours;
[0137] about 5 hours to about 10 hours;
[0138] about 2 hours to about 5 hours; or
[0139] about 1 hour to about 2 hours.
[0140] Example 19. The method of example 16 (as well as subject matter of one or more of any combination of examples 2-15 and 17-18, in whole or in part), further comprising at least one or more additional heating occurrences to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
[0141] Example 20. The method of example 19 (as well as subject matter of one or more of any combination of examples 2-18, in whole or in part), wherein said secondary thermochemical process may comprise: carbonization or microwave-assisted plasma carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
[0142] Example 21. The method of example 20 (as well as subject matter of one or more of any combination of examples 2-19, in whole or in part), wherein said additional heating includes increasing the heat at a ramp rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the ranges of about 1000° C. to about 1700° C. or of about 500° C. to about 3000° C. to achieve the carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
[0143] Example 22. The method of example 21 (as well as subject matter of one or more of any combination of examples 2-20, in whole or in part), wherein the carbonization occurs over a duration of one of the following:
[0144] a range of about 15 minutes to about 3 hours;
[0145] a range of about 1 hour to about 2 hours;
[0146] a range of about 30 minutes to about 60 minutes; or
[0147] about 30 minutes.
[0148] Example 23. The method of example 1 (as well as subject matter of one or more of any combination of examples 2-22, in whole or in part), wherein said exposure to microwaves comprises exposure to microwave frequencies in the range of about 300 GHz to about 300 MHz.
[0149] Example 24. The method of example 23 (as well as subject matter of one or more of any combination of examples 2-22, in whole or in part), wherein said exposure to microwaves comprises exposure to microwave frequency of about 2.45 GHz.
[0150] Example 25. The method of example 1 (as well as subject matter of one or more of any combination of examples 2-24, in whole or in part), wherein said exposure to ultraviolet light comprises exposure to ultraviolet light wavelengths in the range of about 10 nm to about 450 nm.
[0151] Example 26. The method of example 25 (as well as subject matter of one or more of any combination of examples 2-24, in whole or in part), wherein said exposure to ultraviolet light comprises exposure to ultraviolet light wavelength of about 405 nm.
[0152] Example 27. The method of example 1 (as well as subject matter of one or more of any combination of examples 2-26, in whole or in part), wherein said pre-cursor polymeric fiber, tow, yarn, or film is a multi-component polymer composite comprised of a polymeric fiber, tow, yarn, or film and at least one or more constituent materials.
[0153] Example 28. The method of example 27 (as well as subject matter of one or more of any combination of examples 2-26, in whole or in part), wherein said at least one or more constituent materials defines a constituent content having a concentration comprising a range of one of the following:
[0154] about 0.01% to about 1%; or
[0155] about 0.05% to about 0.1%,
[0156] of the multi-component polymer composite.
[0157] Example 29. The method of example 28 (as well as subject matter of one or more of any combination of examples 2-27, in whole or in part), wherein said at least one or more constituent materials may comprise the following: graphene, borophene, boron carbide, carbon nanotubes, or other nanomaterials.
[0158] Example 30. The method of example 27(as well as subject matter of one or more of any combination of examples 2-26 and 28-29, in whole or in part), wherein the polymeric fiber, tow, yarn, or film comprises polyamide, polyethylene, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), other bio-sourced polymer, or a non-PAN-based polymer.
[0159] Example 31. The method of example 27(as well as subject matter of one or more of any combination of examples 2-26 and 28-30, in whole or in part), wherein the polymeric fiber, tow, yarn, or film comprises polyamide.
[0160] Example 32. The method of example 31 (as well as subject matter of one or more of any combination of examples 2-30, in whole or in part), wherein the at least one or more constituent materials comprise graphene.
[0161] Example 33. The method of example 31 (as well as subject matter of one or more of any combination of examples 2-30 and 32, in whole or in part), wherein the at least one or more constituent materials may further comprise one of the following metallic compounds: CuCl, CuCl.sub.2, or FeCl.sub.3.
[0162] Example 34. The method of any one of examples 1, 2, or 13 (as well as subject matter of one or more of any combination of examples 3-12, 14-15 and 17-33, in whole or in part), wherein the treated pre-cursor polymeric fibers, tows, yarns, or films have a diameter in the range of about 5 μm to about 250 μm.
[0163] Example 35. A carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite, comprising:
[0164] a carbonized graphene-polymer hybrid fiber, tow, yarn, or film composed of carbonized pre-cursor polymeric fibers, tows, yarns, or films; and graphene.
[0165] Example 36. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of example 35, wherein the graphene is in the form of graphene sheets.
[0166] Example 37. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of example 36, wherein the graphene sheets are present on the interior and exterior of the composite.
[0167] Example 38. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of example 36 (as well as subject matter in whole or in part of example 37), wherein the graphene is present in an amount ranging from one of the following:
[0168] about 0.01% to about 1%; or
[0169] about 0.05% to about 0.1%,
by weight based on total weight of the composite.
[0170] Example 39. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of example 35 (as well as subject matter of one or more of any combination of examples 36-38, in whole or in part), wherein said pre-cursor polymeric fibers, tows, yarns, or films comprise polyamide, polyethylene, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), other bio-sourced polymer, or a non-PAN-based polymer.
[0171] Example 40. The carbonized graphene-polymer hybrid fiber composite of example 35 (as well as subject matter of one or more of any combination of examples 36-39, in whole or in part), wherein said pre-cursor polymeric fibers, tows, yarns, or films are polyamide.
[0172] Example 41. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of example 35 (as well as subject matter of one or more of any combination of examples 36-40, in whole or in part), wherein said pre-cursor polymeric fibers, tows, yarns, or films are polyethylene.
[0173] Example 42. The carbonized graphene-polymer hybrid fiber, tow, yarn, or film composite of example 35 (as well as subject matter of one or more of any combination of examples 36-41, in whole or in part), wherein the carbonized graphene-polymer hybrid fiber, tow, yarn, or film has the following properties:
[0174] a strength in the range of one of the following: [0175] about 1.00 GPa to about 3.50 GPa; or [0176] about 1.86 GPa to about 2.06 GPa,
[0177] an elastic modulus in the range of one of the following: [0178] about 100 GPa to about 350 GPa; or [0179] about 176 GPa to about 192 GPa, and
[0180] a strain in the range of one of the following: [0181] about 0.6% to about 2.5%; or [0182] about 1.05% to about 1.17%.
[0183] Example 43. A pre-cursor polymeric fiber, tow, yarn, or film that is a multi-component polymer composite comprised of a polymeric fiber, tow, yarn, or film and at least one or more constituent materials, wherein said fiber, tow, yarn, or film is irradiated and stabilized.
[0184] Example 44. The pre-cursor polymeric fiber, tow, yarn, or film of example 43, wherein said at least one or more constituent materials defines a constituent content having a concentration comprising a range of about 0.01% to about 1% of the multi-component polymer composite.
[0185] Example 45. The pre-cursor polymeric fiber, tow, yarn, or film of example 44 (as well as subject matter in whole or in part of example 44), wherein said at least one or more constituent materials may comprise the following: graphene, borophene, boron carbide, carbon nanotubes, or other nanomaterials.
[0186] Example 46. The pre-cursor polymeric fiber, tow, yarn, or film of example 43 (as well as subject matter of one or more of any combination of examples 44-45, in whole or in part), wherein the polymeric fiber, tow, yarn, or film comprises polyamide, polyethylene, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), other bio-sourced polymer, or a non-PAN-based polymer.
[0187] Example 47. The pre-cursor polymeric fiber, tow, yarn, or film of example 43 (as well as subject matter of one or more of any combination of examples 44-46, in whole or in part), wherein the polymeric fiber, tow, yarn, or film comprises polyamide.
[0188] Example 48. The pre-cursor polymeric fiber, tow, yarn, or film of example 47 (as well as subject matter of one or more of any combination of examples 44-47, in whole or in part), wherein the at least one or more constituent materials comprise graphene.
[0189] Example 49. The pre-cursor polymeric fiber, tow, yarn, or film of example 47 (as well as subject matter of one or more of any combination of examples 44-46 and 48, in whole or in part), wherein the at least one or more constituent materials may further comprise one of the following metallic compounds: CuCl, CuCl.sub.2, or FeCl.sub.3.
[0190] Example 50 (as well as subject matter of one or more of any combination of examples 44-49, in whole or in part). The pre-cursor polymeric fiber, tow, yarn, or film of example 43, where said pre-cursor polymeric fiber, tow, yarn, or film is carbonized.
[0191] Example 51. The carbonized pre-cursor polymeric fiber, tow, yarn, or film composite of example 50 (as well as subject matter of one or more of any combination of examples 44-49, in whole or in part), wherein said carbonized pre-cursor polymeric fiber has the following properties:
[0192] a strength in the range of one of the following: [0193] about 1.00 GPa to about 3.50 GPa; or [0194] about 1.86 GPa to about 2.06 GPa,
[0195] an elastic modulus in the range of one of the following: [0196] about 100 GPa to about 350 GPa; or [0197] about 176 GPa to about 192 GPa, and
[0198] a strain in the range of one of the following: [0199] about 0.6% to about 2.5%; or [0200] about 1.05% to about 1.17%.
[0201] Example 52. A system for treating pre-cursor polymeric fibers, tows, yarns, or films, said system comprising:
[0202] an irradiating means for irradiating the pre-cursor polymeric fibers, tows, yarns, or films with specified duration exposure; and
[0203] a heating means for heating the irradiated pre-cursor polymeric fibers, tows, yarns, or films to achieve stabilization of said pre-cursor polymeric fibers, tows, yarns, or films.
[0204] Example 53. The system of example 52, wherein said irradiating means is further configured to apply a specified number of additional doses of irradiation to the irradiated pre-cursor polymeric fibers, tows, yarns, or films, said additional doses of irradiation having a specified duration.
[0205] Example 54. The system of example 52 (as well as subject matter in whole or in part of example 53), wherein said irradiation means is configured to apply the irradiation to a continuous line of precursor fiber, tow, yarn, or film, such as a production line or off-line in batch application format.
[0206] Example 55. The system of example 52 (as well as subject matter of one or more of any combination of examples 53-54, in whole or in part), wherein said irradiating means is configured to provide microwaves with frequencies in the range of about 300 GHz to about 300 MHz.
[0207] Example 56. The system of example 55 (as well as subject matter of one or more of any combination of examples 53-54, in whole or in part), wherein said irradiating means is configured to provide microwaves with a frequency of about 2.45 GHz.
[0208] Example 57. The system of example 52 (as well as subject matter of one or more of any combination of examples 53-56, in whole or in part), wherein said irradiating means is configured to provide ultraviolet light with wavelengths in the range of about 10 nm to about 450 nm.
[0209] Example 58. The system of example 57 (as well as subject matter of one or more of any combination of examples 53-56, in whole or in part), wherein said irradiating means is configured to provide ultraviolet light with a wavelength of about 405 nm.
[0210] Example 59. The system of example 52 (as well as subject matter of one or more of any combination of examples 53-58, in whole or in part), further comprising a cooling means for cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films.
[0211] Example 60. The system of example 59 (as well as subject matter of one or more of any combination of examples 53-58, in whole or in part), wherein said cooling means is further configured to perform one of the following:
[0212] cooling the pre-cursor polymeric fibers, tows, yarns, or films by convection of ambient or chilled air;
[0213] cooling the pre-cursor polymeric fibers, tows, yarns, or films by exposure to the surrounding air; or
[0214] cooling the pre-cursor polymeric fibers, tows, yarns, or films by washing them in a liquid bath.
[0215] Example 61. The system of example 53 (as well as subject matter of one or more of any combination of examples 54-60, in whole or in part), further comprising a cooling means for cooling the irradiated pre-cursor polymeric fibers, tows, yarns, or films following each of one or more additional doses of irradiation.
[0216] Example 62. The system of example 61 (as well as subject matter of one or more of any combination of examples 53-60, in whole or in part), wherein said cooling means is further configured to perform one of the following:
[0217] cooling the pre-cursor polymeric fibers, tows, yarns, or films by convection of ambient or chilled air;
[0218] cooling the pre-cursor polymeric fibers, tows, yarns, or films by exposure to the surrounding air; or
[0219] cooling the pre-cursor polymeric fibers, tows, yarns, or films by washing them in a liquid bath.
[0220] Example 63. The system of example 52 or 53 (as well as subject matter of one or more of any combination of examples 54-62, in whole or in part), wherein the heating means is configured to heat within the following range: about 150° C. to about 300° C.
[0221] Example 64. The system of example 63 (as well as subject matter of one or more of any combination of examples 53-62, in whole or in part), wherein the heating means is further configured to provide stabilization over a duration of one of the following ranges:
[0222] about 15 hours to about 25 hours;
[0223] about 10 hours to about 15 hours;
[0224] about 5 hours to about 10 hours;
[0225] about 2 hours to about 5 hours; or
[0226] about 1 hour to about 2 hours.
[0227] Example 65. The system of example 52 or 53 (as well as subject matter of one or more of any combination of examples 54-64, in whole or in part), wherein the heating means is further configured to provide at least one or more additional heating occurrences to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
[0228] Example 66. The system of example 65 (as well as subject matter of one or more of any combination of examples 53-64, in whole or in part), wherein said secondary thermochemical process may comprise: carbonization or microwave-assisted plasma carbonization of said pre-cursor polymeric fibers, tows, yarns, or films.
[0229] Example 67. The system of example 65 (as well as subject matter of one or more of any combination of examples 53-64 and 66, in whole or in part), wherein the heating means is further configured to include increasing the heat at a ramp rate in the range of about 0.5° C. to about 25° C. per minute to a final temperature in the ranges of about 1000° C. to about 1700° C. or of about 500° C. to about 3000° C. to achieve a secondary thermochemical process to said pre-cursor polymeric fibers, tows, yarns, or films.
[0230] Example 68. The method of example 1, (as well as subject matter of one or more of any combination of examples 2-34, in whole or in part) wherein the pre-cursor polymeric fiber, tow, yarn, or film is already spun or otherwise prepared prior to the irradiation.
[0231] Example 69. The pre-cursor polymeric fiber, tow, yarn, or film of example 43, (as well as subject matter of one or more of any combination of examples 44-51, in whole or in part) wherein the pre-cursor polymeric fiber, tow, yarn, or film is already spun or otherwise prepared prior to the irradiation.
[0232] Example 70. The system of example 52, (as well as subject matter of one or more of any combination of examples 53-67, in whole or in part) wherein the pre-cursor polymeric fiber, tow, yarn, or film is already spun or otherwise prepared prior to the irradiation.
[0233] Example 71. A method of manufacturing any one or more of the composites in any one or more of Examples 35-51.
[0234] Example 72. A method of using any one or more of the composites in industry in any one or more of Examples 35-51.
[0235] Example 73. An article of manufacture produced by any one or more of the methods in any one or more of Examples 1-34.
[0236] Example 74. A system in any one or more of Examples 52-67 applying the methods in any one or more of Examples 1-34.
[0237] Example 75. An article of manufacture produced by any one or more of the systems in any one or more of Examples 52-67.
REFERENCES
[0238] The devices, article of manufacture, materials, compositions, systems, apparatuses, compositions, materials, machine readable medium, computer readable medium, computer program products, and methods of various embodiments of the invention disclosed herein may utilize aspects (such as devices, article of manufacture, materials, compositions, systems, apparatuses, compositions, materials, machine readable medium, computer readable medium, computer program products, and methods) disclosed in the following references, applications, publications and patents and which are hereby incorporated by reference herein in their entirety, and which are not admitted to be prior art with respect to the present invention by inclusion in this section: [0239] 1. Gao Z, et al. “Graphene Reinforced Carbon Fibers”, Science Advances. 2020. 6 (7): eaaz4191. [0240] 2. U.S. Pat. No. 10,446,329 B2, Li, et al., “Process of Forming Electrodes and Products Thereof from Biomass”, Oct. 15, 2019. [0241] 3. U.S. Patent Application Publication No. US 2017/0084924 A1, “Process of Forming Electrodes and Products Thereof from Biomass”, Mar. 23, 2017. [0242] 4. U.S. Patent Application Publication No. US 2018/0244582 A1, Li, et al., “Method of Forming Graphene/Metal-Oxide Hybrid Reinforced Composites and Product Thereof”, Aug. 30, 2018. [0243] 5. International Patent Application Publication No. WO 2017/031403 A1, Li, et al., “Method of Forming Graphene/Metal-Oxide Hybrid Reinforced Composites and Product Thereof”, Feb. 23, 2017. [0244] 6. Korean Patent No. KR 101327972 B1, Jeun, et al., “Preparing Method of Stabilized Carbon Nano-Fiber by Radiation and Thermal Treatment, and the Carbon Nano-Fiber Prepared by the Same Method”, Nov. 13, 2013. [0245] 7. Korean Patent Application Publication No. KR 2011/0115332 A, Jeun, et al., “Preparation Method of Carbon Fiber by Radiation and Thermal Stabilization”, Oct. 21, 2011. [0246] 8. U.S. Pat. No. 10,344,404 B2, Jo, et al., “Nanocarbon Composite Carbon Fiber with Low Cost and High Performance and Their Preparation Method”, Jul. 9, 2019. [0247] 9. U.S. Pat. No. 7,381,752 B2, Muratoglu, “Selective Controlled Manipulation of Polymers”, Jun. 3, 2008. [0248] 10. U.S. Pat. No. 7,786,253 B2, Paulauskas, et al., “Apparatus and Method for Oxidation and Stabilization of Polymeric Materials”, Aug. 31, 2010. [0249] 11. U.S. Pat. No. 7,649,078 B1, Paulauskas, et al.,“ Apparatus and Method for Stabilization or Oxidation of Polymeric Materials”, Jan. 19, 2010. [0250] 12. U.S. Pat. No. 5,160,464, Ward, et al., “Polymer Irradiation”, Nov. 3, 1992. [0251] 13. Platzer. “Stabilization of Polymers and Stabilizer Processes”, Advances in Chemistry. 1968. vii-xvii. [0252] 14. Shin H K, et al. “An Overview of New Oxidation Methods for Polyacrylonitrile-Based Carbon Fibers”, Carbon Letters. 2015. 16 (1): 11-18. [0253] 15. U.S. Pat. No. 8,685,361, Yang, et al., “Method for Preparing Polyacrylonitrile-Based Polymer for Preparation of Carbon Fiber Using Microwave and Method for Preparing Carbin Fiber Using the Same”, Apr. 1, 2014. [0254] 16. U.S. Pat. No. 4,197,282, Bailly-Lacresse, et al., “Manufacture of carbon fibres”, Apr. 8, 1980. [0255] 17. International Patent Application Publication No. WO 2019/071286 A1, Atkiss, S. et al., “Precursor Stabilisation Process”, Apr. 18, 2019. [0256] 18. Kim S Y, et al., “Microwave Plasma Carbonization for the Fabrication of Polyacrylonitrile-Based Carbon Fiber”. Polymer. Jan. 15, 2015. 56: 590-595. [0257] 19. Lee S W, et al., “Efficient Preparation of Carbon Fibers Using Plasma Assisted Stabilization”, Carbon. 2013. 55:361-371. [0258] 20. Yuan H W, et al., “Effect of UV Irradiation on PAN Precursor Fibers and Stabilization Process”. Journal of Wuhan University of Technology-Mater, Sci. Ed. June 2011. 449-454. [0259] 21. Dang W, et al., “Effects of y-Ray Irradiation on the Radial Structure Hetereogeneity in Polyacrylonitrile Fibers during Thermal Stabilization”. Polymers. 2018. 10:943-951.
[0260] In summary, while the present invention has been described with respect to specific embodiments, many modifications, variations, alterations, substitutions, and equivalents will be apparent to those skilled in the art. The present invention is not to be limited in scope by the specific embodiment described herein. Indeed, various modifications of the present invention, in addition to those described herein, will be apparent to those of skill in the art from the foregoing description and accompanying drawings. Accordingly, the invention is to be considered as limited only by the spirit and scope of the disclosure, including all modifications and equivalents.
[0261] Still other embodiments will become readily apparent to those skilled in this art from reading the above-recited detailed description and drawings of certain exemplary embodiments. It should be understood that numerous variations, modifications, and additional embodiments are possible, and accordingly, all such variations, modifications, and embodiments are to be regarded as being within the spirit and scope of this application. For example, regardless of the content of any portion (e.g., title, field, background, summary, abstract, drawing figure, etc.) of this application, unless clearly specified to the contrary, there is no requirement for the inclusion in any claim herein or of any application claiming priority hereto of any particular described or illustrated activity or element, any particular sequence of such activities, or any particular interrelationship of such elements. Moreover, any activity can be repeated, any activity can be performed by multiple entities, and/or any element can be duplicated. Further, any activity or element can be excluded, the sequence of activities can vary, and/or the interrelationship of elements can vary. Unless clearly specified to the contrary, there is no requirement for any particular described or illustrated activity or element, any particular sequence or such activities, any particular size, speed, material, dimension or frequency, or any particularly interrelationship of such elements. Accordingly, the descriptions and drawings are to be regarded as illustrative in nature, and not as restrictive. Moreover, when any number or range is described herein, unless clearly stated otherwise, that number or range is approximate. When any range is described herein, unless clearly stated otherwise, that range includes all values therein and all sub ranges therein. Any information in any material (e.g., a United States/foreign patent, United States/foreign patent application, book, article, etc.) that has been incorporated by reference herein, is only incorporated by reference to the extent that no conflict exists between such information and the other statements and drawings set forth herein. In the event of such conflict, including a conflict that would render invalid any claim herein or seeking priority hereto, then any such conflicting information in such incorporated by reference material is specifically not incorporated by reference herein.