ULTRAFAST FLASH JOULE HEATING SYNTHESIS METHODS AND SYSTEMS FOR PERFORMING SAME
20240116094 ยท 2024-04-11
Assignee
Inventors
Cpc classification
International classification
Abstract
Method and system for soil remediation by flash Joule heating. A contaminated soil that includes organic pollutants and/or one or more metal pollutants can be mixed with carbon black or other conductive additive to form a mixture. The mixture then undergoes flash Joule heating to clean the soil (by the decomposing of the organic pollutants and/or removing of the one or more toxic metals, such as by vaporization).
Claims
1. A method of soil remediation, wherein the method comprises: (a) mixing contaminated soil with a conductive additive to form a mixture, wherein the contaminated soil comprises one or more pollutants; and (b) applying a voltage across the mixture, wherein (i) the voltage is applied in one or more voltage pulses, (ii) duration of each of the one or more pulses is for a duration period, (iii) the one or more voltage pulses increase the temperature of the mixture to at least 1000 K, and iv) the application of the voltage across the mixture decomposes and/or removes the pollutants from the contaminated soil to form remediated soil.
2. The method of claim 1, wherein the one or more pollutants are selected from a group consisting of organic pollutants, metals, metalloids, heavy metals, toxic heavy metals, rare earth metals, main group metals, and transition metals.
3. The method of claim 2, wherein the one or more pollutants comprises one or more organic pollutants.
4. The method of claim 3, wherein the voltage applied in the one more voltage pulses decomposes at least one of the one or more organic pollutants.
5. The method of claim 4, wherein the at least one of the one or more organic pollutants decompose by at least one of graphitization and graphene formation.
6. (canceled)
7. The method of claim 2, wherein the voltage applied in the one or more voltage pulses removes at least one of the one or more organic pollutants.
8. The method of claim 7, wherein the one or more organic pollutants are removed by at least one of boiling, sublimation, and vaporization of the one or more organic pollutants.
9. The method of claim 2, wherein the one or more organic pollutants are organic pollutants selected from a group consisting of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyl (PCB), organochlorine pesticides (OCP), halogenated flame retardants, hydrocarbons, halogenated organic compounds, halogenated aromatics, total petroleum hydrocarbons (TPH), and per- and polyfluoroalkyl substances (PFAS).
10. The method of claim 9, wherein the one or more organic pollutants comprise one or more polycyclic aromatic hydrocarbons (PAH).
11. The method of claim 10, wherein the one or more polycyclic aromatic hydrocarbons (PAH) are selected from a group consisting of pyrene, fluorene, and benz[a]anthracene.
12. A method of soil remediation, wherein the method comprises: (a) mixing contaminated soil with a conductive additive to form a mixture, wherein the contaminated soil comprises one or more pollutants; and (b) applying a voltage across the mixture, wherein (i) the voltage is applied in one or more voltage pulses, (ii) duration of each of the one or more pulses is for a duration period, (iii) the application of the voltage across the mixture decomposes and/or removes the pollutants from the contaminated soil to form remediated soil, (iv) the one or more pollutants are one or more organic pollutants, and (v) the one or more organic pollutants comprise one or more per- and polyfluoroalkyl substances (PFAS).
13. The method of claim 12, wherein the one or more per- and polyfluoroalkyl substances (PFAS) are selected from a group consisting of perfluorosulfonic acids and perfluorocarboxylic acids.
14. The method of claim 12, wherein the one or more per- and polyfluoroalkyl substances (PFAS) are selected from a group consisting of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA).
15. The method of claim 2, wherein (a) the one or more pollutants comprises one or more metal pollutants, and (b) the one or more metal pollutants is selected from a group consisting of metals, metalloids, heavy metals, toxic heavy metals, rare earth metals, main group metals, and transition metals.
16-25. (canceled)
26. A method of soil remediation, wherein the method comprises: (a) mixing contaminated soil with a conductive additive to form a mixture, wherein the contaminated soil comprises one or more pollutants; and (b) applying a voltage across the mixture, wherein (i) the voltage is applied in one or more voltage pulses, (ii) duration of each of the one or more pulses is for a duration period, iii) the duration period of each of the one or more voltage pulses is between 1 microsecond and 20 seconds, and (iv) the application of the voltage across the mixture decomposes and/or removes the pollutants from the contaminated soil to form remediated soil.
27-31. (canceled)
32. The method of claim 1, wherein at least 40% of the one or more pollutants in the contaminated soil are decomposed and/or removed by the method.
33. The method of claim 32, wherein between 40% and 90% of the one or more pollutants in the contaminated soil are decomposed and/or removed by the method.
34-44. (canceled)
45. The method of claim 1, wherein the one or more voltage pulses increase the temperature of the mixture to at least 1500 K.
46. The method of claim 1, wherein the one or more voltage pulses increase the temperature of the mixture to at least 2000 K.
47. The method of claim 1, wherein the one or more voltage pulses increase the temperature of the mixture to at least 2500 K.
48. The method of claim 1, wherein the one or more voltage pulses increase the temperature of the mixture to at least 3000 K.
49. The method of claim 1, wherein the method is performed in a continuous process.
50. The method of claim 49, wherein the continuous process comprises (a) loading the mixture into a cell; (b) compressing the mixture within the cell; (c) applying the voltage across the mixture within the cell; and (d) unloading the remediated soil from the cell.
51-53. (canceled)
54. A system for performing the method of soil remediation utilizing at least one of the method of claim 1, wherein the system comprises: (a) a source of the mixture comprising the contaminated soil and the conductive additive; (b) a cell operably connected to the source such that the mixture can be flowed into the cell and held under compression; (c) electrodes operatively connected to the cell containing the mixture; and (d) a flash power supply for applying a voltage across the mixture in the cell to form the remediated soil from the mixture.
55. The system of claim 54, wherein the system is operable to perform a continuous process.
56. The system of claim 54, wherein the cell is movable.
57. (canceled)
58. The system of claim 54 further comprising a reservoir for collecting the remediated soil.
59. (canceled)
60. The system of claim 54, wherein the system is operable to perform an autonomous process.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0101] The present invention relates to ultrafast flash Joule heating synthesis methods and systems, and more particularly, methods and systems for soil remediation by flash Joule heating.
[0102] Direct electrical heating is emerging as a highly energy-efficient high-temperature technique for materials synthesis [Yao 2018; Liu 2022; Liu C 2020; Liu S 2020], processing [Wang 2020; Cheng 2022], and waste management [Barbhuiya 2021]. The inventors of the present invention have developed flash Joule heating (FJH) processes for converting carbon-containing sources into high-quality graphene. [Luong 2020]. In addition to the materials synthesis capability [Deng I 2022; and Chen I 2021], it has been demonstrated that the FJH process can be used for sustainable management of plastic [Algozeeb 2020; Wyss 2021] and rubber wastes [Advincula 2021], and the recovery of critical metals from industrial wastes [Deng 2021; Deng II 2022]. [See also Tour PCT '000 Application; Tour PCT September 2021 Applications].
[0103] It has now been discovered by the inventors and Applicant that FJH can be utilized as a rapid and broad-based process for the effective removal of pollutants in contaminated soil. I.e., rapid and general FJH processes have been discovered by inventors and Applicant for the effective removal of contaminants in soil regardless of the chemical forms and speciation. The concentrations of toxic heavy metals in contaminated soil, including Cd, Hg, Pb, Co, Ni, and Cu, are reduced by FJH to within the government-set safe limits; the organic contaminants are removed by graphitization to a nontoxic carbon form, as demonstrated by the greatly reduced concentrations of PAHs in the contaminated soil. The FJH is energy efficient due to the rapid heating and cooling rate and short duration with an estimated cost of ?$8 ton.sup.?1 for soil remediation, which is 12% to 25% of the cost of other state-of-the-art innovative technologies. The FJH process, with the benefits of versatility, ultrafast speed, low cost, no water use, and good scalability, would be a harbinger for near-future soil remediation practice.
[0104] For example, in embodiments of the FJH process, such as shown in
System and Process
[0105] A general overall process for the soil remediation by flash Joule heating is shown in
[0106] An exemplary system and process used to perform this method is shown in the electrical circuit diagram and setup of the FJH system depicted in
[0107] In a soil remediation by flash Joule heating process utilizing the FJH system depicted in
[0108] The FJH process was conducted in a mild vacuum (?10 mm Hg) chamber; a vacuum desiccator (
TABLE-US-00001 TABLE I Physical properties of the precursors and corresponding metals Decomposition Melting point Boiling point Precursors temperature (? C.) Metal (? C.) (? C.) CdCl.sub.2 961 Cd 321 767 HgCl.sub.2 138 Hg ?38.8 357 Pb(NO.sub.3).sub.2 200-470 Pb 327 1749 CoCl.sub.2 >873 Co 1495 2927 CuCl.sub.2 993 Cu 1085 2562 NiCl.sub.2 >800 Ni 1455 2913
[0109] In a typical experiment, a FJH voltage of V=100 V, discharging time of t=1 s, and sample resistance of R=1? were used. See TABLE II.
TABLE-US-00002 TABLE II Parameters for FJH Mass after Mass Mass Res Volt T FJH Precursors Ratio (mg) (?) (V) (s) (mg) c-Soil(heavy metals):CB 2:1 200 1.0 60 1 145 c-Soil(heavy metals):CB 2:1 200 1.0 80 1 105 c-Soil(heavy metals):CB 2:1 200 1.0 100 1 81 c-Soil(heavy metals):Metcoke 2:1 206 2.0 100 1 122 c-Soil(heavy metals):FG 2:1 211 1.5 100 1 135 c-Soil(pyrene):CB 2:1 200 0.8 100 1 129 c-Soil(fluorene):CB 2:1 200 0.8 100 1 135 c-Soil(benz[a]anthracene):CB 2:1 200 0.8 100 1 156
[0110] The current curve was recorded during the discharging, showing the maximum value of ?100 A (
Removal of Toxic Heavy Metals by Flash Joule Heating
[0111] Clean soil was collected from the Rice University campus (
[0112] The concentrations of heavy metals in the c-Soil and the remediated soil (r-Soil) by FJH were measured by inductively coupled plasma optical emission spectrometry (ICP-OES) after digestion using the method from the standard from the Environmental Protection Agency (EPA), USA. [US EPA 1996]. For this digestion process, the samples (?50 mg) were added into HNO.sub.3 (2 mL, 67-70 wt %, 1:1 with water) at 95? C. for 2 h. Then, H.sub.2O.sub.2(2 mL, 30 wt %, 1:1 with water) was added and heated to reflux at 95? C. for 2 h. Then, HCl (1 mL, 37 wt %) and H.sub.2O (5 mL) were added, and the mixture was heated at reflux for 15 min. The acidic solution was filtered to remove any undissolved particles using a sand core funnel (Class F). The filtrate was then diluted to the range within the calibration curve.
[0113] The removal efficiency (R) of heavy metals is calculated according to Equation (1),
where m(c-Soil) is the mass of c-Soil used for FJH, c(c-Soil) is the concentration of heavy metals in c-Soil, m(r-Soil) is the mass of r-Soil after FJH, and c(r-Soil) is the concentration of heavy metals in r-Soil.
[0114] The removal efficiencies of heavy metals were investigated at different FJH voltages. As shown in
[0115] At the FJH voltage of 100 V, the removal efficiencies of all the heavy metals are >80% in a single FJH pulse (
[0116] For example, the efficiency of metallurgical coke (Metcoke) or flash graphene as the conductive additives has been demonstrated. See
[0117] The concentrations of heavy metals in Metcoke are Cd undetectable, Hg undetectable, Pb?2.7 ppm, Co?2.1 ppm, Ni?30 ppm, and Cu?41 ppm.
[0118] Flash graphene (FG) was also used as the conductive additive. The FG was synthesized by using Metcoke as the precursor. The concentrations of heavy metals in the FG were Cd undetectable, Hg undetectable, Pb undetectable, Co?1.1 ppm, Ni?8.6 ppm, and Cu?47 ppm.
[0119] Thus, in both cases, removal efficiencies of >60% in a single FJH pulse were realized, which was somewhat smaller than that by using CB as the conductive additives. Again, this might be due to the smaller particle size of CB that permit a more uniform heating during the FJH process.
[0120] To further demonstrate the removal of heavy metals, X-ray photoelectron spectroscopy (XPS) characterization was conducted on the c-Soil and r-Soil. See
[0121] The main crystalline composition of the soil before and after FJH were characterized by X-ray diffraction (XRD). Quartz (SiO.sub.2) and calcite (CaCO.sub.3) were found to be the major crystal components of the soil. See
Reducing the Heavy Metals Content to within the Safe Limit
[0122] Unlike the physicochemical adsorption methods that rely on the capacity of sorbents [Bolan 2014], there is no capacity limit for the FJH process to remove heavy metals. The concentration of heavy metals in c-Soil could be continuously reduced by merely increasing the number of FJH pulses. The concentrations of all representative heavy metals were reduced to below the California Human Health Screening Levels (CHHSL) for residential locales [Cal OEHHA 2010] by 2 to 3 FJH pulses, where each pulse is only 1 s. See
[0123] The number of pulses depends on their initial concentrations, the safety thresholds and the vapor pressure of specific heavy metal. Among all heavy metals, Cd and Hg are the most toxic and have the strictest standards of 1.7 ppm and 18 ppm, respectively (
[0124] The evaporated heavy metals could be further collected. XPS analysis of the inner side of the quartz tube after FJH was conducted. See
Removal of Organic Contaminants by FJH
[0125] In addition to the heavy metals, organic compounds like PAHs [Hussar 2012; Zhang S 2017], PCB [Chekol 2004], OCP [Liu 2021], and TPH [Streche 2018] represent the other severe pollutants in contaminated soil. Here, PAHs were used as examples to show the organic contaminant removal capability of the FJH process. Three PAHs, pyrene, fluorene, and benz[a]anthracene were used. Similar to the heavy metal contamination, the clean soil was first spiked by individual PAH. Then, CB (?30 wt %) was mixed with the PAH-contaminated soil as a conductive additive for FJH. See detail conditions above in TABLE II. The PAH in c-Soil and r-Soil was extracted into an organic phase by solvent extraction using a method from the EPA, USA. [US EPA 2007]. The extraction solvent was composed of 1:1 vol:vol ethanol:dichloromethane (99.5%, Fischer Chemical). Soil samples (?10 mg) were mixed with the extraction solvent (?5 mL) and dispersed in a bath sonicator for 5 min. The solution was filtered to remove all soils and carbon black using a sand core funnel (Class F). The clear filtrate was diluted with ethanol until the concentration of analyte was within the calibration range.
[0126] The concentration of PAH was measured by an ultraviolet-visible (UV-Vis) spectrophotometry (Shimadzu UV-3600 Plus spectrophotometer). [See Giger 1974]. The good linearity of the calibration curves in
[0127] The UV adsorption spectra of pyrene exhibit two characteristic peaks at ?319 nm and ?333 nm. See
[0128] Similarly, the fluorene exhibits characteristic adsorption peak at ?299 nm, whose intensity was greatly reduced after FJH (
[0129] The same strategy pertains to the remediation of benz[a]anthracene contaminated soil (
[0130] The ultrahigh temperature during the FJH process could graphitize the carbon-containing precursors, as demonstrated by the synthesis of flash graphene from various resources in previous reports by the inventors. [Luong 2020; Algozeeb 2020; Wyss 2021; Advincula 2021; Stanford 2020; Tour PCT '000 Application; Tour PCT September 2021 Applications]. The Raman spectra of the r-Soil after flash Joule heating the PAH-contaminated soil show strong 2D bands (
Techno-Economic Analysis and Scalability of the FJH Process
[0131] The energy consumption and cost of the FJH process for soil remediation were evaluated in view of its economic benefit. Due to the direct sample heating feature, the ultrafast heating/cooling rate, and the short treatment duration, the FJH process for soil remediation is highly energy efficient with the electrical consumption of ?420 kWh ton.sup.?1, or ?$8 ton.sup.?1.
[0132] The energy consumption was calculated using Equation (2).
where E is the energy per gram (kJ g.sup.?1), V.sub.1 and V.sub.2 are the voltage before and after FJH, respectively, C is the capacitance (C=60 mF), and M is the mass per batch.
[0133] For a typical trial with V.sub.1=100 V, V.sub.2=0 V, and M=0.2 g, the energy is calculated to be:
E=1.5 kJ g.sup.?1=4.2?10.sup.?4 kWh g.sup.?1=420 kWh ton.sup.?1
[0134] Given that the industrial price of electrical energy in West Texas, USA is presently $0.02 kWh.sup.?1, current cost for treatment of 1 ton of contaminated soil would be P=$8.4 ton.sup.?1.
[0135] As a comparison, the cost of treating contaminated soil with existing innovative technologies ranges from $50,000 to $100,000 per acre-foot. [NJDEP 2022]. Considering the bulk density of soil being ?1.33 g cm.sup.?3, this corresponds to the cost of $30-60 ton.sup.?1. Hence, the cost of the FJH process is ?12% to 25% of the cost compared to other innovative soil remediation technologies.
[0136] The FJH process is scalable. [Deng 2021; Deng I 2022; Deng II 2022; Tour PCT '000 Application; Tour PCT September 2021 Applications]. Since the evaporative removal of the heavy metals and graphitization of organic contaminants rely mainly on the maximum achievable temperature, a constant temperature should be maintained when scaling up the FJH process for soil remediation.
[0137] Since the removal of the heavy metals and graphitization of organic contaminants mostly rely on the maximum temperature of the FJH process, the available temperature across the sample is the key point when scaling up the FJH process. For Joule heating, the heat amount (Q) is calculated by Equation (3).
Q=I.sup.2Rt(3)
where I is the current passing through the sample, R is the resistance of the sample, and t is the heating time. The heat amount per volume (Q.sub.v) is then determined by Equation (4)
Q.sub.v=j.sup.2?.sub.et(4)
where j is the current density, ?.sub.e is the electrical resistivity of the sample, and t is the heating time.
[0138] The change of temperature (?T) is proportional to the heat amount according to Equation (5).
Q=C.sub.pm?T(5)
where C.sub.p is heat capacity of the sample, and m is the mass of the sample. Again, Equation (5) could be revised per volume to Equation (6),
Q.sub.v=C.sub.p?.sub.m?T(6)
where ?.sub.m is the density of the sample. Since the C.sub.p and ? were constant for a specific kind of sample, maintaining a constant Q, is a key to keeping the same available temperature.
[0139] Since the electrical resistivity (?.sub.e) of the sample is constant, to maintain a constant Q, and t when scaling up the sample, according to Equation (6) a constant current density (j) should be maintain.
[0140] The charge (q) in the capacitor bank is calculated by Equation (7).
q=CV(7)
where C is the total capacitance, and V is the charging voltage. Supposing the charges in the capacitor bank are discharged in the heating time (t), the current (I) passing through the sample could be calculated by Equation (8).
[0141] Hence, the current density (j) can be calculated by Equation (9).
where S is the sample cross-sectional area. In the circumstance in which the samples are cylinder-shaped in a quartz tube, the sample mass (m) can be calculated by Equation (10).
m=?.sub.mSL(10)
where ?.sub.m is the sample density, S is the sample cross-sectional area, and L is the sample length. The sample density (?.sub.m) is constant considering the same compression of the sample.
[0142] Equation (11) can then be used obtain and determine the current density.
[0143] As discussed above, to increase the sample mass (m), a constant current density (j) should be maintained, which could be realized by the practices including: (1) linearly increasing the FJH voltage (V), and (2) linearly increasing the capacitance (C). According to the above, the mass per batch can thus be scaled up by linearly increasing the FJH voltage or capacitance.
[0144] The upscaling of the sample mass to 2 g and the removal efficiencies of heavy metals has been demonstrated to be comparable to the small-scale samples.
[0145] A FJH system having a capacitor bank composed of 10 commercial aluminum electrolytic capacitor (450 V, 6 mF, Mouser #80-PEH200YX460BQU2) with the total capacitance of C.sub.0=0.06 F. In a typical experiment, a FJH voltage of V.sub.0=100 V and C.sub.o=0.06 F were used for the treatment of sample with mass of m.sub.0=0.2 g.
[0146] As discussed above with regard to the small-scale experiments (TABLE II), a sample mass of m.sub.0=0.2 g was used (
[0147] For the sample mass of m.sub.1=2 g and C.sub.1=0.624 F, a FJH voltage of V.sub.1=120 V was used, thus fitting with the Equation (11). Since the temperature is a pertinent criterion for the heavy metal removal by evaporation and organic contaminants removal by graphitization, the temperature for the large-scale sample was recorded.
[0148] The FJH process could thus be integrated with some industrial scale-up technologies. For example, as shown in
[0149] Indeed, presently, the FJH process is undergoing industrial-scale scaling up for the conversion of carbon source to flash graphene [Luong 2020] by Universal Matter, Ltd. with the targeted production rate of 100 ton day.sup.?1 by mid-2023. [Universal Matter 2022]. The equipment and processes designed and optimized for the flash graphene synthesis can be transferrable for the soil remediation process.
Capacitor Banks
[0150] As utilized in the embodiments discussed above, capacitors were used to provide the DC supply for the FJH (DC-FJH). Alternating current (AC) could also be used for the FJH process. [Algozeeb 2020; Tour PCT '000 Application; Tour PCT September 2021 Applications]. The application of AC source for FJH (AC-FJH) can also be used for soil remediation.
[0151] The AC-FJH system can include two circuit breakers to avoid the electricity overload. See
[0152] According to calculations using Equations (3)-(12) discussed above, the temperature could be improved when the voltage is increased. In industry, high voltage or even ultrahigh voltage technologies are well-established [Wen 2014; Chen 2015], that could be introduced for further improvement of the removal efficiencies.
Advantages and Applications
[0153] Soil contamination constitutes a significant environmental issue. With the increasing population and increased demand for agriculture, soil contamination has become a global environmental problem. The process to remove heavy metal contaminants in soil is significant for the sustainability of soil and environmental protection. Moreover, the flash Joule heating process of embodiments of the present invention could also be used to treat the solid waste disposals, for examples, the contaminants from Superfund sites.
[0154] For the soil remediation by flash Joule heating, embodiment of the present invention provide: (i) the flash Joule heating is a completely dry process without use of any solvent, while in previous soil washing processes, much wastewater was produced; (ii) the flash Joule heating could remove most of the heavy metals in contaminated soils in one step, including Cd, Hg, Pb, Cu, Ni, Co, etc., which is hard to be realized by other methods due to the different properties of these elements; (iii) the FJH is a general process to remove both the organic and inorganic contaminants; and (iv) the energy conversion efficiency of the flash Joule heating process is high, so the recovery by FJH is an energy-savings process.
[0155] For the soil remediation by FJH, the removal efficiency and the reduction of the concentration in soil can be performed to within the regulatory limits.
[0156] Embodiments of the present invention can include a Joule heating process based on pulsed direct current (PDC), such as discussed and described in the Tour PCT September 2021 Applications. Moreover, the voltage pulse can be performed utilizing direct current (DC), alternating current (AC), or both direct current (DC) and alternating current (AC). [Tour PCT September 2021 Applications]. The direct current (DC) and alternating current (AC) can be switched back and forth and/or concurrently used. [Tour PCT September 2021 Applications].
[0157] 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 modifications 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.
[0158] 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.
[0159] Amounts and other numerical data may be presented 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 approximately 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 1 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.
[0160] Unless defined otherwise, all technical and scientific 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.
[0161] Following long-standing patent law convention, the terms a and an mean one or more when used in this application, including the claims.
[0162] 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. Accordingly, unless indicated to the contrary, the numerical parameters 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.
[0163] As used herein, the term about and substantially 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.
[0164] As used herein, the term substantially perpendicular 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.
[0165] 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.
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