HIERARCHICAL CELLULAR MATERIALS AND METHOD OF MAKING AND USING THE SAME

Abstract

Cellular materials and methods of making and using the cellular materials.

Claims

1. A method of making a cellular material comprising: conducting phase separation of block copolymers resulting in a particular morphology; selective removal of one polymer from the block copolymers to form a lattice; conducting metal deposition on the lattice; and dissolving a remaining polymer to obtain the cellular material.

2. The method according to claim 1, wherein the morphology is a gyroid.

3. The method according to claim 2, wherein the morphology is a double gyroid.

4. The method according to claim 1, wherein the morphology is an octet truss.

5. The method according to claim 1, wherein the metal deposition is by electrodeposition.

6. The method according to claim 1, wherein the block copolymer is block copolymer poly(4-fluorostyrene-r-styrene)-b-poly(d,l-lactide) (PFS-b-PLA).

7. The method according to claim 3, wherein the metal gyroid has a strut diameter of 13 nm.

6. The method according to claim 3, wherein the gyroid is a metal gyroid having a unit-cell size of 45 nm.

7. The method according to claim 3, wherein the gyroid is a metal gyroid having a grain size of 500 nm to 1 micron.

8. The method according to claim 1, wherein the gyroid is a metal gyroid having a volume fraction of 40%.

9. The method according to claim 1, including generating an octet lattice from a gyroid nanolattice.

10. The method according to claim 1, including generating an octet lattice from an octet nanolattice.

11. The method according to claim 1, further comprising laser cutting the cellular material to make trusses.

12. The method according to claim 1, further comprising laser cutting the cellular material to make octet lattice.

13. The method according to claim 11, further comprising laser cutting the cellular material to make octet lattice.

14. The method according to claim 13, further comprising assembling the trusses and octet lattice to form hierarchical octet lattice.

15. A method of making a nanolattice comprising: generating a CAD design for the nanolattice; using two-photon lithography to generate a polymer skeleton; conducting sputter/ALD deposition on the polymer skeleton; exposing internal polymer of polymer skeleton; and plasma etching polymer skeleton to form a hollow nanolattice.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0093] FIG. 1 is a screen shot of Hybrid Cellular Materials.

[0094] FIG. 2 is a screen shot showing an Ashby map.

[0095] FIG. 3 is a screen shot showing a map of compressive strength verses density for engineering materials.

[0096] FIG. 4 is a screen shot showing a map of fracture toughness verses density of engineering materials.

[0097] FIG. 5 is a screen shot showing a map of fracture toughness verses strength of engineering materials.

[0098] FIG. 6 is a screen shot showing examples of various types of cellular structures.

[0099] FIG. 7 is a screen shot showing a map of elastic modulus (Young's modulus) verses density map.

[0100] FIG. 8 is a screen shot showing a graph of average engineering stress at 1% strain verses specimen diameter.

[0101] FIG. 9 is a screen shot showing a diagram of increasing molecular weight verses increasing volume fraction of red component.

[0102] FIG. 10 is a screen shot showing the manufacture of a metal gyroid (e.g. double-gyroid).

[0103] FIG. 11 is a screen shot showing the parent material properties from various measurements.

[0104] FIG. 12 is a screen shot showing other options for nano-scale lattice manufacture.

[0105] FIG. 13 is a screen shot showing a whole range of topologies manufactured by this process.

[0106] FIG. 14 is a screen shot showing a map of compressive strength verses density for various lattices achieved to date.

[0107] FIG. 15 is a screen shot showing a map of compressive strength verses density for carbon based systems.

[0108] FIG. 16 is a screen shot showing that millimeter scale lattices tend to be intrinsically tough.

[0109] FIG. 17 is a screen shot showing a graph of force verses crack-mouth opening displacement and test sample.

[0110] FIG. 18 is a screen shot showing a graph of dimensionless toughness verse relative density.

[0111] FIG. 19 is a screen shot showing micro-architectured materials, including gyroid and octet truss.

[0112] FIG. 20 is a screen shot showing a graph of fracture toughness verses strength.

[0113] FIG. 21 is a screen shot showing the structures of octet lattice from gyroid nanolattice and octet lattice fro octet nanolattice.

[0114] FIG. 22 is a screen shot showing the detail structure of octet lattice from octet nanolattice.

[0115] FIG. 23 is a screen shot showing a graph of fracture toughness verses strength for various hierarchical materials.

[0116] FIG. 24 is a screen shot of making hybrid gyroid lattices.

[0117] FIG. 25 is a screen shot showing the making of gyroid material.

[0118] FIG. 26 is a screen shot showing making hierarchical octet lattice assembly.

[0119] FIG. 27 is a screen shot showing making gyroid material.

[0120] FIG. 28 is a screen shot showing making a hierarchical octet lattice assembly.

[0121] FIG. 29 is a screen shot showing making gyroid material octet lattice via ALD.

DETAILED DESCRIPTION

[0122] A Hybrid Cellular Materials is shown in FIG. 1.

[0123] An Ashby map showing the fracture toughness and strengths of engineering materials is shown in FIG. 2.

[0124] A map of compressive strength and density for engineering materials is shown in FIG. 3. Note that there are no materials that are light and strong. A substantial gap in capability exists before one reaches the theoretical strength verses density line defined b the Hashin-Strickman (H-S) bound for a cellular material made from high quality diamond.

[0125] A map of the fracture toughness and density of engineering materials in shown in FIG. 4. Again note the gap in materials capabilities at low density. Note also that low density cellular materials usually have very low fracture toughness values which limits their applications.

[0126] A map of fracture toughness and strength of engineering materials is shown in FIG. 5. Those with a density of 300 kgm.sup.3 or less are shown dark shaded. Only very weak polymer foams and cork are available. The invention disclosed here designs a state of matter, and proposes methods for making it that, resulting in cellular materials whose strengths and toughness's will be comparable to carbon steels but whose density could be as low as 700 kgm.sup.3.

[0127] Examples of various types of cellular structures is shown in FIG. 6.

[0128] An elastic modulus-density map is shown in FIG. 7. The elastic modulus-density map also has gaps at low density and high modulus.

[0129] An average engineering stress at 1% strain verses specimen diameter is shown in FIG. 8. Materials get stronger as they are made smaller. Defect sources become harder to operate at lower dimensions. Nano foams with small diameter ligaments enable one to make a large scale material with nanoscale ligaments. The modulus is not effected by making the ligaments small.

[0130] A diagram of increasing molecular weight verses increasing volume fraction of red component is shown in FIG. 9. For example, polystyrene-b-polyisoprene (PS-b-PI) and poly(4-fluorostyrene-r-styrene)-b-poly(d,l-lactide) (PFS-b-PLA). Phase separation of block copolymers results in a double-gyroid morphology as shown.

[0131] The manufacture of a metal gyroid is illustrated in FIG. 10. A block copolymer poly(4-fluorostyrene-r-styrene)-b-poly(d,l-lactide) (PFS-b-PLA) is used. A phase separation of lactide and styrene occurs to form a double gyroid of lactide in a styrene matrix. The selective removal of lactide results in a template of styrene. A desired metal is deposited by electrodeposition. The styrene is dissolved to obtain the double gyroid. For example, this results in a material with a strut diameter of approx. 13 nm; a unit-cell size of approx. 45 nm; a grain size of approx. 500 nm-1 micron; and a volume fraction of approx. 40%.

[0132] The parent material properties can be inferred from various measurements illustrated in FIG. 11. For example, comparing a stress verses strain curve for a solid material and a stress verses strain for a gyroid. Further, a hardness verses 0.2 a/R is simulated and measured and compared.

[0133] Other options for nano-scale lattice manufacture is shown in FIG. 12. For example, a CAD design is developed; two-photon lithography is used to generate a polymer skeleton; sputter/ALD deposition is used to generate an expose internal polymer; and O.sub.2 plasma etch is used to generate a hollow nanolattice.

[0134] A whole range of topologies can be manufactured by this process, as shown in FIG. 13.

[0135] A graph of compressive strength verses density for lattices achieved to date is shown in FIG. 14. The gyroid though not an optimal topology is easier to manufacture and can be produced with a truly nano topology and hence better properties.

[0136] A graph of compressive strength verses density for carbon based systems is shown in FIG. 15. There seems to be a factor of 4 gain in strength in going from a macro to a nano C foam.

[0137] Millimeter scale lattices tend to be intrinsically tough, as shown in FIG. 16. Holes act as crack arrestors.

[0138] A measurement of fracture toughness of a 25% lattice is shown in FIG. 17. A graph of force verses crack-mouth opening displacement and test sample is shown. Each load-drop corresponds to a cell wall breaking by ductile necking.

[0139] Predictions of the fracture toughness of elastic/brittle lattices is shown in FIG. 18. A graph of dimensionless toughness verses relative density is shown.

[0140] The structure of micro-architectured materials such as gyroid and octet truss are shown in FIG. 19.

[0141] A graph of the fracture toughness verses strength of gyroid and octet truss is shown in FIG. 20. Large cell lattices have exceptional toughness, but unremarkable strength. Nano-scale lattices have exceptional strength, but very poor toughness.

[0142] The structure of hierarchical materials, including octet lattice from gyroid nanolattice and octet lattice from octet nanolattice are shown in FIG. 21. The detailed structure of octet lattice from octet nanolattice is shown in FIG. 22.

[0143] The manufacture of hierarchical materials with this large length-scale separation is a challenge. These material are shown in the graph of fracture toughness verses strength as shown in FIG. 23.

[0144] The making of hybrid gyroid lattice begins at FIGS. 24 and 25. A PS-b-PI is mixed with PS homopolymer (FIG. 25); phase separated; porous PS after selective PI removal; and finished gyroid material.

[0145] The making of hierarchical octet lattice assembly is shown in FIG. 26. The making includes (a) gyroid materials preparation, including CVD (ALD) conversion to Ni or SiC gyroid lattice; (b) laser cutting octet lattice patterns, including trusses and octet lattice; and (c) hierarchical octet lattice assembly.

[0146] The making of gyroid material is shown in FIG. 27. The making includes mixing together PS-b-PI and PS homopolymer; phase separated; porous PS after selective PI removal; and finished gyroid material.

[0147] The making of a hierarchical octet lattice assembly is shown in FIG. 28. The making includes (a) gyroid materials preparation (i.e. mixing together PS-b-PI and PS homopolymer); (b) laser cutting octet lattice patterns; and (c) hierarchical octet lattice assembly.

[0148] The making of finished gyroid material octet lattice via ALD is shown in FIG. 29. The making includes (a) phase separated octet lattice; (b) selective PI removal; and (c) finish gyroid material octet lattice via ALD.

Technical Support

[0149] The following patents, applications, and/or publications as listed below and throughout this document provide technical support for the invention, and are hereby incorporated by reference in their entirety herein.

[0150] It should be appreciated that various aspects of embodiments of the present method, system, devices, article of manufacture, and compositions may be implemented with the following methods, systems, devices, article of manufacture, and compositions disclosed in the following U.S. Patent Applications, U.S. Patents, Publications, and PCT International Patent Applications and are hereby incorporated by reference herein and co-owned with the assignee (and which are not admitted to be prior art with respect to the present invention by inclusion in this section):

[0151] International Patent Application Serial No. PCT/US2011/035581, entitled Spotless Arc Directed Vapor Deposition (SA-DVD) and Related Method Thereof, filed on May 6, 2011.

[0152] International Patent Application Serial No. PCT/US2011/031592, entitled Multifunctional Armor Panel, filed on Apr. 7, 2011, and corresponding U.S. application Ser. No. 13/640,239, filed on Oct. 9, 2012; U.S. Patent Application Publication No. US 2013/0263727, published Oct. 10, 2013.

[0153] International Patent Application Serial No. PCT/US2011/021121, entitled Multifunctional Thermal Management System and Related Method, filed Jan. 13, 2011, and corresponding U.S. patent application Ser. No. 13/522,264, entitled Multifunctional Thermal Management System and Related Method, filed Jul. 13, 2012; U.S. Patent Application Publication No. US 2013/0014916, published Jan. 17, 2013.

[0154] International Patent Application No. PCT/US2010/025259, entitled Coaxial Hollow Cathode Plasma Assisted Directed Vapor Deposition and Related Method Thereof, filed Feb. 24, 2010, and corresponding U.S. patent application Ser. No. 13/202,828, entitled Coaxial Hollow Cathode Plasma Assisted Directed Vapor Deposition and Related Method Thereof, filed Aug. 23, 2011; U.S. Patent Application Publication No. US 2011/0318498, published Dec. 29, 2011.

[0155] U.S. patent application Ser. No. 12/604,654, entitled Interwoven Sandwich Panel Structures and Related Methods Thereof, filed Oct. 23, 2009; U.S. Patent Application Publication No. US 2010/0104819, published Apr. 29, 2010. International Patent Application No. PCT/US2009/061888 entitled Reactive Topologically Controlled Armors for Protection and Related Method, filed Oct. 23, 2009.

[0156] U.S. patent application Ser. No. 12/479,408, entitled Manufacture of Lattice Truss Structures from Monolithic Materials, filed Jun. 5, 2009; U.S. Patent Application Publication Serial No. US 2009/028610, published Nov. 19, 2009.

[0157] U.S. patent application Ser. No. 12/408,250, entitled Cellular Lattice Structures with Multiplicity of Cell Sizes and Related Method of Use, filed Mar. 20, 2009.

[0158] International Application No. PCT/US2009/034690, entitled Method for Manufacture of Cellular Structure and Resulting Cellular Structure, filed Feb. 20, 2009.

[0159] International Application No. PCT/US2008/073377, entitled Synergistically-Layered Armor Systems and Methods for Producing Layers Thereof, filed Aug. 15, 2008, and corresponding U.S. patent application Ser. No. 12/673,647, entitled Synergistically-Layered Armor Systems and Methods for Producing Layers Thereof, filed Feb. 16, 2010.

[0160] International Patent Application No. PCT/US2008/073071, entitled Thin Film Battery Synthesis by Directed Vapor Deposition, filed Aug. 13, 2008, and corresponding U.S. patent application Ser. No. 12/733,160, entitled Thin Film Battery Synthesis by Directed Vapor Deposition, filed Feb. 16, 2010.

[0161] International Patent Application No. PCT/US2008/071848, entitled Hybrid Periodic Cellular Material Structures, Systems, and Methods for Blast and Ballistic Protection, filed Jul. 31, 2008, and corresponding U.S. patent application Ser. No. 12/673,418, entitled Hybrid Periodic Cellular Material Structures, Systems, and Methods for Blast and Ballistic Protection, filed Feb. 12, 2010; U.S. Patent Application Publication No. US 2011/0283873, published Nov. 24, 2011.

[0162] International Application No. PCT/US2008/060637, entitled Heat-Managing Composite Structures, filed Apr. 17, 2008, and corresponding U.S. patent application Ser. No. 12/596,548, entitled Heat-Managing Composite Structures, filed Oct. 19, 2009; U.S. Patent Application Publication No. US 2010/0236759, published Sep. 23, 2010.

[0163] International Application No. PCT/US2007/022733, entitled Manufacture of Lattice Truss Structures from Monolithic Materials, filed Oct. 26, 2007, and corresponding U.S. patent application Ser. No. 12/447,166, entitled Manufacture of Lattice Truss Structures from Monolithic Materials, filed Apr. 24, 2009; U.S. Pat. No. 8,176,635, issued May 15, 2012, and corresponding U.S. patent application Ser. No. 13/448,074, entitled Manufacture of Lattice Truss Structures from Monolithic Materials, filed Apr. 16, 2012.

[0164] International Application No. PCT/US2007/012268, entitled Method and Apparatus for Jet Blast Deflection, filed May 23, 2007, and corresponding U.S. patent application Ser. No. 12/301,916, entitled Method and Apparatus for Jet Blast Deflection, filed Oct. 7, 2009; U.S. Pat. No. 8,360,361, issued Jan. 29, 2013.

[0165] International Patent Application No. PCT/US2006/025978, entitled Reliant Thermal Barrier Coating System and Related Methods and Apparatus of Making the Same, filed Jun. 30, 2006, and corresponding U.S. patent application Ser. No. 11/917,585, entitled Reliant Thermal Barrier Coating System and Related Methods and Apparatus of Making the Same, filed Dec. 14, 2007; U.S. Pat. No. 8,084,086 issued Dec. 27, 2011, and corresponding U.S. patent application Ser. No. 13/337,133, entitled Reliant Thermal Barrier Coating System and Related Methods and Apparatus of Making the Same, filed Dec. 25, 2011; U.S. Patent Application Publication No. 2012/0160166, published Jun. 28, 2012.

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[0168] International Application No. PCT/US04/04608, entitled Methods for Manufacture of Multilayered Multifunctional Truss Structures and Related Structures There from, filed Feb. 17, 2004, and corresponding U.S. patent application Ser. No. 10/545,042, entitled Methods for Manufacture of Multilayered Multifunctional Truss Structures and Related Structures There from, filed Aug. 11, 2005.

[0169] International Patent Application No. PCT/US2003/037485, entitled Bond Coat for a Thermal Barrier Coating System and Related Method Thereof, filed Nov. 21, 2003, corresponding to U.S. patent application Ser. No. 10/535,364, entitled Bond Coat for a Thermal Barrier Coating System and Related Method Thereof, filed May 18, 2005.

[0170] International Patent Application No. PCT/US2003/036035, entitled Extremely Strain Tolerant Thermal Protection Coating and Related Method and Apparatus Thereof, filed Nov. 12, 2003, and corresponding to U.S. patent application Ser. No. 10/533,993, entitled Extremely Strain Tolerant Thermal Protection Coating and Related Method and Apparatus Thereof, filed May 5, 2005.

[0171] International Application No. PCT/US03/27606, entitled Method for Manufacture of Truss Core Sandwich Structures and Related Structures Thereof, filed Sep. 3, 2003, and corresponding U.S. patent application Ser. No. 10/526,296, entitled Method for Manufacture of Truss Core Sandwich Structures and Related Structures Thereof, filed Mar. 1, 2005; U.S. Pat. No. 7,424,967, issued Sep. 16, 2008.

[0172] International Patent Application Serial No. PCT/US03/27605, entitled Blast and Ballistic Protection Systems and Methods of Making Same, filed Sep. 3, 2003, and corresponding U.S. patent application Ser. No. 10/526,414, entitled Blast and Ballistic Protection Systems and Methods of Making Same, filed Mar. 2, 2005; U.S. Pat. No. 7,913,611, issued Mar. 29, 2011.

[0173] International Patent Application No. PCT/US2003/023111, entitled Method and Apparatus for Dispersion Strengthened Bond Coats for Thermal Barrier Coatings, filed Jul. 24, 2003, and corresponding U.S. patent application Ser. No. 10/522,076, entitled Method and Apparatus for Dispersion Strengthened Bond Coats for Thermal Barrier Coatings, filed Jan. 21, 2005.

[0174] International Patent Application Serial No. PCT/US03/23043, entitled Method for Manufacture of Cellular Materials and Structures for Blast and Impact Mitigation and Resulting Structure, filed Jul. 23, 2003, and corresponding U.S. patent application Ser. No. 10/522,067, entitled Method for Manufacture of Cellular Materials and Structures for Blast and Impact Mitigation and Resulting Structure, filed Jan. 21, 2005.

[0175] International Patent Application No. PCT/US2003/017049, entitled Active Energy Absorbing Cellular Metals and Method of Manufacturing and Using the Same, filed May 30, 2003, and corresponding U.S. patent application Ser. No. 10/516,052 entitled Active Energy Absorbing Cellular Metals and Method of Manufacturing and Using the Same, filed Nov. 29, 2004; U.S. Pat. No. 7,288,326, issued Oct. 30, 2007, and corresponding U.S. patent application Ser. No. 11/857,856, entitled Active Energy Absorbing Cellular Metals and Method of Manufacturing and Using the Same, filed Sep. 19, 2007.

[0176] International Application No. PCT/US03/16844, entitled Method for Manufacture of Periodic Cellular Structure and Resulting Periodic Cellular Structure, filed May 29, 2003, and corresponding U.S. patent application Ser. No. 10/515,572, entitled Method for Manufacture of Periodic Cellular Structure and Resulting Periodic Cellular Structure, filed Nov. 23, 2004.

[0177] International Patent Application No. PCT/US2003/012920, entitled Apparatus and Method for Uniform Line of Sight and Non-Line of Sight Coating at High Rate, filed Apr. 25, 2003, and corresponding U.S. patent application Ser. No. 10/512,161, entitled Apparatus and Method for Uniform Line of Sight and Non-Line of Sight Coating at High Rate, filed Oct. 15, 2004; U.S. Pat. No. 7,718,222, issued May 18, 2010.

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[0190] The following publications as listed below and throughout this document are hereby incorporated by reference in their entirety herein: [0191] 1. Lakes, Materials with Structural Hierarchy, Nature, 361, 11 Feb. 1993. [0192] 2. Soler-Illia et al., Chemical Strategies To Design Textured Materials: from Microporous and Mesoporous Oxides to Nanonetworks and Hierarchical Structures, Chem. Rev. 2002, 102, 4093-4138. [0193] 3. Birnkrant et al., Layer-in-Layer Hierarchical Nanostructures Fabricated by Combining Holographic Polymerization and Block Copolymer Self-Assembly, Nano Lett., 2007, 7(10), pp 3128-3133.

[0194] 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 following disclosure, including all modifications and equivalents.

[0195] 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.