Patent Application
20120282453
The present invention relates generally to carbon nanotube composites and methods for fabricating carbon nanotube composites. More particularly, the present invention relates to a spray winding process for preparing carbon nanotube composites with highly desirable structural characteristics and mechanical properties.
Carbon nanotubes (“CNTs”) may be considered as “nano-fibers” that are an order of magnitude stronger than the strongest engineering fibers (such as carbon fibers and glass fibers), which makes them an ideal reinforcement for advanced multifunctional composites [1-2]. CNTs have highly desirable mechanical, thermal and electrical properties. However, after two decades of extensive research it remains a great challenge to produce CNT-polymer composites with superior properties and in a manner conducive to large-scale production [3-5]. To fully utilize the reinforcing potential of CNTs, it is important to use long CNTs in high volume fractions with a high degree of alignment while uniformly surrounding individual CNTs with the polymer matrix (thus increasing load transfer efficiency, for example) [6-8]. This structure is extremely difficult to achieve in conventional approaches, such as dispersion of CNTs in a polymer matrix by mixing. Long CNTs tend to agglomerate, making them difficult to disperse in any solvent or matrix. In addition, the entanglement of long CNTs makes CNT aligning very challenging, especially at high volume fractions. CNT composites fabricated by dispersion methods usually exhibit low tensile strength (e.g., less than 500 MPa) and low CNT mass fractions (e.g., less than 10 wt %). These issues are more severe when thermoplastic polymers are used as the matrix because the large molecular chains have to penetrate nano-scale interstices between bundled and tangled CNTs. Thermoplastic matrices are desired in composite applications requiring high toughness and/or high strain-to-failure ratios because they can deform plastically to absorb energy. In addition, thermoplastics are inexpensive, recyclable and generally have low toxicity to workers during composite fabrication [9].
Some of the desired characteristics of CNT composites include high CNT volume fractions, good CNT alignment, long CNT length, and significant individualization of CNTs within the polymer matrix (i.e., significant dispersion of CNTs). Reported techniques can produce a few of these desired structural features, but not all of them simultaneously. For example, a matrix-infusion method was developed to infuse epoxy resin into CNT preforms (or “films” or “buckypaper” or “mats”) with thousands of layers of CNT sheets pulled from CNT arrays to produce high volume fraction aligned-CNT composites [10-11]. Another method for producing high volume fraction aligned-CNT composites is shear pressing in which epoxy is infused into dense aligned-CNT preforms produced by shear pressing vertically aligned CNT arrays [12]. Multi-walled carbon nanotube (“MWNT”) sheets were pre-stretched and functionalized to produce composites with a bismaleimide (BMI) matrix [13]. These composites demonstrated the highest reported tensile strength and electrical properties, but exhibited low ductility [14] and the CNTs in the buckypaper sheets are curved or wavy. Matrix-infusion methods are successful in producing CNT-thermosetting polymer matrix composites because the small thermosetting monomers infuse into nanoscale structure before cross-linking. However, since the polymer is incorporated after the formation of the CNT structure, the polymer is not able to penetrate into areas where CNTs experience significant bundling.
Most high volume fraction composites have been produced with thermosetting polymer matrices (e.g., BMI, epoxy, etc.). Often, the strain-to-failure ratios of these composites are low, thus under-utilizing the high strain-to-failure ratios of CNTs. It is much more challenging to produce CNT-thermoplastic composites (as compared to CNT-thermosetting composites) with the desired structural characteristics, for the reasons set forth above. High mass-fraction CNT composites have been produced by solution or melt processing, but the CNTs were randomly oriented and poorly dispersed [15-18]. In-situ polymerization can achieve good dispersion of CNTs in thermoplastics but cannot align CNTs [19-21]. Injection molding and hot drawing can effectively align CNTs, but only at low CNT volume fractions and short CNT lengths [22-25]. The layer-by-layer (“LBL”) method is an effective way to process highly homogeneous, high volume-fraction CNT composites [26-27]. Through the application of a high magnetic field during the process, relatively short SWNTs were successfully aligned in polyelectrolyte. The electrical conductivity of the composites showed great improvement, while desirable mechanical properties are not yet available [28]. LBL-processed single-walled nanobube (“SWNT”)/polyvinyl alcohol (“PVA”) composites have been fabricated. SWNT/PVA composites demonstrated a tensile strength of 500MPa with no preferential CNT alignment [29]. In addition, the LBL process is time consuming
Studies of CNT composites so far have largely focused on improving the nanotube dispersion quality and functionalizing the interface with the polymer matrix [30-32]. To achieve good quality CNT/polymer dispersion, short CNTs in low volume fractions are typically required and utilized. Although short CNT composites have some advantages in certain low volume fraction applications, such as thermally and electrically conducting materials, their mechanical properties have typically fallen far short of traditional high performance structural composites. This results largely from the short CNT length (e.g., less than 10 μm), which cannot efficiently transfer a mechanical load across the weakly bonded interface. Chemical modification may improve interfacial shear strength at the expense of introducing defects in the CNT structures, thus degrading the properties [33-34]. Achieving high volume fractions of dispersed CNTs in polymer is difficult because the resulting high viscosity complicates further processing.
Another approach that has been used for fabricating CNT composites is reinforcing with CNT fiber assemblies [35-37], which include plied or braided CNT fiber assemblies [35-36] and long spun fibers infiltrated by polymer [37]. The most significant component in these composites is the CNT fiber (or yarn). Techniques for making CNT fibers are classified into “liquid” methods [38-39], where CNTs are dispersed into a liquid and solution-spun into fibers, and “solid” methods [40-41], where CNTs are directly spun into ropes or yarns [42]. The last five years have seen rapid progress in the “solid” fiber spinning approach [43-51]. While the mechanical properties of these fibers are promising, they both have limitations. The “liquid” method requires short CNTs for solution spinning, which limits the mechanical properties, while the “solid” method involves fiber twisting, which is a slow and expensive process.
Accordingly, there is a need for new, high-valued, industrially applicable CNT composites, as well as efficient methods for making CNT composites that are conducive to industrial scale-up, where the CNT composites exhibit excellent structural characteristics (e.g., high CNT volume fraction (and/or high CNT mass fraction), good CNT alignment, reduced CNT waviness, long CNT length, good CNT/polymer matrix bonding, etc.), and excellent mechanical and/or electrical properties (e.g., high tensile strength, high Young's modulus, high electrical conductivity, high toughness, good thermal conductivity, etc.).
To address the foregoing problems, in whole or in part, and/or other problems that may have been observed by persons skilled in the art, the present disclosure provides compositions, methods, processes, systems, apparatus, instruments, and/or devices, as described by way of example in implementations set forth below.
According to one implementation, a method is provided for fabricating a carbon nanotube (CNT) composite. An array of CNTs is provided. A CNT ribbon is pulled from the array and wound on a rotating mandrel. A polymer solution is applied to the CNT ribbon as the CNT ribbon is pulled from the array and wound on the mandrel to form a CNT composite laminate. The CNTs in the CNT ribbon may be substantially aligned in a single direction. The CNT ribbon may be attached to the mandrel such that the CNT ribbon may be wound on the mandrel as the mandrel rotates. The polymer solution may comprise a polymer and a solvent.
In some implementations, the polymer solution may be applied to the CNT ribbon by passing the CNT ribbon through a solution path including the polymer solution.
In some implementations, the polymer solution may be applied to the CNT ribbon by spraying the polymer solution on the CNT ribbon.
In some implementations, the mandrel and/or the CNT array may oscillate along a horizontal axis to obtain a predetermined width associated with the CNT composite laminate.
In some implementations, the CNT ribbon may be heated and/or stretched prior to applying the polymer solution to the CNT ribbon. The CNT ribbon may be stretched by pulling the CNT ribbon into contact with at least one tensioning rod.
In some implementations the CNT composite laminate may be removed from the mandrel and subsequently heated and/or stretched.
According to another implementation, a CNT composite is provided. The CNT composite may include a polymer integrated with long, substantially straight CNTs that are highly aligned in a single direction. The CNT composite may have a Young's modulus ranging from about 14 GPa to about 500 GPa. The CNT composite may have a tensile strength ranging from about 0.22 GPa to about 10 GPa.
In some implementations, the CNT composite may have an electrical conductivity ranging from about 140 S/cm to about 5000 S/cm.
In some implementations, the CNT composite may have a thermal conductivity ranging from about 10 W*m−1K−1 to about 400 W*m−1K−1.
In some implementations, the CNT composite may have a toughness ranging from about 16 J/g to about 250 J/g.
In some implementations, the CNT composite may include a thermosetting polymer.
In some implementations, the CNT composite may include a thermoplastic polymer.
According to another implementation, an apparatus for fabricating a CNT composite is provided. The apparatus may include a rotatable mandrel and a spray gun. The rotatable mandrel may be configured for taking up a CNT ribbon from an array of CNTs. The spray gun may be configured for spraying a polymer solution on the CNT ribbon as the CNT ribbon is taken up on the rotating mandrel.
In some implementations, the apparatus may include at least one tensioning rod configured for stretching the CNT ribbon as the CNT ribbon is pulled into contact with the tensioning rod.
Other compositions, devices, apparatus, systems, methods, features and advantages of the invention will be or will become apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the invention, and be protected by the accompanying claims.
The invention can be better understood by referring to the following figures. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. In the figures, like reference numerals designate corresponding parts throughout the different views.
a shows the tensile strength of CNT/PVA composites as a function of the mass fraction of CNTs in the CNT/PVA composites. The corresponding PVA solution concentrations are labeled.
b shows thermogravimetric analysis (TGA) curves of pure CNT arrays, pure PVA polymer, and CNT/PVA composites fabricated with varying PVA solution concentrations. The mass fractions were estimated using TGA results at 600° C.
c shows stress-strain curves of a pure CNT film and three different CNT/PVA composites, under different ambient humidity.
a shows the normalized intensity of G-band peak versus the angle between the sample's longitudinal direction and the polarization axis of the incident laser beam. The normalized intensity at 90° becomes smaller when PVA is introduced into the CNT/PVA composite and further decreases after hot pressing.
b shows Raman spectra at 0° and 90°, before and after hot pressing the CNT/PVA composite. All of the CNT/PVA composites were fabricated using 1-g/L PVA solution.
a is a scanning electron microscope (SEM) image of a cross-section of a CNT/PVA composite fabricated with a PVA solution concentration of 0.5 g/L.
b is a SEM image of a cross-section of a CNT/PVA composite fabricated with a PVA solution concentration of 1 g/L.
c is a SEM image of a cross-section of a CNT/PVA composite fabricated with a PVA solution concentration of 2 g/L.
d is a SEM image of a side view of a CNT/PVA composite fabricated with a PVA solution concentration of 0.5 g/L.
e is a SEM image of a side view of a CNT/PVA composite fabricated with a PVA solution concentration of 1 g/L.
f is a SEM image of a side view of a CNT/PVA composite fabricated with a PVA solution concentration of 2 g/L.
a is an image of another implementation of an apparatus for fabricating a CNT composite.
b is a schematic view of an apparatus for forming CNT composites using the apparatus of
c is an image of a local heating device that may be used to heat the CNT composite formed according to the process shown in
d is a schematic view of a method for locally heating and stretching the CNT composite made according to the process shown in
a is an SEM image of an as-drawn dry CNT ribbon showing wavy CNTs.
b is an SEM image of a stretched CNT dry ribbon showing reduced CNT waviness.
c is an SEM image of a non-stretched CNT/nylon 6,6 composite showing wavy CNTs. The nylon matrix was decomposed in a TGA instrument.
d is an SEM image of a post-stretched CNT/nylon 6,6 composite showing enhanced alignment and reduced waviness of CNTs. The nylon matrix was decomposed in a TGA instrument.
a shows typical stress-strain curves of post-strained CNT/nylon 6,6 composites, pure CNT ribbon, and pure polymer.
b shows a comparison of tensile strength and Young's modulus of CNT/nylon composites with varying stretch ratios.
a is an SEM image of the fracture surface of a CNT/nylon 6,6 composite that was stretched according to a 7% stretch ratio.
b is an SEM image of sheath-core tips of MWNTs used to make CNT/nylon 6,6 composites.
a shows a comparison of the tensile strength and Young's modulus of: stretched CNT/BMI composites made according to the present invention; the best engineering carbon fiber reinforced polymer (CFRP) composites; and previously reported CNT composites. All of the text in
b shows a comparison of the specific tensile strength and specific Young's modulus of: stretched CNT/BMI composites made according to the present invention; and the best engineering carbon fiber reinforced polymer (CFRP) composites. The data are calculated based on a density of 1.6 g/cm3 for CFRP (60 vol. %), and 1.4 g/cm3 for CNT/BMI composites made according to the present invention (46 vol. %).
a is an SEM image of an as-drawn CNT ribbon from a free-standing CNT array. The inset is a TEM image of a CNT in the CNT ribbon, having a diameter of about 7 nm.
b is an image of an apparatus used to make CNT/BMI composites, showing CNT sheets (of CNT ribbon drawn from the array) that are successively stretched by two cylindrical copper wires (tensioning rods) before uptake on the rotating spool. The tensioning rods are highlighted by red circles.
c shows test specimens of CNT/BMI composites fabricated according to the present invention.
d is a schematic of a method for producing CNT composites using the apparatus shown in
a is an SEM image of CNT/BMI composites made without stretching, showing wavy CNTs and the microscale porous structure of the CNT sheets.
b is a high magnification SEM image of the composite shown in
c is an SEM image of a CNT/BMI composite made according to the method shown in
d is a high magnification SEM image of the composite shown in
a shows Raman spectra at 0° and 90°, for the most stretched sample of CNT/BMI composite made according to the method shown in
b shows the normalized intensity of G-band peak versus the angle between the CNT/BMI composite sample's longitudinal direction and the polarization axis of the incident laser beam. The intensity ratio R(R=IG∥/IG⊥) for CNT/BMI composites made without stretching increased to 2.3 and that for CNT/BMI composites made with stretching increased dramatically to 7.6, showing that stretching process imparted a significant alignment factor to the material. The CNT/BMI composites were made with a BMI solution concentration of 1 g/L.
a shows typical stress-strain curves of pristine CNT sheets and CNT/BMI composites with various polymer matrix concentrations.
b shows typical stress-strain curves of CNT/BMI composites with and without stretching, showing significant improvement of mechanical properties through alignment and straightening of CNTs.
c shows a comparison of tensile strength and Young's modulus for CNT/BMI composites made without stretching (R-winding), with stretching before winding (S-winding), and with stretching before winding and after winding (S-winding+P).
a is an SEM image of the typical fracture surface morphology of CNT/BMI composites made with a BMI solution concentration of 2.5 g/L (without stretching).
b is an SEM image of the typical fracture surface morphology of CNT/BMI composites made with a BMI solution concentration of 1 g/L (without stretching).
c is an SEM image of the typical fracture surface morphology of CNT/BMI composites made with a BMI solution concentration of 0.5 g/L (without stretching).
d is an SEM image of the typical fracture surface morphology of CNT/BMI composites made with a BMI solution concentration of 1 g/L (with stretching before winding).
a is a comparison of electrical conductivities measured in the direction of CNT alignment of CNT/BMI composites made with varying BMI solution concentrations. S stands for stretching prior to winding, and P stands for stretching both before and after winding.
b shows the regional strain-conductivity relationship of the resultant unidirectional CNT/BMI composites at a strain range of 0 to about 0.2%.
c shows an overview of the strain-conductivity relationship of the resultant unidirectional CNT/BMI composites at a strain range of 0 to about 1.5%.
d shows tensile strength behavior of the CNT/BMI composites along with in-situ conductivity testing. The increase in Young's modulus shows improved alignment during tensile loading.
The present invention relates to carbon nanotube (CNT) composites with improved structural characteristics and mechanical properties, methods for making CNT composites, and apparatus and/or systems for producing CNT composites. CNT composites according to the present teachings may include, inter alia, one or more of the following microstructural features that lead to exceptional mechanical properties: (1) high CNT volume fraction; (2) good CNT alignment; (3) reduced CNT waviness; (4) long CNT length; and (5) good CNT/polymer matrix bonding.
For purposes of the present teachings, it will be understood that when a layer (or film, region, substrate, sheet, component, device or the like) is referred to as being “on” or “over” another layer, that layer may be directly or actually on (or over) the other layer or, alternatively, intervening layers (e.g., buffer layers, transition layers, interlayers, electrodes interconnects, or the like) may also be present. A layer that is “directly on” another layer means that no intervening layer is present, unless otherwise indicated. It will also be understood that when a layer is referred to as being “on” (or “over”) another layer, that layer may cover the entire surface of the other layer or only a portion of the other layer. It will be further understood that terms such as “formed on” or “disposed on” are not intended to introduce any limitations relating to particular methods of material transport, deposition, fabrication, surface treatment, or physical, chemical, or ionic bonding or interaction.
As used herein, the term “CNT array” refers to a structure of high density, vertically standing, long CNTs that are formed on a substrate (e.g., silicon, glass, quartz, etc.) via a chemical vapor deposition (CVD) method, or any other suitable method known to those skilled in the art. The dimensions of the CNT array may be dependent on the size of the substrate on which the CNT array is formed. For example, the CNT array may be formed on a silicon wafer having a diameter of from about 2 inches to about 4 inches, or in some implementations, up to about 12 inches or greater. In one particular yet non-limiting example, the CNT array may be formed on a quartz substrate having a width of about 1 inch and a length of about 2 inches. A CNT ribbon (or “CNT sheet”) may be drawn from the CNT array (e.g., via a rotating mandrel, a moving substrate, or the like). Each CNT ribbon layer may contain millions of well aligned CNTs. In some implementations, the CNT ribbon may be about 1 micron thick or greater, and may have a width ranging from about 1 mm to about 10 mm (see
The CNTs utilized in conjunction with the present teachings may be single-walled carbon nanotubes (SWNTs) or multi-walled carbon nanotubes (MWNTs), there being no limitation on the number of walls in the CNTs. For example, CNTs having three (3) or four (4) walls may have an outer diameter ranging from about 6 nm to about 8 nm. CNTs having five (5) or six (6) walls may have an outer diameter ranging from about 7 nm to about 10 nm. As another non-limiting example, CNTs having 50 walls may have an outer diameter of about 45 nm. As used herein, the term “long CNTs” may be used to refer to CNTs having a length of about 300 microns or greater.
Some non-limiting examples of polymers that may be utilized in solution to prepare CNT composites according to the present teachings may include: polyvinyl alcohol (PVA), poly(ethylene oxide) (PEO), poly(vinyl pyrrolidone) (PVP), nylon, polyurethane (PU), polystyrene (PS), poly(methyl methacrylate) (PMMA), polyethylene (PE), polypropylene (PP), poly(ethylene terephthalate) (PET), polyacrylamide, bismaleimide (BMI), various epoxy resins, polyimide, and the like. More generally, CNT composites according to the present teachings may be fabricated with various thermosetting polymers and/or thermoplastic polymers, depending on the potential application of the CNT composite (e.g., in general, thermoplastic polymers may be described as flexible, whereas thermosetting polymers may be described as stiff).
The present teachings describe methods (some of which may generally be referred to herein as a “spray winding method”) for fabricating high strength CNT composites having highly aligned CNTs in a single direction, substantially straight CNTs (i.e., non-wavy CNTs), long CNTs (i.e., greater than about 300 microns in length), high CNT volume fractions (and/or high CNT mass fractions), good CNT/polymer matrix bonding, and/or highly dispersed CNTs within the polymer matrix. In some implementations, the CNT composites possess two or more of the foregoing attributes. In some implementations, the CNT composites possess all of the foregoing attributes. All of these structural characteristics may be achieved without functionalizing the CNTs in the composite. The spray winding method generally includes providing an array of CNTs that are substantially aligned in a single direction. A CNT ribbon may be pulled from the array by a rotating mandrel to which the CNT ribbon is attached. As the mandrel rotates, the CNT ribbon is wound on the mandrel (e.g., a cylindrical polytetrafluoroethylene (PTFE) spool or any other suitable rotatable apparatus for taking up the CNT ribbon). As the CNT ribbon is pulled from the CNT array and wound on the mandrel, a polymer solution (i.e., polymer and a solvent) may be sprayed on the CNT ribbon (or otherwise applied to or deposited on the CNT ribbon, such as by passing the CNT ribbon through a polymer solution bath). As the sprayed CNT ribbon is wound on the mandrel, layers of sprayed CNT ribbon are formed on the mandrel. It will be understood that the term “CNT composite laminate” may be used herein to refer to layers of CNT ribbon that have been sprayed and wound on the mandrel, and encompasses implementations in which a thermosetting polymer is utilized, as well as implementations in which a thermoplastic polymer is utilized. In implementations in which the polymer is a thermosetting polymer, the CNT composite laminate may be considered by those skilled in the art as a CNT prepreg. Those of skill in the art will appreciate that subsequent curing of the CNT prepreg (e.g., heating the CNT prepreg to a suitable temperature for a suitable length of time) may be carried out in some implementations. The CNT composite laminates may be stacked to form CNT composites with suitable dimensions.
In some implementations, the polymer solution may be sprayed by a compressed air sprayer (such as a fine-line air sprayer), or any other suitable sprayer that is adjustable and capable of accurately spraying the polymer solution on the CNT ribbon. However, it will be understood that polymer solution may be applied to the CNT ribbon by any suitable method, such as by passing the CNT ribbon through a polymer solution bath. A screen may be positioned between the nozzle of the sprayer and the mandrel, and the polymer solution may be sprayed through an opening in the screen to ensure that polymer solution is sprayed only on the CNT ribbon. The present invention encompasses implementations in which the polymer solution is sprayed on the CNT ribbon as the CNT ribbon is pulled from the array, but before the CNT ribbon starts to wind on the mandrel. As an alternative, or in addition to the foregoing, the polymer solution may be sprayed on the CNT ribbon as the CNT ribbon is being wound on the mandrel. The phrase “spraying a polymer solution on the CNT ribbon as the CNT ribbon is pulled from the array and wound on the mandrel” is meant to encompass the foregoing temporal limitations associated with spraying and/or winding. In some implementations, the mandrel and/or the CNT array may be movable (e.g., in the horizontal direction) such that the sprayed CNT ribbon (or CNT sheet) may be layered on the mandrel to a selected width (e.g., to a width greater than the width of the CNT ribbon). One or more parameters associated with the spray winding process may be adjusted in order to achieve a desired volume fraction of CNTs within the CNT composite. Examples of the parameters that may be adjusted include: the concentration of the polymer in the polymer solution; the speed of the rotating mandrel (and thus the speed at which the CNT ribbon is drawn from the CNT array); and/or the rate at which the polymer solution is applied to the CNT ribbon (e.g., the flow rate of polymer solution out of the sprayer, or “spray throughput”). In one specific yet non-limiting example, the CNT ribbon may be pulled from the array at a rate of about 18 mm/s to about 19 mm/s As another example, the concentration of the polymer in the polymer solution may range from greater than 0 g/L to about 10 g/L. In some implementations, the concentration of the polymer in the polymer solution may be as high as 500 g/L. The spray winding process may be carried out until a predetermined (i.e., desired or selected) value for any one (or more) of a variety of parameters associated with the CNT composite laminate is achieved (e.g., a particular length of CNT ribbon has been pulled from the array; a particular width of the CNT composite laminate is achieved; a predetermined thickness of the CNT composite laminate is achieved; etc.)
The CNT composite laminate may be removed from the mandrel and further processed. For example, the CNT composite laminate may be heated in a hot press (e.g., between heated plates) or placed in an autoclave to remove air voids and to obtain optimal integration of the polymer matrix and CNTs, and/or the CNT composite laminate may be stretched. Those of skill in the art will appreciate that the temperature to which the CNT composite laminate is heated may depend on the type of polymer utilized (i.e., whether the polymer is thermoplastic or thermosetting). For example, when thermoplastic polymers are utilized, the CNT composite laminate may be heated to a temperature that is above the glass transition temperature of the thermoplastic polymer, but below the melting temperature of the thermoplastic polymer. When thermosetting polymers are utilized, the CNT composite laminate may be heated to a temperature that is below the curing temperature of the thermosetting polymer (so that the thermosetting polymer is only partially cured, and the polymer molecules may be reconfigured and realigned with the CNTs). In some implementations, the CNT composite laminate may be heat pressed to a temperature of about 160° C. to about 180° C. In implementations in which a thermosetting polymer is utilized, the CNT composite laminate may be removed from the mandrel and heat pressed up to a temperature of about 450° C., for example.
As mentioned above, either alone or in addition to heating the CNT composite laminate, the CNT composite laminate may be stretched to reduce waviness of CNTs in the CNT composite laminate (leading to improved mechanical and/or electrical properties of the CNT composites as discussed below in conjunction with Examples 2-3). For example, the CNT composite laminate may be simultaneously stretched (e.g., on a tensile tester or any other suitable stretching apparatus known to those skilled in the art) and heated. In some implementations, the CNT composite laminate may be heated by a local heating source while the CNT composite laminate is being stretched. The local heating source may be movable and may include, for example, a heating element with dual extended prongs. The movable heating source may locally heat the CNT composite laminate to a temperature that, again, depends on the type of polymer utilized (e.g., up to about 160° C. to about 180° C., or up to 450° C.). In one non-limiting example, the heating element may be moved along the CNT composite laminate at a speed of about 3 mm/s, and the CNT composite laminate may be uniformly stretched along the length of the CNT composite laminate (i.e., the direction of alignment of the CNTs in the CNT composite laminate) at a stretch rate of 0.1 mm/min. It will be understood that the heating element may be moved along the length of the CNT composite laminate at any suitable speed, and the CNT composite laminate may be stretched at any suitable stretch rate. In some implementations, after stretching and locally heating the CNT composite laminate, the CNT composite laminate may be heat pressed (as discussed above). In various implementations, the CNT composite laminate may be stretched according to a stretch ratio (i.e., (LS-LUS)/LUS, where LS is the length of the stretched CNT composite laminate and LUS is the length of the CNT composite laminate before stretching) ranging from greater than 0% to about 7% or greater (e.g., 100%), depending on how many CNTs in the CNT composite laminate are straightened.
In some implementations, the spray winding process may include stretching the CNT ribbon prior to being sprayed with polymer solution. For example, as the CNT ribbon is pulled from the array, the CNT ribbon may be pulled through a tensioning system before being wound on the mandrel. The tensioning system may include at least one tensioning rod (e.g., a cylindrical copper wire) for applying tension to the CNT ribbon as the CNT ribbon is pulled at least partially around the tensioning rod and subsequently wound around the mandrel. Pulling the CNT ribbon through the tensioning system may straighten the CNTs or CNT bundles in the CNT ribbon in the direction in which the CNT ribbon is pulled.
CNT composites according to the present teachings exhibit excellent structural characteristics and superior mechanical and/or electrical properties. The CNT composites of the present teachings include a polymer and long (i.e., a length of about 300 microns or greater), substantially straight CNTs that are highly aligned in a single direction. In addition, the CNTs in the CNT composites are well-dispersed and well-embedded in the polymer matrix. As discussed above, the CNT composites may include thermosetting or thermoplastic polymers.
In various implementations, CNT composites according to the present teachings may have a Young's modulus ranging from about 14 GPa to about 500 GPa. In some implementations, the CNT composites may include a thermosetting polymer, and the CNT composites may have a Young's modulus ranging from about 216 GPa to about 500 GPa, or from about 216 GPa to about 350 GPa. In some implementations, the CNT composites may include a thermoplastic polymer, and the CNT composites may have a Young's modulus ranging from about 14 GPa to about 100 GPa. In one particular, yet non-limiting example, the CNT composites may include PVA, and the CNT/PVA composites may have a Young's modulus of about 100 GPa. In another non-limiting example, the CNT composites may include nylon 6,6, and the CNT/nylon 6,6 composites may have a Young's modulus of about 60 GPa. In another non-limiting example, the CNT composites may include BMI, and the CNT/BMI composites may have a Young's modulus of about 350 GPa.
In various implementations, CNT composites according to the present teachings may have a tensile strength ranging from about 0.22 GPa to about 10 GPa. In some implementations, the CNT composites may include a thermosetting polymer, and the CNT composites may have a tensile strength ranging from about 1.4 GPa to about 10 GPa, or from about 1.4 GPa to 4.0 GPa. In some implementations, the CNT composites may include a thermoplastic polymer, and the CNT composites may have a tensile strength ranging from about 0.22 GPa to about 2.0 GPa, or from about 1.3 GPa to about 2.0 GPa. In one particular, yet non-limiting example, CNT/PVA composites according to the present teachings may have a tensile strength of about 2.0 GPa. In another non-limiting example, CNT/nylon 6,6 composites according to the present teachings may have a tensile strength of about 1.0 GPa. In another non-limiting example, CNT/BMI composites according to the present teachings may have a tensile strength of about 4.0 GPa.
In various implementations, CNT composites according to the present teachings may have an electrical conductivity ranging from about 140 S/cm to about 5000 S/cm. In some implementations, the CNT composites may include a thermosetting polymer, and the CNT composites may have an electrical conductivity ranging from about 820 S/cm to about 1230 S/cm. In some implementations, the CNT composites may include a thermoplastic polymer, and the CNT composites may have an electrical conductivity ranging from about 140 S/cm to about 781 S/cm, or from about 520 S/cm to about 781 S/cm. In one particular, yet non-limiting example, CNT/PVA composites according to the present teachings may have an electrical conductivity of about 781 S/cm. In another non-limiting example, CNT/nylon 6,6 composites according to the present teachings may have an electrical conductivity of about 420 S/cm. In another non-limiting example, CNT/BMI composites according to the present teachings may have an electrical conductivity of about 1230 S/cm.
In various implementations, CNT composites according to the present teachings may have a thermal conductivity ranging from about 10 W*m−1K−1 to about 400 W*m−1K−1. In some implementations, CNT/BMI composites according to the present teachings may have a thermal conductivity ranging from about 10 W*m−1K−1 to about 400 W*m−1K−1.
In various implementations, CNT composites according to the present teachings may have a toughness ranging from about 16 J/g to about 250 J/g. In some implementations, the CNT composites may include a thermosetting polymer, and the CNT composites may have a toughness ranging from about 16 J/g to about 46 J/g. In some implementations, the CNT composites may include a thermoplastic polymer, and the CNT composites may have a toughness ranging from about 65 J/g to about 112 J/g. In one particular, yet non-limiting example, CNT/PVA composites according to the present teachings may have a toughness of about 112 J/g. In another non-limiting example, CNT/BMI composites according to the present teachings may have a toughness of about 46 J/g.
In one particular, yet non-limiting example, CNT/BMI composites according to the present teachings may have a CNT volume fraction ranging from about 46% to about 60%. In another non-limiting example, CNT/nylon 6,6 composites according to the present teachings may have a volume fraction of about 15%.
In one particular, yet non-limiting example, CNT/BMI composites according to the present teachings may have a specific strength (i.e., the tensile strength of the CNT composite divided by the density of the CNT composite) ranging from about 25*106 cm to about 30*106 cm. In another particular, yet non-limiting example, CNT/BMI composites according to the present teachings may have a specific Young's modulus (i.e., the Young's modulus of the CNT composite divided by the density of the CNT composite) ranging from about 18*108 cm to about 22*108cm.
In some implementations, the CNT composites may include a thermoplastic polymer, and the CNT composites may have a CNT mass fraction ranging from about 28% to about 78%. In one particular, yet non-limiting example, CNT/PVA composites according to the present teachings may have a CNT mass fraction of about 78%. In another non-limiting example, CNT/nylon 6,6 composites according to the present teachings may have a CNT mass fraction of about 20%. In another non-limiting example, CNT/BMI composites according to the present teachings may have a CNT mass fraction of about 50%.
In some implementations, the CNT composites may include a thermosetting polymer, and the CNT composites may have a strain-to-failure ratio ranging from about 1.2% to about 10%. In some implementations, the CNT composites may include a thermoplastic polymer, and the CNT composites may have a CNT strain-to-failure ratio ranging from about 8% to about 13%. In one particular, yet non-limiting example, CNT/PVA composites according to the present teachings may have a strain-to-failure ratio of about 13%. In another non-limiting example, CNT/BMI composites according to the present teachings may have a strain-to-failure ratio of about 3.0%.
CNT composites according to the present teachings may be utilized in various applications. The particular application for which a CNT composite is utilized may depend on various factors, including whether the polymer in the composite is a thermosetting or thermoplastic polymer. Non-limiting examples of potential applications for the CNT composites of the present invention include high performance, ultra-strong multifunctional materials intended for: the automobile, marine and aeronautical industries; electromechanical actuators; cables; resistive wires; chemical detectors; the storage and conversion of energy; electron emitter displays, battery electrodes, electronic components and functional textiles. CNT composites according to the present teachings may be used to prepare strong and light armor for aircraft, missiles, space stations, space shuttles, and other high strength articles. CNT composites according to the present teachings may be supplied to manufacturers of high performance materials in various forms. For example, the CNT composites may be supplied in nanocomposite prepreg form for incorporation into high performance materials.
The following examples are intended to illustrate the invention, and are not intended to limit the scope of the invention.
In this Example, CNT-thermoplastic polymer composites are produced according to a spray winding method (see
Experimental Procedure
Highly aligned CNT arrays were grown on an SiO2/Si substrate with a catalyst of Fe/Al2O3. The vertically aligned CNT arrays have a uniform height of 300 μm, from which a layer of CNT ribbon was pulled out continuously. Each layer of CNT ribbon contains millions of well-aligned CNTs. Each CNT ribbon is about 1 μm in thickness and about 3-5 mm wide. Dilute PVA (Mw=85,000˜124,000, 99+% hydrolyzed) solutions were prepared by dissolving the polymer in a solvent containing equal parts of deionized water and ethanol. The polymer solution was sprayed under 10 psi air pressure onto the ribbons drawn at a speed of 19 mm/s, as the ribbons were wound on a mandrel with a diameter of 3 cm and a rotational speed of 11.5 rpm. A screen with a rectangular slit was kept between the nozzle (of the air sprayer) and mandrel to ensure that polymer solution was deposited only on the CNT ribbon. The solution droplets were micrometer-sized using a commercially available Badger 200NH airbrush. The composite films were prepared by rotating the mandrel for one hour, with a solution-dependent thickness of 10-20 μm. For the tensile tests, the films were cut into 1.5 cm×0 5 mm pieces and tested on a Shimadzu EZ-S testing machine with a load cell of 100 N at a strain rate of 8.3% per minute.
Conductivity results were calculated based on resistance, which were measured along the direction of alignment of the CNTs in the composite by an Agilent 34410A 6.5 digit multi-meter with 4 probe measurement.
The CNT mass fraction was calculated based on TGA analysis, which was completed on a Perkin Elmer Pyris 1 in nitrogen (99.999%) with a heating rate of 10° C. per minute. Based on results of TGA analysis of neat PVA polymer and pure CNT arrays, mass fractions of CNTs in CNT/PVA composites made with 2 g/L and 1 g/L polymer solution were calculated to be 65% and 78%, respectively.
Results and Discussion
In the present Example, a spray winding method was used to fabricate CNT-thermoplastic composites with high, tunable CNT volume fractions. As the mandrel diameter, rotating speed, spray pressure, and the distance between the airbrush and the mandrel were fixed, CNT/PVA composites with different CNT mass fractions were achieved by using PVA solutions with different concentrations, namely 0.5, 1, 1.5, 2, 5, and 10 g/L. With increasing PVA solution concentration, the CNT mass fraction decreases.
c provides the stress-strain curves for a pure CNT film (made by layering hundreds of CNT ribbons that are sprayed with a mixture of water and ethanol) and for three CNT/PVA composites made using the 1-g/L and 2-g/L PVA solutions. The pure CNT film was only 420 MPa in strength, due to the weak van der Waals interaction between CNTs. In the pure CNT film, CNTs might slide against each other under external loads. For example, in the tensile test there was a sudden drop of stress, corresponding to the sliding. When the PVA solution was sprayed onto the CNT ribbon, a stronger interaction between PVA and CNT was introduced, and the long and flexible polymer molecules may interact and bridge CNTs that are not in close contact. Therefore, the interfacial shear stress was improved greatly, resulting in the high tensile strength. Note that both the CNT film and the composites were densified due to the capillary force caused by the evaporation of the solvents.
The tensile behavior was also found to depend on the relative humidity (RH) (see the two red curves in
The high performance of our composites arises from the long CNT length and the high degree of alignment. As the CNT ribbon was pulled out from the CNT array, the CNT length of ˜300 μm (aspect ratio of ˜30000) was not changed and was one order of magnitude longer than the tubes that are normally used for dispersion in a polymer matrix [55,58], which is important for high-performance composites. Using long CNTs results in increased tensile strength, similar to spun CNT fibers [59]. Furthermore, the CNTs were aligned in the form highly aligned in the CNT array. The aligned structure may be investigated by polarized Raman spectroscopy [60, 61], as shown in
As discussed above, the tensile properties strongly depend on the CNT mass fraction. At a PVA solution concentration of 1 g/L, the CNT mass fraction was 65 wt %.
As shown in
In summary, a spray winding method is disclosed in the present Example for fabricating CNT composites. The spray winding technique of the present Example produced CNT composites with the desired structural features, including high CNT volume fraction, long CNT length, improved CNT alignment, and a uniform distribution of PVA molecules among the CNT network. By using CNTs with a large aspect ratio of ˜30000, the strongest composite films had a tensile strength of ˜1.8 GPa, a Young's modulus of 40-96 GPa, and a toughness of 38-100 J/g. The production speed of the CNT composites depends on the rotation speed of the mandrel, and is much higher than the existing techniques such as the resin transfer molding [62] and the layer-by-layer assembly [54,63,64], making it conducive to large-scale production at low cost. Besides the thermoplastic PVA used here, the method of the present Example may also be used to make thermosetting polymer-based composites with ultrahigh mechanical properties.
In this Example, we report an effective method for increasing the strength and stiffness of high volume fraction, aligned CNT composites by reducing CNT waviness using a mechanical stretching approach. Stretching the CNT composites after fabrication improved the ultimate strength by 50, 150, and 200%, corresponding to stretch ratios of 2, 4 and 7%, respectively. Improvement of the electrical conductivities exhibited a similar trend. These results demonstrate the importance of straightening and aligning CNTs in improving composite strength.
The present Example discloses uniformly winding CNT ribbons from free-standing CNT arrays, infusing a nylon 6,6 solution between layers of the CNT ribbon without disturbing the pre-existing alignment, followed by stretching the composite while locally heating it. The present Example identifies a mechanism for optimizing mechanical properties of CNT composites.
Experimental Procedure
Vertically aligned CNT arrays with a height of ˜700 μm were synthesized on a quartz substrate with iron chloride (FeCl2) powder using a thermal chemical vapor deposition (CVD) method described in the literature [65]. The CNTs (i.e., a ribbon of CNTs) were drawn from the arrays onto a rotating cylindrical polytetrafluoroethylene (PTFE) spool (as shown in
The as-wound CNT/nylon 6,6 composite was removed from the PTFE spool. Precise stretching was performed on a tensile tester (Shimazu EZ-S). The composite was locally heated by a fabricated heating element with dual prongs. The temperature between the two extended wire ends (see
Tensile test specimens were cut from the CNT/nylon 6,6 composites into strips that were approximately 10 mm long and 0.3 mm wide. CNT alignment was parallel to the longitudinal direction of the tensile loading. Sample width was measured using an optical microscope (30×) and the sample thickness was measured using a micrometer. The composite specimens with a gauge length of 6 mm were tested at room temperature using the tensile testing machine at a crosshead speed of 0.5 mm/min. Five specimens were tested for each CNT/nylon 6,6 composite. Resistance was measured using the four-probe method. Transmission electron microscopy (TEM) analysis of the nanotubes was performed using a JEOL 2010F microscope at an acceleration voltage of 200 kV. Scanning electron microcopy (SEM) analysis of the CNT ribbons and CNT composite fracture surface was carried out on a JEOL 6400F microscope with an acceleration voltage of 5kV. Thermogravimetric analysis (TGA) was completed on a Perkin Elmer Pyris 1 in nitrogen (99.999%) with a heating rate of 10° C. per minute.
Results and Discussion
The CNTs used to fabricate the composites in the present Example were characterized by Raman spectroscopy and TEM (see
Alignment of CNTs is a major issue for fabricating high performance composites [66, 67]. The drawing process aligns the CNTs by applying tension during uptake on the PTFE spool. In the present Example CNT ribbons are easily formed from the CNT array, which facilitates more rapid fabrication of large engineering structures. Although the CNTs were aligned, significant waviness is present and diminishes the mechanical strength.
In order to maximize the load-carrying efficiency, the waviness of CNTs within the composites should be minimized. To accomplish this, a simple local heating and stretching method was used to uniformly stretch the nanotubes together with the polymer matrix. Stretching has proven to be effective in previous work [68]. With a low glass transition temperature (45° C.) and large strain-to-failure value, nylon stands out as a suitable matrix for stretching. As opposed to stretching a whole CNT composite sample (which results in inhomogeneous elongation), local heating and stretching (see
High CNT volume fraction (and/or high CNT mass fraction) and good CNT dispersion in the polymer matrix are desirable and both were achieved by diluting the polymer solution. However, as the volume fraction of CNTs increased, the heated stretching became more challenging. Following the stretching step, hot-pressing reduced the thickness of the CNT composites by approximately 20% with a final thickness of 16±1 μm. The CNT mass fraction of the CNT/nylon 6,6 composites was determined using TGA. The differences in the mass losses (TGA curves) of nylon 6,6 and the composite sample were measured and a mass fraction of 20% was estimated. Given the densities of nylon 6,6 and CNTs at 1.14 and 2.1 g/cm3, respectively, the volume fraction of CNTs in the composites was estimated to be 15%.
Typical tensile stress-strain curves for the pristine CNT ribbon, pure nylon 6,6, and CNT/nylon 6,6 composites with increasing stretch ratios are shown in
This processing method disclosed in the present Example has produced stronger CNT/nylon composites than those reported in the literature [74-76]. The good mechanical properties of CNT composites in the present Example are rendered by long CNTs, well controlled alignment and reduced waviness. Conventional methods rely on short fiber dispersion, in which inefficient load transfer, misorientation and low volume fraction make it impossible to significantly enhance mechanical properties. In the multi-walled carbon nanotube (MWNT)/nylon composites functionalized with amine groups [77], 1 wt. % of CNTs were incorporated into the matrix by melt compounding, which resulted in limited strength and modulus improvement (up to 59.3 MPa and 3.56 GPa, respectively). Although the CNTs were chemically functionalized with the aim to accomplish good nanotube dispersion and a strong interfacial adhesion with the matrix, the properties of the composites were not improved significantly. Another work [78] on the surface modification of CNTs revealed that only a small degree of functionalization could be applied, otherwise either the damaged surface of CNTs or excessive bonding with the matrix would lead to brittle failure of the materials. Even with moderate surface modification, it is challenging to obtain exceptional mechanical properties due to low CNT volume fraction [79]. The present Example demonstrates that reducing waviness can be an important factor for making strong CNT composites.
a and
Electrical conductivities of the CNT/nylon 6,6 composites are summarized in Table 1 above. Nylon is an insulator and the electrical conductivity of the neat nylon 6,6 is approximately 2.0×10−15 S/cm [81]. The electrical conductivity of pristine CNT sheets and non-stretched composites were 520 S/cm and 140 S/cm, respectively. When the composite was stretched by 7%, the electrical conductivity was increased to 420 S/cm, which is 3 times higher than their non-stretched counterparts. This value is much higher than the electrical conductivity of composites prepared by conventional dispersion methods [82-84]. This is the result of higher CNT volume fraction and enhanced CNT alignment. These results are also consistent with reports on the effect of alignment on electrical conductivities [68, 85, 86].
In the present example, rotational winding and mechanical stretching was used for fabricating CNT/nylon 6,6 composites with good CNT alignment, high CNT volume fraction and straight nanotubes. The rotational winding created aligned CNT composites, while the local heating and stretching led to further reduction of CNT waviness. Both mechanical and electrical properties showed substantial increases (191%, 294% and 207% for tensile strength, Young's Modulus and electrical conductivity, respectively) at the stretch ratio of 7%. Macroscopically aligned CNTs and microscopically reduced waviness were demonstrated as factors that can be important for improving mechanical properties of CNT composites.
In the present Example, experimental results are presented that are associated with a method for fabricating high performance CNT composites without the need for functionalization, where the method includes spray-winding (see Example 1) and stretching. In the present Example, CNT-thermosetting polymer composites CNT/BMI composites) were fabricated. Ultra-high aspect ratio CNTs were incorporated into a high volume fraction composite with aligned and straight CNTs and a molecular level of resin integration. These structural features allowed the CNT composites to reach tensile strengths of 3.8 GPa, Young's modulus of 290 GPa, toughness of 30 J/g and electrical conductivity of 1200 S/cm. These mechanical properties may be achieved simultaneously in a CNT composite fabricated according to the present Example. The unprecedented strength exceeds that of current carbon fiber composites and is almost twice as large as previously reported non-functionalized CNT composites. The stretched, wound nanocomposites demonstrated a unique two-phase conductivity behavior under tensile strain, which has never been observed for CNT composites produced by conventional approaches.
Materials and Experimental Procedure
Aligned arrays of multiwalled carbon nanotubes (MWNTs) were grown on a Si wafer with sputtered iron catalyst by a chemical vapor deposition (CVD) method. The CNTs have an outer diameter ranging from 7 nm to 10 nm and have 5 walls. The density of the CNT was thus calculated as 1.46 g/cm3 based on a wall thickness of 0.34 nm and the theoretical density of graphite of 2.26 g/cm3. The arrays covered an area of about 20 cm2 and had a height of ˜300 as determined using optical microscopy. The CNTs (i.e., CNT ribbon) were drawn from the arrays and passed through a custom tensioning system, which includes a pair of positioning boards and two cylindrical copper rods (tensioning rods) with outer diameters of 0.5 mm. The CNT ribbon formed from the array and the CNT bundles within the array were highly aligned along the drawing direction. As the CNT ribbon passes around the stationary tensioning rods, the increased tension extends and stretches the CNT bundles. Provided that the uniform geometry of the CNT ribbon was maintained and breaking extension was not reached, the optimal contact angle between the CNT sheet and the stretching tensioning rods was controlled at approximately 150°. The aligned CNT ribbon was then taken up onto a rotating cylindrical polytetrafluoroethylene (PTFE) spool.
The polymer matrix used in the present Example was an imide-extended liquid bismaleimide (BMI, Designer Molecules Inc.) resin with a molecular weight of 5000 and functionality of 2. Dicumyperoxide (Sigma Aldrich) was added to the resin system as the initiator. BMI/toluene solutions (with BMI concentrations of 2.5, 1.0, 0.5 g/L) were agitated using a magnetic stirrer for 1 hour. As the CNT ribbon was wound on the spool, the dilute BMI solution was applied to the CNT ribbon using a fine-line air sprayer. Approximately one thousand winding revolutions at a speed of 1.1 m/min produced a unidirectional CNT/BMI composite prepreg (10 cm long, 0.5 cm wide and 10-15 μm thick). The CNT preform was then removed from the PTFE spool and heated in a vacuum oven at 90° C. for 2 hours. This temperature was found effective to remove the residual solvent but was far enough below the peroxide decomposition temperature to prevent unwanted curing. The uncured preform was then cut into strips as tensile testing coupons, hot-pressed between glass blocks coated with a PTFE release agent and cured in a vacuum oven at 180° C. for 2 hours. Hot-pressing reduced the thickness of the CNT composites by approximately 30% to a final thickness of (7˜10)±1 μm.
CNT alignment in the CNT composite was parallel to the longitudinal direction of the tensile loading. Mechanical property tests were performed using a Shimadzu EZ-S tensile tester with a crosshead speed of 0.5 mm/min and a gauge length of 6 mm at room temperature. Sample width was measured using an optical microscope (30×). The sample thickness was measured using a micrometer and the error was verified to be within 15% using thickness measurements via a scanning electron microcopy (SEM). At least five specimens were tested for each CNT/BMI composite. Resistance was measured using the four-probe method. Transmission electron microscopy (TEM) analysis of the nanotubes was performed using a JEOL 2010F microscope at an acceleration voltage of 200 kV. After tensile tests, SEM analysis of the sheets and composite fracture surface was carried out on a JEOL 6400F microscope with an acceleration voltage of 5 kV. TGA was conducted on a Perkin Elmer Pyris 1 machine in nitrogen (99.999%) with a heating rate of 10° C. per minute. A laser flash method was used to measure the room temperature thermal diffusivity of the composites. One surface of a thin flat composite sample (5 mm×25 mm in size) was exposed to a high-intensity energy pulse using a laser beam. The energy of the beam is absorbed by the sample and the temperature rise is monitored as a function of time using a thermocouple. The thermal diffusivity of the sample is obtained by analyzing the linear zone of both the amplitude decay and the phase shift. Resistance was measured using the four-probe method. In situ strain-conductivity (converted from strain-resistance results) measurement was carried out using a combination of an Agilent 34410A 6.5 digit multimeter and the Shimadzu EZ-S tensile tester. To ensure good electrical contact, both ends of the specimen were coated with copper using a magnetron sputtering facility. The coated parts of the composite specimen were then glued to copper wires using silver filled conductive epoxy. The measured resistance was recorded in situ as the specimen was loaded in tension.
The volume fraction (Vf) of CNTs in the CNT composites was calculated to be 46%. It is calculated based on a CNT mass fraction of 50%, a composite density of 1.4 g/cm3 and a resin density of 1.3 g/cm3, according to the following formula:
V
f=1−((1−mf)*ρc)/ρm)
where mf, ρc and ρm are the mass fraction of CNTs in the composite, the density of the composite and the density of the polymer matrix, respectively. The mass fraction of CNTs is determined using TGA, by subtracting the baseline CNT and BMI mass fractions from that of the composite (see
Results and Discussion
In the present Example, a method is disclosed for facile and scalable synthesis of high volume fraction (46%) CNT composites containing aligned and straight nanotubes. The present Example demonstrates the importance of reducing CNT waviness in CNT composites. As shown in
The exceptional properties of the CNT composites in the present Example may be attributed to straightening CNTs before embedding the CNTs into polymer matrix. In the present Example, a vertically aligned CNT array (see
Nanocomposites fabricated according to the rapid S-winding approach contain more straight CNTs than nanocomposites fabricated according to the R-winding approach.
With the structure improvement discussed above, the S-wound composites achieved much higher strength and stiffness than R-wound composites. Three BMI resin solution concentrations were used to maximize the CNT volume fraction, while minimizing voids. BMI solutions with concentrations of 2.5, 1.0 and 0.5 g/L were used to fabricate the composites. As shown in
Scanning electron microscopy (SEM) micrographs (
The room temperature thermal properties of CNT/BMI composites with different levels of CNT alignment are presented in Table 3 below. The in-plane thermal diffusivities of the CNT composites, α, were measured using a scanning laser heating analyzer (Ulvac-Riko, Inc., Laser PIT). The thermal conductivities of the composites, λ, were calculated using λ=αρC, where ρ is the density and C is the specific heat of the composite. It was observed that the thermal conductivities of S-wound composites are 2.5 times larger than those of R-wound composites. The S-wound composite with post straining has the highest thermal conductivity among the tested materials, 37 W/m*K, which is higher than that of unidirectional CFRP [105] and other reported CNT composites [102]. This indicates that stretching improves the alignment and straightness of CNTs and promotes a more efficient conducting path for the heat carrying wave packages (phonons). Additionally, the non-functionalized CNTs with intact structures that were used in this Example would be less likely to scatter phonons than the functionalized ones. However, the phonon mismatch at interfaces of the nanotube and matrix could result in high thermal interface resistance (Kapitza resistance). Therefore, the thermal conductivity of these composites is not as pronounced as that calculated by the rule of mixture [106].
In addition to the increase in strength, stiffness, and thermal conductivity as the nanotubes are straightened, the resultant composites reveal excellent electrical conductivities because the unidirectional pathway of electron transfer is facilitated by the improved CNT alignment and reduced waviness. Electrical conductivities by four-point measurement for the pristine CNT ribbons and resultant CNT composites are shown in
The electrical conductivity of the S-wound CNT composites was also measured in situ during the tensile testing as a function of elastic strain. The conductivity of the composites decreases proportionally with increasing tensile strain from 0 to 0.2% (as shown in
It may be tempting to assign the observed conductivity increase solely to the improvement of CNT alignment during the tensile loading. However, a closer look suggests a more complicated mechanism. When the same in-situ test was carried out for R-wound composites, we did not observe such two-phase behavior. The electrical conductivity of the R-wound composites decreased monotonically as the tensile strain increased up to 1.5%, similar to those reported in the literature [99]. In R-wound composites, CNTs are mostly aligned in the drawing direction. Improvement in straightening the CNTs under tensile strain should also produce a conductivity increase instead of the conductivity reduction that was observed in the present Example. To explain the distinct responses for the two types of composites, two possible contradictory factors may be considered that affect the conductivity change of the composites. One factor may be improved contact between CNTs and their neighbors due to contracting forces under tensile strain, and the other factor may be loss of contact and widening of intertube distances. S-wound composites contain straighter CNTs and fewer network joints. Thus, it is reasonable to infer that the effect of contact loss may be dwarfed by the CNT realignment and increased contact length between CNTs due to Poisson's effect. On the contrary, conductivity of R-wound composites is dictated by the number of contact points and distance between neighboring wavy CNTs. Any effect of realignment and contact improvement would yield to the effect of tensile-strain-induced disruption of the conductive network. Therefore, the distinct electrical conductivity behaviors of S-wound and R-wound composites may be the result of this comprehensive effect. Buldum [100] also pointed out that factors such as contact length and surface, or alignment of the atoms at the interface can dramatically alter the contact resistance between CNTs.
Finally, it is important to note the use of non-functionalized CNTs in this work. Functionalization of CNTs has been considered unavoidable for achieving high strength CNT nanocomposites. Interfacial shear strength between the CNTs and the polymer matrix can be improved through the functionalization of CNTs [101-103]. However, the near-perfect structures of nanotubes make the process challenging, as nanotubes are chemically inert and there are hardly any defects for anchoring a pendent group [104]. Functionalization usually creates defects in the nanotube lattice, which compromises their mechanical properties as the CNTs are incorporated into polymer matrices. Non-functionalized CNTs were utilized in this Example to produce high performance nanocomposites. The dilute BMI solution delivered by the sprayer penetrates into each layer of the CNT sheet (as confirmed by SEM micrographs in
In summary, in the present Example, CNT thermoset nanocomposites were produced with high strength, stiffness, toughness and electrical conductivity, as well as good thermal conductivity, without the functionalization of CNTs. The exceptional properties are derived from four morphological features: long CNTs, superior alignment and straightness of CNTs, integration of CNTs and polymer matrix at the molecular level, and high CNT volume fraction. The strength of these CNT composites has exceeded the properties of commercially available engineering fiber composites and is much higher than CNT composites reported elsewhere. A unique two-phase conductivity behavior was also observed in the CNT composites. These results provide a route for developing next-generation ultrastrong and multifunctional composite materials.
Additional Implementations
Additional implementations provided in accordance with the presently disclosed subject matter include, but are not limited to, the following:
1. A method for fabricating a carbon nanotube (CNT) composite, the method comprising:
providing an array of CNTs that are substantially aligned in a single direction;
pulling a CNT ribbon from the array by attaching the CNT ribbon to a rotating mandrel and winding the CNT ribbon on the mandrel as the mandrel rotates; and
applying a polymer solution to the CNT ribbon as the CNT ribbon is pulled from the array and wound on the mandrel to form a CNT composite laminate, wherein the polymer solution comprises a polymer and a solvent.
2. The method of implementation 1, wherein applying the polymer solution to the CNT ribbon comprises spraying the polymer solution on the CNT ribbon.
3. The method of implementation 2, wherein the polymer solution is sprayed with a compressed air sprayer.
4. The method of implementation 3, wherein the polymer solution is sprayed through an opening in a screen, wherein the screen is positioned between the mandrel and a nozzle of the sprayer.
5. The method of any of implementations 1-4, wherein the CNT ribbon is pulled from the array at a rate ranging from about 0.018 m/s to about 10 m/s.
6. The method of any of implementations 1-5, wherein the CNTs comprise multi-walled CNTs.
7. The method of any of implementations 1-5, wherein the CNTs comprise single-walled CNTs.
8. The method of any of implementations 1-7, further comprising causing the mandrel to oscillate along a horizontal axis to obtain a predetermined width associated with the CNT composite laminate.
9. The method of any of implementations 1-7, further comprising causing the CNT array to oscillate along a horizontal axis to obtain a predetermined width associated with the CNT composite laminate.
10. The method of any of implementations 1-9, further comprising removing the CNT composite laminate from the mandrel.
11. The method of implementation 10, further comprising heating the CNT composite laminate.
12. The method of implementation 11, wherein the CNT composite laminate is heated in a hot press or autoclave.
13. The method of implementation 11, wherein the CNT composite laminate is heated by a local heating source.
14. The method of implementation 13, wherein the local heating source comprises a movable heating element.
15. The method of implementation 11, wherein the polymer is a thermosetting polymer, and wherein the CNT composite laminate is heated to a temperature that is below the curing temperature of the thermosetting polymer.
16. The method of implementation 15, wherein the CNT composite laminate is heated to a temperature up to about 450° C.
17. The method of implementation 11, wherein the polymer is a thermoplastic polymer, and wherein the CNT composite laminate is heated to a temperature that is above the glass transition temperature of the thermoplastic polymer and below the melting point of the thermoplastic polymer.
18. The method of implementation 17, wherein the CNT composite laminate is heated to a temperature up to about 180° C.
19. The method of implementation 11, further comprising stretching the CNT composite laminate.
20. The method of implementation 19, wherein stretching the CNT composite laminate is carried out according to a stretch ratio ranging from greater than 0% to about 100%.
21. The method of implementation 20, wherein stretching the CNT composite laminate is carried out according to a stretch ratio ranging from greater than 0% to about 10%.
22. The method of implementation 11, further comprising stretching the CNT ribbon prior to applying the polymer solution to the CNT ribbon.
23. The method of implementation 22, wherein stretching the CNT ribbon comprises pulling the CNT ribbon into contact with at least one tensioning rod.
24. The method of any of implementations 1-23, wherein the concentration of the polymer in the polymer solution ranges from greater than 0 g/L to about 500 g/L.
25. The method of implementation 24, wherein the concentration of the polymer in the polymer solution ranges from greater than 0 g/L to about 10 g/L.
26. The method of implementation 25, wherein the concentration of the polymer in the polymer solution ranges from 0.5 g/L to about 2.5 g/L.
27. The method of any of implementations 1-26, wherein the polymer solution comprises up to about 50% polymer by weight.
28. The method of any of implementations 1-27, further comprising stretching the CNT ribbon prior to applying the polymer solution to the CNT ribbon.
29. The method of implementation 28, wherein stretching the CNT ribbon comprises pulling the CNT ribbon into contact with at least one tensioning rod.
30. The method of implementation 28, further comprising heating the CNT ribbon prior to applying the polymer solution to the CNT ribbon.
31. The method of implementation 30, wherein the CNT ribbon is heated by a local heating source.
32. The method of implementation 31, wherein the local heating source is movable along the length of the CNT ribbon.
33. The method of any of implementations 1-32, wherein the polymer is a thermosetting polymer.
34. The method of any of implementations 1-32, wherein the polymer is a thermoplastic polymer.
35. A CNT composite comprising a polymer integrated with a plurality of long, substantially straight CNTs that are highly aligned in a single direction;
wherein the CNT composite has a Young's modulus ranging from about 14 GPa to about 500 GPa; and
wherein the CNT composite has a tensile strength ranging from about 0.22 GPa to about 10 GPa.
36. The CNT composite of implementation 35, wherein the thermal conductivity ranges from about 10 W*m−1K−1 to about 200 W*m−1K−1.
37. The CNT composite of implementation 35 or 36, wherein the polymer comprises a thermosetting polymer.
38. The CNT composite of implementation 37, wherein the CNT composite has a toughness ranging from about 16 J/g to about 46 J/g.
39. The CNT composite of implementation 37, wherein the CNT composite has an electrical conductivity ranging from about 820 S/cm to about 1230 S/cm.
40. CNT composite of implementation 37, wherein the tensile strength ranges from about 1.4 GPa to about 10 GPa.
41. CNT composite of implementation 37, wherein the Young's modulus ranges from about 216 GPa to about 500 GPa.
42. CNT composite of implementation 37, wherein the CNT composite has a CNT volume fraction ranging from about 46% to about 60%.
43. CNT composite of implementation 37, wherein the CNT composite has a CNT mass fraction of about 50%.
44. The CNT composite of implementation 35 or 36, wherein the polymer comprises a thermoplastic polymer.
45. The CNT composite of implementation 44, wherein the tensile strength ranges from about 1.3 GPa to about 2.0 GPa.
46. The CNT composite of implementation 44, wherein the CNT composite has a toughness ranging from about 65 J/g to about 112 J/g.
47. The CNT composite of implementation 44, wherein the CNT composite has an electrical conductivity ranging from about 140 S/cm to about 781 S/cm.
48. The CNT composite of implementation 47, wherein the electrical conductivity ranges from about 520 S/cm to about 781 S/cm.
49. CNT composite of implementation 44, wherein the tensile strength ranges from about 0.22 GPa to about 2.0 GPa.
50. CNT composite of implementation 44, wherein the Young's modulus ranges from about 14 GPa to about 100 GPa.
51. CNT composite of implementation 44, wherein the CNT composite has a CNT mass fraction ranging from about 28% to about 78%.
52. The CNT composite of any of implementations 35-51, wherein the CNTs comprise multi-walled CNTs.
53. The CNT composite of any of implementations 35-51, wherein the CNTs comprise single-walled CNTs.
The following references are incorporated in their entireties by reference herein:
In general, terms such as “communicate” and “in . . . communication with” (for example, a first component “communicates with” or “is in communication with” a second component) are used herein to indicate a structural, functional, mechanical, electrical, thermal, signal, optical, magnetic, electromagnetic, ionic, covalent or fluidic relationship between two or more components or elements. As such, the fact that one component is said to communicate with a second component is not intended to exclude the possibility that additional components may be present between, and/or operatively associated or engaged with, the first and second components.
It will be understood that various aspects or details of the invention may be changed without departing from the scope of the invention. Furthermore, the foregoing description is for the purpose of illustration only, and not for the purpose of limitation—the invention being defined by the claims.
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/482,691, filed May 5, 2011, titled “CARBON NANOTUBE COMPOSITES AND METHODS AND APPARATUS FOR FABRICATING SAME”, the content of which is incorporated by reference herein in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61482691 | May 2011 | US |
