Source: https://patents.google.com/patent/US8225704?oq=7565338
Timestamp: 2018-03-23 19:08:18
Document Index: 69834506

Matched Legal Cases: ['§102', '§102', '§103', '§103', '§112', '§112']

US8225704B2 - Armor with transformed nanotube material - Google Patents
Armor with transformed nanotube material Download PDF
US8225704B2
US8225704B2 US12657289 US65728910A US8225704B2 US 8225704 B2 US8225704 B2 US 8225704B2 US 12657289 US12657289 US 12657289 US 65728910 A US65728910 A US 65728910A US 8225704 B2 US8225704 B2 US 8225704B2
US12657289
US20110174145A1 (en )
Douglas Charles Ogrin
Kyle Ryan Kissell
Kurt Lee Lundberg
John Richard Tidrow
NANORIDGE MATERIALS Inc
Ceramic articles with carbon nanotubes are discussed in many publications, including, but not limited to, in “Carbon Nanotube Reinforced Ceramic Matrix Composites—A Review,” Journal of Minerals & Materials Characterization & Engineering, Volume 7, Number 4, 2008, pp. 355-370. Graphene is discussed generally in many publications, including, but not limited to, in “Graphene: Carbon As Thin As Can Be,” Chemical & Engineering News, Volume 87, Number 9, Mar. 2, 2009, pp. 14-20.
The present invention, in certain aspects, discloses armor which includes a ceramic article with a matrix of ceramic material and transformed nanotubes, e.g. graphene ribbon-like material, produced by subjecting nanotubes to pressure and heat, changing the nanotubes to non-tubular material. In one aspect, the ceramic material is alumina oxide. In one aspect, graphene ribbon-like material (“ribbons”) in the finished article is produced by transforming (e.g. by crushing, milling, grinding, etc.) carbon nanotubes in a mixture of ceramic material. In certain aspects the nanotubes, prior to transformation, are single-walled nanotubes, double walled nanotubes, surface-modified nanotubes, multi-walled nanotubes, or combinations thereof. In one particular aspect, graphene ribbon-like material is added to the matrix before pressure is applied.
In certain aspects, the armor is a backing only (with or without nanotubes therein, with or without transformed nanotubes therein); or includes a backing with at least one layer or with multiple layers of ballistic fabric interleaved with a binder material containing nanotubes (“nanotube-modified binder material”). The nanotubes may either be coated on the surface of the binder material or they may be incorporated into a binder material matrix. In certain aspects the nanotubes, prior to transformation, are single-walled nanotubes, double walled nanotubes, surface-modified nanotubes, multi-walled nanotubes, or combinations thereof. The backing may be backed with protective laminate on both sides. The backing, in one aspect, is a polymeric film with nanotubes therein and, in one particular aspect, is a nanofilm with transformed nanotubes, e.g. a graphene ribbon nanofilm.
In another aspect, the armor includes a backing having multiple layers of ballistic fabric which contains nanotubes (“nanotube-modified ballistic fabric”). The nanotubes exist, in certain aspects, as a coating on the surface of the ballistic fabric; the nanotubes are fabricated (“grown”) directly on the surface of the fabric; or the nanotubes are incorporated into a matrix of the ballistic fabric. In addition, the nanotube-modified ballistic fabric layers may be interleaved with a binder material. The binder material may or may not contain nanotubes and/or transformed nanotubes, as described above. Such a backing may then be backed with protective laminate on both sides. The laminated backing is made by pressing the components at a desired pressure and temperature. In one aspect, the resulting backing is formed in a desired shape, e.g. using temperature and/or pressure. In certain aspects the nanotubes, prior to transformation, are single-walled nanotubes, double walled nanotubes, surface-modified nanotubes, multi-walled nanotubes, or combinations thereof.
In one aspect, the armor according to the present invention includes a backing with multiple layers of ballistic fabric interleaved with thin films of nanotubes, commonly referred to as “buckypaper”. In certain aspects the buckypaper nanotubes are single-walled nanotubes, double walled, nanotubes, multi-walled nanotubes, surface-modified nanotubes, or combinations thereof. In addition, the backing may contain nanotube-modified ballistic fabrics and/or nanotube-modified binder materials as described above. Such a backing according to the present invention may then be backed with protective laminate on both sides. This laminated backing is made by pressing the components at a desired pressure and temperature. In one aspect, the resulting backing is formed in a desired shape, e.g. using temperature and/or pressure.
In one aspect, the ceramic article is a matrix of ceramic material and transformed nanotubes e.g. graphene ribbon-like material (“ribbons), in which the ceramic material is sintered together, with the transformed material incorporated into the sintered matrix.
Filed on even date herewith, co-owned with the present invention, and incorporated fully herein for all purposes is U.S. patent application Ser. No. entitled “Ceramic Articles and Methods.” Filed on even date herewith, co-owned with the present invention, and incorporated fully herein for all purposes is U.S. patent application Ser. No. entitled “Metallized Nanotubes.”
As used herein and throughout all the various portions (and headings) of this patent, the terms “invention”, “present invention” and variations thereof mean one or more embodiments, and are not intended to mean the claimed invention of any particular appended claim(s) or all of the appended claims. Accordingly, the subject or topic, of each such reference is not automatically or necessarily part of, or required by, any particular claim(s) merely because of such reference. So long as they are not mutually exclusive or contradictory any aspect or feature or combination of aspects or features of any embodiment disclosed herein may be used in any other embodiment disclosed herein. The drawing figures present the embodiments preferred at the time of filing for this patent.
FIG. 1 illustrates schematically a method 10 according to the present invention. Ceramic material 12 is processed in a processing apparatus 14 and then processed ceramic material is introduced into a mold 20. In one aspect the processing apparatus 14 produces ceramic material within a desired size (largest dimension) range. In one particular aspect the ceramic material is aluminum oxide (alumina) particles and the processing apparatus 14 is a dry ball mill which mills the particles to a median size (largest dimension) of about 700 nanometers (in one aspect within a range of between 10 nanometers and 100 microns), with the milled particles having a surface area between 3.5 to 4.5 square meters per gram.
Carbon nanotube material 16 is processed by a processing method 18 and then processed (“transformed”) nanotube material is introduced into the mold 20. In one aspect, the carbon nanotube material is multi-walled nanotubes. In other aspects, it is any desired nanotube material, including, but not limited to, any nanotube material disclosed or referred to herein, and, e.g. functionalized nanotubes. In one aspect of a method 18, the nanotubes are suspended in ethanol in a bath using any known suitable sonication method for an amount of time sufficient to achieve deagglomeration of bundles of nanotubes, to create a metastable nanotube suspension, and to wet the nanotube surfaces with ethanol, e.g. for about thirty minutes. In one particular aspect, a two-vessel sonication method is used with transducers and wave transfer liquid. The resulting nanotube-ethanol mixture is added to an aluminum oxide-ethanol mixture and the resulting mixture is sonicated. The resulting sonicated mixture is then stirred to produce a homogeneous) mixture, e.g. for about one hour. The stirred mixture is poured into a container so that the ethanol in the mixture evaporates, e.g. the container is a baking dish and the mixture is allowed to sit overnight, e.g. about eight to ten hours, for ethanol evaporation. The resulting dried material is then baked (to insure all water and ethanol are removed), e.g. at eighty degrees centigrade in a vacuum oven for two to three hours. The resulting material is then milled in a ball mill, e.g. to within a size range between ten nanometers and one hundred microns. Then milled material is introduced into the mold 20 producing a ceramic-material/nanotube mixture 22 in the mold 20.
A compression member 30 is applied to the mixture 22 in the mold at a pressure sufficient to achieve crushing of the nanotubes producing graphene ribbon-like material (“ribbons”) in the mixture. In one aspect, the mixture 22 is compressed at between 10,000 psi and 100,000 psi. A compressed mixture 24 is produced. The produced ribbon-like material is one to ten microns in length and one to one hundred nanometers wide (in one aspect, one to ten nanometers wide).
In one aspect the binder 204 is an armor article made according to the present invention which contains carbon nanotubes. In one aspect the binder 204 is a thin film of carbon nanotubes (“buckypaper”). In one aspect, the binder 204 contains carbon nanotubes and/or graphene ribbon-like material. Any binder or film according to the present invention can also include a suitable adhesive (with or without nanotubes therein, with or without ribbons therein) to facilitate adherence to fabric, e.g., but not limited to, spray adhesive 911 from 3M or ABF spray adhesive. In certain aspects, the layers 204 are thermoplastic nanocomposite film which has carbon nanotubes (as the material in U.S. patent application Ser. No. 12/025,662 filed 4 Feb. 2008).
To form a backing according to the present invention a laminate layer 206 is placed on each side of the outermost films 204 and in a press apparatus, the combination is pressed, e.g. at between 100 and 10,000 psi while heated, e.g. to between 25 degrees C. and 300 degrees C. The resulting backing 200 can be formed into a desired shape by applying pressure to it, e.g., with a mold of desired shape and/or by heating it, e.g. in a heated press and then bending it or otherwise mechanically shaping it. FIG. 3B illustrates a backing 200 a which has been formed with a ninety-degree bend. A backing according to the present invention may be any suitable thickness and, in certain aspects, ranges between 0.1 and 10 inches thick. A backing according to the present invention may be formed into any desired shape. Such a backing may itself be used as “soft” armor, e.g. for vehicles, aircraft (planes, helicopters, etc), and boats, or for parts thereof.
The present invention provides new and nonobvious armored clothing neither disclosed in nor suggested by U.S. Pat. No. 5,996,115 (incorporated fully herein for all purposes). This patent has no teaching or suggestion to use carbon nanotubes, graphene or ribbons as taught by the present invention. FIG. 12A shows a vest 400 according to the present invention with a plurality of tiles 410, 412. The tiles 410, 412 may be any tile according to the present invention described above. Parts of the vest 400—front 402, rear 404, sides 406, top 408, straps 409—may be made of or contain, any suitable backing according to the present invention as described above. The sides 406 may include tiles 403 (as any tile according to the present invention).
In conclusion, therefore, it is seen that the present invention and the embodiments disclosed herein and those covered by the appended claims are well adapted to carry out the objectives and obtain the ends set forth. Certain changes can be made in the subject matter without departing from the spirit and the scope of this invention. It is realized that changes are possible within the scope of this invention and it is further intended that each element or step recited in any of the following claims is to be understood as referring to the step literally and/or to all equivalent elements or steps. The following claims are intended to cover the invention as broadly as legally possible in whatever form it may be utilized. The invention claimed herein is new and novel in accordance with 35 U.S.C. §102 and satisfies the conditions for patentability in §102. The invention claimed herein is not obvious in accordance with 35U.S.C. §103 and satisfies the conditions for patentability in §103. This specification and the claims that follow are in accordance with the requirements of 35 U.S.C. §112. The inventors may rely on the Doctrine of Equivalents to determine and assess the scope of their invention and of the claims that follow as they may pertain to apparatus and/or methods not materially departing from, but outside of, the literal scope of the invention as set forth in the following claims. All patents and applications identified herein are incorporated fully herein for all purposes. It is the express intention of the applicant not to invoke 35 U.S.C. §112, paragraph 6 for any limitations of any of the claims herein, except for those in which the claim expressly uses the words ‘means for’ together with an associated function. In this patent document, the word “comprising” is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements.
US12657289 2010-01-16 2010-01-16 Armor with transformed nanotube material Active 2030-04-06 US8225704B2 (en)
US12657289 US8225704B2 (en) 2010-01-16 2010-01-16 Armor with transformed nanotube material
PCT/GB2011/050058 WO2011086384A1 (en) 2010-01-16 2011-01-17 Armour with transformed nanotube material
EP20110707211 EP2524190A1 (en) 2010-01-16 2011-01-17 Armour with transformed nanotube material
US13507577 US8584570B1 (en) 2010-01-16 2012-07-11 Method of making armor with transformed nanotube material
US13507577 Division US8584570B1 (en) 2010-01-16 2012-07-11 Method of making armor with transformed nanotube material
US20110174145A1 true US20110174145A1 (en) 2011-07-21
US8225704B2 true US8225704B2 (en) 2012-07-24
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US12657289 Active 2030-04-06 US8225704B2 (en) 2010-01-16 2010-01-16 Armor with transformed nanotube material
US13507577 Expired - Fee Related US8584570B1 (en) 2010-01-16 2012-07-11 Method of making armor with transformed nanotube material
US (2) US8225704B2 (en)
EP (1) EP2524190A1 (en)
WO (1) WO2011086384A1 (en)
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Owner name: NANORIDGE MATERIALS, INC., TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:OGRIN, DOUGLAS CHARLES;KISSELL, KYLE RYAN;LUNDBERG, KURTLEE;AND OTHERS;SIGNING DATES FROM 20100204 TO 20100208;REEL/FRAME:024143/0154