Patent ID: 12195337

DETAILED DESCRIPTION

Examples of the compositions, materials, systems, methods and apparatuses discussed herein are not limited in application to the details of construction and the arrangement of components set forth in the following description or illustrated in the accompanying drawings. The compositions, materials, systems, methods and apparatuses are capable of implementation in other examples and of being practiced or of being carried out in various ways. Examples of specific implementations are provided herein for illustrative purposes only and are not intended to be limiting. In particular, functions, components, elements, and features discussed in connection with any one or more examples are not intended to be excluded from a similar role in any other examples.

Examples disclosed herein may be combined with other examples in any manner consistent with at least one of the principles disclosed herein, and references to “an example,” “some examples,” “an alternate example,” “various examples,” “one example” or the like are not necessarily mutually exclusive and are intended to indicate that a particular feature, structure, or characteristic described may be included in at least one example. The appearances of such terms herein are not necessarily all referring to the same example.

Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. Any references to examples, components, elements, acts, or functions of the products, systems and methods herein referred to in the singular may also embrace embodiments including a plurality, and any references in plural to any example, component, element, act, or function herein may also embrace examples including only a singularity. Accordingly, references in the singular or plural form are not intended to limit the presently disclosed systems or methods, their components, acts, or elements. The use herein of “including,” “comprising,” “having,” “containing,” “involving,” and variations thereof is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. References to “or” may be construed as inclusive so that any terms described using “or” may indicate any of a single, more than one, and all of the described terms.

This disclosure in part addresses and solves limitations regarding the preparation of CoMo/SiO2catalysts. As discussed above, the fine control in the formation and sizes of highly dispersed nanoparticles of the active metals deposited on the catalyst support surface affect the production of long and straight CNTs. For this purpose, very low metal content (for example, less than 1000 ppm or 0.1 weight percent) together with colloidal silica particles (e.g., Sigma Aldrich Ludox SM-30, 30% suspension in water) are used in the impregnating solution of some examples. Since the metal particles are distributed homogeneously and separated from each other on the surface, as evidenced by Scanning Electron Microscopy (SEM) images, the growth of carbon nanotubes is carried out with decreased steric hindrances and heat and mass transfer limitations. The carbon nanotube growth occurs on the surface of each individual metal particle in a straight form with a mesh-type morphology that covers the surface of the support particles. Although the metal content in the catalyst of the present disclosure is lower than that of the prior art (the prior art disclosing greater than 0.1 wt % Co), nevertheless the carbon yield is comparable (2-5 wt % carbon) since the SWCNTs are in some examples at least approximately 3 to 6 times longer.

In some examples the purification of carbon nanotubes is carried out by digestion of the catalyst particles in the presence of inorganic acids. In the case of SiO2, concentrated HF solutions can be used. Since the metal content is lower in the present catalyst, and the carbon yield is comparable to that of the prior art, lower HF solution concentration is required to efficiently remove catalyst impurities from the product. Another aspect is the fact that the purified long SWCNT product has a different morphology from that of the prior art. This consists of the formation of a “frayed fabric” of SWCNTs, where bundles of CNT stick together in an aligned manner, as might fibers of a frayed fabric. The bundles are easily separated and dispersed in the presence of solutions containing surfactants. Less energy is needed to disperse the carbon nanotubes, which represents a great advantage in the manufacturing of CNT for both membranes and conductive film applications, and other applications that benefit from dispersed, long, narrow SWCNT.

In some examples this disclosure includes a novel heterogeneous catalyst for the production of long, straight carbon nanotubes having controlled diameter distribution. In some examples the CNT are produced in fluidized bed or rotary tube reactors. In some examples the CNT are used for the manufacture of membranes employed in different industrial applications. These applications include but are not limited to: seawater desalination, removal of organic and inorganic water contaminants (heavy metals, organic and inorganic substances), removal of microorganisms (bacteria, viruses and protozoa), personal protection equipment against chemical and biological substances, and air purification systems.

Multiple methods are used for the fabrication of SWCNTs, each providing SWCNTs with characteristic structures and compositions. For commercial SWCNT production, arc discharge, laser ablation, and two types of catalytic chemical vapor deposition (CCVD) are the main processes that have been used. Arc discharge and laser ablation were the first methods employed to synthesize SWCNTs on the scale of some tens of grams. Both of these methods involve evaporation of solid carbon in the presence of a mixed transition-metal catalyst, such as nickel/cobalt, followed by condensation of gaseous carbon atoms into a soot-like material that, in addition to CNTs, contains other forms of amorphous and graphitic carbon. These methods generally yield materials with diameters in the range of 1.3-1.8 nm. The purity of the SWCNTs from the reactor is typically less than 35%, and extensive purification is required to isolate the SWCNTs. Final yields of the purified CNTs can be as low as 10 wt % of the carbonaceous material produced. The high reaction temperature used is believed to produce SWCNTs with low defect concentrations compared with most other methods. However, the high cost of isolating the SWCNTs to obtain pure material suitable for membrane fabrication renders these methods very expensive. Furthermore, these methods have not demonstrated the capability of controlling SWCNT length, chirality, and diameter distribution that are useful for CNT-membrane fabrication and other commercial applications.

The CCVD method involves the decomposition of a carbon feedstock catalyzed at the surface of metallic nanoparticles, which also act as nucleation sites for the growth of carbon nanotubes. CCVD is versatile in the sense that it offers the ability to utilize a number of different carbon sources (carbon monoxide, hydrocarbons, alcohols, aromatics, etc.) with varying catalyst formulations and reactor designs, as well as wide-ranging temperatures and pressures. The three most popular CCVD processes used today are:

1. The lithography method that consists of depositing catalytic metals on a flat substrate (for instance silicon wafers) and then growth of the CNTs in a horizontal reactor in the presence of a carbon source at high temperature. By this method, forests of long-SWCNTs having broad diameter and chirality distribution are obtained. In spite of the high purity of the obtained material after harvesting the CNTs from the flat substrate, this method has technical and economical limitations for commercial production of CNTs.

2. The floating-catalyst method, which utilizes a gaseous unsupported catalyst, typically involves the decomposition of organometallic precursors (iron pentacarbonyl, ferrocene, etc.) at high temperatures to generate metallic nanoparticles in-situ. In the case of the high-pressure carbon monoxide (HiPco) process, CO serves as the carbon source and the SWCNT synthesis takes place at temperatures between 800° C. and 1200° C. and pressures of up to 50 atmospheres that make the HiPco process difficult to scale. The production of SWCNTs using the floating-catalyst method has been scaled to kilograms per day. However, control of diameter and chirality is extremely difficult with the floating-catalyst method because of the inability to control metal particle sizes precisely at the nanoscale prior to SWCNT nucleation and growth. SWCNTs synthesized from floating catalysts also tend to include large amounts of other forms of carbon, because the growth mechanism requires rigorous control of carbon segregation or diffusion on the metal nanoparticle surface. When carbon surface diffusion occurs, the catalyst particles become encapsulated by nontubular carbon. Thus, even though the floating-catalyst synthesis method is more scalable than the laser and arc-discharge methods, it still has the limitations of no controlled chirality, diameter, length and low relative purity (below 50%). The need for extensive purification and non-scalable chiral separation methods to meet quality requirements make the floating-catalyst method very expensive for CNT-membrane fabrication and other applications of SWCNTs.

3. The supported-catalyst CCVD combined with fluidized-bed reactor technology, has enabled SWCNTs to be made at a commercial scale with high purity, diameter and chirality control (CoMoCAT process). This process utilizes catalysts based on cobalt and molybdenum supported on silica particles for making high quality SWCNT from the Boudouard reaction. Fluidized bed reactors enable precise control of temperature and gas composition throughout the entire reaction zone. The combination of precise control of catalyst sites and reactor conditions enables the production of SWCNTs having smaller diameter distributions. The oxide precursor catalyst is submitted to an activation process by contacting the solid particles with a H2flow at high temperature before the SWCNT synthesis. A limitation of supported-catalyst CCVD is that the catalyst support represents a high percentage of mass of the as-produced SWCNT products but there are practical limits to the efficiency of digesting the supported catalyst. Rotary tube reactors have enabled the production in continuous operation mode of high quality MWCNT at commercial scale with high carbon yield (>85% carbon CNT yield). However, a more homogeneous product is obtained when using a fluidized bed reactor because of the uniform heat and mass transfer resulting from fluidization of the catalyst particles.

Fluidized bed and rotary tube reactors offer significant advantages for controlling the diameter and chirality distribution of SWCNTs compared to other synthesis methods described above. Under optimal gas-solid contact conditions the catalyst controls the process performance (carbon yield and selectivity to tubular carbon) and the morphology (length and diameter of the individual SWCNT and bundle sizes), structural (defects of the CNTs) and chirality (semiconducting, semi-metallic and metallic) properties of the material.

FIG.1Ais a simplified representation of a metallic cobalt nanocluster (having approximately 0.6-0.9 nm primary particles sizes).FIG.1Bis a simplified schematic representation of the SWCNT growth using this metallic cobalt nanocluster.FIG.1Cis a simplified schematic representation of SWCNT bundle formation on a CoMo/SiO2catalyst. The role of Mo2C/SiO2is to support the metallic cobalt nanoclusters. The size of the active metal nanoclusters determines the diameter of the SWCNT whereas the bundle diameter is related to the diameter of and quantity of the SWCNT in the bundle.

The technical requirements for the manufacture of CNT-based membranes include relatively uniform CNT diameter, few individual CNT per bundle (smaller bundle diameter), long and straight CNTs, and fewer structural defects (i.e., high purity SWCNTs). The catalysts used in the prior art do not produce SWCNTs that meet these technical requirements, for example in the manufacture of seawater desalination membranes. Despite the fact that the CoMoCAT process can produce SWCNT with uniform diameter distribution, few structural defects and high purity in tubular carbon and residual catalyst, the tubes are shorter (<5 microns) and entangled and the bundle diameter is large (>10 nm) as compared to what is most needed for a desalination membrane. This requires the use of high energy and effective surfactants agents to disperse and de-bundle the tubes during the membrane fabrication. These problems are mainly due to the high concentration of active metals deposited on the support surface, which allows the formation of coarse active metal clusters. Consequently, the SWCNT bundles are shorter and larger in diameter (higher number of individual SWCNT per bundle) due to hindering effects that affect the kinetics of CNT growth.

Solutions to these technical issues involve one or more of: decreasing the size of the Mo2C nanoparticles, decreasing the number of active metals nanoclusters, increasing the surface dispersion of the nanoclusters, and controlling the number of SWCNT per bundle. In this manner, the reaction becomes more efficient for producing long SWCNT having smaller bundle sizes.

There are different technical pathways that can be adopted to achieve these solutions, for instance: the use of diluted cobalt and molybdenum solution concentration (to result in less than 0.1 weight % of both Co and Mo in the catalyst), and Mo/Co atomic ratio in the catalyst of less than 1.0, and the use of colloidal silica together with diluted cobalt and molybdenum solution concentration for modifying the surface properties of the silica and controlling the metal deposition during the impregnation and drying steps.

FIG.2Aschematically illustrates the SWCNT growth when the catalyst contains high Co and Mo content (Co greater than 0.3% and Mo greater than 0.5%) and Mo/Co ratio greater than 1.0 according to the prior art.FIG.2Bschematically illustrates the SWCNT growth when the catalyst is prepared according to this disclosure using diluted metal solution concentration such that both Co and Mo are present at less than 0.1% and Mo/Co atomic ratio less than 1.0. As can be seen, in the prior art a dense carpet having short entangled SWCNTs was formed on the support surface. Because a very low active metal concentration and a lower Mo/Co atomic ratio (e.g., 0.5-1.0) was used in the catalyst preparation in examples of the present disclosure, long (e.g., ≥7 microns) and straight SWCNTs having smaller bundles diameter (e.g., <12 nm) were obtained.

In addition to catalysts comprising Co and Mo supported on SiO2or MgO, in some examples other transition metals can be used, such as Ni, Cu, Ru, W and combinations of them, for the synthesis of long and straight SWCNTs. In examples herein the carbon source(s) for SWCNT synthesis includes one or more of carbon monoxide, methane, alcohol, etc. The diameter distribution of the carbon nanotubes is controlled by the type of metal of the catalyst support, the metallic composition of the catalyst, the type of reaction (e.g., 2CO=C+CO2, CH4→C+2H2) and the reaction temperature. In some examples both SiO2support particles and metallic impurities are removed from CNTs by digestion in the presence of a HF solution. In some examples the purity of the purified product is greater than 98 wt % which is suitable for its use in at least the manufacture of CNT-membranes and transparent conductive film applications.

With regard to the use of laminar solids for long and straight CNT synthesis, when used the material in some examples is submitted to a grinding process and then sieved to a particle sizes between 50 and 500 microns, preferably between 70 and 300 microns. It is subsequently treated in the presence of a flow of chlorine gas diluted in an inert gas (e.g., N2, Ar) at high-temperature (>700° C.) to remove the iron oxide impurities. The material is then contacted in the presence of a metal solution containing a combination of nickel, cobalt and iron salts in the NixCoyFe2atomic composition (where; x+y=1) at temperatures between 50-80° C., preferably between 55-70° C. in a closed container equipped with a condenser, and then the system remains for about 3 hrs. under continuous agitation to promote ionic exchange. The metal exchanged solid particles are separated by filtration, dried under controlled conditions (room temperature for 2 hrs., 60° C. for 2 hrs. and 120° C. for 2 hrs.) and finally calcined in airflow at 500° C. for 4 hrs.

Long MWCNT synthesis over metal/vermiculite catalyst was carried out in a fluidized bed or rotary tube reactor in the presence C2H4, H2and inert gas flow, at atmospheric pressure at temperatures ranging between about 650 and about 750° C., preferably between 675-720° C. Product purification is accomplished using different acid treatments, such as a first digestion in the presence of HCl+H2SO4acid solution to remove Al2O3, MgO and residual metals, and a second digestion in the presence of HF to dissolve SiO2particles.

Examples that illustrate the prior art and aspects of the present disclosure follow:

Example 1: Synthesis of SWCNT on CoMo/SiO2Catalyst from Prior Art

A catalyst was prepared by an incipient impregnation method of silica support with a solution containing cobalt nitrate and ammonium hepta-molybdate. The impregnated material was aged at room temperature for 3 hrs. under controlled moisture and then dried at 120° C. for 3 hrs. and calcined at 450° C. for 4 hrs. The cobalt content in the catalyst was 0.6 wt % and the Mo/Co molar ratio was 2.0. The synthesis of SWCNTs was carried out by using CO as a carbon source in a fluidized bed reactor which was operated at a temperature of 760° C., 40 psig and 50 min. reaction time. The metal oxide precursor catalyst was activated by reduction in the presence of H2at 680° C. temperature before the SWCNT synthesis.

FIGS.3A and3Bshow SEM images (at 12KX and 25KX respectively) corresponding to as produced SWCNTs synthesized using this CoMo/SiO2catalyst, andFIGS.4A,4B,4C and4Dshow SEMs taken at different magnification (30×, 10KX, 25KX and 100KX respectively) of the obtained and purified SWCNTs. A dense carpet of about 0.7 to 1.2 microns thickness containing short and entangled SWCNTs (≤3 microns length) can be observed. Due to the high degree of entanglement of carbon tubes, the material has low dispersibility in aqueous solution dispersions containing surfactant agents, or dispersed using organic solvents.

Example 2: Synthesis of Long Tubes Using Low Metal Solution Concentration Together with Colloidal Silica in the Catalyst Preparation

A second catalyst was prepared according to one aspect of the present disclosure by impregnating the silica catalyst support substrate with an aqueous solution containing cobalt and molybdenum salts and a colloidal silica (10 wt % of SiO2in the solution). In this case, the Co content in the catalyst was about 0.1 wt % and the Mo/Co atomic ratio was 0.5. Aging, drying, calcination steps and SWCNTs synthesis were conducted under the same conditions as those described in Example 1.

FIGS.5A,5B and5Cshow SEM images taken at different magnification (25KX, 50KX, 75KX respectively) of the as produced SWCNTs synthesized using this catalyst. As can be observed, a mesh of SWCNT is formed on both silica nano-particles coming from the colloidal silica additive and the silica support. This mesh is formed from individual long SWCNT bundles having length between 5 to 7 microns. In contrast with the prior art, the purified SWCNTs of the present invention are easier to disperse in organic as well as in aqueous surfactant solutions, even at lower sonication power and time.

To demonstrate the effect of adding colloidal particles together with the metallic salts in the impregnating solution to control the SWCNTs growth, a third catalyst was prepared following the same procedure, but instead using graphite as a catalyst support. SWCNT synthesis was carried out in a rotary tube reactor at the same reduction, reaction temperature and time employed in previous examples. The SEM images at different magnifications (50KX and 100KX) corresponding to the SWCNT-graphite product are shown inFIGS.6A and6B, respectively. These images clearly illustrate the formation of a mesh containing long and straight SWCNTs on the SiO2nanoparticles coming from the colloidal silica aggregates.

FIGS.7A and7Bare SEM images (at 20KX and 15KX respectively) andFIG.8is a thermogravimetric analysis (TGA) corresponding to the purified sample illustrated inFIGS.7A and7B. InFIGS.7A and7Bveils of long SWCNT bundles of about 8 microns in length can be observed. The TGA analysis shows a single signal whose maximum combustion carbon rate is about 524° C. that is typical for SWCNTs. No other types of carbon (amorphous or graphitic carbon) are observed. The SWCNT purity is about 95 wt %.

Example 3: Synthesis of Long Tubes Using Very Low Metal Solution Concentration and Mo/Co Atomic Ratio in the Catalyst Preparation

A fourth catalyst was prepared by diluting the Co and Mo concentration in the impregnating solution employed in Example 2. In this case, the Co content in the finished catalyst was about 0.04 wt % (400 ppm Co) and the Mo/Co atomic ratio was 0.5. The SWCNT synthesis was performed at 760° C. in a fluidized bed reactor. The catalyst activation was carried out following the same protocol previously described.

FIGS.9A,9B and9Cshow SEM images taken at different magnifications (FIGS.9Aat 20KX,9B at 15KX and9C at 5KX) corresponding to the product obtained using the CoMo/SiO2catalyst preparation method of Example 3.FIG.9Ashows the formation of a mesh of straight SWCNTs bundles on the surface of the silica support. The SWCNT bundles diameter varies between 3 and 12 nm, most of them between 5 to 8 nm, and the length between 8 and 16 microns (FIGS.9B and9C).

SWCNTs can be distinguished from other types of CNTs by their light absorption capacity.FIG.10shows the absorption spectra corresponding to the SWCNTs synthesized at 760° C. by using the catalyst preparation method in Example 3. The signals appearing at frequencies between 800 and 1300 nm are characteristic SWCNT semiconductors (region S11) of the absorption whereas, signals between 500 and 800 nm correspond to the regions S22and M11, where “M” stands for metallic SWCNTs that absorbs at frequencies between 400 and 600 nm. In the S11region, four main signals at 976 nm, 1,024 nm, 1120 nm and 1,265 nm correspond to the chirality (6,5), (7,5), (7,6) and (8,7), respectively.

The semiconductor SWCNTs unlike the metallic ones, show fluorescence properties in the near infrared region (NIRF). Through this spectroscopic technique of analysis, information about the chirality and diameter distribution can be obtained. The average diameter of the semiconductor tubes is obtained through the integration of the signals obtained by the different lasers.FIG.11shows the diameter distribution obtained from NIRF spectra corresponding to the SWCNTs synthesized at 760° C. by using the catalyst preparation method in Example 3. A narrow diameter distribution of the SWCNTs can be observed, more than 90% have a diameter between 0.75 and 0.92 nm. The average diameter for the sample is about 0.83 nm, which is suitable for the CNT-membrane fabrication.

Thermogravimetric analysis (TGA) provides information on the thermal stability of CNTs, the presence of other types of carbon compounds, and the purity of the material.FIG.12shows TGA analysis corresponding to SWCNTs synthesized at 760° C. using the catalyst preparation method in Example 3. A single signal observed at around 500° C. corresponds to the combustion of SWCNT. The presence of other types of carbon compounds in the sample were not observed. The product after purification contains about 1.2 wt % of residual metals (Mo and Co carbides), which are insoluble in HF.

FIGS.13A,13B and13Cshows SEM images taken at different magnifications (FIG.13Aat 9KX,FIG.13Bat 30KX andFIG.13Cat 25KX) of the purified SWCNTs synthesized at 760° C. Straight and long SWCNTs bundles forming an aligned frayed fabric-like structure were observed. The obtained purified SWCNTs are easy to de-bundle, such as by dispersion in aqueous surfactant solutions and in organic solvents.

Example 4: Effect of the Synthesis Temperature on the Diameter Distribution and Morphology of the SWCNTs

In this example, the SWCNT synthesis was performed at 690° C. in the presence of the catalyst prepared in Example 3. The catalyst activation was carried out following the same protocol previously described. The SWCNT synthesis was carried out in a fluidized bed reactor.

InFIG.14, the image obtained by SEM (35KX) of the as produced SWCNTs synthesized at 690° C. shows the formation of a fine mesh of long SWCNT bundles of about 7 to 10 microns on the surface of the support.

The optical absorption spectra of the as produced SWCNT sample synthesized at 690° C. (FIG.15) shows in the S11region an intense signal located at around 976 nm which corresponds to the (6,5) chirality and three small absorption signals located between 110 and 1200 nm. These signals correspond to SWCNTs chiralities having diameters larger than 0.80 nm.

The analysis of the sample by NIRF shown inFIG.16indicates a significant decrease in the average diameter of the SWCNTs when the reaction was carried out at a lower temperature. In this case, the average diameter of the SWCNTs is approximately 0.77 nm with semiconducting composition>95%. The (6,5) composition in this sample was about 50% making this material suitable for transparent semi-conducting film applications.

FIGS.17A,17B and17Cshows SEM images taken at different magnification (9KX, 25KX, and 25KX, respectively) of the purified SWCNT sample synthesized at 690° C. by using the catalyst preparation method in Example 3. The images also show clear evidence of the formation of straight and long SWCNTs bundles forming a frayed fabric-like structure.

Example 5: Transparent Conductive Films Based on SWCNTs Applications

Transparent Conductive Films (TCFs) are used in a wide range of commercial applications, including information displays, capacitive touch sensors, solar photovoltaic modules, EMI shielding windows, and transparent heaters, etc. There are several materials that are transparent and others that are electrically conductive, but there are only few materials that are both. For flexible and transparent conductive films applications, polythiophene materials (PEDOT) are standard commercial conductive materials, but these suffer from environmental stability problems, especially during UV and high temperature/humidity aging tests. CNTs offer all the advantages of PEDOT without compromising environmental stability.

The transport model correlates the thin film conductivity (UDC) with the following: a) CNT aspect ratio (bundle length and diameter), b) the junction resistance between semiconducting and metallic SWCNTs and the c) network morphology of the film.

σDC=K〈Rj〉⁢Vf2〈D〉3Where:K=Bundle length proportionality factor (˜L1.7).Vf=Network morphology though film fill factor.Rj=Mean junction resistance.D=Bundle diameter.

According to this model, the thin film conductivity increases significantly when the bundle or individual CNTs aspect ratio (L/D) increases. The SWCNTs of present disclosure showed a bundle diameter of about 5-8 nm and a length of about 8-16 microns while the CNTs of the prior art showed a bundle diameter of about 8-15 nm and a length of about ≤3.0 microns. Since the present SWCNTs have a much greater aspect ratio the thin film conductivity is expected to increase.

In this section, the performance of two SWCNTs synthesized according to prior art (Example 1) and the present invention (Example 3) are compared by their TCF properties. The carbon nanotubes were dispersed in an aqueous solution using a sonication technique with 2 wt % of an anionic surfactant (such as Dowfax anionic surfactant available from The Dow Chemical Company). After sonication and centrifugation, the SWCNT supernatant fraction was coated on a polyethylene substrate by using the drawdown technique. The sheet resistance was determined using a 4-point probe technique for various visible light transmittances (%). The results are shown inFIG.18, including results at 85% T and 90% T. The SWCNTs synthesized according to the current disclosure are about 2.2 and 2.3 times, respectively more conductive than that of the prior art. Also, the SWCNTs were observed to disperse better than the prior art due to their morphology properties and high aspect ratio (seeFIGS.4and13).

Example 6: Conductivity Properties of Thin Film Produced with CNT-Organic Solvent

In this example both CNTs synthesized by following the procedures in examples 1 and 3, were dispersed in iso-propanol solution and then blended with an organic solvent vehicle consisting of a primary amine, a carbamate compound and isopropanol. The viscosity and density properties of the vehicle is suitable for producing transparent conductive films based on CNTs by using a printing technique. The procedure for preparing the organic vehicle was described in the prior art (e.g., U.S. Pat. No. 9,777,168).FIG.19compares the TCF properties of the SWCNTs synthesized according to the prior art and the present disclosure using organic solvent. In this case, the surface resistivities values are higher than those in which the CNTs are disbursed by aqueous dispersions containing surfactant agents. However, there are important differences in conductivity measurements at various % transmittance between these two materials. In this case, the SWCNT synthesized in the present disclosure has a conductivity that is about 2.0 and 1.6 times higher than the SWCNTs of the prior art at 85% and 90% transmittance, respectively.

Having described above several aspects of at least one example, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements are intended to be part of this disclosure and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only, and the scope of the invention should be determined from proper construction of the appended claims, and their equivalents.