Abstract:
Some embodiments include a method of preparing a membrane by dispersing carbon nanotubes in a solvent, and preparing a slurry from the dispersion by removing at least a portion of the solvent. The method includes applying the slurry to a first surface, and forming a carbon nanotube membrane by compressing the slurry between the first surface and at least a second surface. Some embodiments forming a composite assembly by sandwiching the carbon nanotube membrane between two or more bleeder cloth layers to form an uncured assembly, and applying a curable resin to a first side of the uncured assembly, and applying a curable resin to a second side of the uncured assembly, and curing the uncured assembly.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application claims priority to U.S. provisional application Ser. No. 62/161,150, filed on May 13, 2015, the entire contents of which are incorporated herein by reference. 
     
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT 
       [0002]    Some research conducted for conception and development of at least one embodiment of the invention described herein was made using Federal awarded by the Office of Naval Research under Grant No. N00014-14-1-0068. The U.S. Federal Government has certain rights in the invention. 
     
    
     BACKGROUND 
       [0003]    Since the discovery of carbon nanotubes (“CNTs”) by Sumio Iijima in 1991, CNTs have gained immense popularity in the field of nanocomposites by exhibiting an unprecedented combination of beneficial mechanical, thermal and electrical properties. The use of CNTs as nano-fillers in polymer composites has demonstrated the potential for improvements in mechanical properties such as tensile and compressive strength, elastic modulus and fatigue resistance, in addition to enhanced thermal and electrical properties. More recently, polymer/CNT nanocomposites have received extensive recognition for the versatility they offer in a variety of applications such as water purification, gas sensing, strain sensing, super capacitance, fuel cell electrodes, fire retardant coatings, artificial muscles, EMI shielding and self-heating hybrid composites for de-icing. These applications employ CNTs in the form of a thin porous membrane of highly entangled CNTs held together by van der Waals forces, sometimes referred to as “buckypaper”. 
         [0004]    The current fabrication methods for CNT membranes are often complex, require long processing times, and impose significant size limitations on the membrane. As a result, the applications of carbon nanotube (“CNT”) membranes are still in their infancy, and prototype feasibility is often limited to laboratory scale demonstrations. A more rapid, large-scale manufacturing technique is critical to extend the application of these multifunctional capabilities to the industrial scale. 
         [0005]    Vacuum filtration is currently used used by many researchers for manufacturing CNT membranes. This method involves vacuum assisted filtration of a homogeneously dispersed CNT solution using a Polytetrafluoroethylene (PTFE) or nylon filter with sub-micron sized pores. CNTs are deposited on the filter surface and form a thin CNT membrane (hereinafter referred to as “CNT membrane”). The CNT membrane can be lifted from the filter surface after drying and used for applications such as water purification (see for example Dumée L. F, Sears K., Schütz J., Finn N., Huynh C., Hawkins S., Duke M., Gray S 2010, “Characterization and evaluation of carbon nanotube bucky-Paper membranes for direct contact membrane distillation”, Journal of Membrane Science 351, 36-43.) This technique has been used for manufacturing CNT membranes as an embedded strain sensor in epoxy dog-bone specimens (see for example Rein M D, Breuer O., and Wagner H D 2011, “Sensors and sensitivity: carbon nanotube buckypaper films as strain sensing devices”, Composites Science and Technology, 71, 373-381), and as a smart skin for strain sensing in aircraft wings (see for example Dharap P., Li Z., Nagarajaiah S., and Barrera E V 2004, “Nanotube film based on single-wall carbon nanotubes for strain sensing”, Nanotechnology, 15, 379-382), and as a de-icing glass fiber reinforced polymer (“GFRP”) nanocomposites (see for example Chu H, Zhang Z., Liu Y., and Leng J 2014, “Self-heating fiber reinforced polymer composite using meso/macropore carbon nanotube paper and its application in deicing”, Carbon 66, 154-163.) 
         [0006]    The use of vacuum filtration methods tends to limit the size of the manufactured CNT membranes to the diameter of the filter being used, and can also lead to heterogeneous distribution of CNT bundles in the finished product (see for example Cherng-Shii Y., “Characterization of nanotube buckypaper manufacturing process”, 2004. Electronic Theses, Treatises and Dissertations. Paper 420.) Further, the use of filters with larger diameters may not be practically feasible because of the large volume of CNT solution that would need to be filtered. Moreover, maintaining homogeneous dispersion in a large volume of CNT solution is a challenging task due to the tendency of CNTs to form agglomerates/clusters. Filtering larger quantities of solution through sub-micron filters can take several hours depending on the diameter and pore size of the filter, the volume of solution being filtered, and the pressure difference applied by a vacuum pump. 
         [0007]    Current CNT membrane fabrication methods typically require the use of surfactants, organic binders, and/or chemical functionalization of the CNTs to assist in obtaining a stable uniform dispersion during filtration, any one of which can affect the properties of the CNTs in the final product. For example, following filtration, the surfactants can be difficult to remove from the CNT membrane, and can hamper the efficiency of the membrane for applications such as water purification, gas separation and bio fuel cell electrodes. Chemical modification of CNTs prior to the filtration can also degrade the functionality of CNT membranes for the aforementioned applications. Other less commonly used fabrication methods for CNT membranes include hydro-entanglement, which involves impregnation of high speed water jets onto CNTs present on a porous substrate, where the high pressure of water jets induces entanglement of the CNTs in the membrane (see for example Zhang X 2008, “Hydroentangling: A novel approach to high-speed fabrication of carbon nanotube membranes”, Adv. Mater. 20, 4140-4144). Not only is this method complex to set up, the use of high speed water jets demands a high power consumption, and thus is limited to the production of smaller size membranes. 
         [0008]    Accordingly, there exists a need for fabrication methods for CNTs membranes that enable the formation of larger CNT membranes with production scale efficiency and speed, while reducing or substantially eliminating chemical and physical degradation of the CNTs. 
       SUMMARY OF THE INVENTION 
       [0009]    Some embodiments of the invention include a membrane forming method comprising preparing a dispersion of at least one solvent and a plurality of carbon nanotubes, preparing a slurry from at least a portion of the dispersion by removing at least a portion of the at least one solvent, and applying at least a portion of the slurry to a first surface. Further, the method includes forming a carbon nanotube membrane by compressing at least a portion of the slurry between the first surface and at least a second surface. 
         [0010]    In some embodiments, the at least one solvent comprises at least one alcohol. In some further embodiments, the at least one alcohol includes methanol, ethanol, and/or isopropyl alcohol. In some embodiments, the at least one solvent comprises acetone. In some embodiments of the invention, the at least one solvent is removed thermally. In other embodiments, the at least one solvent is removed through agitation. In some embodiments, the at least one solvent is removed using sonication. In some further embodiments, the sonication is induced using a tip-sonicator. In some embodiments, the tip-sonicator operates at a frequency of about 20 KHz. In other embodiments, the tip-sonicator operates at a power level of about 15 Watts. 
         [0011]    In some embodiments of the invention, the carbon nanotube membrane is mechanically self-supporting upon removal from at least one of the first surface and the second surface. In some embodiments, the first surface and the second surface are pressed together at a rate of about 0.2 mm/s. In some further embodiments, the plurality of carbon nanotubes include at least one of single-wall carbon nanotubes and multi-wall carbon nanotubes. 
         [0012]    Some embodiments include a composite assembly method comprising forming a membrane using a method comprising preparing a dispersion of at least one solvent and a plurality of carbon nanotubes, and preparing a slurry from at least a portion of the dispersion by removing at least a portion of the at least one solvent. The method comprises applying at least a portion of the slurry to a first surface, and forming a carbon nanotube membrane by compressing at least a portion of the slurry between the first surface and at least a second surface. Further, the composite assembly method comprises sandwiching the carbon nanotube membrane between two or more bleeder cloth layers to form an uncured assembly, applying a curable resin to a first side of the uncured assembly, applying a curable resin to a second side of the uncured assembly, and curing the uncured assembly. 
         [0013]    In some embodiments of the composite assembly method, the at least one solvent is removed thermally. In some further embodiments of the composite assembly method, the at least one solvent is removed by sonication. In some further embodiments of the composite assembly method, the sonication is induced using a tip-sonicator. In some further embodiments of the composite assembly method, the carbon nanotube membrane is at least partially dried prior to forming the uncured assembly. 
         [0014]    In some embodiments, the curable resin at least partially permeates at least a portion of the carbon nanotube membrane. Some embodiments include a curable resin that comprises an epoxy-based monomer. 
     
    
     
       DESCRIPTION OF THE DRAWINGS 
         [0015]      FIG. 1A  illustrates a schematic of a CNT membrane manufacturing process in accordance with some embodiments of the invention. 
           [0016]      FIG. 1B  shows a flowchart illustrating a CNT-based nanocomposite assembly in accordance with some embodiments of the invention. 
           [0017]      FIG. 2A  illustrates a free-standing CNT membrane lifted off a compression plate in accordance with some embodiments of the invention. 
           [0018]      FIG. 2B  illustrates a 20 cm×16 cm CNT membrane manufactured by scaling up quantity of methanol/MWNT slurry in accordance with some embodiments of the invention. 
           [0019]      FIG. 3A  illustrates a SEM micrograph of a CNT membrane at 15000× magnification showing inter-bundle and intra-bundle pores in accordance with some embodiments of the invention. 
           [0020]      FIG. 3B  illustrates a SEM micrograph of a CNT membrane at 25000× magnification showing inter-bundle and intra-bundle pores in accordance with some embodiments of the invention. 
           [0021]      FIG. 3C  illustrates a SEM micrograph of a CNT membrane at 35000× magnification showing inter-bundle and intra-bundle pores in accordance with some embodiments of the invention. 
           [0022]      FIG. 4  illustrates uniformity in thickness across the width of a 4 inch wide CNT membrane specimen in accordance with some embodiments of the invention. 
           [0023]      FIG. 5  illustrates pore size distribution as derivative plot of pore volume with respect to pore width versus pore width, and surface area distribution as derivative plot of surface area with respect to pore width versus pore width in accordance with some embodiments of the invention. 
           [0024]      FIG. 6A  illustrates uniform strain distribution in CNT membrane embedded region of the composite laminate until 1% strain in accordance with some embodiments of the invention. 
           [0025]      FIG. 6B  illustrates strain distribution in CNT membrane embedded region of the composite laminate just before failure in accordance with some embodiments of the invention. 
           [0026]      FIG. 6C  illustrates the failed specimen of CNT membrane embedded composite laminate after tensile test accordance with some embodiments of the invention. 
           [0027]      FIG. 7A  illustrates the piezoresistive response of the CNT membrane embedded GFRP until failure in accordance with some embodiments of the invention. 
           [0028]      FIG. 7B  illustrates piezoresistive response of the CNT membrane embedded GFRP until 1.3% strain showing stable sensitivity in accordance with some embodiments of the invention. 
           [0029]      FIG. 7C  illustrates a piezo-resistive response of a CNT membrane sensor mounted on GFRP in accordance with some embodiments of the invention. 
           [0030]      FIG. 7D  illustrates a sensitivity/gauge factor analysis of the data plotted in  FIG. 7C  in accordance with some embodiments of the invention. 
           [0031]      FIG. 8  illustrates the evaluation of through-thickness resin impregnation quality using SEM in accordance with some embodiments of the invention. 
           [0032]      FIG. 9  illustrates stress-strain curves of polymer films with 0, 1, and 30 wt % MWNTs in accordance with some embodiments of the invention. 
           [0033]      FIG. 10  shows piezoresistive response of self-sensing glass fiber epoxy laminates in accordance with some embodiments of the invention. 
           [0034]      FIG. 11  shows a SGFRP specimen used in a measurement model for in-situ crack length detection and quantification in accordance with some embodiments of the invention. 
           [0035]      FIGS. 12A-12C  show plots of actual crack lengths and sensed crack lengths as a function of fatigue cycles for three specimens in accordance with some embodiments of the invention. 
           [0036]      FIG. 13A  illustrates fatigue crack propagation in silver electrode glass fiber epoxy laminates specimen in accordance with some embodiments of the invention. 
           [0037]      FIG. 13B  illustrates fatigue crack propagation in a baseline glass fiber epoxy laminate specimen in accordance with some embodiments of the invention. 
       
    
    
     DETAILED DESCRIPTION 
       [0038]    Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. Unless specified or limited otherwise, the terms “mounted,” “connected,” “supported,” and “coupled” and variations thereof are used broadly and encompass both direct and indirect mountings, connections, supports, and couplings. Further, “connected” and “coupled” are not restricted to physical or mechanical connections or couplings. 
         [0039]    The following discussion is presented to enable a person skilled in the art to make and use embodiments of the invention. Various modifications to the illustrated embodiments will be readily apparent to those skilled in the art, and the generic principles herein can be applied to other embodiments and applications without departing from embodiments of the invention. Thus, embodiments of the invention are not intended to be limited to embodiments shown, but are to be accorded the widest scope consistent with the principles and features disclosed herein. The following detailed description is to be read with reference to the figures, in which like elements in different figures have like reference numerals. The figures, which are not necessarily to scale, depict selected embodiments and are not intended to limit the scope of embodiments of the invention. Skilled artisans will recognize the examples provided herein have many useful alternatives and fall within the scope of embodiments of the invention. 
         [0040]    Some embodiments of the invention include CNT membrane materials and methods of fabricating CNT membrane materials. In some embodiments, the fabrication method can enable the production of CNT membrane materials of greater size (e.g., diameter) than is possible with conventional manufacturing techniques. In some embodiments, the fabrication method can enable the production of membranes with a controlled thicknesses ranging from about 150 μm to about 1.3 mm. The fabrication method does not require the use of surfactant assisted dispersion, chemical functionalization, or the use of any filtration technique. Therefore, processing time can be reduced by about six to eight times depending upon the size of the CNT membrane. Unlike conventional techniques, where some fraction of the CNTs passes through the filtration membrane, there is no loss of CNTs in the proposed method. This technique provides the potential to advance CNT membranes from laboratory scale demonstrations to industrial scale applications since there is no size limitation for the CNT membrane. Some further embodiments of the invention include compositions, methods of fabrication, and methods of use of embedded or mounted CNT membranes as strain sensors for glass fiber epoxy composites. 
         [0041]    In some embodiments, CNT membranes can be formed using multi-wall carbon nanotubes (hereinafter “MWNT&#39;s). In some further embodiments, the CNT membranes can be formed using single-wall carbon nanotubes (hereinafter “SWNT&#39;s). In some other embodiments, the CNT membranes can be formed using mixtures of SWNT&#39;s and MWNT&#39;s. MWNT materials used in this research were obtained from US Research Nanomaterials Inc. produced using chemical vapor deposition. In some embodiments, the average outer diameter of the CNTs can be about 10 nm to about 30 nm with an average length of about 15 μm to about 30 μm. In some embodiments, the purity of the MWNTs can be about 90%. Other embodiments can include MWNT&#39;s with purities greater than or less than 90% In other embodiments of the invention, CNTs with sizes different than those described above can be used. For example, in some embodiments, the CNTs can comprise an average outer diameter less than about 10 nm, or as described above, SWNT&#39;s can be used instead of MWNTs depending upon the application for which the CNT membrane is manufactured for. 
         [0042]      FIG. 1A  illustrates a schematic of a CNT membrane manufacturing process  100  in accordance with some embodiments of the invention. In some embodiments, a step  110  of the CNT membrane manufacturing process can comprise preparation of a solution of MWNT&#39;s in a solvent. In some embodiments, MWNT&#39;s can be dispersed into at least one solvent using stirring, ultrasonic mixing, or any other convention mixing technique. In some embodiments, the solvent can comprise an alcohol such as methanol or ethanol. In some other embodiments, other solvents can be used including acetone, and isopropanol, and mixtures thereof. 
         [0043]    In some embodiments, the MWNT/solvent mixture formed in step  110  of the CNT membrane manufacturing process  100  can comprise a concentration of about 25 mg/ml. In other embodiments of the invention, more or less concentrated solutions can be prepared. For example, in some embodiments, the MWNT/solvent mixture can comprise a concentration greater than about 25 mg/ml, and in some other embodiments, the MWNT/solvent mixture can comprise a concentration less than about 25 mg/ml. In some embodiments, a volume of about 15 ml of the MWNT/solvent mixture formed in step  110  can be used to fabricate a CNT membrane that comprises a diameter of about 4.4 cm in with an average thickness of about 200 μm. 
         [0044]    In some embodiments of the invention, the MWNT/solvent mixture can be ultrasonically agitated with a tip-sonicator  115 . In some embodiments, this can lead to evaporation of at least some portion of the solvent (e.g., methanol), that can eventually result in the formation of a highly viscous slurry of MWNTs and solvent (e.g., such as methanol.) The use of a tip-sonicator to vaporize solvent can enable controlled evaporation of solvent, and can be a significant factor in achieving homogeneous slurry with the desired concentration of solvent. In some embodiments, the tip-sonicator can produce ultra-sonic waves that can reduce the MWNT/solvent mixture to a slurry form by vaporizing the solvent. Volatile solvents such as methanol and ethanol are suitable for this purpose since they can be vaporized instantly in small pocket around the tip of the sonicator  115 . In some embodiments, the sonication frequency of the tip-sonicator  115  can be about 20 KHz, with a power level of about 15 Watts. In some further embodiments, the sonication frequency can be less than about 20 KHz or more than about 20 KHz. Further, in some embodiments, the power level can be less than or greater than about 15 Watts. The choice of solvent can be crucial since the solvent&#39;s evaporation rate due to sonication governs the wetness of slurry, and in turn the processing time and quality of finished product (i.e., the CNT membrane). In some embodiments, the tip-sonicator  115  can produce a mist of solvent (the mist evaporates since the solvent is volatile) as it comes in contact with the MWNT/solvent mixture, leaving behind a wet slurry. In some embodiments, the wet slurry can be manipulated to form a continuous layer which can be compressed between two surfaces (e.g., between two or more steel plates.) In some embodiments of the invention, the tip-sonicator  115  can be used to target any free flowing solvent present in the slurry to obtain the desired wetness in the slurry. Further, in some embodiments, CNT&#39;s can sometimes exist in aggregates through entanglement in the form of bundles. In some embodiments, these aggregates can be disintegrated into finer bundles using the tip-sonicator  115  resulting in homogenous slurry that can be used to produce quality membranes with fewer defects. 
         [0045]    In some embodiments of the invention, the slurry can be stirred with a glass rod or other conventional tool to improve homogeneity, and then laid up for compression between two generally flat surfaces (e.g., such as steel plates.) For example, in a second step  120  of the CNT membrane manufacturing process, the slurry  122  can be deposited (e.g., poured or otherwise dispensed) on a first steel plate  124 , and a second steel plate  126  (shown in step  130 ) can be placed against the first steel plate  124 . In some embodiments, one or more of the steel plates  124 , 126  can be covered with plastic sheets to prevent adhesion between the CNT membrane and the plates. In a third step  130  of the CNT membrane manufacturing process, a hydraulic press  132  (e.g., such as a 20 ton press) can be used to compress the slurry into a thin membrane between the plates  124 , 126 . In some embodiments, to produce a CNT membrane of about 4.4 cm diameter, the slurry can be laid down in a generally circular disc shape with a diameter of about 2.5 cm and a thickness of about 3 mm (depicted as slurry  123  in step  120 ). 
         [0046]    In some embodiments of the invention, the compression of the MWNT/solvent slurry can be performed at a rate that can prevent or reduce the quantity of solvent ejected from the MWNT/solvent slurry. In some embodiments, rapid ejection of solvent can create undesirable cracks in the CNT membrane. For example, in some embodiments, the pressing can be performed at an actuation rate of about 0.2 mm/s, with a pressing process time of about two minutes to complete for pressing a layer of slurry that is approximately 24 mm in height, and with pressing halted when the hydraulic press reaches full load (e.g., 20 Tons). In some further embodiments, the press actuation rate can be more or less than about 0.2 mm/s. In some further embodiments, the load applied on the slurry during compression can be more than or less than 20 Tons, which in some embodiments can enable the formation of a desired thickness of the CNT membrane. Turning now to the fourth step  140  depicted in  FIG. 1A , in some embodiments of the invention, the two plates  124 ,  126  sandwiching the membrane can be removed from the press and placed into an oven at about 60° C. for about 1 hour. Moving to a fifth step  150 , in some embodiments, after drying, plates  124 ,  126  can be separated, and a free-standing MWNT CNT membrane (shown as membrane  160 ) can be degassed for about 12 hours. 
         [0047]    Some further embodiments of the invention include compositions and methods of fabrication, and methods of use of CNT membrane-based nanocomposites. Some embodiments can include fabrication of CNT membrane/epoxy nanocomposites. In some embodiments, PRI2002-3-R-A and hardener PRI2000-5-HR-B, obtained from Pipe Reconstruction Inc., with a 100/22 weight ratio can be used in the fabrication of nanocomposites films. 
         [0048]      FIG. 1B  shows a flowchart  170  illustrating a CNT-based nanocomposite assembly in accordance with some embodiments of the invention. In some embodiments, a first step  172  can comprise preparation of a CNT membrane (e.g., as described earlier and shown in  FIG. 1A ). In some further embodiments, for the fabrication of CNT membrane/epoxy nanocomposite films including MWNT content, a CNT membrane can be sandwiched between a porous structure such as two pieces of bleeder cloth (step  174 ), and resin can be applied to the bleeder cloth surface (step  176 ). In one non-limiting example embodiment, the resin can be spread over the bleeder cloth surface using a conventional hand layup tool. In other embodiments, the resin can be spread over the bleeder cloth surface using any conventional tool or method (process  178 ). In some embodiments, this layup technique can force the resin through various pores in the bleeder cloth (process  178 ), allowing it to permeate into the CNT membrane (through various pores in the membrane). In some embodiments, both sides of the CNT membrane can be impregnated using this layup method (process  180 , and resin spreading process  182 ). In some embodiments, specimens of the resin coated CNT membrane can be cured (step  184 ). In some embodiments, the specimens can be cured for about 12 hours at about 65° C. In some embodiments, using the method shown in  FIG. 1B , CNT membrane/epoxy films with a MWNT content of about 26 wt % to about 30 wt % can be obtained. 
         [0049]    The quality of resin impregnation in CNT membrane/epoxy nanocomposites was determined by cross-sectional examination using SEM. Randomly dispersed CNT and pristine specimens were also fabricated for comparison of mechanical properties. A concentration of about 1 wt % randomly dispersed MWNT/epoxy was fabricated by first sonicating MWNTs in epoxy using the tip-sonicator  115  for about 1 hour and stopping at intervals of about 10 minutes for manually stirring the mixture with glass rod. The mixture of randomly dispersed MWNTs and epoxy was cast into films by solution casting. Tensile tests on the films were conducted using a desktop Test Resources load frame at a displacement rate of about 0.0063 mm/s. The strain response of the films under tension was analyzed using a DIC system. 
         [0050]      FIG. 2A  illustrates a free-standing CNT membrane  200  lifted off a compression plate in accordance with some embodiments of the invention. This image demonstrates the mechanical and structural stability of the CNT membrane produced using the above described method of  FIG. 1A . Using larger quantities of MWNT/solvent slurry, larger areas of CNT membrane can be manufactured with similar mechanical and structure stability. For example,  FIG. 2B  illustrates a 20 cm×16 cm CNT membrane  225  manufactured by scaling up a quantity of MWNT/solvent slurry in accordance with some embodiments of the invention. In some embodiments of the invention, CNT membranes obtained from this technique can include uniform thickness and a robust structure with an average density of about 0.42 g/cc, which is close to density of CNT membranes fabricated by other techniques such as vacuum filtration. 
         [0051]    In some embodiments, qualitative analysis of CNT membranes made using the method shown in  FIG. 1A  and described above method was performed using a JEOL XL-30 scanning electron microscope (“SEM”). The morphology and surface quality of the CNT membranes was analyzed from SEM scans starting with low magnification, and progressing to higher magnification levels. SEM micrographs of CNT membrane cross-sections were obtained at different locations along the width to determine the degree of uniformity in thickness. For example,  FIG. 3A  illustrates SEM micrograph  300  of a CNT membrane at 15000× magnification showing inter-bundle and intra-bundle pores in accordance with some embodiments of the invention. Further,  FIG. 3B  illustrates a SEM micrograph  310  of a CNT membrane at 25000× magnification showing inter-bundle and intra-bundle pores, and  FIG. 3C  illustrates an SEM micrograph  320  of a CNT membrane at 35000× magnification showing inter-bundle and intra-bundle pores in accordance with some embodiments of the invention. As shown by the images of  FIGS. 2A and 2B , and the SEM images of  FIGS. 3A-3B , in some embodiments, the CNT membrane manufacturing process can produce substantially uniform, and substantially crack free, mechanically stable structures composed of highly entangled MWNTs. The uniformly distributed and randomly oriented MWNT bundles and the absence of large voids tends to suggest homogeneity in microstructure and isotropic material properties. In some embodiments, two types of pores can be produced (marked with arrows  322  and arrows  324  in  FIG. 3C ). In some embodiments, a first type can comprise an intra-bundle pores (marked with arrows  322 ) present within a CNT bundle. In some further embodiments, a second type can be an inter-bundle pores (marked with arrows  324 ) present between at least two or more CNT bundles. 
         [0052]      FIG. 4  illustrates uniformity in thickness across the width of a 4 inch wide CNT membrane specimen (shown in image  400  with inset images  410 ,  415 ,  420  of regions of the cross-section) in accordance with some embodiments of the invention. In some embodiments, the average and standard deviation of thickness of a membrane produced by the CNT membrane manufacturing process shown in  FIG. 4  can be about 242.06 μm and about 7.86 μm, respectively. 
         [0053]    The DC electrical resistance of CNT membrane produced by the CNT membrane manufacturing process of  FIG. 1A  was measured at room temperature with a digital multimeter (Fluke  189 ). The DC conductivity (σ) of CNT membranes and CNT membrane/epoxy films were calculated at room temperature from the following relation: 
         [0000]    
       
         
           
             σ 
             = 
             
               L 
               AR 
             
           
         
       
     
         [0054]    where L is the effective length of specimen between electrodes, A is its cross-sectional area, and R is the measured DC resistance value from the multimeter. 
         [0055]    The average electrical conductivity of CNT membranes produced by the CNT membrane manufacturing process was found to be about 13.228×10 3  S/m. After being impregnated with epoxy to form the nanocomposite films (using the process depicted in  FIG. 1B ) the conductivity value dropped to 2.124×10 −4  S/m. 
         [0056]    Nitrogen adsorption-desorption isotherms were collected at 77K using a Micrometrics Tristar II 3020 surface area and porosity analyzer. The specific surface area (SSA) was obtained by BET technique whereas the pore-size distribution and cumulative pore content were obtained by the Barrett-Joyner-Halenda (“BJH”) method. The BET SSA as obtained from N 2  adsorption isotherms of six different samples of CNT membrane produced by the CNT membrane manufacturing process was found to be in the range of about 94.62 to about 107.20 m 2 /g, with the average value of about 102.60 m 2 /g. The BET SSA of the MWNTs is about 200 m 2 /g. The SSA value for CNT membrane membranes produced by the CNT membrane manufacturing process is high considering the SSA of MWNTs was 200 m 2 /g. A high SSA is suitable for a variety of applications such as fuel cell electrodes, gas/vapor sensing, catalyst, water purification and high weight fraction nanocomposites. 
         [0057]    The graph  500  of  FIG. 5  illustrates pore size distribution as derivative plot of pore volume with respect to pore width versus pore width, and surface area distribution as derivative plot of surface area with respect to pore width versus pore width in accordance with some embodiments of the invention. As shown, the pore size distribution obtained from BJH analysis for the CNT membrane specimen with maximum SSA of about 107.20 m 2 /g enables comparison of the relative pore volumes between pore size range as the apparent area under the curve is directly proportional to the real volume being occupied by pores in that size range. The plot of dV/dlog(W) versus W (shown as the solid line  505 ) reveals that pores ranging from about 70 nm to about 120 nm in size occupy relatively larger volume than the micro-size pores (about 1.7 nm to about 4 nm), meso-size pores (about 10 nm to about 40 nm), and large macropores (about 120 nm to about 250 nm). The peak  501  observed in the size range of about 70 nm to about 120 nm represents pores between CNT bundles (i.e., inter-bundle pores). The very local sharp peak  502  corresponding to pore size range of about 20 nm to about 30 nm can be associated with the presence of intra-bundle pores since these pores generally have dimensions close to average CNT diameter. Further, a set of micropores at about 1.7 nm to about 4 nm can be observed in pore volume plots due to inter-tube channels between adjacent MWNTs and smaller intra-bundle pores. Further, SSA distribution as a function of pore width is also presented in  FIG. 5 . It can be seen from this plot (dotted line  507 ) that while the pore volumes are mainly associated with mid-sized macropores, the SSA is dominated by micropores (inter tube channels and smaller intra-bundle pores) of width of about 1.7 nm to about 4 nm providing an indication of their higher concentration. The total porosity (φ) was calculated from relation: 
         [0000]      Φ=1−ρ bp /ρ cnt  
 
         [0000]    where ρ bp  is the bulk density of CNT membrane and ρ cnt  is the density of MWNTs (about 2.1 g/cc). The total porosity was in the range of about 76.3% and about 84.4% with an average value of about 81%. 
         [0058]    Some further embodiments of the invention include compositions and methods of fabrication, and methods of use of glass fiber reinforced polymer self-sensing (hereinafter “GFRP”) hybrid composites. In some embodiments, the GFRP composites can be self-sensing. Eight harness satin (“8HS”) weave of S2 glass fiber from Fibre Glast Development Corporation, 385 Can Drive, Brookville, Ohio 45309, and FS-A23 Part A resin with FS-B412 hardener (also available from Fibre Glast Development Corporation) with a 100/27 weight ratio was used to fabricate self-sensing GFRP laminates using a wet layup method (such as the method shown in  FIG. 1B ). A CNT membrane was embedded in the center layer (between the 3 rd  and the 4 th  lamina), spanning the gauge length, while laying up the laminate. The six layer composite laminates were cured at room temperature for about 7 days. The laminate was cut into about 8 inch by about 1 inch strips for tensile tests. Tensile tests were conducted on both types of GFRP specimens at a constant displacement rate of about 0.5 mm/min on an MTS Bionix servo-hydraulic test system. Under monotonic tensile loading, the piezo-resistive response of CNT membrane embedded GFRP laminates was recorded using a Fluke 289 multimeter with a data logging feature, and the strain fields on the specimen surface were analyzed using a Digital Image Correlation (DIC) Aramis 5M system. Sensitivity, also known as gauge factor of the CNT membrane sensors was calculated from the relation: 
         [0000]    
       
         
           
             GF 
             = 
             
               
                 ( 
                 
                   
                     R 
                     - 
                     
                       R 
                       o 
                     
                   
                   
                     R 
                     o 
                   
                 
                 ) 
               
                
               
                 ( 
                 
                   1 
                   ɛ 
                 
                 ) 
               
             
           
         
       
     
         [0059]    where R is the electrical resistance at strained state, R o  is the original resistance and ε is the longitudinal strain increment. 
         [0060]    Strain distribution in the CNT membrane embedded region of the GFRP specimens, obtained from DIC is illustrated in  FIGS. 6A-6B  (showin in images  600 ,  610 ) according to some embodiments. Further, image  620  of  FIG. 6C  illustrates a failed specimen of CNT membrane embedded GFRP after the tensile test in accordance with some embodiments of the invention. Strains along the loading axis are shown at an intermediate and failure stages at  FIGS. 6A and 6B  respectively. Reasonably uniform strain distribution was observed until about 1% average strain and the sensor data directly correlates with the average global strain until this point. At average strain values above 1%, the strain distribution starts to become non-uniform, and sensor data cannot be considered to represent average strain in the region between electrodes. 
         [0061]    The piezoresistive response of the CNT membrane embedded GFRP strips under tensile loading is presented in plots  700 ,  710  of  FIGS. 7A and 7B . For example,  FIG. 7A  shows the normalized resistance change as the strain evolves until failure, and  FIG. 7B  shows stable sensitivity of the embedded CNT membrane up to 1.3% strain. The average sensitivity of five self-sensing GFRP specimens as calculated by a linear fit between about 0.2% to about 0.6% strain was found to be 4.21. This is significantly higher than sensitivity values reported in literature for many conventionally produced carbon nanotube based sensors. 
         [0062]    In some further embodiments, a CNT membrane was applied to the surface of the GFRP specimen using cyanoacrylate super glue obtained from Stewart-MacDonald, P.O. Box 900, Athens, Ohio 45701, USA, rather than being embedded in the center layer. The plot  730  of  FIG. 7C  illustrates a piezo-resistive response of CNT membrane sensor mounted on GFRP in accordance with some embodiments of the invention, and the plot  740  of  FIG. 7D  illustrates a sensitivity/gauge factor analysis of the data plotted in  FIG. 7C  in accordance with some embodiments of the invention. As illustrated, the strain response of the surface mounted CNT membrane sensor was stable and continuous till failure of glass-fiber laminate. In some embodiments, these structures exhibited about a twenty times greater sensitivity than the above described embedded GFRP specimens, and about forty times higher sensitivity than commercially available strain gauges, and much higher than most conventional CNT sensors. From results calculated in  FIG. 7D , showing the sensitivity/gauge factor analysis, for a strain of 0.2% to 0.6%, the gauge factor was 70.2, and for a strain of 0.6% to 1.2%, the gauge factor was 100.6. 
         [0063]      FIG. 8  illustrates the evaluation of through-thickness resin impregnation quality using SEM in accordance with some embodiments of the invention. For example, during an analysis of a cross-section  810  of a CNT membrane/epoxy film produced by the above-described methods, areas for analysis were picked from the low magnification cross-sectional image (38×, shown as image  800 ) and are represented by boxes. High magnification SEM images at different depths from the top (image  805  and image  810 ) surface reveal substantially full penetration of the resin through the thickness of the CNT membrane and good impregnation quality. 
         [0064]    The stress-strain response of the films under tensile loading was analyzed in order to better understand the interfacial interaction/adhesion between epoxy resin and the embedded CNTs. For example, the plot  900  of  FIG. 9  illustrates stress-strain curves of polymer films with no MWNT&#39;s (line  920 ), 1 wt % MWNT (line  930 ), and 30 wt % MWNTs (line  910 ) in accordance with some embodiments of the invention. Further, the corresponding average mechanical properties are presented in Table 1 below, showing mechanical properties of pristine, 1 wt % MWNT, and CNT membrane epoxy films. 
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Mechanical properties of pristine, 1 wt 
               
               
                 % MWNT and CNT membrane epoxy films 
               
             
          
           
               
                   
                   
                 Wt % of 
                 Young&#39;s 
                 Tensile 
               
               
                   
                 Specimen Description 
                 MWNTs 
                 Modulus 
                 strength 
               
               
                   
                   
               
             
          
           
               
                   
                 Neat Epoxy film 
                 0 
                 3.01 Gpa 
                 37.08 
               
               
                   
                 MWNT/Epoxy film 
                 1 
                 2.72 Gpa 
                 38.60 
               
               
                   
                 Buckypaper/Epoxy film 
                 30 
                 3.66 Gpa 
                 45.42 
               
               
                   
                   
               
             
          
         
       
     
         [0065]    Strains obtained from DIC were used to plot the stress strain curves in order to analyze mechanical properties accurately. In some embodiments of the invention, CNT membrane epoxy films exhibited 20% greater Young&#39;s modulus when compared to pristine epoxy films (i.e., those without the presence of CNT membrane produced by the methods described herein). In some embodiments, this can be attributed to good resin penetration and strong interfacial interaction between resin and CNTs of the reinforcing CNT membrane. Moreover, the higher Young&#39;s modulus indicates that effective stress transfer takes place between epoxy matrix and CNT membrane. In some embodiments, the average tensile strength in the case of CNT membrane epoxy films was found to be about 17% greater than pristine epoxy films suggesting homogeneous and consistent microstructure of CNT membrane and good interfacial adhesion between constituent CNTs and resin. In some embodiments, the lower modulus in the case of randomly dispersed 1 wt % MWNT films can be attributed to non-homogeneous distribution of MWNTs, and formation of agglomerations since the use of surfactants and surface functionalization was avoided during the dispersion phase. In some embodiments, regions with agglomerated MWNTs may lack resin and this can lead to decrease in elastic modulus of the films. 
         [0066]    In some embodiments, self-sensing glass fiber epoxy laminates (hereinafter “GFRPs”) were fabricated using six layers of eight harness satin (8HS) weave of S2 glass fiber from Fibre Glast and Epon 863 with hardener EPI-CURE 3290 with a 100/27 weight ratio. Other embodiments can be fabricated using more or less than six layers. Using a wet layup procedure, a CNT membrane extending the gauge length of the sample or specimen was embedded in a center layer (i.e., between the third and fourth layers of glass fiber) of the laminate. In some embodiments, silver adhesive tracks were painted on to the CNT membrane surface (hereinafter referred to as “SGFRP”) prior to embedding in order to avoid the use of invasive electrodes. Other conventional conductor materials can be used in place of silver. In some embodiments, this structure can result in high conductivity in the glass fiber epoxy laminates since the contact resistance at the electrode-membrane interface is minimized. Following the wet layup procedure, the specimens were cured in a hot press. The laminates were cut into 8 inch×1 inch strips for mechanical and piezoresistive characterization. In order to analyze the piezoresistive response of the SGFRP under cyclic tensile loading, specimens were mounted on a MTS Bionix servo-hydraulic test frame and the load was applied under displacement control mode, with a strain range of about 0.002 to about 0.009 at a rate of about 0.5 mm/min. The changes in the electrical resistance of the embedded CNT membrane were recorded in real-time using a digital multimeter (Fluke 289) with a data logging feature. 
         [0067]    The plot  1000  of  FIG. 10  shows piezoresistive response of self-sensing glass fiber epoxy laminates. In this plot, (R−Ro)/R ( 1020 ) is the normalized change in electrical resistance of the embedded CNT membrane. The SGFRP specimens showed stable and repeatable piezoresistive response under cyclic loading. The electrical resistance change in the embedded CNT membrane as cyclic strain was applied is illustrated (data line  1010 ). In some embodiments, the gauge factor was found to be higher for the first loading cycle (9.34 for ascending and 5.08 for descending) as compared to the subsequent loading cycles, retaining a stable sensitivity over the next five cycles with an average value of 5.62 for ascending and 4.17 for descending segments of the cycles. Delamination was observed in the CNT membrane layer of the composite after 80,000 cycles indicating the end of the functional life of the embedded sensor. The fatigue tests were stopped after 210,000 cycles and complete failure of the specimen was not observed. However, consistent load drop after 100,000 cycles indicates cyclic softening in the polymer matrix. 
         [0068]      FIG. 11  shows a SGFRP specimen used in a measurement model for in-situ crack length detection and quantification in accordance with some embodiments of the invention. The measurement model was developed to correlate the growing fatigue crack length at any instant to the change in electrical resistance of the embedded CNT membrane in the SGFRP laminate. A semicircular single edge notch was made on the specimens as shown in  FIG. 11 , and the specimens were subjected to displacement controlled tension-tension fatigue with strain range of about 0.002 to 0.0065, with a frequency of about 5 Hz, and the load ratio was about 0.2. The electrical resistance readings were obtained at regular intervals during the fatigue test. Since the loading was uniaxial, the fatigue crack grows along a straight line, approximately perpendicular to the loading axis. In some embodiments, this can lead to a reduction in the effective conducting width of the embedded CNT membrane as the crack length increases. The measurement model is derived from the resistivity equation and is given as, 
         [0000]    
       
         
           
             
               
                 
                   R 
                   = 
                   
                     
                       ρ 
                        
                       L 
                     
                     
                       t 
                        
                       
                         ( 
                         
                           w 
                           - 
                           a 
                         
                         ) 
                       
                     
                   
                 
               
               
                 
                   ( 
                   1 
                   ) 
                 
               
             
           
         
       
     
         [0069]    where R is the measured electrical resistance of the specimen at any instant during the fatigue test, L is the length of embedded CNT membrane (measured between the silver painted electrodes), and t, w and ρ are the thickness, width, and electrical resistivity of the membrane respectively. The crack length at any instant as calculated from equation (1) is given by ‘a’. 
         [0070]      FIGS. 12A-12C  show plots of actual crack lengths and sensed crack lengths as a function of fatigue cycles for three specimens in accordance with some embodiments of the invention. The  FIGS. 12A-12C  show the comparison between crack lengths sensed in SGFRPs from in-situ electrical resistance measurements and actual crack lengths which were obtained from high resolution camera. For example, plot  1200  of  FIG. 12A  shows data actual crack length  1220  and sensed crack length  1210 . Further, plot  1230  of  FIG. 12A  shows data actual crack length  1260  and sensed crack length  1250 , and plot  1260  of  FIG. 12A  shows data actual crack length  1270  and sensed crack length  1280 . The experimental results shown in  FIGS. 12A-12C  indicate significantly high accuracy of the proposed real-time crack length sensing methodology. The crack lengths obtained from the measurement model in real-time showed close agreement with the actual crack length values obtained from the high resolution camera. 
         [0071]      FIG. 13A  illustrates fatigue crack propagation in silver electrode glass fiber epoxy laminates specimen in accordance with some embodiments of the invention, and  FIG. 13B  illustrates fatigue crack propagation in a baseline glass fiber epoxy laminate specimen in accordance with some embodiments of the invention. The series of images obtained for the SGRFP specimens at progressive stages of the fatigue test and are presented in  FIG. 13A , where the trend in crack propagation is representative of six specimens tested under the same fatigue loading. The average crack growth rate from six specimens was found to be 5.36×10-4 mm/cycle over the stable crack propagation regime (between crack initiation and fast fracture regime). In comparison, the average crack growth rate in baseline GFRP specimens for the stable crack propagation regime was found to be 1.53×10-3 mm/cycle, which is significantly higher than SGFRPs. In some embodiments, the order of magnitude reduction in the fatigue crack growth rate due to the introduction of buckypaper into the interlaminar region of the GFRP laminates can be explained by the presence of the randomly oriented and densely entangled microstructure of the embedded buckypaper. In some embodiments, this can result in a highly torturous crack path leading to retardation in the fatigue crack growth rate and even crack arrest phenomenon at various instances during crack propagation. As shown in  FIG. 13A , the crack path in SGFRPs was highly torturous and crack tip blunting takes place at various stages of the fatigue test. Further, in some embodiments, in the stable crack propagation regime, between the 15000 to 21500 fatigue cycles, it can be seen that the crack tip becomes blunt without significant increase in crack length.  FIG. 13B  shows fatigue crack propagation trend in one of the baseline GFRP specimens where relatively sharp and defined crack tip can be observed and the trend is representative of six GFRP specimens tested under the same fatigue loading. This observation points to an additional crack deceleration type attribute of the SGFRP. 
         [0072]    It will be appreciated by those skilled in the art that while the invention has been described above in connection with particular embodiments and examples, the invention is not necessarily so limited, and that numerous other embodiments, examples, uses, modifications and departures from the embodiments, examples and uses are intended to be encompassed by the claims attached hereto. The entire disclosure of each publication cited herein is incorporated by reference, as if each publication were individually incorporated by reference herein. Various features and advantages of the invention are set forth in the following claims.