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as) United States cz) Patent Application Publication 0) Pub. No.: US 2025/0236521 Al TOUR et al. US 20250236521A1 (43) Pub. Date: Jul. 24, 2025 (4) (71) (72) (73) (25) (22) (86) 104 FLASH JOULE HEATING FOR PRODUCTION OF 1D CARBON AND/OR BORON NITRIDE NANOMATERIALS Applicant: William Marsh Rice University, Houston, TX (US) Inventors: James Mitchell TOUR, Houston, TX (US); John Tianci LI, Houston, TX (US); Kevin WYSS, Houston, TX (US), Jinhang CHEN, Houston, TX (US); Weiyin CHEN, Houston, TX (US); Lucas EDDY, Houston, TX (US); Phelecia SCOTLAND, Houston, TX (US) WILLIAM MARSH RICE UNIVERSITY, Houston, TX (US) Assignee: Appl. No.: 18/863,937 PCT Filed: May 15, 2023 PCT No.: PCT/US2023/067000 § 371 (c\(1), (2) Date: Nov. 7, 2024 Flash Joule Heating Controllable duration and power Related U.S. Application Data (60) Provisional application No. 63/341,934, filed on May 13, 2022. Publication Classification (51) Int. Cl. COIB 21/064 (2006.01) COIB 32/205 (2017.01) HOSB 3/14 (2006.01) (52) US.CL COIB 21/064 (2013.01); CO1B 32/205 (2017.08); HOSB 3/14 (2013.01); COIP 2002/72 (2013.01); COIP 2002/82 (2013.01); COIP 2004/03 (2013.01); COP 2004/04 (2013.01); COLP 2004/13 (2013.01) (57) ABSTRACT Flash Joule heating (FJH) for production of one-dimensional (1D) carbon and/or boron nitride nanomaterials, and 1D materials integrated with OD, 1D, 2D, and 3D nanomaterials, composites, nanostructures, networks, and mixtures thereof. Such materials produced by FJH include 1D carbon and hybrid nanomaterials, boron nitride nanotubes (BNNTs), turbostratic boron-carbon-nitrogen (BCN), doped (substi- tuted) graphene, and heteroatom doped (substituted) re- flashed graphene. Earth abundant catalyst Mixed waste plastic Solventiinert gas-free method
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US 2025/0236521 Al Jul. 24,2025 Sheet 1 of 106 Patent Application Publication VT ‘Old poujow sasj-seh pourqueajosg onsed osem pexiy ysAjeyeo yuepunge yey = Burneay ono ysel ony Sunes quan aemod pue uoreinp epye}osque5 Bunesy anor ysel4 TOT
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Patent Application Publication Jul. 24,2025 Sheet 2 of 106 US 2025/0236521 Al FIG. 1B
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Patent Application Publication Jul. 24,2025 Sheet 3 of 106 US 2025/0236521 Al ae FIG. 1€
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Patent Application Publication Jul. 24,2025 Sheet 4 of 106 US 2025/0236521 Al FIG. 1F FIG. 1D FIG. 1E
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Patent Application Publication Jul. 24,2025 Sheet 8 of 106 US 2025/0236521 Al $ # Two Theta (°) FIG. 2F i 42 44 46 48. Ayisuejui pezipeuu0y 27 26 Two Theta (°) FIG. 2E FE 25 Ajisuayu] pezijeuoN
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Patent Application Publication Jul. 24,2025 Sheet 9 of 106 US 2025/0236521 Al 1500 2000 2500 3000 Raman Shift (cm) FIG. 3A 4000 500 y Aysuajuy pezyewsion
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Patent Application Publication Jul. 24,2025 Sheet 11 of 106 US 2025/0236521 Al ro) ° L ro N S Q = © Pog i > co. L eo | .8 Wu oO OO BS} | & Ae a] Q 2 | & Oo : & | on) t t ® } ¥ 53 ® ¥
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Patent Application Publication Jul. 24,2025 Sheet 12 of 106 US 2025/0236521 Al FIG. 3D
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Patent Application Publication Jul. 24,2025 Sheet 13 of 106 US 2025/0236521 Al FIG. 3F Be FIG. 3E
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Patent Application Publication Jul. 24,2025 Sheet 14 of 106 US 2025/0236521 Al FIG. 4B FIG. 4C FIG. 4A
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Patent Application Publication Jul. 24,2025 Sheet 15 of 106 US 2025/0236521 Al q 8 : 3 a t wi + ane : t oO - x FIG. 4F 442 FIG. 4D
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Patent Application Publication Jul. 24,2025 Sheet 16 of 106 US 2025/0236521 Al FIG. 4H FIG. 41 461 FIG. 4G
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Patent Application Publication Jul. 24,2025 Sheet 17 of 106 US 2025/0236521 Al Coll!) FIG. 5A ‘Fe(ill). Diameter vs Catalyst identity Nid) oO Oo oOo oo © N © Wh © 130+ eon ~ (wu) Jojoweic
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Patent Application Publication Jul. 24,2025 Sheet 18 of 106 US 2025/0236521 Al I FIG. 5B —o— ¥ Diameter vs Catalyst loading 0.1gmL* 0.01gmL* 0.001 gmL* . is Ea OQ OQ ia © oO 8) ie oe (wu) JeJoWeIC] 100 50
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Patent Application Publication Jul. 24,2025 Sheet 20 of 106 US 2025/0236521 Al 0.73 mF mg? mF mg? mF mgt mF mg™ \ 0.97 FIG. 5D 1.46 3.12 Diameter vs Capacitance Density 100 - ° © 2 . # © (WU) JO}OWEIC]
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Patent Application Publication Jul. 24,2025 Sheet 26 of 106 US 2025/0236521 Al 4 [a0] te) o S g de Lhe N fo} N te} co) ie) ‘owe : 4 ‘ oes of a : a se Q oO ee 613
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Patent Application Publication Jul. 24,2025 Sheet 27 of 106 US 2025/0236521 Al Time (ns} FIG. 6C S289 8 ° (%) uonezuiydesg
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Patent Application Publication Jul. 24,2025 Sheet 28 of 106 US 2025/0236521 Al J, Time (ns) FIG. 6D do i j uy © wy ia oI rd (%) Swoye paydayje IN
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Patent Application Publication Jul. 24,2025 Sheet 29 of 106 US 2025/0236521 Al (2g) sninpoy s,Buno, es “ oO uO af _ 2% 2% FIG. 7A 0.5% FIDM FIDM MWCNTMWCNT VE 0.5% (2qIN) uiBUaS eAlssosdw05
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Patent Application Publication Jul. 24,2025 Sheet 32 of 106 US 2025/0236521 Al = Process = Materials ~ FIG. 7D ba Surface Melt Mix 2D Flash Wet F1DM F1DM Graphene FJH Prepartion Method (yonpoid , By ba “Qo 6y) jenuajog Buruuen jeqoig
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Patent Application Publication Jul. 24,2025 Sheet 35 of 106 US 2025/0236521 Al iggy) ssoupaey FIG. 8C @go) sssupiey e a e oe s e ae l 4 FIDM Loading in VE (wt%) FIG. 8A lego} ssaupiey % ca ‘3 4 : os S ee Eo bd lego) snynpoy sGuno,, oe co legal snmpow ofan,
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Patent Application Publication Jul. 24,2025 Sheet 36 of 106 US 2025/0236521 Al (edo) sninpoy ¢,Buno, = cr FIOM FIDM CT FIG. 8E oe 6 *g (wr) ssauy6no} (eaw) buenas eaissoiduiog 8228883 q 46.3% a ee a 43 eT 05% 2% 2% FIOM FIDM CT FIG. 8D 0.5% Hf H H t i i i : i i : : i : i r | 3 (3) wens ununxey
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Patent Application Publication Jul. 24,2025 Sheet 46 of 106 US 2025/0236521 Al FIG. 11B or o 2 o oe 2 & & 5 S sg Oe ey ay (y) aunjesodwia L
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Patent Application Publication Jul. 24,2025 Sheet 47 of 106 US 2025/0236521 Al ES go oS © sit a 6 fe.) 23 “- i, & 2 : He n FIG. 11C H N f 110 °C Hy, (g)
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Patent Application Publication Jul. 24,2025 Sheet 48 of 106 US 2025/0236521 Al FIG. 11D es eee
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Patent Application Publication Jul. 24,2025 Sheet 52 of 106 US 2025/0236521 Al 80 E Seas 28 Le 3 1 2 2 8 a4 o 0 9 . cit ? FIG. 12C 40 50 2-theta (deg) a ae eee 30 20 (ne) Ayisuajzu|
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Patent Application Publication Jul. 24,2025 Sheet 55 of 106 US 2025/0236521 Al FIG. 131 FIG. 13H FIG. 13G
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Patent Application Publication Jul. 24,2025 Sheet 56 of 106 US 2025/0236521 Al FIG. 14C § e ee 3 es eae FIG. 14E ee FIG. 14B FIG. 14D ae a _ _ ponents oo oe . paientnnats we 2a FIG. 14A
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Patent Application Publication Jul. 24,2025 Sheet 57 of 106 US 2025/0236521 Al FIG. 14F
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Patent Application Publication Jul. 24,2025 Sheet 58 of 106 US 2025/0236521 Al FIG. 14G FIG. 14H
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Patent Application Publication Jul. 24,2025 Sheet 63 of 106 US 2025/0236521 Al Stacking structure Cooling stage FIG. 15C Turbostratic Heating stage Reaction progress eunyeiedway]
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Patent Application Publication Jul. 24,2025 Sheet 78 of 106 US 2025/0236521 Al FIG. 17D : “yeoqueyoayy |
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Patent Application Publication Jul. 24,2025 Sheet 92 of 106 US 2025/0236521 Al FIG. 20C
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Patent Application Publication Jul. 24,2025 Sheet 93 of 106 US 2025/0236521 Al (,w) Bole eDeLNS oOo o & & Oo © © & t mo WN a oo FIG. 20D
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Patent Application Publication Jul. 24,2025 Sheet 94 of 106 US 2025/0236521 Al fee FIG. 20E
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Patent Application Publication Jul. 24,2025 Sheet 95 of 106 US 2025/0236521 Al FIG. 20F
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Patent Application Publication Jul. 24,2025 Sheet 96 of 106 US 2025/0236521 Al FIG. 20G
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Patent Application Publication Jul. 24,2025 Sheet 97 of 106 US 2025/0236521 Al FIG. 20H
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Patent Application Publication Jul. 24,2025 Sheet 99 of 106 US 2025/0236521 Al FIG. 22A FIG. 22B
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Patent Application Publication Jul. 24,2025 Sheet 100 of 106 US 2025/0236521 Al 2302 2304 FIG. 23 2303 2301
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Patent Application Publication Jul. 24,2025 Sheet 102 of 106 US 2025/0236521 Al 2200 000 2 Raman Shift (cm) FIG. 25B 1800 snes nan (ne) Aysuaquy aanejoy ap mmm DOrae Raman Shift (cm) FIG. 25A (ne) Asuayyy aaneloy
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Patent Application Publication Jul. 24,2025 Sheet 103 of 106 US 2025/0236521 Al FIG. 25C nding Energy (eV) ‘. n me heesaine OAL = nejow
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Patent Application Publication Jul. 24,2025 Sheet 104 of 106 US 2025/0236521 Al FIG. 26B “FIG. 26C FIG. 26A
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Jul. 24,2025 Sheet 105 of 106 US 2025/0236521 Al Patent Application Publication aZ¢ "Did (ae) AGseug Burpurg (re) Aysuaqu eanejey OG0e Vie Dld (,2u9) yg uewey Hose HOoe Oost (re) Ajisuaqy aaneiey
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Patent Application Publication Jul. 24,2025 Sheet 106 of 106 US 2025/0236521 Al FIG. 28
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US 2025/0236521 Al FLASH JOULE HEATING FOR PRODUCTION OF 1D CARBON AND/OR BORON NITRIDE NANOMATERIALS CROSS-REFERENCED TO RELATED PATENT APPLICATIONS [0001] The application claims priority to U.S. Patent Appl. Ser. No. 63/341,934, filed May 13, 2022, entitled “Flash Joule Heating For Production Of 1D Carbon And/Or Boron Nitride Nanomaterials, 1D Materials Integrated With 0D, 1D, 2D, And 3D Nanomaterials, Composites, Nanostruc- tures, Networks, Or Mixtures Thereof,” which Patent appli- cation is commonly owned by the owner of the present invention. This patent application is incorporated herein in its entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH [0002] This invention was made with government support under Grant No. FA9550-22-1-0526, awarded by the United States Air Force Office of Scientific Research, and Grant No. FE0031794, awarded by the National Science Foundation (Graduate Research Fellowship) and the US Army Corp. of Engineers, ERDC No. W912HZ-21-2-0050. The United States government has certain rights in the invention. TECHNICAL FIELD [0003] The present invention relates to flash Joule heating for production of 1D carbon and/or boron nitride nanoma- terials, 1D materials integrated with OD, 1D, 2D, and 3D nanomaterials, composites, nanostructures, networks, doped or substituted materials, and mixtures thereof. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH [0004] This invention was made with government support under Grant No. FA9550-22-1-0526, awarded by the Air Force Office of Scientific Research, and Grant No. FE0031794, awarded by the National Science Foundation, and Grant No. W912HZ-21-2-0050 awarded by the Army Corp. of Engineers. The government has certain rights in the invention. BACKGROUND [0005] One-dimensional (1D) carbon materials. One-di- mensional (1D) carbon materials have received substantial research and attention since their discovery in the late 20” century. [Ajayan 2001; Rathinavel 2021; Ruiz-Cornejo 2020; Yang 2015]. Although carbon nanotubes present the most widely acknowledged example of such 1D materials, many subclasses and different morphologies have been characterized. [Shi 2019; Kou 2017]. Examples of these 1D carbon nanomaterials include carbon nanotubes (CNTs), both single- and multi-walled, as well as ribbon- and plate- like carbon nanofibers, bamboo-like carbon nanotubes, cup- stacked carbon nanofibers, and many more. [Feng2014; Jai 2017; Liu 2021; Wang2019]. 1D materials are used exten- sively in composites, coatings, sensors, electrochemical energy storage, and electrocatalysts, capitalizing upon their strength, conductivity, low density, broadband electromag- netic absorption, high surface area, and chemical robustness. [Restivo 2020; Kumar 2021; Kour 2020; Wu 2021]. Due to Jul. 24, 2025 their broad utility and scientific interest, identifying new methods of synthesizing 1D carbon materials remains criti- cal. The majority of synthetic strategies to form 1D carbon materials, including arc-discharge, laser ablation, chemical vapor deposition, plasma torch, and high partial pressure carbon monoxide involve the mobilization of carbon atoms in feedstocks on the surface of a catalytic metal which then grow into a graphitic 1D morphology. [Xu 2019]. These current methods often result in mixtures of 1D materials and amorphous carbon that require separation, and 1D materials syntheses often suffer from low production rates of <1 g hr’. [Lee S 2021; McLean 2021; Rao 2018]. [0006] Some recent work has focused on converting waste plastic into higher value carbon nanomaterials, inspired by the low cost and high availability of the feedstock. [Yaqoob 2022; Wang 2020; Williams 2021]. However, these methods often use a two-step chemical vapor deposition pyrolysis process: the first stage deconstructs the plastic into volatile hydrocarbons under an inert atmosphere at temperatures of 700-900° C. for 0.5-2 h. [Zhuo 2014; Sharma 2020]. In the second stage, the hydrocarbon gases then grow into 1D materials on complex transition metal catalysts, once again under inert atmosphere at similarly high temperatures for multiple hours. [Wang 2022; Bazargan 2012; Gong 2013]. The growth catalysts generally require dedicated synthesis or templating methods that can be time, energy, and resource intensive. [Jie 2020; Ahamed 2020; Jia 2022]. [0007] Further, many of these methods use 1:1 ratios of waste plastic to growth metal complex, meaning that every 1 ton of waste plastic processed would require 1 ton of metal complex be manufactured, which would hamper widespread implementation and economic viability. [Cai 2021]. To Applicant’s knowledge, production of complex carbon hybrid materials from waste plastic has not been demon- strated. Current methods of carbon nanomaterial production from waste plastic are hampered by long reaction durations and high resource consumption, large amounts of metal complex additive, and minimal scalability of chemical vapor deposition techniques. [0008] Flash Joule heating (FJH) synthesis. Flash Joule heating (FJH) was recently leveraged as efficient methods for the solvent-free synthesis of a variety of carbonaceous and inorganic nanomaterials. [Luong 2020; Wyss I 2022; Yao 2016; Deng 2022; Guo 2022]. Particularly, FJH has presented a facile method to upcycle low-value waste mate- rials into high-value nanomaterials. [Algozeeb 2020; Wyss I 2021; Advincula 2021; Wyss II 2021]. For the FJH synthesis of graphene, electrical energy and resistance are leveraged to rapidly generate high temperatures and form turbostratic, or rotationally mismatched, graphene as the short duration of FJH (0.05 to 1 seconds) limits the rotational movement. Temperatures >3,100 K are accessed in milliseconds, allow- ing for the reorganization of amorphous carbon bonding into highly ordered sp?-hybridized sheets. [Wyss I 2022]. Flash graphene sheets form through a ‘mobile carbon’ mechanism, with temperatures generated by high resistance junctions within the sample allow for annealing and formation of crystalized nanoparticles. [Stanford 2020]. The capacitance density of the reaction can also control reaction conditions; increasing charge per unit mass shifts the nucleation process from reaction limited to diffusion-controlled reaction kinet- ics. [Algozeeb 2020; Beckham 2022]. [0009] Boron nitride nanotubes (BNNTs). Boron nitride (BN) is a highly intriguing group TII-V compound due to its
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US 2025/0236521 Al exceptional properties, including high thermal conductivity [Terao 2010; Zeng 2017], stability [Zhu 12005; Lee 2016], excellent mechanical strength [Chen 2017; Lahiri 2010], and insulating capabilities [Zh 2009]. The two most studied BN allotropes are one-dimensional (1D) boron nitride nanotubes (BNNTs) and two-dimensional (2D) hexagonal BN (h-BN). BNNTS are considered the structural analog of CNTs, with carbon atoms are replaced by alternating boron and nitrogen atoms. This substitution enhances the nanotubes oxidation resistance in air and results in stronger interaction with polymers compared to CNTs. [Huang 2011; Chen 2015]. [0010] In 1994, Rubio et al. made a theoretical prediction about the existence of BNNTs [Ruio 1994], which were later synthesized by Chopra et al. in 1995 using are-discharge methods [Chopra 1995]. Since then, various methods were used to synthesize BNNTs. including laser ablation [Yu 1998; Kim 2019; Bae 2022], ball-milling combined anneal- ing method [Chen 1999, Kim 2011; Zhuang 2016], tem- plate-assisted synthesis [Tay 2015; Wang 2008], chemical vapor deposition (CVD) [Pakdel 2012; Lourie 2000; Kim J 2018], thermal plasma [Kim 2020; Fathalizadeh 2014]. [0011] The preparation method directly determines the length, diameter and purity of BNNT, which plays a vital role in the applications. CVD is widely regarded as the most promising method for producing high-quality BNNT. This technique operates on a Vapor-Liquid-Solid (VLS) growth mechanism. [Zhi II 2005]. The yield and shape of BNNTs are extremely dependent on device design, gas flow, pre- cursors, and catalysts. However, the CVD technique is still limited in its ability to produce BNNTs on a large scale. The method of using ball-milling and annealing is acknowledged for its ability to produce BNNTs with a high yield at a low cost. The BNNTs prepared by this method mainly possessed a bamboo-like structure. Laser ablation and thermal plasma are feasible to prepare BNNTs with a high production rate. Laser or high temperature plasma are used as the heat source to provide high energy, so that the surface temperature of the precursor is instantly raised and gasified to obtain thin- walled BNNT. The reaction mechanism remains unclear and the purification processes are required to remove these impurities, such as B and h-BN. [0012] Turbostratic Boron-Carbon-Nitrogen (BCN). Canonical layered materials usually have a distinct and thermodynamically favored stacking sequence under stan- dard temperature and pressure conditions. [Luong 2020; Stanford 2020]. The stacking sequence is determined by various non-covalent interactions, such as van der Waals, London, and Keesom interactions. [Smith 2011]. Deviation from these stacking morphologies leads to the formation of turbostratic lattices with the expansion of intrinsic interlayer distances and the weakening of coupling interactions between the neighboring layers [Advincula 2021; Algozeeb 2020], which can introduce unique optical, electrical, and magnetic properties for turbostratic materials, thus broad- ening their applications. [Wyss 12021; Chen 112021]. [0013] A major concern for the synthesis of turbostratic materials lies in the unfavorable formation energy and the spontaneous relaxation towards the thermodynamically favored stacking sequence. Once a sustained heat source is provided, products with thermodynamically most stable layered sequences dominate, making the access to tur- bostratic structures difficult.2*!") [Stanford 2020; Ba 2017; Song 2010; Xu D 2018] Therefore, most bottom-up methods for preparing layered materials cannot be adopted for syn- Jul. 24, 2025 thesizing turbostratic materials because of an insuflicient relaxation energy barrier (<4 kJ mol~') [Rydberg 2003] and. limited cooling rate (<10 K s7*). [Chilkoor 2020; Wang 2017]. The organization of regular in-plane configurations is usually accompanied by the formation of self-limited mono- layer or well-aligned multilayer structures. [0014] Although previous work has demonstrated that the formation of turbostratic structures can be induced by low- temperature (~500 K) heat treatment, or bias-assisted hot- filament chemical vapor deposition (CVD), these products usually have a semi-crystalline in-plane configuration with hybrid nanocrystalline and amorphous domains. [Kakiagea 2013; Ahn 2000]. The semi-crystalline in-plane structures can prevent the precise stacking of individual layers, which induces the formation of the turbostratic stacking structures. In addition, guest intercalation methods using ionic liquids [Lian 2009] and chemical functionalization [Cao 2022] have been used to stabilize turbostratic materials. These methods are ascribed to the modification of interlayer interactions, such as hydrogen bonds and 71-71 stacking between neigh- boring basal planes. Therefore, the direct synthesis of tur- bostratic materials with high in-plane crystallinity remains challenging when one wants to study the unique properties caused by the weak coupling effect between neighboring layers. [0015] The semi-crystalline in-plane structure is common for multicomponent systems when starting from gaseous precursors, such as boron-nitrogen dual compounds [Demirci 2020] and boron-carbon-nitrogen ternary com- pounds (BCN). [Ahn 2000; Puyoo 2017]. These reactive precursors, such as BCI, and NH, [Puyoo 2017], or ammo- nia borane (BH;NH;) [Zhong 2017], achieve fast conver- sion and cause the formation of amorphous products with numerous structural imperfections. Although the in-plane crystallinity of the products can be improved by controlling the annealing time and temperature, either semi-crystalline structures or well-aligned stacking structures eventually form [Chilkoor 2020; Ahn 2000] because of the thermody- namic limitation of these traditional bottom-up methods and metastable features of turbostratic materials with high in- plane crystallinity. [Luong 2020; Stanford 2020]. [0016] Turbostratic layers in 2D materials have an inter- layer misalignment. The lack of alignment expands the intrinsic interlayer distances and weakens the optical and electronic interactions between adjacent layers. This intro- duces properties distinct from those structures with well- aligned lattices and strong coupling interactions. However, direct, and rapid synthesis of turbostratic materials remains a challenge owing to their thermodynamically metastable properties. [0017] Doped Graphene. Graphene is a 2D material with exceptionally high mechanical strength, electrical conduc- tivity, and other desirable chemical properties. [Ye 2019]. Graphene is often doped (or one could use the term “sub- stituted” since the replaced or added atoms can be as greater than 5 wt %) with non-carbon atoms in order to chemically modify the graphene and tune its chemical, physical, and optical properties. [Wang 2014; Xu H 2018; Agnoli 2016]. These atoms can be placed into the graphene lattice and are thus most commonly similar in atomic radius to carbon atoms, or added above and below the place of the graphene lattice as in, for example, the addition of fluorine atoms. The resulting lattice is often comprised of up to a few percent heteroatoms by atomic ratio. A prominent technique to
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US 2025/0236521 Al mass-produce graphene known as flash Joule heating (FJH) was published in 2020 by which amorphous carbon com- pounds can be converted to turbostratic graphene using an electrical pulse. [Luong 2020]. The amorphous carbon can be derived from a variety of sources, including coal prod- ucts, waste plastic [Wyss II 2022; Wyss II] 2022; Wyss 1 2021], and rubber waste [Advincula 2021]. In 2022, an article was published presenting the mixing of amorphous carbon feedstocks with organic feedstocks that contain non- carbon atoms, such as melamine and boric acid, and flashing of these feedstocks together to make heteroatom (non- carbon) doped flash graphene. [Chen 2022] [0018] In this previously reported technique, the organic heteroatom feedstocks along with the amorphous carbon feedstocks are destroyed. During the subsequent graphene formation, the non-carbon heteroatoms formerly present in these feedstocks place themselves inside the graphene struc- ture or above and below the plane such that the product is doped graphene. The quantity of the non-carbon heteroa- toms present in the graphene lattice was described in terms of a doping percentage, which is an atomic percentage of the graphene lattice that is comprised of non-carbon atoms. By this method, doping percentages of up to 7.4% for single- dopant flashes were achieved in the graphene lattice in different trials with sulfur, nitrogen, boron, and fluorine atoms, and slightly higher doping ratios were achieving by the simultaneous use of combinations of these dopants. SUMMARY OF THE INVENTION [0019] The present invention relates to flash Joule heating (FJH) for production of one-dimensional (1D) carbon and/or boron nitride nanomaterials, and 1D materials integrated with OD, 1D, 2D, and 3D nanomaterials, composites, nano- structures, networks, and mixtures thereof. Such materials produced by FJH include 1D carbon and hybrid nanomate- rials, boron nitride nanotubes (BNNTs), turbostratic boron- carbon-nitrogen (BCN), doped (substituted) graphene, and heteroatom doped (substituted) re-flashed graphene. [0020] In general, in one embodiment, the invention fea- tures a method that includes flash Joule heating a mixture of a material and a catalyst to form a 1-dimensional structure. [0021] Implementations of the invention can include one or more of the following features: [0022] The flash Joule heating can be a process that includes applying a voltage across the mixture, which drives a current through the mixture to form the 1-dimensional structure. The voltage can be applied in one or more voltage pulses. The duration of each of the one or more voltage pulses can be for a duration period. [0023] The material can be a carbon material that is substantially not graphene. [0024] The 1-dimensional structure can be a graphitic 1D and/or hybrid material nanomaterial. [0025] The method can further include forming the 1-di- mensional structure forms along with one or more other dimensional structures selected from the group consisting of 0-dimensional structures, 2-dimensional structures, and mixtures thereof. [0026] The 1-dimensional structure and the one or more other dimensional structures can be conjoined covalently or non-covalently. [0027] The 1-dimensional structure and the one or more other dimensional structures can be conjoined to form a 3-dimensional network. Jul. 24, 2025 [0028] The material can be a carbon material including a polymer. [0029] The mixture can be formed by loading the polymer with particles of the catalyst through surface wetting. [0030] The mixture can be formed by loading the polymer with particles of the catalyst through melt mixing. [0031] The materials can be a waste product including carbon. [0032] The catalyst can be selected from the group con- sisting of iron(II) chloride, nickel(II) chloride, cobalt(II) chloride, and ferrocene. [0033] The catalyst can be selected from the group con- sisting of any transition metal or main group metal or transition metal or main group metal complex, salt, oxide, halide, or combinations thereof. [0034] The mixture can further include a conductive car- bon additive. [0035] The conductive carbon additive can be selected from the group consisting of graphene, flash graphene, turbostratic graphene, anthracite coal, coconut shell-derived carbon, higher temperature-treated biochar, activated char- coal, calcined petroleum coke, metallurgical coke, coke, shungite, carbon nanotubes, asphaltenes, acetylene black, carbon black, ash, carbon fiber, and mixtures thereof. [0036] The conductive carbon additive can include carbon black and/or metallurgical coke. [0037] The method can further include that, after the flash Joule heating, separating at least some of the conductive carbon additive from the formed the 1-dimensional struc- ture. [0038] The step of separating can be based grain size of the conductive carbon additive and size of the 1-dimensional structure formed. [0039] The step of separating can include sieving to sepa- rate the small 1-dimensional structure from the large grain conductive carbon additive. [0040] After the step of separating, % yield of 1-dimen- sional structure formed in the method can be at least 80%. [0041] After the step of separating % yield of the 1-di- mensional structure formed in the method can be between 80% and 90%. [0042] The % yield of 1-dimensional structure formed in the method can be at least 65%. [0043] The % yield of the 1-dimensional structure formed in the method can be at least 80%. [0044] In general, in another embodiment, the invention features a 1-dimensional structure that is made by any of the above-described methods. [0045] Implementations of the invention can include one or more of the following features: [0046] The 1-dimensional structure can be any form of nanostructure or microstructure in which length of the 1-dimensional structure is at least 3 times longer than the width of the 1-dimensional structure. [0047] The 1-dimensional structure can be not a single atomic sheet thick. [0048] In general, in another embodiment, the invention features a composite that includes any of the above-de- scribed the 1-dimensional structures. [0049] Implementations of the invention can include one or more of the following features: [0050] The composite can include the 1-dimensional structure and a vinyl ester.
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US 2025/0236521 Al [0051] The composite can be a 1-dimensional structure reinforced vinyl ester resin nanocomposite. [0052] In general, in another embodiment, the invention features a structure or network that is made by any of the above-described methods. [0053] Implementations of the invention can include one or more of the following features: [0054] The 1-dimensional structure of the structure or network can be any form of nanostructure or microstructure in which length of the 1-dimensional structure is at least 3 times longer than the width of the 1-dimensional structure. [0055] The 1-dimensional structure of the structure or network can be not a single atomic sheet thick. [0056] In general, in another embodiment, the invention features a method that includes flash Joule heating a mixture to form boron nitride nanotubes. The mixture includes (i) a material comprising boron, (ii) a material comprising nitro- gen and (iii) a catalyst. [0057] Implementations of the invention can include one or more of the following features: [0058] The flash Joule heating can be a process that includes applying a voltage across the mixture, which drives a current through the mixture to form the boron nitride nanotubes. The voltage can be applied in one or more voltage pulses. The duration of each of the one or more voltage pulses can be for a duration period. [0059] The material including the boron and the material including the nitrogen can be different materials. [0060] The material include the boron and the material including the nitrogen are the same material. [0061] The same material can be ammonia borane. [0062] The catalyst can be Ni(acac), and/or Fe(acac),. [0063] The catalyst can include Ni and/or Fe. [0064] The mixture can further include a conductive car- bon source. [0065] The conductive carbon source can be selected from the group consisting of graphene, flash graphene, tur- bostratic graphene, anthracite coal, coconut shell-derived carbon, higher temperature-treated biochar, activated char- coal, calcined petroleum coke, metallurgical coke, coke, shungite, carbon nanotubes, asphaltenes, acetylene black, carbon black, ash, carbon fiber, and mixtures thereof. [0066] The conductive carbon source can include carbon black and/or metallurgical coke. [0067] The mixture can include (i) the material including the boron and the material including the nitrogen and (b) the conductive carbon source in a weight ratio between 1:2 and 2:1. [0068] The method can further include that, after the flash Joule heating, separating at least some of the conductive carbon source from the boron nitride nanotubes formed. [0069] The step of separating can be based grain size of the conductive carbon source and size of the boron nitride nanotubes formed. [0070] The step of separating can include sieving to sepa- rate the small boron nitride nanotubes from the large grain conductive carbon source. [0071] After the step of separating, % yield of boron nitride nanotubes formed in the method can be at least 45%. [0072] After the step of separating, % yield of the 1-di- mensional structure formed in the method can be at least 60%. [0073] The % yield of the boron nitride nanotubes formed in the method can be at least 45%, Jul. 24, 2025 [0074] The % yield of the boron nitride nanotubes formed in the method can be at least 60%. [0075] The n products of the method can include the boron nitride nanotubes and a sheet-like structure. [0076] At least 30% of the products of the method can be boron nitride nanotubes. [0077] In general, in another embodiment, the invention features a composition that include boron nitride nanotubes made by any of the above-described methods. [0078] In general, in another embodiment, the invention features a method that includes flash Joule heating a mixture to form turbostratic nanomaterial including (a) boron, (b) nitrogen, and a (c) third element selected from the group consisting of carbon, tungsten, or iron. The mixture includes (i) a material including boron, (ii) a material including nitrogen, and (iii) a material including the third element. [0079] Implementations of the invention can include one or more of the following features: [0080] The flash Joule heating can be a process that includes applying a voltage across the mixture, which drives a current through the mixture to form the turbostratic nanomaterial. The voltage can be applied in one or more voltage pulses. The duration of each of the one or more voltage pulses can be for a duration period. [0081] The third element can be carbon, and the tur- bostratic nanomaterial can be turbostratic BCN. [0082] The third element can be tungsten, and the tur- bostratic nanomaterial can be turbostratic BN-W. [0083] The third element can be iron and the turbostratic nanomaterial can be turbostratic BN-Fe. [0084] The mixture can include (i) the material including the boron and the material including the nitrogen and (b) the material including the third element in a weight ratio above 4:1. [0085] The mixture comprises (i) the material including the boron and the material including the nitrogen and (b) the material including the third element in a weight ratio between 1:2 and 2:1. [0086] The % yield of the turbostratic nanomaterial formed in the method can be at least 20%. [0087] The % yield of the turbostratic nanomaterial formed in the method can be at least 30%. [0088] In general, in another embodiment, the invention features a composition including a turbostratic nanomaterial including (a) boron, (b) nitrogen, and (c) a third element selected from the group consisting of carbon, tungsten, and iron. The composition is made by any of the above-de- scribed methods. [0089] In general, in another embodiment, the invention features a method to form doped or substituted graphene. The method includes performing a first flash Joule heating process using a first mixture to form a first formed graphene. The first mixture includes (i) a carbon source that is sub- stantially not graphene and (ii) a catalyst. The method further includes mixing one or more heteroatom doping compounds with the first formed graphene to form a second mixture. The method further includes performing a second flash Joule heating process using the second mixture to form the doped or substituted graphene. [0090] Implementations of the invention can include one or more of the following features: [0091] The first flash Joule heating process can include applying a first voltage across the first mixture, which drives a first current through the first mixture to form the first
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US 2025/0236521 Al formed graphene. The first voltage can be applied in one or more first voltage pulses. The duration of each of the one or more first voltage pulses can be for a first duration period. The second flash Joule heating process can include applying a second voltage across the second mixture, which drives a second current through the second mixture to form the doped or substituted graphene. The second voltage can be applied in one or more second voltage pulses. The duration of each of the one or more second voltage pulses can be for a second duration period. [0092] The first formed graphene can be a 1-dimensional structure. [0093] The 1-dimensional structure can be formed by any of the above-described methods. [0094] The first formed graphene can be holey and wrinkled graphene. [0095] The first formed graphene can be turbostratic gra- phene. [0096] The carbon material can include a polymer. [0097] The carbon material can be a waste product com- prising carbon. [0098] The carbon material can be a plastic. [0099] The carbon material can be selected from the group consisting of graphene, flash graphene, turbostratic gra- phene, anthracite coal, coconut shell-derived carbon, higher temperature-treated biochar, activated charcoal, calcined petroleum coke, metallurgical coke, coke, shungite, carbon nanotubes, asphaltenes, acetylene black, carbon black, ash, carbon fiber, and mixtures thereof. [0100] The conductive carbon material can include met- allurgical coke and/or bituminous activated charcoal. [0101] The catalyst can be selected from the group con- sisting of iron(II) chloride, nickel(II) chloride, cobalt(II) chloride, and ferrocene. [0102] The catalyst can be selected from the group con- sisting of any transition metal or main group metal or transition metal or main group metal complex, salt, oxide, halide, or combinations thereof. [0103] The method can further include that, after the first flash Joule heating process, separating at least some of the carbon material from the formed the first formed graphene. [0104] The step of separating can be based grain size of the carbon material and size of the first formed graphene. [0105] The step of separating can include sieving to sepa- rate the small first formed graphene from the large grain carbon material. [0106] The step of mixing to form the second mixture can include mixing exactly one heteroatom doping compound with the first formed graphene. [0107] The step of mixing to form the second mixture can include mixing two or more heteroatom doping compounds with the first formed graphene. [0108] The one or more heteroatom doping compounds each can include at least one heteroatom selected from the group consisting of boron, nitrogen, sulfur, and fluorine. [0109] The one or more heteroatom doping compounds can be each selected from the group consisting of boric acid, melamine resin, polyphenylene sulfide, perfluorooctanoic acid. [0110] The one or more heteroatom doping compounds can include an organic powder having a low melting point. [0111] The ratio of (i) one or more heteroatom doping compounds and (ii) the first formed graphene can be in a weight ratio between 1:8 and 1:2. Jul. 24, 2025 [0112] The second flash Joule heating process can be performed under an argon atmosphere. [0113] The carbon source can have a large grain size. [0114] The second flash Joule heating process can be performed using a first second-flash-Joule-heating voltage and a second-flash-Joule-heating voltage. The second sec- ond-flash-Joule-heating voltage can be greater than the first second-flash-Joule-heating voltage. [0115] The second second-flash-Joule-heating voltage can be at least twice the first second-flash-Joule-heating voltage. [0116] The second second-flash-Joule-heating voltage can be at least five times the first second-flash-Joule-heating voltage. [0117] The second flash Joule heating process can be performed with a pulse width modulated DC electrical pulse from a capacitor bank discharge. [0118] The second flash Joule heating process can be performed with a modulated or non-modulated AC and DC current source. [0119] The first flash Joule heating process can be per- formed in a first cylindrical reactor having a first diameter. The second flash Joule heating process can be performed in a second cylindrical reactor having a second diameter. The first dimeter can be greater than the second reactor. [0120] The doped or substituted graphene can include heteroatoms doped into the graphene lattice. [0121] The doped or substituted graphene can include heteroatoms above or below the graphene lattice. [0122] The doped or substituted graphene can include heteroatoms doped into the graphene lattice and heteroatoms above or below the graphene lattice. [0123] The doping ratio of the doped or substituted gra- phene can be at least 10%. [0124] The doping ratio of the doped or substituted gra- phene can be at least 20%. [0125] In general, in another embodiment, the invention features doped or substituted graphene that is made by any of the above-described methods. [0126] In general, in another embodiment, the invention features a method that includes mixing any of the above- described doped or substituted graphene in a concrete to increase mechanical strength of the concrete. [0127] In general, in another embodiment, the invention features a concrete that includes any of the above-described doped or substituted graphene. [0128] In general, in another embodiment, the invention features a method that includes mixing any of the above- described doped or substituted graphene in an epoxy to increase mechanical strength of the concrete. [0129] In general, in another embodiment, the invention features an epoxy that includes any of the above-described doped or substituted graphene. [0130] In general, in another embodiment, the invention features a battery having a battery electrode that includes any of the above-described doped or substituted graphene. BRIEF DESCRIPTION OF THE DRAWINGS [0131] FIGS. 1A-1F show preparation of flash 1D mate- rials (FIDM). FIG. 1A is a schematic of FJH process forming FIDM with a representative scanning electron microscope (SEM) image showing carbon F1DM-rich area of the sample. FIGS. 1B-1C are SEM images of FIDM rich areas within the sample, showing the tangled arrangement of 1D materials produced. TEM images of different FIDM
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US 2025/0236521 Al morphologies including ribbon-type nanofiber (FIG. 1D), bamboo-like nanofiber (FIG. 1E), and multi-walled nano- tubes (FIG. 1F). Lattice fringes are highlighted with yellow lines to help guide the eye, and the average interlayer spacing for each morphology is also provided. The fast Fourier transform of FIG. 1F is shown in the inset demon- strating the prominent (002) fringe of the nanotube. The scale bars in images correspond to (i) 5 um for FIG. 1A, (ii) 3 wm for FIG. 1B, (iii) 300 nm for FIG. 1C, and (iv) 10 nm for FIGS. 1D-1F. [0132] FIGS. 2A-2F show characterization of FIDM syn- thesized from virgin HDPE powder. FIG. 2A shows repre- sentative high resolution extended Raman spectrum of a sample of FIDM compared to a control sample where no metal was incorporated but all FJH parameters were the same. FIG. 2B is Raman spectra comparing the FIDM sample to the control sample, showing the average Raman spectra from a 36 um? area and the absence of radial breathing mode peaks in the control sample. FIG. 2C is Raman spectra comparing the M, TS,, and TS, peaks in the high resolution FIDM sample to the control sample, show- ing the presence of the M peak only in the FIDM sample. FIG. 2D is powder XRD comparing the FIDM to the starting material and a control sample where no metal catalyst was used, but all other parameters are identical. FIG. 2E is powder XRD spectra comparing the (002) peak of the FIDM and control sample, showing the multi-Lorentzian peak of the F1DM. FIG. 2F is powder XRD spectra showing the (101) and (100) peak area, showing the enhanced (101) peak in the FIDM sample. [0133] FIGS. 34-3F show characterization of F1DM syn- thesized from post-consumer mixed waste plastic. FIG. 3A is a Raman spectrum that shows mixed waste plastic derived F1DM characterized by large area Raman average spectrum. FIG. 3B is powder XRD comparing the waste plastic to the synthesized FIDM. FIG. 3C is survey and high resolution XPS. FIGS. 3D-3F are SEM images showing morphologies of waste plastic derived FIDM. [0134] FIGS. 4A-41 show electron microscope images showing areas of 1D and 2D morphologies colocalizing to form graphitic hybrid materials and molecular dynamics models. FIGS. 4A-4D are SEM images showing colocaliza- tion and coalescence of 1D and 2D graphitic materials, with 2D morphologies attached to the ends of 1D morphologies. FIG. 4E is a TEM image showing an area of colocalization of a bamboo-like carbon nanofibers with the edge of a graphene sheet. FIG. 4F is a high-resolution TEM image of the area highlighted in FIG. 4F. FIG. 4G is a TEM image of a bamboo-like nanofiber merging with a graphene flake. FIG. 4H is an atomic resolution bright field TEM image of the area highlighted in FIG. 4G. FIG. 41 is the fast Fourier transform showing AB stacking in the hybrid material shown in FIG. 4H. The scale bars in images correspond to (i) 20 wm for FIG. 4A, (ii) 3 pm for FIGS. 4B-4C, (iii) 1 pm. for FIG. 4D, (iv) 20 nm for FIGS. 4E-4F, (v) 100 nm for FIG. 4G, and (vi) 20 A for FIG. 4H. [0135] FIGS. 5A-5] show quantitative analysis of size and morphology control through FJH parameter tuning. FIGS. 5A-5D are confidence interval plots examining, respec- tively, the effect that (a) catalyst species, (b) catalyst con- centration in the wetting solution, (c) peak voltage during FJH, and (d) capacitance density applied during FJH has on the diameter of the FIDM, as determined by SEM images. The mean diameter is shown by the dot, with a 95% Jul. 24, 2025 confidence interval shown by the error bars. A line connect- ing the mean of each sample is provided to guide the eye. FIGS. 5E-5H are stacked column plots examining, respec- tively, the effect that (e) catalyst species, (f) catalyst con- centration in the wetting solution, (g) discharge voltage applied during FJH, and (h) capacitance density applied during FJH has on the morphology of the F1DM, as deter- mined by SEM images. FIG. 5I are stacked column plots examining the morphological composition of the sample used in the vinyl ester composites; the sample obtained after sieving; and the sample obtained from iterative mixing twice. Each data point in FIGS. 5A-5D represents 120 individual carbon nanofibers or nanotubes, from 6 randomly selected areas of the sample to ensure an accurate average was obtained. In FIGS. 5E-5I, 108 randomly selected areas for each sample (12 images, each divided into 9 equal area regions) were imaged and assigned a dominant morphology, either 1D, 2D or hybrid. The optimized parameters to maximize 1D and hybrid morphology share is 0.1 g mI-' of Fe(III), with discharge of 200 V and capacitance density of 1.46 mF mg”. [0136] FIGS. 6A-6D show atomistic simulations of the amorphous carbon annealed at 3000 K in contact with a Ni nanoparticle. FIG. 6A shows configuration after initial pre- annealing, while FIG. 6B shows the final structure shows the beginning of the carbon fiber formation through carbon interaction and catalytic graphitization. FIG. 6C shows graphitization level of all carbon and carbon affected by Ni. FIG. 6D shows the percentage of carbon affected by Ni particle throughout the simulation. [0137] FIGS. 7A-7F show quantitative comparison of FIDM utility in composites and sustainability with com- mercial alternatives. FIGS. 7A-7B show, respectively, mechanical analysis of vinyl ester nanocomposites rein- forced with F1DM in (a) bulk scale compressive testing as compared with commercial multiwalled carbon nanotubes (MWCNT) and (b) FIDM in tensile testing as compared to neat matrix material. FIGS. 7C-7E show, respectively, the (c) cumulative energy demand, (d) global warming poten- tial, and (e) cumulative water use associated with F1DM synthesis of FIDM through the surface wetting or melt mixing catalyst loading strategy, as compared to the FJH synthesis of 2D flash graphene where metal catalyst is not required. FIG. 7F shows a comparison of the two FJH synthesis of FIDM strategies considered in the life-cycle assessment, as compared with literature life-cycle assess- ment probing the synthesis of carbon nanotubes or nanofi- bers. [0138] FIGS. 84-8G show mechanical testing of FIDM and vinyl ester epoxy composites, as compared to SO nm diameter commercial MWCNT obtained from the company Cheap Tubes (5% CheapTubes), as well as 2D flash gra- phene synthesized by the FJH. FIGS. 8A-8C show nanoscale compressive testing, FIGS. 8D-8E show macro-scale com- pressive testing, and FIGS. 8F-8G show macro-scale tensile testing [0139] FIGS. 9A-9D show representative stress-strain curves for mechanical testing shown in FIGS. 8A-8G. FIG. 9A shows nanoscale compressive testing, FIGS. 9B-9C show macro-scale compressive testing, and FIG, 9D shows macro-scale tensile testing. [0140] FIGS. 10A-10C are schemes for life cycle inven- tory for the considered FH scenarios to synthesize F1DM, as compared to predominant industrial methods. FIG. 104
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US 2025/0236521 Al
shows a scheme for general commercial methods, FIG. 10B
shows a scheme for melt mixing and FJH for FIDM, and
FIG. 10C shows a scheme for surface wetting and FJH for
FIDM.
[0141] FIGS. 11A-11E show synthesis of boron nitride
nanotubes (BNNT) by flash Joule heating. FIG. 11A is a
schematic diagram of FJH device and BNNT production
from ammonia borane (AB) precursors. FIG. 11B is the
temperature measurement curve of sample during the FIH
process. FIG. 11C is the conversion of AB in melt-mixing
and FJH process. FIGS. 11D-11E are photographs of flash
device with quartz tube and polyetheretherketone (PEEK)
tube.
[0142] FIGS. 12A-12D show characterizations of synthe-
sized BNNT by FJH. FIG. 12A FTIR spectra of AB precur-
sor and flashed product. FIG. 12B is Raman spectra of AB
precursor and flashed product. FIG. 12C is XRD patterns of
AB precursor and flashed product. FIG. 12D is B is spectra
of AB precursor and flashed product.
[0143] FIGS. 13A-13] are SEM images of BNNT product
formation. FIGS. 13A-13C are SEM images of BNNTs
formation in quartz tube. FIGS. 13D-13F are SEM images of
BNNTs formation in PEEK tube. FIG. 13G is low-magni-
fication SEM image of tube-rich region. FIG. 13H is low-
magnification SEM image of sheet-rich region. FIG. 13] is
an SEM image of BN sheets formation in quartz tube.
[0144] FIGS. 14A-14K are images of BNNTs in the
flashed products. FIGS. 14A-14E are TEM images of
BNNTs and BN sheets formed in quartz tube. FIG. 14F are
HAADF-STEM images, and corresponding elemental dis-
tribution of BNNT. FIGS. 14G-14H are HAADF-STEM.
images, and corresponding elemental distribution of BN
sheets. FIG. 141 is a TEM image of the catalyst particle.
FIGS. 14]-14K are HAADF-STEM images, and corre-
sponding elemental distribution of BNNT bamboo-like
structure.
[0145] FIGS. 154-15D shows all-solid-state synthesis of
f-BCN by flash Joule heating. FIG. 15A is a schematic
diagram for the formation of fBCN from BH,NH, and
carbon via FJH. FIG. 15B shows real-time temperature
measurement from the sample during the FJH process. FIG.
15C is a time-temperature-transformation diagram showing,
the kinetic formation of the turbostratic structure with ultra-
fast cooling (+10° K s~'). FIG. 15D is the potential energy
profiles of h-BN sheets of various sizes (per atom) along the
rotational minimum energy pathways from AA‘ to AB
stacking.
[0146] FIGS. 16A-16] shows spectroscopic analysis and
crystal structure of f-BN. FIG. 16A is FTIR spectra of
BH;NH, f-BN and commercial h-BN. FIG. 16B is Raman
spectra of BH,NH; and f-BN. FIG. 16C is representative
high-resolution Raman spectra reporting E,, peak positions
of BN and commercial h-BN. FIG. 16D is the statistic
survey about E,, peak positions of {BN and commercial
h-BN. The number of samples N=100. FIG. 16E are
schemes showing the structures of h-BN and t-BN. FIG. 16F
is XRD spectra of f-BN and commercial h-BN. FIGS.
16G-16H are high resolution XPS spectra of commercial
h-BN and f£-BN. FIG. 16G is B is spectra, and FIG. 16H N
is spectra. FIG. 16] is HR-TEM images of f-BN sheets. FIG.
16] is BF-SSTEM, HAADF-STEM images and correspond-
ing elemental distribution of {BN sheets.
[0147] FIGS. 174-171 show mechanical exfoliation tests
of BN. FIGS. 17A-17B are SEM images showing the tape
Jul. 24, 2025
exfoliation results of, respectively, (a) {BN and (b) com-
mercial h-BN. FIG. 17C shows the size distributions of f-BN
and commercial h-BN by the tape exfoliation method. The
number of samples N=100. FIGS. 17D-17E are SEM images
showing the monodirectional mechanical shearing results of,
respectively, (d) f-BN and (e) commercial h-BN. FIG, 17F
shows the size distributions of {BN and commercial h-BN
by the monodirectional mechanical shearing method. The
number of samples N=100. FIGS. 17G-17H are TEM
images of, respectively, (g) BN and (h) commercial h-BN
after bath sonication treatment, both atop a lacy carbon grid.
FIG. 171 shows the layer number distributions of the {-BN
by the bath sonication treatment. The number of samples
N-16.
[0148] FIGS. 18A-18D show the electrochemical anticor-
rosion tests of {-BN composites. FIGS. 18A-18B are,
respectively, (a) Bode plots and (b) Tafel plots for the
electrochemical analysis of bare Cu, Cu-PVA, Cu-PVA-h-
BN and Cu-PVA-f-BN in 3.5 wt % NaCl (aq). FIGS.
18C-18D are, respectively, (c) Bode plots and (d) Tafel plots
for Electrochemical analysis of bare Cu, Cu-PVA, Cu-PVA-
h-BN and Cu-PVA-f-BN in 0.5 M H,SO,.
[0149] FIGS. 19A-19D show the electrochemical LPR
tests of different coating materials in 3.5 wt % NaCl (aq) for,
respectively, (a) bare Cu, (b) Cu-PVA, (c) Cu-PVA-b-BN,
and (d) Cu-PVA-f-BN.
[0150] FIGS. 20A-20H show characterizations of {-BCN
with different chemical compositions. FIG. 20A is schematic
of fBCN with variable atomic ratios. FIG. 20B shows the
elemental distributions of different f-BCN samples. FIG.
20C shows valence band maximum (VBM) of different
£BCN samples. FIG. 20D shows interlayer spacing and
surface area of different {-BCN samples. FIG. 20E shows a
TEM image and Moiré pattern of fBCN-30 and FIG. 20F
shows the corresponding FFT results. FIG. 20G is an HR-
TEM image showing in-plane crystallinity of {-BCN-30.
FIG. 20H is HAADF-STEM, BF-STEM images, and cor-
responding elemental distribution of {-BCN-30 sheets. The
scale bars are 20 nm.
[0151] FIG. 21 shows a boron-carbon-nitrogen ternary
phase diagram before thermal treatment.
[0152] FIGS. 22A-22B show a schematic of a general
workflow for the synthesis process of heteroatom doped
reflash graphene (FG) from, respectively (a) metallurgical
coke (MC) and (b) bituminous activated charcoal (BAC) by
flash Joule heating (FJH).
[0153] FIG. 23 shows a schematic illustration of a flashing
vessel used in an embodiment of the present invention.
[0154] FIGS. 24A-24B show a schematic of the flashing
vessels inputs and outputs. The re-flash doping process is
composed of two separate flashing reactions (shown in
FIGS. 24A-24B, respectively)
[0155] FIGS. 25A-25C show spectroscopic analysis of
N-doped BAC flash graphene. FIG. 25A shows average of
100 Raman spectra (with standard deviation). FIG. 25B
shows high resolution Raman spectrum showing the TS, and
TS, peaks, which are positive indicators of turbostraticity.
FIG. 25C shows XPS spectrum in which the nitrogen peak
is deconvoluted based on its bonding types. The nitrogen
content was measured here to be over 5%.
[0156] FIGS. 26A-26C show an SEM image and EDX
elemental analysis of N-doped flash graphene.
[0157] FIGS. 27A-27B show spectroscopic analysis of
N-doped MC reflash graphene. FIG. 27A shows average ofPage 115
US 2025/0236521 Al 100 Raman spectra (with the standard deviation). FIG. 27B shows B XPS spectrum in which the nitrogen peak is deconvoluted based on its bonding types. [0158] FIG. 28 shows summary of re-flash doping results. DETAILED DESCRIPTION [0159] The present invention relates to flash Joule heating (FJH) for production of one-dimensional (1D) carbon and/or boron nitride nanomaterials, and 1D materials integrated with OD, 1D, 2D, and 3D nanomaterials, composites, nano- structures, networks, and mixtures thereof. Such materials produced by FJH include 1D carbon and hybrid nanomate- rials, boron nitride nanotubes (BNNTs), turbostratic boron- carbon-nitrogen (BCN), heteroatom doped (substituted) gra- phene, and heteroatom doped (substituted) re-flashed graphene. One-Dimensional (1D) Carbon and Hybrid Nanomaterials Synthesis by FJH [0160] In embodiments, the present invention relates to the conversion of plastic into 1D materials and hybrid graphitic 1D/2D materials, with controllable morphologies. The process utilizes in situ catalysis and enables directional control over the assembly of mobile carbon during FJH. The produced F1DM demonstrate excellent mechanical behavior in vinyl ester composites, attributable to the hybrid mor- phology and indicative of the value and utility of the waste plastic upcycled product. Further, FJH presents substantial advantages over classical 1D synthesis when analyzed using a cradle-to-gate perspective life cycle assessment. [0161] Graphitic one-dimensional (1D) and hybrid nano- materials represent a powerful solution in composite and electronic applications due to exceptional properties, but large-scale synthesis of hybrid materials has yet to be realized. The process, which is scalable, produces graphitic 1D materials from polymers using flash Joule heating (FH). This avoids lengthy chemical vapor deposition and uses no solvent or water. The flash 1D materials (F1DM), synthe- sized using a variety of earth-abundant catalysts, have controllable diameters and morphologies by parameter tun- ing. Furthermore, the process can be modified to form hybrid materials, with F1DM bonded to turbostratic gra- phene. In nanocomposites, FIDM outperform commercially available carbon nanotubes. Compared to current 1D mate- rial synthetic strategies using life cycle assessment (LCA), FJH synthesis represents an 86-92% decrease in cumulative energy demand and 92-94% decrease in global warming potential. FJH affords a cost-effective and sustainable route to upcycle waste plastic into valuable 1D and hybrid nano- materials. Synthesis of FIDM [0162] Flash Joule heating (FJH) was recently identified as an efficient method for the solvent-free synthesis of carbo- naceous and inorganic nanomaterials, in which electrical energy and resistance are leveraged to rapidly (0.05-3 sec) generate high temperatures (~3,000 K), allowing for the solvent-free upcycling of low-value waste materials into high-value products. [Luong 2020; Yao 2016; Xie 2018]. Graphitic 1D and hybrid nanomaterials often grow through the deposition of mobile carbon on metallic nanoparticles, Jul. 24, 2025 and FJH is known to efficiently produce mobile carbon, inspiring study of the growth of 1D nanomaterials using FJH. [0163] Introducing low concentrations of simple, earth- abundant transition metal salts into the carbonaceous poly- mer feedstock results in graphitic 1D material growth, catalyzed in situ during the FJH process. See schematic 101 shown in FIG. 1A. Iron(II) chloride, nickel(II) chloride, cobalt(II) chloride, and ferrocene were used as the growth catalysts. A polymer feedstock was selected due to the abundance and low cost of waste plastic and resulting yield of FIDM. The resistance of the reaction mixture was easily controlled by adjusting the amount of conductive carbon additive, such as carbon black or metallurgical coke. The high resistance of a plastic precursor allows for many high-resistance junctions between particles in the sample, resulting in high overall and local temperatures. The FJH system that can be utilized (and parameters) can be based on the system set forth and described in the Tour ’642 Appli- cation and the Tour °111 PCT Application with the modifi- cations as discussed below. [0164] The polymer feedstock can be loaded with catalyst particles through surface wetting or melt mixing. For surface wetting, the polymer can be sonicated in an aqueous alcohol solution containing 0.1 g mL~? of salt, then filtered and dried to coat the surface of the polymer with small amounts of the catalyst. For solvent-free catalyst loading, melt-mixing can be used wherein metal complexes such as ferrocene and polymers with similar melting points are mixed mechani- cally in the melt state and no solvent is used. Scanning electron microscope (SEM) images (SEM image 102 of FIG. 1A and SEM images of FIGS. 1B-1C) show fibers of varying diameters are formed during the FJH process. A typical aspect ratio of 330 was observed but often the entire intertwined length could not be continuously tracked so this is likely an underestimate. [0165] Inembodiments, the F1DM were synthesized using a flash Joule heating reactor as described in in the Tour ’642 Application and the Tour *111 PCT Application. Specifi- cally, the catalyst-loaded polymer feedstock were prepared by surface wetting or melt mixing. For the surface wetting method: a solution of 80/20 v/v mixture of water and ethanol was prepared, with the salt of choice dissolved in the solution. For example, FeCl, at a concentration of 0.1 g mL’ of solution. Then, 5 g of <0.1 mm grain size virgin or waste polymer was submerged in the solution and sonicated for 15 min. The polymer with salt solution was vacuum filtered to remove excess salt solution. The polymer was dried overnight at room temperature to afford the catalyst loaded polymer, which has a slight color change depending on the salt used. [0166] For the melt mixing method: ferrocene was used as the catalyst due to its low melting point of 173° C. The heater in the melt mixer was set to 175° C., and a mixture of 4.95 g of HDPE and 0.05 g of ferrocene is melt-mixed to homogeneity using a Braebender 350-E heated zone melt mixer. The melt mix was then cooled to room temperature and ground to a fine powder using an electric hammer mill. [0167] The catalyst-loaded polymer resulting from surface wetting or melt mixing was then mixed with the conductive additive. Amorphous carbon black (Cabot) was used for all samples herein, except when metallurgical coke is specified to have been used as a less expensive alternative.
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US 2025/0236521 Al [0168] When amorphous carbon black was used as the conductive additive, 20 wt % was ground with 80 wt % of the catalyst-loaded polymer. Due to the small particle size of the amorphous carbon black, it coated the polymer homo- geneously. The higher cost of carbon black relative to waste plastic, an alternative feedstock of metallurgical coke, a coal-derived product that costs $150 ton7!, was also dem- onstrated effective. [0169] Since metallurgical coke has a larger grain size of ~150 jum, a higher weight percent must be used to achieve a similar final sample conductivity. For the use of metallur- gical coke as the conductive additive, 40 wt % was used, and was mixed with 60 wt % of catalyst loaded polymer. Grain size of both the polymer and the conductive additive might impact the ratio of polymer feedstock and conductive addi- tive. The conductive additive and polymer were mixed by hand, using mortar and pestle. Then, 0.20 g the homoge- neous mixture was loaded into a quartz tube, with an internal diameter of 8 mm, with the sample compressed in tube by graphite electrodes to contain the powder. [0170] The sample was then loaded into the FJH reactor, connecting the capacitors to be able to discharge through the resistive sample. An initial sample resistance of 6-8Q was used for the samples as described here. The sample was enclosed in a vacuum desiccator at ~20 mmHg to facilitate outgassing of heteroatoms and volatiles. A FJH current discharge pulse of the desired voltage, using the desired capacitance, was then discharged to completion through the sample, lasting 1-3 s, depending on the voltage and capaci- tance, with higher capacitance resulting in longer durations. The circuit was closed fully for 5 s, with a typical discharge only lasting 1-3 s. The voltage on the capacitors was fully discharged, which may require multiple discharges. A bright flash could be observed from the sample because of the black body radiation produced. [0171] After the FJH, the resistance of the sample decreased to 0.6-1Q. The FIDM was then emptied from the quartz tube, ground using a mortar and pestle, and charac- terized without further purification. The yield of FIDM ranges (40-60 wt % of reactant recovered as graphitic product) depending on the parameters, polymer type, grain size, and amount of conductive additive used. [0172] Quantitatively differentiating between graphitic carbon morphologies can be a difficult task, as 1-D and 2-D morphologies look almost identical by common analytical methodologies such as XPS and TGA, with Raman and powder XRD showing only minor differences. Due to the combination of morphologies obtained during FJH, exten- sive SEM imaging was used to determine the morphological share of each sample. At low magnifications, 1D and 2D morphologies can look similar, so for each sample 108 different images over 9 different areas were examined and assigned a dominant morphology (1D, 2D, or hybrid). This allows for the morphological percentage, in area %, to be quantitatively determined. Area % is used herein when discussing FIDM morphology yield. A maximum of ~65% of the solid product is 1D morphology with the remainder including 2D turbostratic graphene. FIGS. 1D-1F show high resolution TEM images of ribbon-like carbon nanofibers, graphitic bamboo-like carbon, and multi-walled carbon nanotubes. Bamboo-like carbon nanofibers with many layers stacking in a cup-like manner comprise the dominant FIDM. morphology. The 2D morphologies present were observed by TEM imaging. Graphene nanoribbons were observed Jul. 24, 2025 through TEM imaging which could result from the high- temperature unzipping of carbon nanotubes. Characterization of FIDM [0173] F1DM were characterized using Raman spectral mapping, which demonstrated highly graphitic character over a large area. The FIDM were compared to a control sample, where no metal was included but all other condi- tions were identical and both samples yield products with 97-98% graphitic character. The graphitic content was deter- mined by three different characterization methods including Raman spectroscopy, TGA, and high resolution XPS. Wide area Raman mapping was carried out by collecting 100 unique spectra, over a 4 mm? area, which were then pro- cessed using MatLab scripts which characterize spectra with a 12D/IG ratio >0.3 to be graphitic. TGA can be used to determine graphitization by measuring the thermally stable mass at 550° C. under an air atmosphere, since amorphous carbon will degrade lower than this temperature. High- resolution XPS and fitting of the Cls peak allow for gra- phitic character to be determined, and a more accurate method of C KLL XPS can also probe graphitic content. [0174] High resolution, extended exposure scans revealed the presence of radial breathing mode peaks in the FIDM sample indicating the presence of carbon nanotubes in the F1DM sample, but not in the metal-free control sample. FIG. 2A (with plots 201-202 for control (no catalyst) and FIDM, respectively), FIG. 2B (with plots 211-212 for control (no catalyst) and F1DM, respectively). By varying the Raman excitation wavelength, different radial breathing mode peaks can be observed. The low intensity M, TS, and TS, peaks can also be observed. FIG. 2C (with plots 221-222 for control (no catalyst) and F1DM, respectively). [0175] The M peak, located at 1750 cm™', indicated ordered AB stacking. [Ferrari 2013]. The TS, and TS, peaks, located at 1875 cm™' and 2050 cm”, respectively, indicated disordered turbostratic stacking. [Merlen 2017; Chen I 2021]. The presence of both the M and TS peaks indicated that both aligned and misaligned stacking of graphitic domains were present. Flash graphene is turbostratic, so M peak presence was unexpected. [Luong 2020; Wyss I 20222]. Catalytically synthesized plate- and ribbon-like carbon nanofibers often demonstrate rotationally ordered AB stacking, which could explain the presence of the M peak and further indicate the bulk presence of nanofiber morphologies in FIDM. [Carozo 2011; Brar 2002]. [0176] To characterize the bulk FIDM product, powder X-ray diffraction (XRD) was used. FIG. 2D (with plots 231-233 for starting material, control (no catalyst) and FIDM, respectively). This showed a broad, intense, and multi-Lorentzian (002) peak indicating graphitic structure. The FIDM (002) peak is fit by two distinct Lorentzians, occurring at 26.46° and 26.11°. See FIG. 2E (with plots 241-242 for control (no catalyst) and F1DM, respectively). The (002) peak of the catalyst-free control sample is fit with a single Lorentzian centered at 26.12°. Graphitic 1D mate- rials, such as MWCNT and CNF have nearly identical diffractograms to that of 2D graphene because they share the same unit cell. The only difference is the interlayer spacing of turbostratic graphene (0.35 nm) as compared to that of graphitic 1D materials (0.34 nm), reflected by the position of the (002) peak. A lattice spacing of 0.350 nm corresponds to a diffraction peak of 26.1°, while a decreased lattice spacing would result, shifting the diffraction peak to higher angles.
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US 2025/0236521 Al 10 The fitting of the FIDM (002) peak by two distinct Lorent- zian functions indicates that both 1D materials and tur- bostratic graphene were present in the sample, whereas the single peak in the control sample corresponds only to turbostratic graphene. It is also known that the position of the (002) peak is dependent on the diameter of the carbon nanotube or nanofiber, and (002) peaks that can be fit by multiple sub-peaks. [Singh 2010]. [0177] Further, an enhanced (101) peak at 45.3° can be observed in the F1DM, but not in the catalyst-free control (FIG. 2F, with plots 251-252 for control (no catalyst) and FIDM, respectively), as observable for large diameter car- bon nanotubes. [Singh 2010] [0178] X-ray photoelectron spectroscopy (XPS) was used. to probe the elemental content and bonding of FIDM (Figure $10a). During FJH, the high boiling carbon content of the plastic is enriched to 97.8% graphitic product. High resolution spectra of the Cls transition demonstrates mini- mal oxygen content and the 1-n* transition, located at 291 eV. The D-parameter of the starting material polymer is 12.8 eV, which increases to 20.2 eV after FJH, signifying a transition from sp*- to sp*-hybridization. Thermogravimet- ric analysis of FIDM under air atmosphere shows high degradation onset temperature of 630° C., confirming the bulk graphitic character. [0179] The limit of detection for XPS survey scans is typically 0.5 to 1.0 at %. Thus, at the concentrations deter- mined by ICP-MS, with a maximum of 0.3 wt %, one would not expect to detect any signal by XPS survey scans. Further, the penetration depth of XPS detection is only 1-2 nanome- ters. Since TEM imaging shows that the iron was present in nanoparticles below many layers of graphitic carbon, it is also likely that the iron photoelectrons were not detected. [0180] In contrast, the iron is solubilized following sample digestion as it is prepared for ICP-MS testing, and ICP-MS has much lower limits of detection. Inductively coupled plasma mass spectrometry revealed that FIDM formed using the surface wetting method of 0.1 g mL7! FeCl, ona virgin high density polyethylene (HDPE) feedstock showed only 0.3 wt % Fe content in the starting material, decreasing during FJH to 0.06 wt %. The reduction in catalyst content during the FJH process was likely due to sublimation and outgassing of the metal ions at high temperatures. [Deng 2021]. The catalyst content could be further reduced to <10 ppm with 1 M HCI wash. FIDM from Untreated, Post-Consumer, Mixed Plastics [0181] There are 27 million tons of mixed waste plastic landfilled annually. Mixed post-consumer waste plastic was converted into F1DM by grinding, surface wetting, and FJH. FIGS. 3A-3F shows that mixed waste plastic composed of HDPE, low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET), can be easily upcycled into F1DM by a 3-sec-long FJH pulse. FIG. 3A is a Raman spectrum (plot 301) that shows mixed waste plastic derived FIDM characterized by large area Raman average spectrum with inset (plot 302) showing the radial breathing modes. FIG. 3B is powder XRD comparing the waste plastic (plot 311) to the synthe- sized FIDM (plot 312). FIG. 3C is survey and high reso- lution XPS (plots 321-322). FIGS. 3D-3F are SEM images showing morphologies of waste plastic derived FIDM. [0182] Other recent research described the synthesis of graphitic 1D materials from waste plastic. [Williams 2021; Wang 2022; Jie 2020]. However, those methods often relied Jul. 24, 2025 on two-stage 2-h-long pyrolysis followed by catalyst-aided chemical vapor deposition methods and have not been shown to accommodate mixed waste plastic streams, and can result in mixtures composed of ~30 wt % amorphous carbon or large excesses of catalyst that must be further removed. [Tripathi 2017; Wu 2016]. [0183] The mixed waste plastic mixture used was com- posed of 42% HDPE, 20% PP, 20% LDPE, 10% PS, 8% PET, replicating the global plastic waste composition. It is known that pyrolysis and FJH or PET result in lower carbon yields, and a lower yield of 1-D graphitic materials. [Al- gozeeb 202; Yao 2022]. The conversion of polystyrene was further investigated as some studies have reported that the aromatic structures result in thicker CNTs. [Yao 2022]. This trend was also observed for F1DM. Radial breathing modes can be observed for the waste derived FIDM (FIG. 3A), as well as complete conversion of the waste plastic into gra- phitic structures, as determined by powder XRD (FIG. 3B) and TGA. The enhanced (101) peak can also be observed in FIG. 3B, confirming the bulk presence of FIDM from mixed waste plastic. [0184] High elemental purity in the produced F1DM can be further studied by XPS (FIG. 3C, which shows a 2% increase in oxygen content as compared to HDPE derived FIDM despite the inclusion of PET, which is 25 wt % oxygen. Additives, such as colorants, plasticizers, adhesives, or residual waste from the plastics’ primary use are regarded as impurities. [0185] The TGA and XRD (FIG. 3B) of the mixed waste plastics do not show substantial metallic impurities, as signified by low residual TGA mass and minimal unidenti- fied XRD peaks. The atomic carbon in these impurities can be converted to graphene while heteroatoms such as oxygen, metals, or halides, are sublimed out. FIDM morphologies, including hybrid morphologies, can be observed by SEM imaging as shown in FIGS. 3D-3F. [0186] The particle size of the waste polymer feedstock has been demonstrated to impact the results of FJH [AI- gozeeb 2020], and the finer particle size will allow for more catalyst loading and higher surface area of high resistance junctions, improving the yield of F1DM. Thus, the yield of FIDM in the post-consumer polymer samples may be fur- ther increased by improved grinding. The mixed waste plastic was ground as fine as the utilized hammer mill allowed, but industrial scaling can afford smaller particles and thus more surface for the FIDM to form. [0187] Many types of polymers exist, and high melting temperatures of some may not allow for the catalyst to be introduced by melt-mixing. To demonstrate process gener- ality, polyurethane, a thermoset polymer, was converted into FIDM through a simple surface wetting technique. These FIDM synthesized from waste polyurethane demonstrated similar properties and morphologies as those derived from virgin HDPE. Polyurethane derived FIDM did have slight increases in oxygen (2.3%) and nitrogen (1.4%) content, indicating that the formation of heteroatom doped 1D and hybrid morphologies was possible by FJH, something that has already been demonstrated for FJH graphene. [Chen 2022). Controllable Hybrid and F1DM Morphologies. [0188] 1D and 2D hybrid materials, such as rebar gra- phene, are desirable for application due to their exotic mechanical and electronic properties. [Vedhanarayanan
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US 2025/0236521 Al 2018; Yan 2014]. However, these materials are almost singularly synthesized through multi-step chemical vapor deposition methods that are high-cost and low-yielding. [Xia 2017; Zhao 2012]. FJH produced areas of 2D graphene morphologies, FIDM morphologies, and commonly observ- able areas of colocalization and coalescence of 1D and 2D morphologies. FIGS. 4A-4I. [0189] SEM imaging demonstrated F1DM decorated with 2D graphene sheets at their ends, with the 1D morphology occasionally extending all the way through the 2D graphene (FIGS. 4A and 4C-4D). Areas of the sample (FIG. 4B) also exhibited the coalescence of 1D morphologies into larger- diameter 1D materials and then networks of 2D graphitic morphologies. TEM imaging (FIGS. 4E-41) shows colocal- ization of F1DM and graphene. FIG. 4F is a high-resolution TEM image of the area 441 highlighted in FIG. 4F. The circled area 442 highlights the lattice fringe between the bamboo-like carbon nanofibers and graphene sheet, showing that they are part of the same crystal lattice. FIG. 4H is an atomic resolution bright field TEM image of the area 461 highlighted in FIG. 4G showing the hexagonal arrangement of carbon atoms in the graphene sheets uninterrupted at the junction between the 1D and 2D morphologies. [0190] High resolution imaging (FIGS. 4E-4G) showed that the lattice fringe and edge was uninterrupted from the external wall of the nanofiber to the larger graphene sheet, indicating van der Waals interactions connecting the 1D and 2D domains together. Atomic resolution TEM imaging (FIG. 4H) revealed hexagonal sp’-hybridized graphene sheets, uninterrupted along the edge at the junction between the 1D and 2D morphology, suggesting coyalently linked hybrid materials. The fast Fourier transform (FIG. 41) indicated AB-stacked graphene, suggesting that hybrid materials can show decreased lattice spacings by XRD and an M peak in Raman spectral analysis (FIGS. 2A-2F). [0191] FJH parameters, including discharge voltage. cata- lyst type, loading, and capacitance density, can impact the product morphologies. Capacitance density is defined herein as the system capacitance per unit mass reacted. [Beckham 2022]. SEM analysis revealed that catalyst loading and type impact the diameter of the produced FIDM (FIGS. 5A-5B) with decreasing catalyst loadings resulting in thinner 1D materials being produced, with Fe(III) producing the thin- nest FIDM and Co(II) producing the thickest. [0192] It is well known that catalyst type can have sub- stantial impact on the size of produced CNTs, since different metals have different catalytic graphitization rates and car- bon solubilities. [Yuan 2008; Thambiliyagodage 2018; Hunter 2022]. Consistent with herein, many literature reports suggest that iron is more effective than cobalt and nickel, possibly due to these impacts. FJH parameters such as capacitance density and pulse voltage directly correlate with the capacitive current by Eq (1) and affect the diameter of FLDM (FIGS. 5C-5D), where L, C, V, and t correspond to current, capacitance, voltage, and time, respectively. wy wo 13CTR [0193] Intriguingly, capacitance and pulse voltage dis- charge resulted in opposite trends in FIDM diameter, despite both contributing additional charge to the reaction. However, the discharge rate of a capacitor was not uniform, Jul. 24, 2025 so doubling the capacitance will not double the current but would instead double the discharge time. The amount of time required for the capacitors to discharge can be deter- mined by using Eq (2), where R represents the resistance. 7=C#Rlog(v) Q) [0194] Increased peak discharge voltage allowed for increased instantaneous current discharge through the sample, resulting in higher overall power and heating rates. The non-monotonic correlation of capacitance density and discharge voltage with diameter was unexpected but appeared to indicate a shift in mechanism. This has previ- ously been observed in a partial dependence analysis of a machine learning guided FJH study that found that an increasing current density results in a shift from reaction- limited to diffusion-controlled kinetics. [Stanford 2020; Beckham 2022]. This shift in growth kinetics is common in crystalline materials and may be observed here as well. [Carroll 2018; Viswanatha 2007]. Representative SEM images of the FIDM as each parameter was varied that demonstrated that formation of FIDM was parameter-sen- sitive, allowing for control of product morphologies. [0195] Qualitative analysis also indicated that catalyst type, loading, capacitance density, and discharge voltage can be used to control the morphological makeup of FIDM (FIGS. 5E-5H). Use of Ni(II) resulted in the highest share of 2D materials while Co(II) yields the most hybrid materials. As the catalyst loading decreased, the amount of hybrid and 1D morphologies produced also decreased, likely due to a lower density of catalytic sites for mobile carbon deposition (FIG. 5F). As power input to the system increased, through applied voltage or capacitance density, the amount of 1D and hybrid materials increased. The diameter of the FIDM product was positively correlated to the amount of hybrid morphology present. Optimized reaction parameters yielded 68% of the ID/hybrid morphology (FIG. 51). Iterative mixing or sieving was used to further increase the yield of FIDM up to 90%. [0196] As the catalyst was loaded on or in the plastic, and the conductive CB reaches lower temperatures, it is believed that only the polymer feedstock forms the FIDM morphol- ogy, while the conductive additive forms 2D morphologies. The conductive additive can be essential to the FJH process to reduce the resistance of the sample and allow for high power discharge. To increase the yield of the 1D morphol- ogy, iterative mixing can be used, where the FIDM product (50/50 LD and 2D morphologies) is used as the conductive additive in a second FJH reaction, increasing the 1D share to ~75%, without degradation in quality. Use of a larger grain conductive additive, such as metallurgical coke, allows the use of simple sieving to separate the small FIDM product from the large grain conductive additive. Sieving or iterative mixing allows for the production of FLDM that is composed of 80-90% 1D and hybrid morphologies without using solyent- or centrifugation-based separation methods. Mechanism of FIDM Formation [0197] Catalyst-loaded conductive additive does not result in the formation of FIDM, but rather 2D graphene mor- phologies surface decorated with metal nanoparticles. High resistance junctions and volatile decomposition imparted by
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US 2025/0236521 Al 12 the plastic feedstock can be essential for the formation of F1DM. It is believed that these junctions form hot spots that facilitate FIDM nucleation. To further analyze this effect, a homogeneous sample with similar overall resistance and density was tested and evaluated. Ash resulting from the industrial pyrolysis of plastic waste has a similar 7Q resis- tance to the carbon-added F1DM feedstock but is homoge- neous. Surface wetting was used to introduce metal salt to the pyrolysis ash, and the sample was subjected to FJH using the same parameters used to form FI1DM. No 1D morpholo- gies were observed by SEM and TEM imaging indicating that resistive junctions at the plastic surface are required to form 1D morphologies. [0198] To further probe if the resistive junctions are a mechanistic cause of the FIDM formation, the process was replicated using sand (silica) rather than plastic. All param- eters, including surface wetting the sand to introduce the catalyst, mixing with carbon black conductive additive, and FJH settings, remained identical. The sample was ground after FJH and sieved to remove the residual inert silica. The results showed graphitization of the carbon black, as well as minor SiC formation, with <20 area % of the carbon being converted to F1DM, while the remainder was converted to 2D graphene morphologies. [0199] This testing demonstrated that the resistive junc- tions can be necessary for the formation of F1DM, but also indicated that the carbon from the plastic can be important for large amounts of F1DM to be produced. Recent work has shown that carbonization in the presence of carbon black or other conductive amorphous carbons can result in the metal catalyst free formation of turbostratic carbon nanoparticles. [Jia 2022]. Amorphous carbon can be converted to graphene sheets as the minor side products in CNT formation. [Gog 2013]. This further supports the observation that the 2D graphene sheets were produced from the carbon black. [0200] TEM images showed the presence of metallic nanoparticles at the base of plastic derived FIDM. The lattice spacing matched that of the metal oxide of the original catalyst used, indicating that during the FJH pro- cess, the high temperatures resulted in degradation of the metal salt to form nanoparticles that facilitate deposition of mobile carbon which then nucleated to form the thermody- namically favored graphitic domains that elongate into FIDM. At lower catalyst loading concentrations, fewer or smaller nanoparticles will form, and 2D graphene morpholo- gies will form, explaining why FIDM morphology and diameter vary with catalyst concentration. [0201] Similarly, the type of salt catalyst will determine the degradation temperature at which catalytic nanoparticles will form, and the rate of nanoparticle formation, impacting F1IDM formation. Both metal nanoparticles and metal oxide nanoparticles are known to catalyze the growth of CNF and CNT materials, so it is unknown if the nanoparticles formed in situ during the FJH reaction are metal or metal oxide. It is believed that the catalytically active species is the neutral metal species, which is then converted to oxide once the sample is removed from the FJH reactor and exposed to air. Since the metal or metal oxide catalyst nanoparticles are formed in situ during the FJH reaction, there would be no need to add expensive catalysts, such as noble metal nan- oparticles to the reaction scheme, as are often used in CVD methods. [0202] To better understand the relationship between cata- lyst concentration and F1DM diameter, TEM imaging was Jul. 24, 2025 used to probe the size of the catalytic nanoparticles as catalyst concentration is changed. These showed that when the catalyst loading concentration was decreased, the size of the catalytic nanoparticles decreased, which resulted in a decrease in the diameter of FIDM. At high metal salt loadings, some catalytic nanoparticles could be seen without a surrounding F1DM coating. This indicated that the catalyst concentration in the wetting solution has control over the size and abundance of nanoparticles formed. [0203] The catalytic effect of Fe, Ni, and Co particles in synthesis of carbon 1D structures is commonly considered in CVD conditions, where carbon feedstock containing is deposited on the nanoparticle’s surface, diffuses through the particle, and is incorporated into the growing graphitic domain. [Fouquet 2012]. The majority of previous studies were focused on carbon nanotube formation from gaseous sources, leaving catalytic graphitization of amorphous car- bon unexplored. [Wang 2007]. Previous work has demon- strated that stopping the FJH reaction early results in a carbonized product with substantial amorphous content, and considerable graphitic lattice disorder, suggesting an amor- phous intermediate between polymer and graphitic product. [Algozeeb 2020]. Further, since a mixture of morphologies was obtained, rather than only 1D morphologies as is commonly obtained from the catalytic pyrolysis of plastics, this revealed that a different mechanism may be occurring. The solid amorphous intermediate can be converted to graphitic products, which are 1D when on the catalytic nanoparticles. [0204] To investigate the effect of metal inclusions within the FJH setup, the behavior of the amorphous carbon domain in contact with the Ni nanoparticle (FIG. 6A) was examined through molecular dynamics. FIG. 6A shows configuration after initial pre-annealing already shows some carbon atoms of the amorphous carbon 602 dissolved within the Ni nanoparticle 601. The system was heated and kept at 3000 K for 4 nsec to simulate high temperatures of FJH. The amorphous carbon underwent thermal and catalytic graphi- tization, both accelerated due to high FJH temperatures. Catalytic graphitization involves dissolution of carbon atoms, both from amorphous and already partially graphi- tized domains, into the Ni particle which then deposit on the surface, forming large 1D or hybrid graphitic domains (FIG. 6B). FIG. 6B shows the final structure shows the beginning of the carbon fiber formation through carbon interaction and catalytic graphitization, as indicated by the arrow 613. [0205] The large size of the catalytic nanoparticle (450 Ni atoms) resulted in a large diameter carbon product distinct from existing literature results. [Chiang 2009]. Analyzing the graphitization rate, it was determined that the catalytic process accelerates amorphous carbon conversion (FIGS. 6C-6D) and the curvature and size of the metallic nanopar- ticles favored the formation of 1D and hybrid morphologies. FIG. 6C (plots 621-622 for Ni affected and total, respec- tively) shows graphitization level of all carbon and carbon affected by Ni, indicating the catalytic effect that the Ni atoms have on the graphitization of affected carbon atoms. FIG. 6D shows the percentage of carbon affected by Ni particle throughout the simulation indicating interaction of the mobile carbon with the Ni catalyst even in the short simulated timescale.
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US 2025/0236521 Al 13 Utility in Nanocomposites [0206] Due to high tensile strengths, thermal and electric conductivities, and low densities, both 1D and 2D graphitic morphologies can be utilized in composites. Hybrid mate- rials can result in excellent mechanical properties due to the 2D morphology increasing interfacial attachment between nanomaterial and matrix. [0207] The F1DM are highly dispersible in a 1% Pluronic surfactant aqueous medium allowing concentrations of 1.63 mg mL". Varying amounts of ground FIDM powder were weighed into centrifuge tubes, and solvent was added to yield the initial loading concentration (~1 mg FIDM powder mL™ of solvent). The centrifuge tubes were then sonicated in a cup-horn sonicator for 10 min (Cole-Parmer Qsonica 448) and centrifuged at 550 relative centrifugal force for 5 min to remove larger aggregates. The supernatant was decanted after centrifugation and diluted 100x since the graphene concentration leads to a very high absorbance. The absorbance of the solution was measured at 660 nm. The concentration was determined using Beer’s Law with an extinction coeflicient of 66 L g™! em™'. [0208] 7 g of FIDM was produced to test loadings of 0.5, 2, and 5 wt %. The FIDM was readily dispersible in the vinyl ester matrix material through brief cup horn sonica- tion. Vinylester (VE) resin was obtained from Fiberglass Supply Depot and used as received. Methyl ethyl ketone peroxide (MEKP) was obtained from Fiberglass Supply Depot and used as received as a catalyst/hardener for the resin. FLDM/VE Composites were prepared by combining 5.0 g of vinyl ester and 20-200 mg of FIDM, depending on. the desired loading, in a 20 mL scintillation vial. The solution was then mixed using a magnetic stir bar for 30 min at 300 rpm. After stirring, the solution was then shear mixed with a homogenizer obtained from Cole-Parmer (Tissue Tearor 986370-07 Homogenizer; 120 VAC, 1.2 A) for 5 min. at ~10,000 rpm. 5 drops (~0.15 g) of MEKP were then added to the solution while stirring with a magnetic stir bar at 300 rpm for 5 min. The solution was then poured into a PDMS mold coated with release agent and allowed to cure over- night. [0209] The FIDM reinforced vinyl ester resin nanocom- posites tested using nanoindentation demonstrated a dra- matic increase in compressive modulus at even 0.5 wt % resulting in a 21% increase. Macro-scale mechanical testing indicates substantial improvements under tensile extension and compression (FIGS. 7A-7B) with the FIDM composites showing 92%, 130%, and 48% increases in tensile strength and 174%, 304%, and 63% increases in toughness at 0.5, 2, and 5 wt %, respectively. [0210] The decrease in mechanical properties as the load- ing is increased from 2% to 5% is believed to be a result of FIDM aggregation in the vinyl ester matrix material. It is well known that nanocomposites do not exhibit a linear increase in mechanical properties as more reinforcing agent is added, but rather have an optimal maximum, usually less than 5% loading. [Medupin 2019; Roy 2018]. The inter- phase properties of polymer nanocomposites is complex and directly impact the macroscale mechanical properties, but can depend of surface area, aspect ratio, and dispersibility of nanomaterials, viscosity of the matrix material, and interfa- cial interactions between the phases. [Ashraf 2018; Zare 2016). [0211] F1DM loaded vinyl ester was compared with the composite properties of vinyl ester loaded with commer- Jul. 24, 2025 cially available carbon nanotubes made using traditional methods (FIG. 7A). FIDM outperformed commercial nano- tubes tested in nanoindentation and macro-scale compres- sive testing (FIG. 7A), likely due to the hybrid morphology and high graphitic purity, and F1DM improves the properties of neat vinyl ester matrix material (FIG. 7B). [0212] To show the advantage of FIDM as compared to graphene produced by FJH without the inclusion of cata- lysts, the best-performing sample (5% FIDM) was com- pared with a similarly prepared sample that contains 5% 2D graphene produced by FJH. FIGS. 8A-8G and FIGS. 9A-9D show that F1DM outperforms graphene produced by flash Joule heating in nanoindentation testing. FIGS. 8A-8C show nanoscale compressive testing, FIGS. 8D-8E show macro- scale compressive testing, and FIGS. 8F-8G show macro- scale tensile testing. [0213] FIG. 9A (plots 901-905 for blank, 0.5% FIDM, 2% FIDM, 5% FIDM, and 5% CT, respectively) shows nanoscale compressive testing. FIG. 9B (multiple plots 911-913 for neat VE, 0.5% cheap tubes in VE, and 0.5% FIDM in VE, respectively) and FIG. 9C (multiple plots 921-923 for neat VE, 2% cheap tubes in VE, and 2% FIDM. in VE, respectively) show macro-scale compressive testing. FIG. 9D (multiple plots 931-934 for 0% F1DM in VE, 0.5% FIDM in VE, 2% FIDM in VE, and 5% FIDM in VE, respectively) shows macro-scale tensile testing. [0214] F1DM outperforming graphene produced by flash Joule heating in nanoindentation testing is likely due to the hybrid morphology of FIDM improving matrix penetration and strain propagation properties of the vinyl ester. Thus, it is shown that the FIDM hybrid morphology mechanically outperforms both 1-D and 2D graphitic carbon nanomate- rials as an additive in vinyl ester. [0215] 1D graphitic nanomaterials are well-known for their conductivity, and this property is often capitalized upon in nanocomposite materials. As such, the conductivity of the produced FIDM/viny] esters was measured as shown in TABLE I, which demonstrates an increase in conductivity as the loading increases; however, commercial MWCNT out- performs the FIDM as a conductive additive. This is likely a result of the longer aspect ratio of commercial MWCNT when compared to the FIDM. TABLE I Conductivity Measurements Of Nanomaterial Enhanced Vinyl Ester Composites Sample DC Electrical Material Conductivity (Sim) Raw Vinyl Ester Matrix <1E-10 0.5 wt % added F1DM. <1E-10 2 wt % added FIDM 1.72E-08 5 wt % added FIDM 4.26E-08 5 wt % added Commercial MWCNT 1.19E-02 Cradle-to-Gate Life Cycle Assessment [0216] A cradle-to-gate life-cycle assessment was con- ducted to examine the FJH method of FIDM synthesis as the impacts of application and disposal will vary negligibly based on the synthetic method of the graphitic 1D material. [0217] Regarding the life-cycle assessment scope, goal, functional unit, and inventory, a cradle-to-gate life-cycle assessment is a systematic analysis of the demands and
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US 2025/0236521 Al 14 impacts associated with a product from raw materials required for synthesis to the processing and manufacturing of the product and does not examine the final disposal end-use application or disposal of the product. The specific goal of the life-cycle assessment herein was to evaluate the demands and environmental impacts resulting from the FH production of FIDM to compare with literature benchmarks studying the production of graphitic 1D materials synthe- sized using other methods. The system considered here covers three main steps: raw material production, reaction feedstock preparation, and FJH reaction. Transportation of raw materials was not considered here, and a lab-scale process was assumed. The functional unit considered here was | kg of high purity graphitic 1D material powder, with a >95% graphitic content, as this is the purity level com- monly sold for gram-scale or larger applications, such as composites or coatings. The environmental impacts pertain- ing to the production of waste polyethylene were not con- sidered herein; however, the burdens for collection and separation of postconsumer waste polyethylene have been included. [Martin-Lara 2022]. Direct energy inputs for the FJH process were measured experimentally, and cumulative demands and impacts were calculated using Argonne National Laboratory GREET life-cycle assessment. [0218] The surface wetting method used virgin HDPE powder, wet by 4 L of 80/20 vv water/EtOH solution per kg of polymer, bath sonicated for 15 min, and centrifugation recovering 75% of the solution. The polymer mixture was air dried, and 20 wt % carbon black was mixed in using ball milling. The mixture of salt loaded polymer and conductive additive was then FJH and used without further purification, resulting in 1 kg of FIDM mixed morphologies that is >95% carbon and graphitic content. Alternatively, the melt mixing method considered waste polyethylene with iron acetylac- etonate at a 0.25 wt % loading. The homogeneous melt mix was cooled and electrically hammer milled to 1 mm particle size, then mixed with 33 wt % metallurgical coke (3 mm particle size) to give a conductive mixture. The mixture was then FJH, pushed from the quartz tube, and sieved to separate the FIDM from the metallurgical coke, affording highly pure 1D morphologies with >95% carbon and gra- phitic content. Direct comparison of our life-cycle assess- ment with other literature values was possible if all data- bases utilized (e.g. GREET, SimaPro, Ecoinvent, and Gabi) follow International Standards Organization best standard procedures. [0219] A general scheme for the industrial synthesis of nanotubes and the life cycle inventories are shown in FIGS. 10A-10C. FIG. 10A shows a scheme for general commercial methods, FIG. 10B shows a scheme for melt mixing and FJH for FIDM, and FIG. 10C shows a scheme for surface wetting and FJH for FIDM. This life-cycle assessment considered two different synthetic scenarios: melt mixing of waste polymer and surface wetting of virgin polymer to determine the cumulative energy demand, global warming potential, and cumulative water use (FIGS. 7C-7E). [0220] FIDM synthesis was compared to FJH 2D gra- phene synthesis from post-consumer waste plastic, where no catalyst loading is needed. [Wyss II 2022]. FIDM synthesis using surface wetting consumed 683 MJ and 185 L of water and produced 27 kg of CO, equivalent per kg of graphitic product produced. Most of the impacts resulted from the virgin polymer and conductive additive. When considering the melt mixing scenario, the process used 395 MJ and 111 Jul. 24, 2025 L of water, while producing 26 kg of CO, equivalent per kg of graphitic product produced. The impacts resulting from the synthesis of the waste polyethylene were disregarded, but the collection and separation burdens were considered. For the waste polymer melt mixing scenario, most burdens result from FJH. [0221] Comparing the FJH synthesis of graphitic 1D and hybrid materials to literature was complicated by the wide variety of morphologies produced. Single-walled nanotubes were not considered a comparable product; only multi- walled nanotubes or nanofibers are compared. Comparing the FJH synthesis of FIDM to International Standards Organization compliant life-cycle assessments of graphitic 1D materials indicated a reduction in both energy use and global warming potential to synthesize 1 kg of graphitic 1D material. FIG. 7F shows the comparison of the two FJH synthesis of FIDM strategies considered in the life-cycle assessment, as compared with literature life-cycle assess- ment probing the synthesis of carbon nanotubes or nanofi- bers. TABLE II provides the numerical values and refer- ences for the data plotted in FIG. 7F, comparing the cumulative energy demand (CED) and global warming potential (GWP) of FIDM strategies (which are within oval 701) to literature life cycle assessment (LCA) probing the synthesis of MWCNT and CNF (which are within block 702). The units for CED is MJ kg". while the units for GWP is g CO, eq kg"! product. TABLE II Material CED. GWP Reference M-CVD1 2960 212 Temizel-Sekeryan M-CVD2 10400 445 2021 M-CVD4 8780 704 M-CVD5 3640 265 M-CVD6 2590 150 CVD vegenf 2872 128 Khanna 2008 CVD vegenf 10925 640 CVD MWCNT 2334 160 Wu 2020 CVD MWCNT 2480 652 Trompeta 2016 CVD MWCNT 1100 211 Melt mix, MC, WP 363.0 19.5 Herein Surface Wet, CB. VP 683.1 27.3 CVD MWCNT 3650 480 Teah 2020 CVD MWCNT 6523 210 [0222] The literature average for cradle-to-gate energy demand to form 1 kg of graphitic 1D materials is 4,855 MJ, while the average global warming potential is 355 kg of CO, equivalent, represent 86-92% decreased in cumulative energy demand and 92-94% decreased global warming potential for the FJH route. Further Applicability [0223] FJH can rapidly and controllably synthesize a variety of high value graphitic 1D or hybrid materials using earth-abundant simple salts and waste plastic, with demon- strated value, in an inexpensive, sustainable, and efficient manner. Further the FIDM can be doped or functionalized. Boron Nitride Nanotubes (BNNTs) Synthesis By FJH [0224] In embodiments, the present invention further relates to the synthesis of BNNT by using flash Joule heating (FJH) processes. The processes are carried in a solid-phase and under moderate reaction pressure (1 atm Ar) and tem-
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15
perature (~1800 K) and no solvent was used. Ammonia
borane(AB) and nickel(II) bis(acetylacetonate) (Ni(acac),)
can be used as the precursor and catalyst, respectively. The
products, mainly BNNT and h-BN, can be directly separated
from the conductive additives after the synthesis.
[0225] Boron nitride nanotubes (BNNTs), known as the
structure analog of carbon nanotubes (CNTs), have attracted
significant attention for their exceptional intrinsic properties
and wide-ranging applications. Despite their potential, rapid
synthesis of BNNTs with high yield and quality remains
challenging to attain, which limits their development of
practical applications. Using an all-solid-state catalytic flash
Joule heating method (a catalytic growth process), BNNTs
can be synthesized within 1 second, resulting in high yield
and selectivity of BNNT and BN nanosheets. The products
can be directly separated from the conductive additives, such
as carbon or metal powders. This further provides for a
continuous, scalable synthesis of BNNTs using the FJH
method and provides potential catalytic synthesis of other
materials.
[0226] f-BCN with various chemical compositions and
turbostratic characteristics can be synthesized from
BH,NH, and carbon black in <1 s using the ultrafast and
solvent-free FJH method. The atomic percentage of carbon
can be controlled from ~0% to ~100% and spectroscopic
analyses show the VBM can be correspondingly tuned. At
the lower percentages of carbon, the f-BN is very close to
t-BN in its spectroscopic characteristics. Calculations sup-
port the existence of turbostratic structures along with the
energy barriers that impede conversion to the well-aligned
counterparts. The obtained {-BCN layers with disordered
orientation are easily exfoliated. Compared to commercial
h-BN nanoplates, f-BCN samples demonstrate stable dis-
persibility in aqueous Pluronic (F-127, 1 wt % in deionized
water).
[0227] Furthermore, the addition of f-BCN as barrier
fillers in PVA nanocomposites shows better compatibility
and they confer higher corrosion protection efficiency. The
turbostratic morphology of f-BCN is difficult to reproduce
by common bottom-up methods, such as CVD and hydro-
thermal methods, whose cooling rates are 100-1000x lower
than that of FJH. The FJH method offers a high-yield process
to synthesize bulk quantities of turbostratic materials.
Synthesis of BNNT by FJH
[0228] To synthesized BNNT by FJH, ammonia borane
(AB) was chosen as the representative precursor because its
decomposition at different temperatures has been studied
and both B and N are provided at a stoichiometric ratio. AB
has been extensively studied as the monolayer h-BN pre-
cursor in CVD. [Tay 2014; Stehle 2015; Koepke 2016]. Suib
et al. demonstrated that decomposition of AB yields semi-
crystalline h-BN. [Frueh 2011] Prior to h-BN growth, it is
common practice to perform low-temperature decomposi-
tion of AB to generate polymeric radical species and bora-
zine, which are more reactive in CVD. B-N bonds are
maintained during the decomposition while H, experienced
a stepwise loss. The FJH system that can be utilized (and
parameters) can be based on the system set forth and
described in the Tour °642 Application and the Tour °111
PCT Application with the modifications as discussed below.
[See also Luong 2020; Chen 2022; Deng 2022].
[0229] In embodiments of the present invention, the
device diagram and temperature curve are shown in FIGS.
Jul. 24, 2025
11A-11B. In a typical FJH process, the mixture of AB,
Fe(acac),/Ni(acac), catalyst, and metallurgic coke (met-
coke) is compressed inside a quartz tube between two
graphite rods. The two graphite electrodes were connected to
a capacitor bank with a total capacitance of 60 mF. Then the
current passing through the sample was measured after the
rapid discharge under different voltages. The real-time tem-
perature can be measured using an infrared sensor as plotted
(FIG. 11B). The heating rate is up to 5x10° K/s. To reduce
the carbon content in the product, metcoke (12-20 mesh, or
840-1680 jum) was used as the conductive additive instead
the carbon black powder. The large particle size of metcoke
allows for a convenient separation by sieving and weight
loss of metcoke at reaction temperature is negligible. AB and
its decomposed species are susceptible to oxidation at high
temperature. To reduce the oxygen contamination, O-ring
sealing was used on both electrodes in the quartz tube and
Ar was used as the protective atmosphere. AB, Ni(acac),
were mixed and heated to 110° C. to ensure a uniform
melt-mixing (FIG. 11C). Two types of tubes can be used in
the FJH process (FIGS. 11D-11E).
[0230] For example, in a typical experiment, ammonia
borane was mixed and ground with 3 wt % Ni(acac), and 3
wt % Fe(acac), and heated to 120° C. for 10 min. Then the
mixture was mixed with metcoke at a mass ratio of 1:1. The
reactant was added into a quartz tube (inner diameter of 8
mm and outer diameter of 12 mm). Graphite rods were used
as the electrode on both sides of the quartz tube and copper
wool was used between the graphite rods and the electrodes.
The tube was sealed by two O-rings and loaded into the jig.
Ar gas (~1 atm) was used as an inert atmosphere to avoid
sample oxidation during the FJH reaction. The capacitor
bank with a total capacitance of 60 mF was charged by a DC
supply. The discharge time was controlled by the Arduino
controller relay with programmable millisecond-level delay
time. The optimized condition for BNNT synthesis is 90 V
500 ms for twice. After the FJH reaction, the apparatus was
allowed to vent and cool to room temperature. The flashed
products were sieved from a 40-mesh sieve (425 jum metric)
to separate metcoke and BNNT/BN products. The mass
yield is ~45% of the theoretical BN yield in the quartz tube
and ~60% in the PEEK tube. ~30% the products are in
tubular structure and the rest are sheet-like structure.
Characterization of BNNT
[0231] Spectroscopic analysis and imaging techniques
were used to confirm the formation of BNNT in the flashed
product. FIGS. 12A-12D. In the FTIR spectra, the flashed
product showed a B-N stretching peak at 1317 cm™! anda
B-N-B bending peak at 780 cm™'. FIG. 12A (with plots
1201-1202 for AB precursor and flashed product, respec-
tively). The peaks are in accordance with those in commer-
cial h-BN. Some peaks are consistent with the peaks of AB
precursor, which indicates a small mount of AB presence.
[0232] The Raman peaks for AB precursors are absent in
flashed product. FIG. 12B (with plots 1211-1212 for AB
precursor and flashed product, respectively). The character-
istic E,, peak appears at ~1361 cm” in plot 1212, which is
lower than the E,, peak in the h-BN (~1368 em”), The
blueshift can be ascribed to the strain in the tubular structure
and hardening of E,, mode. [Arenal 2006].
[0233] In XRD patterns, the AB precursor peaks disap-
peared in the products. FIG. 12C (with plots 1221-1222 for
AB precursor and flashed product, respectively). In plotPage 123
US 2025/0236521 Al 16 1222, the peak at 26.0° corresponds to the characteristic (002) diffraction peak of BN and peaks at 43.4° and 44.5° correspond the (100) and (001) diffraction peaks. The broad- ened peaks suggest the formed BN sheets and BNNT are not highly crystallized. BNNTs also showed broadened (002) peaks compared to h-BN materials in previous reports. [Lee J 2021; Kim H 2021]. [0234] The B is spectra confirmed the purity of BN products. FIG. 12D (with plots 1231-1232 for AB precursor and flashed product, respectively). Slight oxidation can be observed in AB precursor (~10%) since AB absorbs water rapidly in air. In flashed product, only B-N bonds present and no obvious B-O and B-C bond formed. The B/N ratio is ~1.06. [0235] The formed BNNT structure can be seen in the SEM images. FIGS. 13A-131. BNNT can be found both in quartz tube (FIGS. 13A-13C) and PEEK tube (FIGS. 13D- 13F), revealing the tube growth is not dependent on the outer container. The multi-walled BNNTs showed both hollow and non-hollow morphology in the sample. However, the formed tubular structure in the PEEK exhibited higher hollow ratio likely due to higher pressure can be maintained in the PEEK tube. The high pressure promotes the BNNT selectivity to BN sheets and BNNT crystallinity. [Bae 2022] The length and diameter of BNNT were 20-50 um and 50-100 nm, respectively. It was observed in the flashed product with a selectivity of ~30% and the rest of the product are sheet-like BN structure. FIGS. 13H-131. [0236] Two types of BNNTs morphology could be distin- guished in the TEM images. The tube without an obvious hollow structure exhibited a diameter of 30-50 nm while the hollow tube showed a diameter of 50-100 nm. TEM analysis showed crystalline domains on the outer region of BNNTs. The interlayer spacing of 0.353 nm was slightly larger than that of crystallized h-BN (0.333 nm). The result is consistent well with the broadened (002) and shifted peak in the XRD pattern. An increased lattice spacing would result in result- ing the diffraction peaks to higher angle. [0237] BN sheets (lateral size of ~100 nm) were also noticed in the FIGS. 14A-14B. The clear edge fringes suggest the good crystallinity of the few-layer BN nanosheets. The bright-field (BF) and high-angle annular dark-field scanning transmission electron microscopy Jul. 24, 2025 (HAADF-STEM) images, together with elemental mapping, indicate the existence of B, N in BNNTs and BN nanosheets (FIGS. 13G-13]), which is consistent with XPS results. Catalyst Effect [0238] The catalyst effect in the FJH technique is dis- cussed above with regard to the synthesis of 1D carbon materials. The usage of proper catalyst enabled promotion of the reaction rate and selectivity. To investigate the catalyst effect in the catalytic decomposition and BNNT growth process, various types of catalyst were used in the synthesis. No obvious tubular structure formations were observed in the reactions using metal borides, metal chlorides, metal powders as the catalysts, which suggested the catalyst effect might be different from the BNNT growth process in the CVD method. [0239] It has been found that the combined Ni(acac),/Fe (acac), catalyst showed an enhanced selectivity towards tubular structure over sheets. The presence of Ni/Fe catalyst was confirmed in the elemental mapping of HAADF-STEM. images. FIG. 14K. The major decomposition product of Fe(acac); is Fe,O;/Fe,0, at ~400° C. [Kim H 2021; Toyos- Rodriguez [0240] The metal oxide particles can be found in the heads of the BNNT. The growth mode is accordance with the typical VLS mechanism in CVD. The growth mechanism of BNNT during the FJH process is believed to be as follows: Active B-N species first forms and evaporates during the rapid dehydrogenation process over 200° C., followed by the decomposition of Ni(acac),/Fe(acac), into metal oxide par- ticles at ~400° C. The last dehydrogenation step from NHBH(s) to BN(s) require a high temperature of over 1200K. [Demirci 2020]. Semi-erystalline h-BN was found to form at ~1500K [Frueh 2011] and the h-BN morphology is similar to the BN sheets in our flashed products. BNNTs started to grow at the temperature window of 1500-1800K. The rapid dehydrogenation and high local B-N species concentration enabled the selectivity towards BNNTs instead of h-BN. The comparison of FJH-synthesized BNNT between other BNNT synthesizing methods are listed in TABLE III. FJH method reduces the cost of producing BNNT in a large scale by decreasing the reaction tempera- ture, pressure, and duration. TABLE II] Comparison of Recent BNNT Synthesizing Methods Method Temp Pressure Prec/Cat Duration —_ Impurities Ball-milling —/ LbarN, —B,O; 80 h, 12 h NH; BN sheets, annealing — B,O3, amorphous B Ball-milling — / LbarN, B,Oy/Mg 4h, 2 h NHy_ BN sheets, annealing — ByO, Laser ablation 3800K l4barN, BB ! Amorphous boron Laser ablation 400K 2-12 bar Ar BHsNHy 30 min h-BN sheets DC plasma 5000-7000K Ar h-BN continuous —h-BN sheets DC plasma 550K N B continous Boron particles RF plasma 400K Ny, Hy, Ar -h-BN sh D-BN sheets RF plasma 4200K No, Ha, Ar -h-BN continuous Boron particles, BN sheets BOCVD 1500K NH ByOy! 2h BN sheets Fe,OyS
Page 124
US 2025/0236521 Al Jul. 24, 2025 TABLE III-continued. Comparison of Recent BNNT Synthesizing Methods Method Temp Pressure Preo/Cat Duration Impurities PECVD 1200K Ny, Op BBHNG! 30 min Shell BN, cu B,O3 cvb 1700K NH BIN 3h Boron particles cvb 100K NH, B/KFeO, th Boron patticles, B50; BOCVD 1300K NH B,O,/Mg lb BO, FIA 1800K lbarAr — BH3NHy/ ls BN sheets NiFe Turbostratic Boron-Carbon-Nitrogen (BCN) Synthesis by FJH [0241] In embodiments, the present invention further relates the synthesizes of BCN with turbostratic structures and high in-plane crystallinity via an all-solid-state flash Joule heating (FJH) system. It provides short pulses of high electrical energy followed by rapid cooling (10°~10°K s~'), all in <I s. Starting from BH,NH, and carbon black, the FJH-product is named flash BCN (f-BCN-x, where x is the carbon percentage in the reactants). Other conductive pow- der additives, such as iron and tungsten can also be used to replace the carbon black. [0242] The atomic percentage of carbon can be controlled from ~0% to ~100% as determined via X-ray photoelectron spectroscopy (XPS) by changing the carbon content in the reactants. At the lower percentage of carbon, closely aligned spectroscopic features to those of pure turbostratic h-BN (t-BN) are observed. [0243] The f-BCN has a turbostratic arrangement, which facilitates its exfoliation by different mechanical methods, such as adhesive tape exfoliation, monodirectional mechani- cal shearing, and bath sonication. Calculation results show the existence of turbostratic structures and the energy bar- riers converting to well-aligned counterparts. [0244] Hexagonal boron nitride (h-BN) and graphene are two common layered materials whose interlayer interactions are ~26 meV atom”! (~2.5 kJ mol~') [Rydberg 2003], while the in-plane binding energy is ~450 kJ mol"!, more than two orders of magnitude higher than the interlayer interactions. Therefore, the formation of turbostratic materials with high in-plane crystallinity can be kinetically controlled by a thermal annealing followed by an ultrafast cooling process. The thermal annealing facilitates the formation of ordered in-plane structures,!! and the ultrafast cooling process pre- serves the misaligned stacking sequences in local, rather than global energy minima. This can be extended to doped graphene as well.[?"] [0245] Compared to commercial h-BN and graphene, £BCN has better temporal stability when dispersed in aqueous Pluronic (F-127, 1 wt % in deionized water). Polyvinyl alcohol (PVA) nanocomposites containing 10 wt % f-BCN that are coated on copper foils confer improved corrosion resistance when subjected to 0.5 M sulfuric acid or 3.5 wt % saline solution. Synthesis of fBCN [0246] FIG. 15A illustrates the ultrafast all-solid-state preparation process based on FJH to synthesize the f-BCN in <1 s. As discussed previously herein, the FJH system that can be utilized (and parameters) can be based on the system set forth and described in the Tour ’642 Application and the Tour *111 PCT Application with the modifications as dis- cussed below. [0247] Ina typical flash process, a mixture of BH,NH, and commercial carbon black is slightly compressed inside a quartz tube between two copper electrodes. BH;NH, is chosen as the reactant since it serves as both a boron and nitrogen source, and there are preformed B-N bonds in the precursor. Carbon black simultaneously acts as the carbon source and the conductive agent during the reaction. The capacitor banks in the circuit are used to provide electro- thermal energy to the reactants. [0248] By changing the carbon content in the mixture, the FJH process can be used to synthesize f-BCN with various compositions and turbostratic structures. During a typical flash reaction with a voltage of 150 V and a sample resis- tance of ~40Q, the current passing through the sample reaches ~15 A in ~600 ms discharge time. The total amount of electrical energy is 3.1 kJ g™' and the energy cost for converting 1-ton BH;NH;, precursor into flash product is presently ~$19. The real-time temperature can be measured using an infrared sensor as plotted in FIG. 15B. The tem- perature reaches ~1220 K within ~600 ms with a ramp rate in the heating stage that is estimated to be ~1300 K s?, followed by rapid cooling at ~1600 K s~’. [0249] Other carbon-free conductive additives, such as tungsten and iron, were also tried, and the flash products are named f-BN-W and f-BN-Fe, respectively. Specifically, iron powder can be collected by a magnet and reused. This resulted in the formation of BN without obvious carbon signal. [0250] Due to the possible catalytic effect of Cu during the reaction, the graphite spacers were used as the alternatives of the Cu wool plugs. To facilitate the outgassing and avoid the explosion of the tube, the diameter of the graphite spacer was ~1 mm smaller than the quartz tube. BN was prepared using such graphite spacers. [0251] Previous pyrolytic dehydrogenation analysis has reported that there are three thermal decomposition steps to form BN-based structures from the BH,NH, precursor [Frueh 2011], and that the overall reaction is highly exo- thermic (~171 kJ mol"'). This drives the reaction to comple- tion, even though the third step, dehydrogenation, NHBH(s) to BN(s), has a high kinetic barrier and generally requires a higher temperature of 1200~1400K. [Demirci 2020; Frueh 2011]. The thermochemical equation is shown in Eq (3),
Page 125
US 2025/0236521 Al
18
BHNH;(s) = 3 Hy(g) + BN(s) Ap H® = 171.1 mol! 3)
[0252] There are three stepwise thermal decompositions
(shown in Eqs (4)-(6)) to form the BN crystals from the
BH,NH, precursor [Frueh 2011], and the overall reaction is
highly exothermic. The third step dehydrogenation, NHBH
(s) to BN(s) in Eq (6). is the rate-limiting step and generally
requires a higher temperature of 1200~1400 K.
BHNHs(s) = H(g) + HB = NEh{s) 343 K-373 K) @
HB = NH3(s) = Ha(g) + HBNH (g) (393 K- 403 K) 6)
Jul. 24, 2025
sheet is very small; (2) except for the smallest h-BN sheet
(13x13 nm’), all other energy profiles exhibit an energy
barrier realigning from turbostratic (rotation angle 40° or
60°) stacking to AA'- or AB-stacking. This energy barrier of
realignment accounts for t-BN’s is metastability; (3) the
slope of the energy profile near 0° is steeper for larger h-BN
sheets. This results because a larger h-BN sheet has a higher
chance of interlayer misalignment (e.g., N on top of N or B
on top of B, leading to large electrostatic repulsion), even
when the rotation angle is small. The energy barrier of
realignment per atom is nearly size-independent (~0.054 kJ
mol '=0.56 eV to AA’, and ~0,039 kJ mol!=0.40 eV to AB)
as listed in TABLE IV. (In other words, the energy barrier of
realignment for the whole h-BN sheet scales as the total
number of atoms and scales as the sheet area.) Therefore, the
formation of BN-based turbostratic structure is kinetically
possible, which can be achieved by the FJH method with the
ultrafast heating and cooling process.
TABLE IV
Energy Barriers Of Realignment Of Different Sizes Of
H-BN Sheets From Turbostratic To AA’ Or To AB Stackin;
Energy Energy
Sheet Sheet Total barrier of Energy barrier barrier of -—_Energy barrier of
size size number realignment of realignment —_—realignment —_ realignment per
inx iny of to AA’ per atom to AA’ to AB atom to AB (kJ
(am) (nm) atoms (KJ mol!) (KI mol! atom!) (KJ mol!) mol! atom”)
1300 13 96 0 0 0 0
18 17 160 84 0.0523 Td 0.0445
20° 22 216 10.8 0.0498 54 0.0248
25 26 308 12.6 0.0408 17.6 0.0571
45 43 836 54.4 0.0651 317 0.0450.
58 56 1344 77.0 0.0573 38.5 0.0286
68 69 1904 115.9 0.0609 65.3 0.0343
-continued
HBNH (g) = Hz(g) + BN (3) (1200 K~ 1400 K) 6)
[0253] Compared to other bottom-up methods, such as
CVD [Xu D 2018: Tan 2015] and hydrothermal methods
[Ding 2021; Ding 2019], which usually involve a much
slower cooling rate of <10 K s~’ and result in the formation
of well-aligned stacking morphologies, the FJH method has
a 100-1000x faster cooling rate and generates turbostratic
BCN (t-BCN) as shown in FIG. 15C. Simulations were
performed using the finite element method (FEM), and the
temperatures reached in the bulk of the sample are found to
be sufficient for driving the third decomposition step since
the timescale of the uniform energy input is relatively short
compared to that of heat diffusion.
[0254] Nudged elastic band (NEB) simulations were per-
formed to study the thermodynamic stability against in-
plane rotation by using h-BN as an example. FIG. 15D (with
plots 1501-1507 for 1.3x1.3 nm?, 1.7x1.7 nm’, 2.0x2.2 nm’,
2.5x2.6 nm”, 4.3x4.5 nm”, 5.65.8 nm”, and 6.8x6.9 nm’,
respectively) shows the potential energy profiles of h-BN
sheets with different sizes along the rotational minimum
energy pathways from AA'- to AB-stacking. All potential
energies were normalized by the total number of atoms in
the small h-BN sheets and were relative to the most stable
AA' stacking mode. The calculations indicate that: (1) t-BN
is generally ~0.5 kJ mol! higher in energy than AA'-stacked
h-BN. The energy difference may be larger when the h-BN
Spectroscopic Analysis and Crystal Structure of f-BCN
[0255] When a mixture of BH,NH, and 20 wt % carbon
black is used as the reactant, the flash product showed
similar spectroscopic features as h-BN. Therefore, f-BCN-
20 (or any f-BCN-x in which x is less than or equal to 20)
is also called flash BN (f-BN) in this context. BH,;NH; and
f-BN can be analyzed by Fourier-transform infrared spec-
troscopy (FTIR); it is noted that there were no interfering
peaks of carbon black or flash graphene (FG) [Luong 2020]
in the IR. There were no obvious N-H or B-H stretching
band in the f-BN product as shown in FIG. 16A (with plots
1601-1603 for BH,NH;, f-BN, and h-BN, respectively),
which indicated the complete conyersion of BH,NH, [Frueh
2011]. The £-BN product showed a B-N stretching peak (E,,,
mode, ~1353 cm7') and a B-N-B bending peak (A,,, mode,
~782 cm™') [Zou 2019] in the IR spectrum, which is similar
to the spectrum of commercial h-BN. The shoulder peak at
~1074 cm is ascribed to the B-C band.
[0256] FTIR result is consistent with the Raman spectra in
Figure FIG. 16B (with plots 1611-1612 for BH,;NH, and
f{-BN, respectively}. There were many Raman peaks for
BH,NH, between 500 and 1200 cm™', whereas these peaks
are absent in {-BN and the characteristic E,, peak appears.
Compared to bulk h-BN, the E,, peak in the Raman spec-
trum showed a blue shift as the number of layers decreased
and there was a ~4 cm™ blue shift in isolated monolayer
h-BN due to the shorter BN bonds and the hardening of E,,
mode. [Gorbachev 2011; Cai 2017].Page 126
US 2025/0236521 Al
[0257] From representative high-resolution Raman spec-
tra shown in FIG. 16C (with plots 1621-1622 for f-BN and
h-BN, respectively), there was a ~3 cm! blue shift of the
characteristic B,, peak and a lower integrated intensity
I(E,,) for the f-BN, which resembled features of few-layer
h-BN sheets and indicated the weakened coupling interac-
tion between adjacent layers. [Gorbachev 2011].
[0258] The E,, peak positions of 100 different spots on
{BN and h-BN were studied in FIG. 16D (with circles
1631-1632 for f-BN and h-BN, respectively). Commercial
h-BN belongs to bulk h-BN, whose E,, peaks were centered
at 1365.3 cm™! with a narrow distribution (~0.2 cm™', red
shadow region). The f-BN had a higher average E,, peak
(~1368.7 cm7') with a broader distribution (~2.6 em”), and
~72% of the region showed a blue shift of the E,, peak,
which indicated the prevailing decoupling effect in the BN
sample.
[0259] The scheme in FIG. 16E displayed a normal in-
plane lattice constant ~0.25 nm and interlayer spacing ~0.33
nm in well-aligned h-BN crystals 1641. There were random
translational and rotational orientations of individual sheets
in t-BN crystals 1642 with larger average interlayer dis-
tances.
[0260] The turbostratic nature of the f-BN sample was
further explored by X-ray diffraction (XRD) in FIG. 16F
(with circles 1651-1652 for f-BN and h-BN, respectively).
The (002) diffraction peak became broader but less intense
and shifted toward a lower angle from ~26.7° to 26.1°,
indicating the expansion of the interlayer spacing by ~2.3%.
The (100) and (101) peaks merged into a broad (10) peak in
f£-BN and the long-range order diffraction peaks, such as
(110) and (004), were absent. These results support the
absence of an ordered structure of basal planes, and the
existence of a turbostratic structure. [Alkoy 1997; Thomas
1963; Gladkaya 1986].
[0261] Elemental analyses carried out by XPS indicated
the atomic ratio of B to N is ~1.05 and the existence of 6.7
wt % C. See TABLE V.
TABLE V
Element Content As Determined By XPS Spectral Analysis
B N ro) c
Commercial h-BN 45.8% 47.5% 51% 1.7%
£BN 411% 38.9% 13.3% 6.7%
BH,NH 46.7% 49.0% 43% L
[0262] High-resolution B is and N is spectra indicated the
dominance of typical B-N bonds (~190.5 eV) and N-B
bonds (~398.2 eV). FIG. 16G (with plots 1661-1662 for
f-BN and h-BN, respectively); FIG. 16H (with plots 1671-
1672 for f-BN and h-BN, respectively). [Ba 2017; Hu 2019].
A small B-C peak (~187.3 eV) was observed, which was
consistent with the B-C band as shown in FTIR in FIG. 16A.
The valence band of f-BN shows the valence band maxi-
mum (VBM) is ~3.10 eV, which slightly downshifts com-
pared with that of commercial h-BN (~2.70 eV), with this
downshift caused by introducing some O and C atoms in
f£-CN. UV-vis spectra of commercial h-BN and f-BN indi-
cated the optical bandgap of ~6.0 eV (FIG. 510, Supporting
Information). [Ba 2017]. Thus, FJH synthesis could become
an effective method to tune the VBM by introducing het-
eroatoms
Jul. 24, 2025
[0263] The Brunauer-Emmett-Teller (BET) method
showed that the specific surface area of f-BN (~143 m* g~')
was ~7 fold larger than that of commercial h-BN (~22 m?
g7'). The larger surface area of f-BN was likely the result of
small flake sizes and average layer numbers. The larger
nanopore size distribution can come from the gaps between
the small flakes. On the other hand, the commercial h-BN
samples were composed of the thick microplates with >10
layers and well-aligned structure.
[0264] The f-BN sheets can reach up to ~4.3 jum in lateral
size with a wrinkled structure. High-resolution transmission
electron microscopy (HR-TEM) analysis showed two stack-
ing f-BN layers. Corresponding fast Fourier transform (FFT)
patterns indicated the existence of two sets of six-fold
diffraction patterns close to each other with a rotational
mismatch of ~12°, which resulted from the turbostratic
structure of the f-BN. FIG. 16] (with inset 1681 showing the
FFT patterns, and the scale bar is 5 nm‘),
[0265] Polycrystalline materials are composed of many
crystalline domains with various sizes and orientations,
which also give multiple sets of diffraction patterns. For the
polycrystalline films, the in-plane crystal boundaries sepa-
rate the individual domains in the real space and the films
show multiple sets of diffraction patterns in the reciprocal
space. The turbostratic materials are the solids whose basal
planes have misalignments. Each individual sheet has its
own translational and rotational orientation in the real space,
and it shows one set of diffraction patterns in the reciprocal
space. Therefore, the diffraction patterns for polycrystalline
films comes from the in-plane domains, while the diffraction
patterns for turbostratic materials is caused by out-of-plane
domains (each individual sheets).
[0266] This means there are several solutions to distin-
guish polycrystalline materials and turbostratic materials by
TEM, namely
[0267] (1) The inverse Fourier transform can be carried
out for each set of diffraction patterns in the reciprocal
space, and the reconstructed images in the real space
reflect the relative association among the different sets
of spots. Specifically, if the reconstructed images show
the crystal structures from different areas of the same
sheets, it belongs to polycrystals. Otherwise, it is the
turbostratic materials.
[0268] (2) The HR-TEM can be carried out from the top
view. The Moiré patterns can be observed for the
turbostratic materials, while there are no Moiré patterns
for polycrystals. There are many different types of the
Moiré patterns. The Moiré patterns generated by only
one rotational stacking fault is the simplest type with
the period 4 and rotation angle 6. With more than two
rotational orientations, more complex Moiré patterns
can be observed.
[0269] (3) The Fourier transform can be carried out at
different position of the sample in the same images and
the as-obtained diffraction patterns can be compared in
the reciprocal space. Specifically, if all the diffraction
patterns are not the same (orientation and spot number),
then it belongs to polycrystals. Otherwise, it is the
turbostratic materials.
[0270] Solutions (2) and (3) were used to demonstrate the
turbostratic feature of flash samples.
[0271] To identify the turbostratic structure [Ci 2010;
Warner 2009], top-view atomic HR-TEM images were car-
ried out. The in-plane Moiré patterns were observed fromPage 127
US 2025/0236521 Al
20
few layers area. The clear fringes and FFT patterns indicated
good crystallinity of the flash products. The FFT patterns
were compared at different positions atop the same sheets.
Due to the unchanged orientations and spot numbers of the
diffraction spots, the possibility of polycrystals in this area
was excluded. Therefore, the various sets of diffraction spots
were resulted from the turbostratic structure.
[0272] The bright-field (BF) and high-angle annular dark-
field scanning transmission electron microscopy (HAADF-
STEM) images, together with elemental mapping, indicated
the existence of B, N, and a small amount of C in f-BN
sheets (FIG. 16]J), which was consistent with the XPS
results.
[0273] Plate-like f-BN with lateral sizes of 20-50 nm was
also observed. HR-TEM images showed the crystallinity of
f£-BN nanoplates with the majority of these nanoplates only
several layers thick. Corresponding FFT images showed
there were at least three sets of six-fold diffraction patterns.
The estimated mass yield of {-BN was ~34%. The conduc-
tive carbon additive could be removed from f-BN by thermal
treatment under air. However, oxidation would occur simul-
taneously on the surface. See TABLE VI. There are small
amounts of B-C and B-O bonds in f-BN, which is reasonable
since previous studies have shown that the oxidation of B-C
bonds starts at ~600° C. [Hu 2019; Li 2014].
TABLE VI
Element Content After Thermal Treament_
B N oO Cc
Commercial h-BN 46.0% 471% 5.2% 1.7%
f-BN 34.7% 12.5% 46.6% 6.1%
BH;NH; 44.9% 46.4% 6.4% 2.3%
Mechanical Exfoliation Tests of f-BN
[0274] The turbostratic characteristics of f-BN facilitates
its exfoliation by various mechanical methods, such as
adhesive tape exfoliation, monodirectional mechanical
shearing, and bath sonication. TABLE VII.
TABLE VII
Results Of Mechanical Exfoliation Tests
£BN — Commercial h-BN
Tape exfoliation Yes No
Mechanical shearing Yes No
Bath sonication (without surfactant) Yes No
[0275] Few-layer f-BN sheets obtained by adhesive tape
exfoliation can be distinguished from top-view scanning
electron microscopy (SEM) as shown in FIG. 17A. In
contrast, due to the strong coupling between adjacent layers
in commercial h-BN, there was no obvious exfoliation and
only thick nanoplates of several hundred nanometers were
observed in FIG. 17B. The average lateral size of BN and
commercial h-BN, obtained from the tape exfoliation
method, were 0.40 and 0.34 jum, respectively. FIG. 17C
(with circles 1701-1702 for {-BN and h-BN, respectively).
The size distribution results showed that the majority of the
£-BN flakes have the lateral size no more than 1.0 ym, which
makes it difficult to be applied in electronic devices, such as
field effect transistors. [Gupta 2020].
Jul. 24, 2025
[0276] However, the merits of BN, such as the nanoscale
feature and good dispersibility, show the potential applica-
tions of f-BN as the nano-fillers to enhance the mechanical
properties and to improve the electrochemical anticorrosion
performance as discussed below.
[0277] The same exfoliation phenomena can be observed
by applying monodirectional shearing force. The mechani-
cal exfoliation of f-BN sheets is demonstrated in FIG. 17D,
representing exfoliated f-BN sheets with the same edge
feature (delineated by the white dashed lines 1711 outlining
each sheet). The direction of the monodirectional shearing
force is shown by arrow 1712 in FIG. 17D. The atomic force
microscopy (AFM) profile showed the bilayer to few-layer
features of the exfoliated f-BN sheets. These results indi-
cated effective exfoliation of {-BN. In contrast, few-layer
BN sheets cannot be directly prepared from commercial
h-BN by monodirectional shearing under the same condi-
tions (FIG. 17E). The average lateral size of f-BN and
commercial h-BN, obtained from the mechanical shearing
method, were 0.47 and 0.40 um, respectively. FIG. 17F
(with circles 1721-1722 for f-BN and h-BN, respectively).
[0278] Compared to commercial h-BN nanoplates with
>10 layers, few layer {-BN flakes of several hundred nano-
meters with ripple-like structures were obtained by bath
sonication in ethanol without surfactant. FIGS. 17G-17H.
The layer number distributions of the f-BN, obtained by the
bath sonication treatment showed that ~80% of the {-BN
sheets have 3-5 layers. FIG. 171. In some regions, small
black particles can be found, presumably from the carbon
conductive additives. HR-TEM images and corresponding
FFT patterns demonstrate the high quality of the turbostratic
£BN sheets and the well-aligned structure of commercial
h-BN nanoplates.
Electrochemical Anticorrosion Tests of F-BN Composites
[0279] The turbostratic feature improves the dispersibility
and stability of f-BN in aqueous solution. After dispersal in
aqueous Pluronic (F-127) (1 wt % in deionized water), the
concentration of f-BN can reach up to ~18 wt % higher than
that of commercial h-BN. The percentage of commercial
h-BN and f-BN still in solution were ~6% and 77% after 21
days, respectively, which indicates the {-BN dispersion has
a higher temporal stability. Good dispersibility of {-BN
makes it possible to prepare stable nanocomposites with
f£-BN as a compatible additive.
[0280] A prerequisite is the dispersion and distribution of
the nano-fillers inside polymer matrices, since strengthening
of the composite relies on the interactions between the
polymer and the surface area of the fillers. [Luong 2020;
Albdullah 2018]. PVA has been studied as a surface coating
model system for testing additives to reduce chemical and
electrochemical metal corrosion. [Sarkar 2016; Owuor
2017]. The barrier films provide tortuous diffusion pathways
for corrosive electrolytes, delaying the metal corrosion pro-
cess. Likewise, they prevent metal ions from migrating, thus
building up a local Nernst potential at the polymer-metal
interface. The addition of appropriate nano-fillers can
occupy the free volume within the polymer matrix and
improve the film’s blocking properties. [Sarkar 2016].
[0281] Since f-BN has shown good dispersibility in aque-
ous solution, further demonstrations of f-BN as fillers in
PVA composites, which act as an electrochemical anticor-
rosion coating, are shown in FIGS. 18A-18D.Page 128
US 2025/0236521 Al
21
[0282] Before the electrochemical tests, the coating thick-
ness was characterized by cross-sectional SEM images. The
average thickness of the coating layer was ~9 um. The
electrochemical linear polarization resistance (LPR) tests of
bare Cu, PVA coated Cu (Cu-PVA), commercial h-BN and
PVA composite coated Cu (Cu-PVA-h-BN), and f-BN and
PVA composite coated Cu (Cu-PVA-f-BN) in 3.5 wt %
saline solution are shown in FIGS. 19A4-19D. The Cu-PVA-
f£:BN showed the largest polarization resistance (R,,) ~22.8
kQ em’, which was ~47% higher than Cu-PVA.
[0283] The open circuit potential (E,,,,.) represents the
thermodynamic tendency of the electrode to lose electrons to
the solution. [Warner 2009; Li 2014]. According to the
Nernst equation, the metal surface remains relatively stable
when the measured potential is lower than E,,,,,. The poten-
tiodynamic polarization measurements in FIG. 18A (with
plots 1801-1804 for bare Cu, Cu-PVA, Cu-PVA-h-BN, and
Cu-PVA-f-BN, respectively) and FIG. 18B (with plots 1811-
1814 for bare Cu, Cu-PVA, Cu-PVA-h-BN, and Cu-PVA-f-
BN, respectively) demonstrate that Cu-PVA-f-BN had the
more positive E.,.,,. (~188 mV vs Hg/Hg,SO,), thus there is
less tendency for the surface metal to take part in the
electrochemical oxidation process. Compared with pure
PVA and PVA-h-BN composite coatings, the PVA-f-BN
composite has higher corrosion protection efficiency (>92%)
and better anti-corrosion performance as shown in TABLE
VU.
TABLE VIII
Jul. 24, 2025
[0285] The optical and microscopic morphology after
electrochemical testing indicated that the Cu under the
PVA-f-BN composite coating is least affected, and surface
elemental analyses also showed there is no obvious forma-
tion of the oxides for Cu-PVA-f-BN. These results are
consistent with the highest corrosion protection efficiency
from the electrochemical tests and demonstrates one poten-
tial application of f-BN as a filler for nanocomposites.
[0286] Mechanical performance, such as hardness and
Young’s modulus of epoxy resin with 1 wt % f-BN additive
shows ~54% and ~70% increase, respectively, compared to
pure epoxy resin. These improvements cannot be achieved
by replacing {-BN with equal amounts of commercial h-BN.
Synthesis of f-BCN with Different Chemical Compositions
[0287] The atomic ratios of carbon can be tuned by
directly changing the weight percent of carbon black in the
reactants. Ifa mixture of BH;NH, and 30 wt % carbon black
is used as the reactant, the flash product is called {-BCN-30.
The same naming convention is used herein for the other
{-BCN samples prepared. As the weight percent of carbon
increases, the atomic percentage of carbon in flash products
can be controlled from ~0% to ~100% as determined by
XPS results. FIG. 20A (with illustrations 2001-2004 for
f£-BN-W, f£-BN, f-BCN-50, and f-BCN-100, respectively).
The elemental analyses demonstrated the monotonic
decrease of B and N from f-BN to f-BCN-100. FIG. 20B.
High resolution XPS of C is spectra showed the existence of
Electrochemical Parameters Determined From Potentiodynamic Polari
ization
For Bare Cu-PVA, Cu-PVA-h-BN, And Cu-PVA-f-BN In 3.5 Wt % NaCl (Aq)
Corr Corr
R Be Be icwr Boor Fate protect
Sample (kom?) (mV dee!) (mV dee!) GuAcm™) (mV) (mpy) eff)
bare Cu 137 3S 67 8.36 496 3.82 f
Cu-PVA, 15.47 118 107 1.58 4560.72. 81
Cu-PVA-h-BN_ 3.34 43 50 3.01 4901.37 64
Cu-PVA-f-BN 22.77 i) 69 0.66 188 030 92
[0284] The same enhanced anti-corrosion trend is also
observed in 0.5 M H,SO, as shown in FIG. 18C (with plots
1821-1824 for bare Cu, Cu-PVA, Cu-PVA-h-BN, and Cu-
PVA-fBN, respectively) and FIG. 18D (with plots 1831-
1834 for bare Cu, Cu-PVA, Cu-PVA-h-BN, and Cu-PVA-f-
BN, respectively). The Cu-PVA-f-BN showed the largest
polarization resistance (R,,) ~10.0 kQ cm?, which is >20 fold
higher than Cu-PVA. The corrosion protection efficiency for
Cu-PVA-f-BN is >97% vs 68% for Cu-PVA-h-BN as shown
in TABLE IX. This further shows to the superior dispers-
ibility and compatibility of {-BN in the polymer matrix.
TABLE IX
C-B and C-N bonds in f-BCN samples. As the mass ratios
of the carbon increased, the C-B and C-N ratios also
increased. High resolution XPS of B is and N is spectra also
confirmed the existence of B-C and N-C bonds.
[0288] The presence of B-C and N-C bonds confirmed the
formation of in-plane hybrid structures instead of the out-
of-plane stacked heterostructures, the latter being often more
thermodynamically stable. This can be attributed to an
ultrafast heating and cooling rate (~10* K s~’) of the FJH
reaction.
Electrochemical Parameters Determined From Potentiodynamic Polarization
For Bare Cu, Cu-PVA, Cu-PVA-h-BN, And Cu-PVA-f-BN In 0.5M H)SO4
Cor Corr
R Be B. Leorr ‘cor ~=—sTate~—oprrotectt
Sample (kQ em?) (mV dee!) (mV dee!) (wAcm™) (mV) (mpy) — eff (%)
bare Cu 0.23 87 69 72.74 414 33.22 f
Cu-PVA O47 7 OL 38.58 -394 17.62 47
Cu-PVA-h-BN_ 0.65 72 67 23.21 403 10.60 68
Cu-PVA-EBN 10.02 146 68 195-179 089 97Page 129
US 2025/0236521 Al
[0289] There are several possibilities for the flash products
after the reaction between carbon black and BH;BH3;,
namely:
[0290] (1) The mixture of BN and carbon black.
[0291] (2) The mixture of NC, BC, BN and graphene or
carbon black.
[0292] (3) Boron-carbon-nitrogen ternary compound
and carbon black.
[0293] The high-resolution XPS results reflected the exis-
tence of B-C, B-N and C-N bonds, which exclude the
possibility that the product is just the mixture of BN and
carbon black.
[0294] For NC and BC, there are two possibilities. At first,
BC and NC might be boron carbide and carbon nitride. The
boron carbide has a covalent B,C part at ~187.4 eV in B is
spectrum and it has characteristic XRD peaks (Powder
Diffraction File 35-0798, B,C). However, the deconvolution
result of the B is spectrum showed no peak at ~187.4 eV, and
there was no characteristic XRD peaks, which excluded the
possibility of the boron carbide. Similarly, there was no
characteristic XRD peaks of carbon nitride (Powder Dif-
fraction File 50-1250, C,N.,), which excluded the possibility
of the carbon nitride. The other possibility of BC and NC is
the co-doped graphene, which can be regarded as the car-
bon-rich boron-carbon-nitrogen components.
[0295] From TEM images, existence of the conductive
carbon materials was seen with some graphitic structures in
the flash products. Use f-BCN-30 as an example, the con-
ductive carbon materials had an average size of ~25 nm,
which made it distinguishable from f-BCN-30. This obser-
vation indicated that the flash product had unconverted
carbon materials. Therefore, the flash products are the mix-
ture of boron-carbon-nitrogen ternary compound and carbon
black. Due to the existence of the conductive carbon mate-
rials in the products, the carbon ratios determined by the
XPS analysis can be overestimated.
[0296] Due to the thermal stability difference of the con-
ductive carbon materials and substitutional carbon species
chemically bonded with boron and nitrogen, thermogravi-
metric analysis (TGA) can be used to oxidize the conductive
carbon materials. The first-order derivative of thermogravi-
metric curve showed 2 peaks starting from ~540° C. and
~750° C., and the first peak is mainly attributed to the
oxidation of conductive carbon materials. Therefore, the
conductive carbon materials can be removed from the flash
products by control the temperature at ~675° C. under air
condition (i.e., the carbon contents for the carbon-rich
boron-carbon-nitrogen ternary compounds can be underes-
timated). XPS results of various f-BCN samples before and
after thermal treatment reflected the existence of the substi-
tutional carbon species and the ratio of carbon contents can
reach 35.7 at % in f-BCN-70 after thermal treatment at
~675° C. under air condition for 30 min.
[0297] The carbon ratio of the in-plane hybrid structure
affects the electronic structures and changes the VBM. As
the atomic ratios of carbon increase, the VBM of f-BCN
changes from ~3.10 eV to -1.85 eV. FIG. 20C. The Raman
spectra of different {-BCN samples showed the appearance
of the G peak (~1580 cm™', single resonance), D peak
(~1350 cm, intervalley double resonance), 2D peak
(2695 cm, second order zone boundary phonons), D+G
peak (~2930 cm7!, a combination of scattering peak), 2D'
(~3250 cm™) and G* (~2450 cm™). [Huang 2020; Hong
2013; Yoon 2012]. As the carbon ratio increased in the
Jul. 24, 2025
reactants, the intensity of D+G peak decreased and 2D peak
increased. The intensity ratio between D and G peaks for
£-BCN-70 is ~1.10, which is similar to boron and nitrogen
co-doped graphene, which belongs to the carbon rich BCN.
£-BCN-100 (FG) shows a high 2D to G ratio (~8) and a low
D peak, which is similar with Luong 2020. The introduction
of carbon to the f-BCN sample also confers magnetic
properties [Sarkar 2016], which is different from commer-
cial h-BN.
[0298] h-BN shows a diamagnetic response since boron is
bonded with nitrogen and the total magnetic moment is ~0.
However, f-BCN-50 has B-C/O and N-C/O bonds, which
can contribute to the total magnetic moment. [-BCN-50
shows a ferrimagnetic response with a small coercivity of
~22 Oe. The saturation magnetic moment of f-BCN-50 is
0.115 emu g. Inductively coupled plasma mass spectrom-
etry (ICP-MS) confirmed the negligible contribution from
magnetic metals, such as Fe, Co and Ni, and other d-block
metals. [Fan 2019; Zhao 2014]. (HNO; (67-70 wt %,
TraceMetal™ Grade, Fisher Chemical), HCl (37 wt %,
99.99% trace metals basis, Millipore-Sigma), and water
(Millipore-Sigma, ACS reagent for ultratrace analysis) were
used for sample digestion. All the samples were digested
using a dilute aqua regia method. The samples were soaked
in HNO,/HC1 (1 M each) solution at 85° C. for 6 h. The
acidic solution was filtered to remove any undissolved
particles. The solution was then diluted to the appropriate
concentration range using 2 wt % HNO, within the calibra-
tion curve. ICP-MS was conducted using a Perkin Elmer
Nexion 300 ICP-MS system).
[0299] The boron-carbon-nitrogen ternary phase diagram
in FIG. 21 shows the chemical compositions (boron, carbon,
and nitrogen) of different {-BCN products before thermal
treatments, showing broad accessibility to varied BCN
materials via FJH methods. In FIG. 21, spheres 2101 and
dots 2102 refer to the classic compounds and the experi-
mental results for embodiments as described herein, repre-
sentatively. The atomic ratios were determined by XPS
results.
[0300] All of these f-BCN samples have turbostratic struc-
tures with larger interlayer spacings, since (002) diffraction
peaks shift to lower angles with broad (10) peaks by XRD.
The interlayer spacing of f-BCN was 3 to 6% larger than in
commercial h-BN and f-BCN-50 had the largest interlayer
spacing, which was ~6.1% larger than in commercial h-BN.
FIG. 20D: see also TABLE X.
TABLE X
Crystal Structure Of LBCN Samples
, Percentage
Materials (002) positiondlegree Interlayer spacing/A change!
h-BN 26.17 333 /
£BN 25.84 3.45 43.5%
EBCN-30 25.73 3.46 14.0%
£BCN-5O 25.21 3.53 46.1%
£BCN-70 25.87 3.44 43.4%
£BCN-100 26.09 341 42.6%
"The values show the percentage change of interlayer spacing compared with commercial
h-BN, where Eq (7) is used to calculate the percentage change.
Interlayer spacing gcy —Interlayer spacing, gy
Percentage Change =|{——— 2-4 EERIE 19096
Interlayer spacing, jy
(4)Page 130
US 2025/0236521 Al
23
[0301] There are larger surface areas for f-BCN samples
(110-310 m? g™') and they have abundant micropores as well
as mesopores. FIG. 20D. The Moiré patterns can be seen
from the HR-TEM image of {-BCN samples (FIG. 20E),
which indicates the existence of turbostratic stacking struc-
ture. Corresponding FFT patterns reflect multiple sets of the
diffraction spots from [002] direction. FIG. 20F. Atom-scale
HR-TEM image shows the complex Moiré patterns and
good in-plane crystallinity. FIG. 20G. STEM images con-
firm the nonaligned edges and elemental mapping results
demonstrate the existence of B, C and N for f-BCN-30
samples. FIG. 20H.
[0302] To confirm the existence of substitutional carbon
species in the structure and exclude the hydrocarbon con-
tamination resulted in fake positive carbon signal, electron
energy loss spectroscopy (EELS) was carried out and the C
K-edge spectrum showed the existence of 1s-a* and 1s-o*
peaks, which indicates the existence of substitutional carbon
atoms in the conjugated structure and excludes the possi-
bility that the carbon signal is sorely from amorphous
hydrocarbon contamination. [Langenhorsta 2002; McGil-
very 2012].
Heteroatom Doped (Substituted) Re-Flashed Graphene
[0303] In embodiments, the present invention further
relates to utilizing already synthesized flash graphene for the
flash doping process. Thus, a carbon feedstock is initially
flashed to convert it to turbostratic flash graphene. Then, the
flash graphene is mixed with a heteroatom doping com-
pound(s) before undergoing a second flash. This new
method achieves doping ratios higher than those achieved by
the previously referenced single flash doping method. A
schematic of this process is illustrated in FIGS. 22A-22B.
Synthesis of Heteroatom-Substituted Re-Flash Graphene by
FJH
[0304] The FJH system that can be utilized (and param-
eters) to synthesize heteroatom-substituted re-flash graphene
can be based on the system set forth and described in the
Tour °642 Application and the Tour 111 PCT Application
with the modifications as discussed below. [See also Luong
2020; Chen 2022; Deng 2022]. Parameters/declarations for
heteroatom-substituted re-flashed graphene can include the
following:
[0305] (1) Flash graphene can be converted into doped
flash graphene after it has already been flashed once.
[0306] (2) This method can be performed in varying
degrees with multiple different carbon feedstocks, as
well as multiple different doping compounds.
[0307] (3) The doping ratio can generally be maximized
when the doping compound-flash graphene weight
ratio is 1:4,
[0308] (4) Lower surface area amorphous carbon feed-
stocks can generally have higher doping ratios.
[0309] (5) Organic powders with low melting points
can, in some embodiments, be the most effective dop-
ing compounds.
[0310] (6) Performing the doping flash reaction under
argon atmosphere can, in some embodiments, be
needed for higher doping ratios.
Jul. 24, 2025
[0311] (7) Smaller grain size amorphous carbon feed-
stocks can, in some embodiments, be less effective for
initial graphene conversion but can be more effective
for subsequent doping.
[0312] (8) The doping flash can, in some embodiments,
yield the highest doping ratios when ref-lashed once at
around 3 kJ/g and then again at around 16 kI/g.
[0313] (9) This re-flash method can be performed with
a pulse width modulated DC electrical pulse from a
capacitor bank discharge, and can also be performed
with modulated or non-modulated AC and DC current
sources.
[0314] The synthesize heteroatom-substituted re-flash gra-
phene uses flash graphene as an initial reactant instead of
amorphous carbon, allowing higher doping ratios to be
achieved. The flash graphene that is used for re-flashing can
be the flash graphene synthesized from FJH, including, but
not limited to, the flash graphene described hereinabove for
the 1D carbon nanomaterials, the flash graphene described
in the Tour *642 Patent, and the holey and wrinkled flash
graphene described in the Tour °987 PCT Application.
[0315] For example, in embodiments, the desired carbon
feedstock for graphene conversion is selected. The two
feedstocks for the graphene that have been discovered to
achieve high doping ratios, are metallurgical coke (MC) and
bituminous activated charcoal (BAC) are described here, but
this can vary and include plastic derived flash graphene,
holey and wrinkled flash graphene (HWFG) or graphene
obtained from any source and any method. A schematic for
the reaction vessel for both is illustrated in FIG. 23. In FIG.
23, the graphite electrodes 2302, the copper electrodes 2301,
and the feedstock 2304 (in quartz tube 2303) are all con-
ductive enough to allow for the passage of electrical current
necessary for Joule heating. The graphite and the copper are
sufliciently more conductive than the feedstock such that
most of the heat is expended in the feedstock. The copper
helps provide a more even electrical contact and keeps
smaller grains of feedstock in more effectively.
[0316] Inan example process utilizing metallurgical coke,
several kilograms of metallurgical coke chunks were
obtained from Suncoke. This metallurgical coke was then
ground and sieved until the grain size diameters were
between 0.84 and 1.68 mm. The coke was then placed into
a fused quartz tube with an inner diameter of 16 mm and a
length of approximately 10 cm and the tube was closed on
either end by two graphite electrodes. The sample was then
compressed until it reaches 1.3Q. The metallurgical coke
was reacted in this vessel via flash Joule heating with batch
sizes of 5.7 g at 7.5 kJ/g using a pulse-width modulated
signal divided into 3 duty cycles of 10% for 1 s, 20% for 0.5
s, and 50% for 5 s. The resulting flash graphene was
determined via Raman spectroscopy analysis to be ~99%
converted to turbostratic flash graphene.
[0317] In an example process utilizing bituminous acti-
vated charcoal, bituminous activated charcoal was obtained
already with grain sizes between roughly 1 and 2 mm in
diameter. It was then filled into flashing vessels in 4.2-gram
batches, compressed to 1.0, and flashed at 7.5 kJ/g with the
same duty cycle pattern as were used with metallurgical
coke. The graphene conversion was also measured at ~99%.
[0318] Once the flash graphene is made, it initially
remained in grains that are too large for effective mixing.Page 131
US 2025/0236521 Al Hence, it was placed in a planetary ball mill among steel balls for 60 min to reduce its size to grains less than 0.2 mm in diameter. [0319] Thereafter, a heteroatom compound or a combina- tion of different compounds (for co-doping) was then mixed by mortar and pestle with the flash graphene in a 1:4 weight ratio in batches of 200 mg. Boric acid was used for boron doping, melamine resin was used for nitrogen doping, polyphenylene sulfide was used for sulfur doping, and perfluorooctanoic acid was used for fluorine doping. These compounds were chosen for the testing as described herein based upon their low decomposition temperature as well as the high doping ratios they achieve compared to other tested doping compounds. However, there is no particular limita- tion on the dopant material that can be used, and the dopant used in the present invention is not limited to the dopant selected for testing. [0320] 200 mg of this mixture was then loaded into a quartz tube ~4 cm Jong and with an inner diameter of 8 mm. Fine copper wool was then rolled into small electrodes 8 mm. in diameter and ~4 mm thick on either end, in electrical contact with the feedstock. Small graphite cylinders 8 mm in diameter and ~8 mm long were then placed in the quartz tube on either end and in electrical contact with the copper electrodes. The resulting vessel was placed between two electrodes attached to a flash Joule heating system and compressed until measuring below 5Q. The vessel was then placed under an argon atmosphere. [0321] Thereafter, flash Joule heating was then performed in two steps to maximize yield. The first pretreating flash was performed at ~3.1 kJ/g and the second, primary flash was performed at ~15.6 kJ/g. The flash reactions were performed using a pulse width modulated discharge with a 3-step duty cycle pattern of 10% for 1 s, 20% for 0.5 s, and 50% for 5 s. The difference between this flash and the one performed in step one is illustrated in FIGS. 24A-24B. Characterization of Heteroatom Substituted Re-Flash Graphene [0322] Standard characterization tools were utilized to verify both that the resulting product was converted to graphene and that the graphene is doped with heteroatoms. FIGS. 25A-25C show Raman and X-ray photoelectron spec- troscopy (XPS) analyses of N-doped BAC-derived reflash graphene. The presence of the D, G, and 2D Raman peaks, as illustrated in FIG. 25A, as well as the height of the 2D peak relative to that of the G peak, indicate that this sample was converted into high quality graphene (the high 2D peak is a positive indicator of graphene). FIG. 25B demonstrates the presence of the TS, and TS, Raman peaks, which further indicate that the stacking of the layers of graphene is turbostratic (not ordered) in nature. The doping of nitrogen in the graphene lattice is demonstrated in FIG. 25C (with plots 2501-2504 for Nla, graphitic, pyrrolic, and pyridinic, respectively), which further elaborates on the chemical bonding character of the nitrogen bonds. From this XPS spectroscopic analysis, it was calculated that the N doping percentage in this sample was ~S%, meaning that 5% of the atoms present in the sample were nitrogen. [0323] The morphology and elemental composition of the product was further verified by using scanning electron microscopy (SEM) and energy-dispersive X-ray spectros- copy (EDX), as shown in FIGS. 26A-26C, which displays N-doped BAC-derived reflash graphene. The EDX analysis Jul. 24, 2025 demonstrated that the N atoms are distributed evenly across the face of the graphene (carbon) sample. The fading colors around the edges of the sample were due to the sample being out of focus outside the center. Using these methods, this verified that the product, which was confirmed to be gra- phene via Raman spectroscopic analysis, was primarily composed of C but also exhibits N atoms near the surface. This analysis served as confirmation in addition to the XPS analysis of the presence of nitrogen in the product. [0324] FIGS. 27A-27B demonstrated the analysis of N-doped MC-derived reflash graphene. The graphene char- acter of the product is again confirmed by Raman spectros- copy analysis (again the high 2D peak is a positive indicator of graphene), and the XPS spectroscopy analysis of FIG. 27B (with with plots 2701-2703 for Nla, graphitic, and pyrrolic, respectively) confirmed that this sample has a particularly high doping ratio of almost 28%. [0325] In the embodiments tested, the results of the best doping ratios achieved are summarized in FIG. 28, which includes the results from co-doping experiments during in several different heteroatoms were doped into the graphene lattice at once. (The right part FIG. 28 (marked “BACFG”) shows the co-doping of multiple different types of heteroa- toms). In the embodiments tested, the doping reactions were generally more successful with metallurgical coke derived flash graphene than with bituminous activated charcoal derived flash graphene. Applications [0326] Various applications for this process and the result- ing product exist. The method solves the difficulty of effec- tively achieving high doping ratios well above 10% in heteroatom doped graphene. In addition, this process is easily scalable and can be used to create doped graphene in bulk. In addition, the low price of feedstocks that are required to produce this heteroatom doped graphene allows this method to effectively compete with other methods of producing doped graphene. [0327] Further, possible applications of the resulting het- eroatom substituted re-flash graphene include use as con- crete and epoxy additives to increase mechanical strength as well is use in battery electrode materials to increase perfor- mance. [0328] Still further, the ability to dope graphene using varied heteroatom compounds also provides the opportunity for the upcycling of organic waste sources via FJH (as described above) into heteroatom-substituted re-flash gra- phene. [0329] While embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described and the examples provided herein are exemplary only, and are not intended to be limiting. Many variations and modifica- tions of the invention disclosed herein are possible and are within the scope of the invention. The scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. [0330] The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated herein by reference in their entirety, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein.
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US 2025/0236521 Al 25 [0331] Amounts and other numerical data may be pre- sented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of approximately 1 to approxi- mately 4.5 should be interpreted to include not only the explicitly recited limits of 1 to approximately 4.5, but also to include individual numerals such as 2, 3, 4, and sub- ranges such as | to 3, 2 to 4, etc. The same principle applies to ranges reciting only one numerical value, such as “less than approximately 4.5,” which should be interpreted to include all of the above-recited values and ranges. Further, such an interpretation should apply regardless of the breadth of the range or the characteristic being described. [0332] Unless defined otherwise, all technical and scien- tific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently disclosed subject matter belongs. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the presently disclosed subject matter, representative methods, devices, and materials are now described. [0333] Following long-standing patent law convention, the terms “a” and “an” mean “one or more” when used in this application, including the claims. [0334] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accord- ingly, unless indicated to the contrary, the numerical param- eters set forth in this specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the presently disclosed subject matter. [0335] As used herein, the term “about” and “substan- tially” when referring to a value or to an amount of mass, weight, time, volume, concentration or percentage is meant to encompass variations of in some embodiments +20%, in some embodiments +10%, in some embodiments +5%, in some embodiments +1%, in some embodiments +0.5%, and in some embodiments +0.1% from the specified amount, as such variations are appropriate to perform the disclosed method. [0336] As used herein, the term “substantially perpendicu- lar” and “substantially parallel” is meant to encompass variations of in some embodiments within +10° of the perpendicular and parallel directions, respectively, in some embodiments within +5° of the perpendicular and parallel directions, respectively, in some embodiments within +1 of the perpendicular and parallel directions, respectively, and in some embodiments within +0.5° of the perpendicular and parallel directions, respectively. [0337] As used herein, the term “and/or” when used in the context of a listing of entities, refers to the entities being present singly or in combination. Thus, for example, the phrase “A, B, C, and/or D” includes A, B, C, and D individually, but also includes any and all combinations and subcombinations of A, B, C, and D. Jul. 24, 2025 REFERENCES [0338] U.S. Patent Appl. Publ. 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Coat., 2019, 133, 139 (“Zou 2019”). 1. A method comprising flash Joule heating a mixture of a material and a catalyst to form a 1-dimensional structure. 2. The method of claim 1, wherein (a) the flash Joule heating is a process comprising apply- ing a voltage across the mixture, which drives a current through the mixture to form the 1-dimensional struc- ture; (b) the voltage is applied in one or more voltage pulses; and (c) duration of each of the one or more voltage pulses is for a duration period. 3. (canceled) Jul. 24, 2025 4. The method of claim 1, wherein the 1-dimensional structure is a graphitic 1D and/or hybrid material nanoma- terial. 5. The method of claim 1, wherein the method further comprises forming the 1-dimensional structure forms along, with one or more other dimensional structures selected from the group consisting of 0-dimensional structures, 2-dimen- sional structures, and mixtures thereof. 6. The method of claim 1, wherein the 1-dimensional structure and the one or more other dimensional structures are conjoined covalently or non-covalently. 7. The method of claim 6, wherein the 1-dimensional structure and the one or more other dimensional structures are conjoined to form a 3-dimensional network. 8. The method of claim 1, wherein the material is a carbon material comprising a polymer. 9. The method of claim 8, wherein the mixture is formed by loading the polymer with particles of the catalyst through surface wetting. 10. The method of claim 8, wherein the mixture is formed by loading the polymer with particles of the catalyst through melt mixing. 11. The method of claim 1, wherein the materials is a waste product comprising carbon. 12. The method of claim 1, wherein the catalyst is selected from the group consisting of iron(II) chloride, nickel(II) chloride, cobalt(II) chloride, and ferrocene. 13. The method of claim 1, wherein the catalyst is selected from the group consisting of any transition metal or main group metal or transition metal or main group metal com- plex, salt, oxide, halide, or combinations thereof. 14. The method of claim 1, wherein the mixture further comprising a conductive carbon additive. 15. The method of claim 14, wherein the conductive carbon additive is selected from the group consisting of graphene, flash graphene, turbostratic graphene, anthracite coal, coconut shell-derived carbon, higher temperature- treated biochar, activated charcoal, calcined petroleum coke, metallurgical coke, coke, shungite, carbon nanotubes, asphaltenes, acetylene black, carbon black, ash, carbon fiber, and mixtures thereof. 16. (canceled) 17. The method of claim 14, wherein the method further comprises that, after the flash Joule heating, separating at least some of the conductive carbon additive from the formed the 1-dimensional structure. 18. The method of claim 17, wherein the step of separat- ing is based grain size of the conductive carbon additive and size of the 1-dimensional structure formed. 19. The method of claim 18, wherein the step of separat- ing comprising sieving to separate the small 1-dimensional structure from the large grain conductive carbon additive. 20-21. (canceled) 22. The method of claim 1, wherein % yield of 1-dimen- sional structure formed in the method is at least 65%. 23-32. (canceled) 33. A method comprising flash Joule heating a mixture to form boron nitride nanotubes, wherein the mixture com- prises (i) a material comprising boron, (ii) a material com- prising nitrogen and (iii) a catalyst.
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US 2025/0236521 Al Jul. 24, 2025 29 34. The method of claim 33, wherein (a) the flash Joule heating is a process comprising apply- ing a voltage across the mixture, which drives a current through the mixture to form the boron nitride nano- tubes; (b) the voltage is applied in one or more voltage pulses; and (c) duration of each of the one or more voltage pulses is for a duration period. 35. The method of claim 33, wherein the material com- prising the boron and the material comprising the nitrogen are different materials. 36. The method of claim 33, wherein the material com- prising the boron and the material comprising the nitrogen are the same material. 37. The method of claim 36, wherein the same material is ammonia borane. 38. The method of claim 33, wherein the catalyst is Ni(acac), and/or Fe(acac);. 39. The method of claim 33, wherein the catalyst com- prises Ni and/or Fe. 40. The method of claim 33, wherein the mixture further comprises a conductive carbon source. 41-48. (canceled) 49. The method of claim 40, wherein % yield of the boron nitride nanotubes formed in the method is at least 45%. 50-104. (canceled) ke eRe
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