Crystalline and Electrical Property Improvement of Filtrated, Exfoliated Graphite Sheets by an In-Plane Current and Heating Treatment.

We report an approach to fabricate high conductivity graphite sheets based on a heat-and-current treatment of filtrated, exfoliated graphite flakes. This treatment combines heating (~ 900 °C) and in-plane electrical current flow (550 A·cm-2) to improve electrical conductivity through the reduction of crystalline defects. This process was shown to require only a 1-min treatment time, which resulted in a 2.1-fold increase in electrical conductivity (from 1088 ± 72 to 2275 ± 50 S·cm-1). Structural characterization by Raman spectroscopy and X-ray diffraction indicated that the improvement electrical conductivity originated from a 30-fold improvement in the crystallinity (Raman G/D ratio increase from 2.8 to 85.3) with no other observable structural transformations. Significantly, this treatment was found to act uniformly across a macroscopic (10 mm) sheet surface indicating it is on the development of applications, such as electrodes for energy generation and storage and electromagnetic shielding, as well as on the potential for the development of large-scale treatment technologies.

A sweet spot for highly efficient growth of vertically aligned single-walled carbon nanotube forests enabling their unique structures and properties.

We investigated the correlation between growth efficiency and structural parameters of single-walled carbon nanotube (SWCNT) forests and report the existence of a SWCNT "sweet spot" in the CNT diameter and spacing domain for highly efficient synthesis. Only within this region could SWCNTs be grown efficiently. Through the investigation of the growth rates for ∼340 CNT forests spanning diameters from 1.3 to 8.0 nm and average spacing from 5 to 80 nm, this "sweet spot" was found to exist because highly efficient growth was constrained by several mechanistic boundaries that either hindered the formation or reduced the growth rate of SWCNT forests. Specifically, with increased diameter SWCNTs transitioned to multiwalled CNTs (multiwall border), small diameter SWCNTs could only be grown at low growth rates (low efficiency border), sparse SWCNTs lacked the requirements to vertically align (lateral growth border), and high density catalysts could not be prepared (high catalyst density border). As a result, the SWCNTs synthesized within this "sweet spot" possessed a unique set of characteristics vital for the development applications, such as large diameter, long, aligned, defective, and high specific surface area.

Scalability of the Heat and Current Treatment on SWCNTs to Improve their Crystallinity and Thermal and Electrical Conductivities.

We have investigated the scalability of our post-synthesis graphitization process for single-walled carbon nanotubes (SWCNTs), which applies heat and current to SWCNTs to improve the thermal and electrical conductivities. This investigation was performed by examining the relationship between the processing conditions and the amount of treated SWCNTs. Characterization of all cases of treated SWCNTs showed the same level of improvement of ~3 times to both the thermal and electrical conductivities and that the SWCNTs remained SWCNTs, i.e., no change in diameter or wall number. These results provided evidence that the ability to improve the crystallinity of the SWCNTs was independent of the treatment amount. Further, our results showed that an increase in SWCNT amount required increased applied current density or increased in applied temperature to achieve optimum property improvement. Finally, we found a trade-off between the current density and temperature indicating that either a high current or high temperature was required to achieve the optimum process conditions. These results demonstrated that our heat and current SWCNT treatment was fundamentally scalable and applied towards larger scale (i.e., gram-level or more) amounts of SWCNT.

Current treatment of bulk single walled carbon nanotubes to heal defects without structural change for increased electrical and thermal conductivities.

By applying electrical current with heat, we succeeded in improving the graphitization of single walled carbon nanotubes (SWCNTs) without increasing the diameter and wall number. At 800 °C, 150 A cm(-2) (1150 W cm(-2)) for 1 min, we achieved a 3.2-times increase in the Raman G- to D-band ratio, a 3.1-times increase in electrical conductivity (from 25.2 to 78.1 S cm(-1)), a 3.7-times increase in thermal conductivity (from 3.5 to 12.8 W m(-1) K(-1)), and even a 1.7-times increase in dispersibility (from 1.7 to 2.9 mg L(-1)). The electrical and thermal conductivities did not only increase simultaneously, but their relative increases were identical across our experimental range that stems from defect healing without any change in diameter and wall number. In contrast, a significant increase in diameter and wall number was observed when current was not applied. These results demonstrate the importance of applying current to improve the graphitization of SWCNTs while maintaining their structure as SWCNTs.

The relationship between the growth rate and the lifetime in carbon nanotube synthesis.

We report an inverse relationship between the carbon nanotube (CNT) growth rate and the catalyst lifetime by investigating the dependence of growth kinetics for ∼330 CNT forests on the carbon feedstock, carbon concentration, and growth temperature. We found that the increased growth temperature led to increased CNT growth rate and shortened catalyst lifetime for all carbon feedstocks, following an inverse relationship of a fairly constant maximum height. For the increased carbon concentration, the carbon feedstocks fell into two groups where ethylene/butane showed an increased/decreased growth rate and a decreased/increased lifetime indicating different rate-limiting growth processes. In addition, this inverse relationship held true for different types of CNTs synthesized by various chemical vapor deposition techniques and continuously spanned a 1000-times range in both the growth rate and catalyst lifetime, indicating the generality and fundamental nature of this behavior originating from the growth mechanism of CNTs itself. These results suggest that it would be fundamentally difficult to achieve a fast growth with a long lifetime.

Quantitative assessment of the effect of purity on the properties of single wall carbon nanotubes.

We quantitatively demonstrate the importance of high purity for the application of single wall carbon nanotubes (SWCNTs), materials solely composed of one surface, by examining the effects of carbon impurities on the electrical, thermal, and mechanical properties of both as-grown SWCNT forests and processed buckypaper. While decreases in properties were expected, our results showed the extreme sensitivity of SWCNT properties to carbonaceous impurities either through scattering in the individual SWCNTs or an inhibition of the ability to form inter-SWCNT junctions. Each property showed a nonlinear decrease (as high as 40%) with the addition of low levels of carbon impurities (∼15 wt%), which demonstrates that purity is as important as the crystalline structure.

The Application of Gas Dwell Time Control for Rapid Single Wall Carbon Nanotube Forest Synthesis to Acetylene Feedstock.

One aspect of carbon nanotube (CNT) synthesis that remains an obstacle to realize industrial mass production is the growth efficiency. Many approaches have been reported to improve the efficiency, either by lengthening the catalyst lifetime or by increasing the growth rate. We investigated the applicability of dwell time and carbon flux control to optimize yield, growth rate, and catalyst lifetime of water-assisted chemical vapor deposition of single-walled carbon nanotube (SWCNT) forests using acetylene as a carbon feedstock. Our results show that although acetylene is a precursor to CNT synthesis and possesses a high reactivity, the SWCNT forest growth efficiency is highly sensitive to dwell time and carbon flux similar to ethylene. Through a systematic study spanning a wide range of dwell time and carbon flux levels, the relationship of the height, growth rate, and catalyst lifetime is found. Further, for the optimum conditions for 10 min growth, SWCNT forests with ~2500 µm height, ~350 µm/min initial growth rates and extended lifetimes could be achieved by increasing the dwell time to ~5 s, demonstrating the generality of dwell time control to highly reactive gases.

Elastomeric thermal interface materials with high through-plane thermal conductivity from carbon fiber fillers vertically aligned by electrostatic flocking.

Electrostatic flocking is applied to create an array of aligned carbon fibers from which an elastomeric thermal interface material (TIM) can be fabricated with a high through-plane thermal conductivity of 23.3 W/mK. A high thermal conductivity can be achieved with a significantly low filler level (13.2 wt%). As a result, this material retains the intrinsic properties of the matrix, i.e., elastomeric behavior.

Diameter control of single-walled carbon nanotube forests from 1.3-3.0†nm by arc plasma deposition.

We present a method to both precisely and continuously control the average diameter of single-walled carbon nanotubes in a forest ranging from 1.3 to 3.0 nm with ~1 Šresolution. The diameter control of the forest was achieved through tuning of the catalyst state (size, density, and composition) using arc plasma deposition of nanoparticles. This 1.7 nm control range and 1 Šprecision exceed the highest reports to date.

Influence of lengths of millimeter-scale single-walled carbon nanotube on electrical and mechanical properties of buckypaper.

The electrical conductivity and mechanical strength of carbon nanotube (CNT) buckypaper comprised of millimeter-scale long single-walled CNT (SWCNT) was markedly improved by the use of longer SWCNTs. A series of buckypapers, fabricated from SWCNT forests of varying heights (350, 700, 1,500 µm), showed that both the electrical conductivity (19 to 45 S/cm) and tensile strength (27 to 52 MPa) doubled. These improvements were due to improved transfer of electron and load through a reduced number of junctions for longer SWCNTs. Interestingly, no effects of forest height on the thermal diffusivity of SWCNT buckypapers were observed. Further, these findings provide evidence that the actual SWCNT length in forests is similar to the height.

The infinite possible growth ambients that support single-wall carbon nanotube forest growth.

We report the virtually infinite possible carbon feedstocks which support the highly efficient growth of single-wall carbon nanotubes (SWCNTs) using on the water-assisted chemical vapor deposition method. Our results demonstrate that diverse varieties of carbon feedstocks, in the form of hydrocarbons, spanning saturated rings (e.g. trans-deca-hydronaphthalene), saturated chains (e.g. propane), unsaturated rings (e.g. dicyclopentadiene), and unsaturated chains (e.g. ethylene) could be used as a carbon feedstocks with SWCNT forests with heights exceeding 100 ums. Further, we found that all the resultant SWCNTs possessed similar average diameter indicating that the diameter was mainly determined by the catalyst rather than the carbon feedstock within this synthetic system. A demonstration of the generality was the synthesis of a carbon nanotube forest from a highly unorthodox combination of gases where trans-decahydronaphthalene acted as the carbon feedstock and benzaldehyde acted as the growth enhancer.

Absence of an ideal single-walled carbon nanotube forest structure for thermal and electrical conductivities.

We report the fundamental dependence of thermal diffusivity and electrical conductance on the diameter and defect level for vertically aligned single-walled carbon nanotube (SWCNT) forests. By synthesizing a series of SWCNT forests with continuous control of the diameter and defect level over a wide range while holding all other structures fixed, we found an inverse and mutually exclusive relationship between the thermal diffusivity and the electrical conductance. This relationship was explained by the differences in the fundamental mechanisms governing each property and the optimum required structures. We concluded that high thermal diffusivity and electrical conductance would be extremely difficult to simultaneously achieve by a single SWCNT forest structure within current chemical vapor deposition synthetic technology, and the "ideal" SWCNT forest structure would differ depending on application.

One hundred fold increase in current carrying capacity in a carbon nanotube-copper composite.

Increased portability, versatility and ubiquity of electronics devices are a result of their progressive miniaturization, requiring current flow through narrow channels. Present-day devices operate close to the maximum current-carrying-capacity (that is, ampacity) of conductors (such as copper and gold), leading to decreased lifetime and performance, creating demand for new conductors with higher ampacity. Ampacity represents the maximum current-carrying capacity of the object that depends both on the structure and material. Here we report a carbon nanotube-copper composite exhibiting similar conductivity (2.3-4.7 × 10(5) S cm(-1)) as copper (5.8 × 10(5) S cm(-1)), but with a 100-times higher ampacity (6 × 10(8) A cm(-2)). Vacuum experiments demonstrate that carbon nanotubes suppress the primary failure pathways in copper as observed by the increased copper diffusion activation energy (~2.0 eV) in carbon nanotube-copper composite, explaining its higher ampacity. This is the only material with both high conductivity and high ampacity, making it uniquely suited for applications in microscale electronics and inverters.

Direct wall number control of carbon nanotube forests from engineered iron catalysts.

We present the direct wall number control of carbon nanotube (CNT) forests grown on engineered iron (Fe) catalysts in a catalytic chemical vapor deposition (CVD). Engineered Fe catalysts were fabricated by annealing thickness-tuned (0.8-3 nm) Fe films with small thickness variations prepared by a low-deposition-rate sputter deposition. Extensive scanning electron microcopy (SEM) characterization confirmed that vertically-aligned CNT forests were grown on Fe catalyst films with thickness larger than 1.5 nm. Detailed high-resolution transmission electron microscopy (HRTEM) and micro Raman spectroscopy analysis indicated that 75% of the CNTs grown on an Fe film with 1.5 nm mean thickness were single-walled CNTs while about 67% and 59% of CNTs grown on Fe films with 2.0 and 3.0 nm mean thickness were double-walled and triple-walled CNTs, respectively. The average wall number and outer diameter of CNT forests were found to linearly depend on the mean thickness of Fe catalyst films.

Diameter and density control of single-walled carbon nanotube forests by modulating Ostwald ripening through decoupling the catalyst formation and growth processes.

A continuous and wide range control of the diameter (1.9-3.2 nm) and density (0.03-0.11 g cm(-3) ) of single-walled carbon nanotube (SWNT) forests is demonstrated by decoupling the catalyst formation and SWNT growth processes. Specifically, by managing the catalyst formation temperature and H2 exposure, the redistribution of the Fe catalyst thin film into nanoparticles is controlled while a fixed growth condition preserved the growth yield. The diameter and density are inversely correlated, where low/high density forests would consist of large/small diameter SWNTs, which is proposed as a general rule for the structural control of SWNT forests. The catalyst formation process is modeled by considering the competing processes, Ostwald ripening, and subsurface diffusion, where the dominant mechanism is found to be Ostwald ripening. Specifically, H2 exposure increases catalyst surface energy and decreases diameter, while increased temperature leads to increased diffusion on the surface and an increase in diameter.

Unexpectedly high yield carbon nanotube synthesis from low-activity carbon feedstocks at high concentrations.

We report a new direction for highly efficient carbon nanotube (CNT) synthesis where, in place of conventional highly reactive carbon feedstocks at low concentrations, highly stable carbon feedstocks at high concentrations were shown to produce superior yields. We found that a saturated hydrocarbon that is considered to possess a low reactivity, delivered at high concentrations, could achieve an extremely high growth yield (2.5 times that when using ethylene). This result stems from the unique behavior where the CNT yield linearly increased with carbon concentration, in contrast to more reactive carbon feedstocks, where the yield peaks. We propose that the mechanisms for the growth kinetics for high- and low-reactivity carbon feedstocks are fundamentally different, where the latter benefits from a longer catalyst lifetime because of a relatively low production rate of carbon impurities.

Electron Density Modification of Single Wall Carbon Nanotubes (SWCNT) by Liquid-Phase Molecular Adsorption of Hexaiodobenzene.

Electron density of single wall carbon nanotubes (SWCNT) is effectively modified by hexaiodobenzene (HIB) molecules using liquid-phase adsorption. UV-Vis-NIR absorption spectra of the HIB-adsorbed SWCNT, especially in the NIR region, showed a disappearance of S11 transitions between the V1 valance band and the C1 conduction band of van Hove singularities which can be attributed to the effective charge transfer between HIB and the SWCNT. The adsorption of HIB also caused significant peak-shifts (lower frequency shift around 170 cm-1 and higher shift around 186 cm­1) and an intensity change (around 100-150 cm-1 and 270-290 cm-1) in the radial breathing mode of Raman spectra. The charge transfer from SWCNT to HIB was further confirmed by the change in the C1s peak of X-ray photoelectron spectrum, revealing the oxidation of carbon in SWCNT upon HIB adsorption.

A Fundamental Limitation of Small Diameter Single-Walled Carbon Nanotube Synthesis-A Scaling Rule of the Carbon Nanotube Yield with Catalyst Volume.

Understanding the fundamental mechanisms and limiting processes of the growth of single-walled carbon nanotube (SWCNT) would serve as a guide to achieve further control on structural parameters of SWCNT. In this paper, we have studied the growth kinetics of a series of SWCNT forests continuously spanning a wide range of diameters (1.9-3.2 nm), and have revealed an additional fundamental growth limiting process where the mass of the individual SWCNT is determined by the individual catalyst volume. Calculation of the conversion rate of carbon atoms into CNTs per Fe atom is 2 × 10² atoms per second. This rate limiting process provides an important understanding where the larger diameter SWCNT would grow faster, and thus be more suited for mass production.

Alignment control of carbon nanotube forest from random to nearly perfectly aligned by utilizing the crowding effect.

Alignment represents an important structural parameter of carbon nanotubes (CNTs) owing to their exceptionally high aspect ratio, one-dimensional property. In this paper, we demonstrate a general approach to control the alignment of few-walled CNT forests from nearly random to nearly ideally aligned by tailoring the density of active catalysts at the catalyst formation stage, which can be experimentally achieved by controlling the CNT forest mass density. Experimentally, we found that the catalyst density and the degree of alignment were inseparably linked because of a crowding effect from neighboring CNTs, that is, the increasing confinement of CNTs with increased density. Therefore, the CNT density governed the degree of alignment, which increased monotonically with the density. This relationship, in turn, allowed the precise control of the alignment through control of the mass density. To understand this behavior further, we developed a simple, first-order model based on the flexural modulus of the CNTs that could quantitatively describe the relationship between the degree of alignment (HOF) and carbon nanotube spacing (crowding effect) of any type of CNTs.

Mechanically durable and highly conductive elastomeric composites from long single-walled carbon nanotubes mimicking the chain structure of polymers.

By using long single-walled carbon nanotubes (SWNTs) as a filler possessing the highest aspect ratio and small diameter, we mimicked the chain structure of polymers in the matrix and realized a highly conductive elastomeric composite (30 S/cm) with an excellent mechanical durability (4500 strain cycles until failure), far superior to any other reported conductive elastomers. This exceptional mechanical durability was explained by the ability of long and traversing SWNTs to deform in concert with the elastomer with minimum stress concentration at their interfaces. The conductivity was sufficient to operate many active electronics components, and thus this material would be useful for practical stretchable electronic devices.