Research Summary

Carbon Nanotubes

Improving the Heat Transfer of Nanouids and Nanolubricants with Carbon Nanotubes
F.D.S. Marquis and L.P.F. Chibante
Low thermal conductivity is a primary limitation in the development of energyefcient heat transfer uids required in many industrial and commercial applications. To overcome this limitation, a new class of heat transfer uids was developed by suspending nanoparticles and carbon nanotubes in these uids. The resulting heat transfer nanouids and nanolubricants possess signicantly higher thermal conductivity compared to unlled liquids. Three types of heat transfer nanouids and nanolubricants, each containing controlled fractions of single-wall carbon nanotubes, multiwall carbon nanotubes, vapor grown carbon bers, and amorphous carbon have been developed for multifunctional applications, based on their enhanced heat transfer and lubricity properties. INTRODUCTION Despite considerable prior R&D efforts focused on industrial provisions, major improvements in uid cooling capabilities have been held back because of a fundamental limit in the heat transTable I. Thermal Conductivities of Various Solids and Liquids Thermal Conductivity (W/m-K)

Material Carbon

Form

Nanotubes 1,8002,000 Diamond 2,300 Graphite 110190 Fullerenes (lm) 0.4 Metallic Solids Silver 429 Copper 401 Aluminum 237 Nickel 158 Non-Metallic Silicon 148 Solids Alumina 40 Metallic Liquids Sodium 72.3 @644K Others Water 0.613 Ethylene Glycol 0.253 Engine Oil 0.145

fer properties of conventional uids. This limitation is associated with the relatively low thermal conductivity of the heat transfer uids (HTFs). However, solid materials typically have orders-of-magnitude larger thermal conductivity than commonly used liquids. For example, the thermal conductivity of carbon nanotubes at room temperature is over 3,000 times greater than that of water and over 10,000 times greater than that of engine oil. This large difference in thermal conductivity between liquids and carbon nanotubes is shown in Table I as compared to a variety of materials. Therefore, fluids containing suspended carbon nanotubes are expected to exhibit signicantly higher thermal conductivity relative to conventional HTFs. Since Maxwells theoretical work,1 other theoretical and experimental efforts have been conducted to examine the effect of particle additions on the thermal conductivity of HTFs. However, all previous studies of the thermal conductivity of suspensions have been conned to those containing millimeter- or micrometer-sized particles. Maxwells model shows that the effective thermal conductivity of liquid suspensions containing spherical particles increases with the volume fraction of the solid particles. In addition, it is also known that the conductivity of the liquids increases with the surface area-to-volume ratio of the added particles. The application of Hamilton and Crossers model,2 in addition to recent calculations,3 predict that for constant particle size, the thermal conductivity of a suspension containing large particles is more than doubled by decreasing the sphericity of the particles from a value of 1.0 to 0.3. The sphericity is dened as the ratio of the surface area of a particle with a perfectly spherical shape to

that of a non-spherical particle with the same volume. These results suggest that a dramatic improvement in the effective thermal conductivity is expected by decreasing the particle size in a solution compared to the incremental improvement that can be obtained by altering the shape of large particles since the surface-area-tovolume ratio is 1,000 times larger for particles with a 10 nm diameter than that of 10 m diameter particles. Consequently, nanouids are expected to have superior heat transfer properties compared to conventional uids and uids containing micrometer-sized particle additions. Also, heat transfer nanouids (HTNFs) with carbon nanotubes are expected to possess even better heat transfer properties due to the nonspherical shape of the carbon nanotubes. The aspect ratio (length/diameter) of carbon nanotubes is typically between 103 and 105. Recent work at Argonne National Laboratory has demonstrated that nanouids consisting of copper, CuO, or Al2O3 nanoparticles dispersed in water or eth-

2,250 2,000 $2,000 1,750 1,500 1,250 $1,000 1,000 750 $500 $500 500 $400 $200 250 $20 0 1997 1998 1999 2000 2001/ 2003 2004 2002 Year

Figure 1. The price evolution of SWNTs demonstrating a continued decrease in price that results from increase in SWNT yield and higher volume demand.

Cost per Gram($)

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ylene glycol exhibit enhanced thermal conductivity compared to that of nonparticle-containing uids.46 An increase in thermal conductivity of ~20% was observed for 4 vol.% CuO nanoparticles with an average diameter of 35 nm dispersed in ethylene glycol. Similar behavior was observed by Masuda and co-workers in another study of Al2O3 nanoparticles dispersed in water.7 Larger improvements in effective thermal conductivity were obtained for a nanouid containing smaller-sized and higherconductivity copper nanoparticles.6 In recent work Choi and co-workers demonstrated anomalous enhancements in the thermal conductivity due to multiwall nanotube (MWNT) additions to a synthetic poly (-olen) oil.8 The thermal conductivity was seen to increase with MWNT additions at loads up to 1% in volume. These results exceed those based on the theoretical predictions of Hamilton and Crosser, which predict no effect of particle size and a weak effect of particle intrinsic conductivity on uid effective thermal conductivity. In this work Choi and co-workers did not consider the uid properties, such as viscosity, carbon nanotube dispersion, and nanotube settling time and stability. Carbon nanotubes have generated great interest since they were discovered in 1991.9 The thermal conductivity of unroped single-wall carbon nanotubes (SWNTs) have been theoretically calculated to be above 2,000 W/mK and the thermal conductivity of SWNT ropes was measured at 200 W/mK, consistent with the values measured in Buckypaper.10,11 This means that the potential for contribution to the enhancement of the thermal conductivity of heat transfer nanouids is much higher with SWNTs. However, carbon nanotubes are highly anisotropic and the transverse thermal conductivity is expected to be as low as that of fullerenes (0.4 W/mK). In principle, carbon bers, SWNTs, MWNTs, and vapor-grown carbon bers (VGCFs) all have high thermal conductivity in the axial direction. Note also that all of them except the carbon bers are discontinuous. Based on the thermal conductivity of carbon bers and carbon composites, thermal conductivity of these materials is expected to be rather high for loads up to 25%. While the thermal conductivity of individual SWNTs
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EXPERIMENTAL PROCEDURES
Nanomaterials Single-wall carbon nanotubes (SWNTs) of many grades and characteristics were produced by the HiPco facility of Carbon Nanotechnologies, Inc. The metal catalyst content and the amorphous carbon content varied considerably with the batch used, as presented under results and discussion. Multi-wall carbon nanotubes (MWNTs) were produced by the vacuum-arc method by the NanoTex Corporation (NTC). In addition, NTC produced SWNT soot for this research. Multi-wall carbon nanotubes were also produced by the chemical-vapor deposition (CVD) method at Clemson University under the direction of A. Rao and by the microwave CVD method at the University of California, San Diego, under the direction of S. Jin. Thermal Measurements of Nanouids Hot-disk thermal conductivity testing apparatus was utilized which allowed the unique feature of testing uids with a home-built testing cell. The commercial instrument is a transient plane-source method that is rapid, exhibits good precision, and is typically within 3% of known standards. The essential feature of the apparatus is that the heat source/probe is sandwiched within the sample and the temporal thermal prole is monitored, as shown in Figure A. In this study, the sensor was placed in a sealed, insulated uid cell. The technique allows the direct measurement of thermal conductivity without previous knowledge of specic heat or density. The Thermal Haake thermal conductivity (TC) measuring system was also used to evaluate the thermal conductivity of a number of the heat transfer nanouids (HTNFs). This system is similar to a transient hot wire system but works with an embedded probe rather than an exposed wire. The system is easy to use and the entire sample can, in most cases, be fully recovered. The values are consistent with those measured by the hot-disc system. Thermal Gravimetric Analysis Thermal gravimetric analysis (TGA) of the SWNTs was performed with a TA instruments SDT-TGA apparatus and opened platinum pans using an air ow at about 100 cc using 3 mg of material. The material was weighed in an analytical balance that used up to four decimal places. This data was necessary to determine the rate of decomposition as a function of weight and temperature in an inert gas such as argon and in an oxidizing environment using air. The run in argon yields information on thermal degradation characteristics, while the air runs provide information on the effect of oxidation on thermal degradation properties. Fourier Transform Infrared Spectroscopy In this study, the various HTNFs were evaluated by Fourier transform infrared spectroscopy (FTIR). Droplets of the various uids are placed on lter paper for vacuum evacuation and the residue is removed and placed on test coupons for analysis. Scans were made of each sample over a similar spectral range. The base uids are evaluated as well as the starting nanotubes in solutions that will not produce peaks in the spectral range of interest. The goals of this study are to identify the surface species on the starting carbon nanotubes and to identify their interactions and inuence on the various heat transfer uids. Raman Spectroscopy Raman spectroscopy was carried out as a characterization method in the study of carbon nanotubes using a Renishaw Micro Raman spectrometer with a 780 nm laser with a resolution of 2 cm1. The objective used was 50 with a 0.55 m aperture. Several scans were run for each sample. The various types (SWNT or MWNTs) are easily distinguished from one another and even differences in the various types of SWNTs, including effects from functionalization, can be seen via Raman. Typically used in carbon nanotube analysis are the radial breathing modes between 200 cm and 300 cm1, the disorder mode that occurs at ~1,300 cm1 giving information about defects, and the tangential stretching mode indicative of sp2 carbon bonding at approximately 1,590 cm1. From the Raman, one can about learn differences from the puried form, including cross-linking, that can occur within the ropes. Functionalizations change the Raman spectra, introducing a different state for the nanotubes when compared to the pure nanotube condition.
Figure A. The hot disc heating element/sensorsample conguration.

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500 nm Figure 2. SWNTs are shown with ~20 wt.% SWNTs (1.2 nm average, micrometer length) with ~20 wt.% amorphous carbon, 50 wt.% graphitic particles, 10 wt.% residual catalyst. Degree of entanglement and interconnection is moderate.

1 m Figure 3. MWNTs are shown with 4050 wt.% MWNTs (1015 nm diameter, micrometer length), 5060 wt.% graphitic particles, no residual catalyst. Degree of roping and interconnection is minimal.

expected gains from these nanouids are cost effectiveness and improved thermal transfer properties, minimized clogging, long-term chemical stability, and longterm effective performance life. In this article, a series of HTNFs and lubricants are processed based on water, water/ethylene glycol, diesel and commercial oils to identify the increase in thermal conductivity of the uid with nanotube concentration and mixing procedure. These nanouids are compared to the HTNFs produced by Choi et al. and to similar uids mixed with corresponding properties. The uids have been characterized based on starting nanotube conditions, conditions of the nanotubes after mixing, and stability (settling time and thermal degradation) of the nanotubes in the oils. In the end, for the use of these oils and diesel oils in engines, the HTFs play a number of important roles that could affect the thermal and mechanical efciency of the engine. The HTFs tend to remove unwanted heat from the engines while providing lubricity and temperature control. ANTICIPATED BENEFITS OF HTNFs The anticipated benefits of these nanomaterials are several-fold. Since SWNTs have high thermal conductivity (1,8002,000 W/m-K) they will enhance uids for heat transfer use. The addition of carbon nanotubes together with their inherent miscibility in hydrocarbons, such as engine oils, will reduce the potential for severe clogging in cooling systems. Because of the relative softness of nanotubes, the abrasion and erosion of the cooling circuit are both expected to be greatly reduced. Further, nanotubes are expected to possess antioxidant properties. Many degradation mechanisms involve the generation of free radicals and subsequent propagation to degrade the uid. Nanotubes may be efcient free-radical scavengers and hence hinder these pathways. This would increase uid temperature performance limits and/or prolong HTF lifetime. Associated with these antioxidant properties, derivatized nanotubes may have antibacterial and antiviral properties. Dermatological and animal studies done to date generally agree that these nanocarbons are nontoxic.

This is imperative for environmentally benign use of HTFs. Carbon nanotubes are oxidatively stable up to 550C and chemically stable to over 1,000C. Under excessive thermal conditions, the nanotubes will not degrade in the uid and should help protect the nanouid. In addition, the availability of improved HTFs for automotive cooling will be an incentive for the auto industry to design smaller engines by taking advantage of the improved cooling response of the engine thermal cycle. This would have benecial implications both on the engine fuel efciency and reduced size and operation of cooling components (i.e., pumps, lters, and lines). The potential economic benets of commercializing nanofluids include cost reduction and energy savings due to the ability to manufacture smaller and lighter heat exchange systems, reduced heat transfer uid inventories, and lower pumping energies required for existing heat exchange systems. The impact of nanotube-laden nanouids is signicant, considering that improved heat transfer properties are vital to a number of multibillion-dollar industries both in the

is expected to be very high, Buckypaper has been measured to be only 200 W/mK, consistent with the thermal conductivity of nanoropes. Buckypaper is a dense lm of SWNT ropes and the thermal conduction is likely limited by poor contact, the presence of impurities, and potential mechanisms that lead to scattering rather than transport. Another possible explanation has to do with the control of thermal scattering mechanisms and this may be one of the most important issues to engineers so that transport is optimized and scattering is reduced. Two of the major challenges that need to be overcome for the production of effective heat transfer nanouids and nanolubricants are carbon nanotube dispersion and carbon nanotube stability. Recently various investigators have studied methods for carbon nanotube dispersion1216 in uids and other media. The combination of robust carbon nanoparticles with superior thermal conductivity and well-established chemical stability to develop a new class of very novel, unique, and efcient nanouids with much lower additive concentrations is the focus of this research. Some of the
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500 nm Figure 4. HiPco raw uff: The openness of the entangled SWNT ropes can be seen. These SWNTs appear highly interconnected, probably due to the van der Waals attractions.

500 nm Figure 5. HiPco puried uff: ~70 wt.% SWNT (0.81.5 nm diameter, micrometer length), 30 wt.% residual catalyst (Fe). >95% SWNT, <1 wt.% residual catalyst. Degree of roping and interconnection is very high.

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RESULTS AND DISCUSSION Carbon Nanomaterials Single-walled carbon nanotubes, MWNTs, VGCFs, and carbon black systems were manufactured for nanouid production and evaluation. These carbon nanomaterials are characterized to provide an understanding of the relationships between the type and the characteristics of these materials and the performance of the nanouids containing them. Scanning and Transmission Electron Microscopy Scanning-electron microscopy (SEM) and transmission-electron microscopy (TEM) are some of the best methods for observing and characterizing carbon nanotubes. While SEM can see VGCFs, MWNTs, and SWNT ropes with high resolution, TEM is one of a few methods where single unroped SWNTs can be observed. Carbon nanotubes are conducting and semiconducting materials but may be coated to enhance certain features when they occur in low concentrations. Figures 2 through 11 show SEM and TEM micrographs of various carbon nanomaterials that were used as nano-additives in this study. Not shown are SWNT pearls and various other forms of SWNTs where further preparation was used. The gures also note the general composition of the various nanomaterials used. Typical types of contamination include amorphous carbon and metal catalyst. The degree of entanglement is a function of the processing mode and the subsequent preparation by the manufacturer. Care has to be taken when coating CNTs since the coating material only sees a portion of the nanotubes and they may curl up during the process and give a different appearance due to being coated only on one side. The coatings can enlarge the diameter and one might estimate the size (rope size) to be larger than what it actually is. Typically the nanomaterials used in this investigation had the following characteristics: SWNTs, unroped, 11.4 nm in diameter; SWNTs, roped, 1050 nm; MWNTs, typically 1050 nm, unroped; A. Raos material from Clemson Univeristy, 20300 nm from the SEM pictures: and VGCFs,

2 m Figure 6. Multi-walled nanotubes produced by CVD and taken from the source substrate; open, entangled, and swirling morphology; >80 wt.% MWNT (1020 nm diameter, 10 m length), 15% amorphous carbon, 5 wt.% catalyst; low defect rate; degree of roping and interconnection is moderate-high.

500 nm Figure 7. Multi-walled nanotube taken from the source substrate: variation in nanotube size and the openness to the agglomerates (not highly entangled). Some small particles can be seen distributed on the nanotubes.

30200 nm and on average 100150 nm. The current data shows that SWNT lengths are 0.310 m (before cutting), MWNTs are 1100 m, and VGCFs are 1100 m. Typical results are presented in Figures 2 to 11. These results show that VGCFs have one or two orders of magnitude more surface area than conventional carbon bers, MWNTs and SWNT ropes have three orders of magnitude more surface area, and unroped SWNTs have four orders of magnitude more surface area than conventional bers. This means that VGCFs, MWNTs, and roped SWNTs in a uid may produce what is still considered to be a solid percolated network while the unroped SWNTs have a chance to take on similar properties to the uid and, therefore, may have thermal conduction by other means. In addition, SWNTs are molecular and on a similar scale to polymers and uid molecules. This means that two distinct paths exist for engineering the nanouid: produce a mixture where the nanotubes are added in order to change the thermal conductivity via the rule of mixtures starting conditions, and produce a hybrid uid where

military and in the domestic sectors. To further reiterate the potential economic benets of carbon nanotube nanouid technology, the example of the ethlyene-glycol-based nanouids can be used. In the United States alone, more than $80 billion are spent annually on energy for air conditioning and refrigeration equipment. Increasing the efciency of this equipment by 25% could result in annual energy savings of $20 billion. To make this possible, the price of the carbon nanotubes must be established below a certain threshold. This price is interconnected with demand and demand will depend on how the technological challenges are answered. Figure 1 shows the price evolution of SWNTs, demonstrating a continued decrease in price that results from increasing SWNT yield and higher volume demand. See the sidebar for experimental procedures.
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0.5 m Figure 8. A TEM of MWNTs substrate. Note the variation in nanotube size and the open nature of the network.

500 nm Figure 9. An SEM micrograph of asreceived MWNTs taken from the wall of a production vessel. Some nanotubes are very large. Note the small particles that are impurities distributed on the nanotubes.The material is not in a puried condition.

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Raman Spectroscopy Several Raman spectra were acquired for typical samples of the following nanomaterials: amorphous carbon, MWNTs (wall), MWNTs (substrates), SWNTs in raw uff, SWNT puried bucky pearls, and SWNT functionalized. As the nanotubes are functionalized, the ~1,300 cm1 peak changes in height since this D-band peak is related to the covalent character of the nanotubes and therefore covalent bonding is shown here (this is the disorder peak). The peak increase, depending on the type of functionalization, can be related to an increase in number of sp3hybridized carbons and this can be taken as a degree of functionalization. A signicant change in the Raman spectra occurs when nanotubes are functionalized by fluorination. For uorination, the typical nanotube peaks at 200263 cm1 and ~1,590 cm1 tend to decrease with the uorination while the ~1,300 cm1 peak and ~1,590 cm1 increases. The spectra obtained show that when nanotubes get crossed-linked, the small peak on the side of the largest peak (~1,590 cm1) tends to go away and the 1,300 cm1 peak also changes. In general, the sizes of nanotubes have a higher average diameter for the arch grown and laser-ablated than do the HiPco nanotubes manufactured by Carbon Nanotechnologies, Inc. The Raman spectra give information about functionalization but not rope size. This is shown in the Raman spectrum for uorinated nanotubes. Carbon Nanotube Functionalization Carbon nanotubes are carbon molecules that have a hollow core and are relatively defect free. This carbon-carbon bonding and lack of defects makes nanotubes inert in many acids and even in a number of strong acids. The strong bonding and lack of defects add to the nanotube having high strength and good electrical and thermal properties. Much of the authors research on nanotubes in uids is directed toward dispersing nanotubes at levels where they are soluble in the uid, in order that these uids will be practically effective. To this end, the quantities of nanotubes that go in solution in a uid have been limited to milligrams per liter. There are several cases where

0.5 m Figure 10. VGCFs > 99 wt.% MWNT (50 nm-submicrometer diameters, tens of micrometers in length), high defect rate. Degree of roping and interconnection is small.

500 nm Figure 11. Carbon black N234 un-pelletized: >99% carbon particles (3040 nm primary particles assembled in ~300 nm aggregates), ppm levels of metals. Degree of roping and interconnection: minimal.

the dispersion of nanotubes in uids requires higher quantities; these studies are directed toward achieving high dispersion of nanotube suspensions in uids such as starting uids for dispersing nanotubes in thermal plastics and epoxies and nanotube/ceramic powder slurries for producing nanotube-reinforced ceramic nanocomposites. Some routes seem sophisticated but to produce commercially viable heat transfer nanouids and nanolubricants it is important to use low-cost processing rst. Since the need for driving up the nanotube content is so important it has been determined that one way to accomplish this is by functionalizion of the nanotubes. Functionalization is the process of attaching radicals and functional groups to the carbon nanotube. Functionalization provides an efcient approach to the unroping of nanotube bundles and improving their ability to disperse in organic matrixes and uids (e.g., motor oils, coolants, etc.). Sidewall covalent derivatization of SWNTs with uorine, alkyl, and aryl groups and with the side-chains that are terminated with the hydroxyl, carboxyl, or ester-terminated

the nanotubes are integrated into the uid to take on more uid-like properties (produce a more uid-like system). The second approach is expected to generate the best performance with the highest degree of effectiveness. The SEM was used to characterize the nanotube rope size, entanglement, type of entanglement, and rope aws. The SEM was also used to look for contamination type and distribution and for nanotube ends, but with SWNTs, the ends are almost never visible (a product of van der Waals bonding). The ends of MWNTs and VGCFs can be seen by SEM and they tend to be open when large enough to see. During this investigation, SWNTs were found to differ considerably from each other, based on how they are produced. These conditions impacted how well they could be processed and how thermally conducting they were. One of the advantages of MWNTs is not being in rope form, and thus being easier to disperse. It is likely, though, that they may tangle again in dynamic use (owing conditions) and cause clogging at higher loads, although this was not observed up to 0.5% volume load.
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Figure 12. A TEM of the as-produced HiPCo SWNTs bundled into ropes and amorphous carbon and metal catalysts adhering to the surface of the CNT ropes. This has a signicant effect on dispersion.

Figure 13. A TEM of puried, HiPCo ESD SWNTs showing the multi-rope morphology. The striations running in the longitudinal direction of the ropes are individual SWNTs. The average diameter of the individual tubes is 1.5 nm.

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200 mm Figure 14. A TEM of partial exfoliation of multi-ropes of SWNTs showing the split of 7 into 3+3+1.

moieties offer new opportunities in the fabrication of nanotube-based nanouids for heat transfer and lubrication management. By using chemical methods, functional groups can be tailored and attached to the nanotubes to enhance the dispersion of the functionalized SWNTs in the specic type of HTF. The side-wall functionalization routes used involve two major strategies: uorination of SWNTs to yield uoronanotubes (F-SWNTs) which can be further derivatized when uorine is substituted by a number of nucleophiles, RLi, Grignard reagents, Li3N followed by quenching, diamines and aminoacids; and the addition of organic free radicals generated by thermolysis of acyl peroxides. In some cases the functionalization is a noncovalent processing that includes wrapping. The chemistry of the tube is not changed but the chemistry attached to the tube changes the nature of the nanotube. A number of approaches to functionalizing nanotubes were used, and some of them are of proprietary nature. Initially, nanotubes were end functionalized. This occurred when they were puried and the ends were opened up during the purication process and the acids used left COOH groups attached to the open ends. The open ends had free carbon bonds and a COOH easily occurred. Other functionalizations were directed toward the side walls. Fluorination places uorine atoms bonded to the sidewalls of the nanotubes and helps to separate the individual nanotubes from the rope (bundle). This research used uorination as a rst step in achieving the right functionalization for the application. The F-SWNTs are in smaller bundles and in many cases are single tubes separated out from the ropes. Additional functionalization can occur to the F-SWNTs just like for the roped unuorinated nanotubes. Since
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oils are hydrocarbon-based, the various bonding methods mentioned here were effective for the HTNFs. A quantitative evaluation is under way of the chemistry needed to achieve well-dispersed nanotubes in the oils and water/ethylene glycol mixtures. The functionalization types identied previously are useful but do not always give individual nanotubes in the optimal condition. In some cases the nanotubes can easily be functionalized but will remain as functionalized ropes, which limits their effectiveness. In other cases, a form of wrapping was used with or without functionalization. Fluorination is one of the main chemical tools in the preparation of the side-wall functionalized SWNTs that have already been successfully applied for the fabrication and manufacturing of the SWNT-reinforced composites and ceramics. The second strategy is based on the use of inexpensive peroxides applied as polymerization initiators in industry. The resulting oxidized tubes were then dispersed in BP166 and mineral oils using simple homogenization. An ashless succinimide dispersant and oleylamine (a surfactant suitable for

hydrocarbon media) were used to aid in dispersing the SWNTs in oil. This is covalent functionalization and is currently in progress. In addition, the role of covalent modication of SWNTs is being explored to increase dispersion of SWNTs in oil. Some of the functionalizations are: attaching carboxylic acids to the ends of SWNTs via oxidation; uorination of oxidized tubes; uorination of nonoxidized tubes; carboxylation at the walls of the SWNTs; hydroxilated SWNTs; aminated SWNTs; and esteried SWNTs using two mechanisms. The series of functionalized SWNTs prepared according to these methods is described in a number of pending patent applications. This research shows that the preparation of the functionalized nanotubes can be easily scaled up to meet the quantity demand for nanouid applications. Cutting of SWNT Ropes and MWNTs and Exfoliation of SWNT Ropes One of the major obstacles in the dispersion of SWNTs is the inability to resolve the entanglements of multi-ropes

Figure 15. The intensityweighted nanop a r t i c l e s i ze distribution for 0.05% MWNTs in water/ethylene glycol (50/50).

Figure 16. The intensityweighted particle size dist r i bu t i o n fo r 0.01% ESD CNI SWNTs in water/ethylene glycol (50/50).

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450 400 350 300 Absorbance 250 200 150 100 50 0 50 4,000 3,500 3,000 2,500 2,000 Wavenumbers (cm-1) 1,500 1,000 500

Figure 17. The FTIR spectrum of a 15W-40 oil in the as-received condition. Samples that were sonicated show similar FTIR results.

35 30 25 Absorbance 20 15 10 5 0 4,000 3,500 3,000 2,500 2,000 Wavenumbers (cm-1) 1,500 1,000 500

Figure 18. The FTIR spectrum of a sample with 1% raw HiPco SWNTs. Notice changes at ~2,300 cm-1 and <1,800 cm-1 show the inuence of the SWNTs.

100 90 80 70 Absorbance 60 50 40 30 20 10 0 2,500 2,000 1,500 3,000 500 Wavenumbers (cm-1) Figure 19. The FTIR spectrum of a sample with 1% Bucky Pearls processed with sonication and homogenization. Features at ~2,300 and <1,800 show the inuence of the SWNTs. 4,000 3,500 3,000

into single ropes and the inability to exfoliate the single ropes into single SWNTs. The entanglement of the multi-ropes is often magnied during purication of the as-produced SWNTs as shown in Figures 4 and 5. One of the most promising methods for exfoliating these ropes is cutting. Cut (shortened) nanotubes, both bare and functionalized, are of further interest for these applications. This process can both contribute to the exfoliation of the ropes and help retard the process of re-agglomeration by shortening the nanotubes. The ropes and the nanotubes were cut either physically or chemically, leaving them open on the ends for end-cap functionalization. Chemical and physical means are used to cut the multi-ropes and the nanotubes at the ends, shorten them over time, and exfoliate the ropes by penetration between individual tubes in bundles. One process of exfoliation is achieved through complex and proprietary processing used in conjunction with sonication to shorten the nanotubes from the end caps inward. These sites at the end of nanotubes, once opened up, are inhabited by a COOH group until replaced with a nal group used to functionalize the nanotubes, leading to higher solubility in a particular solvent. This is conrmed by the data presented in Figures 12 to 14. This data is in very good agreement with the in-situ particle size distribution observed in typical nanouids as shown in Figures 15 and 16. Figures 15 and 16 show that the agglomerate size for the same base nanouid is much smaller for MWNTs than for SWNTs. This is consistent with a higher dispersibility of MWNTs due to their unroped condition. Design and Manufacture of Nanomaterials Three types of advanced nanomaterials have been developed, manufactured, and tested. They consisted of both uid and grease materials based on water, water/ethylene glycol mixtures, antifreeze, and mineral and synthetic oils. The rst type of nanomaterials, Type 1, is heat transfer nanouids or nanocoolants based on three base uids: water, water/ethylene glycol mixtures, and water/antifreeze mixtures. The primary capability of these nanomaterials is to transfer heat due to their higher thermal
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conductivity, modied heat transfer coefcient, and heat capacity, which are the main design parameters. Typical applications of this type of nanomaterials are radiator coolants for all types of vehicles both military and domestic, air conditioning systems, cutting uids, quenching uids, and many others based on heat transfer capabilities. In radiator coolants, an anticipated benet is the downsizing of the entire coolant system. Type 2 nanomaterials are nanolubricant uids based on three types of base fluids: commercial 15W-40 oil, BP Amoco DS-166 Durecene oil (synthetic poly-- olen oil), and military and U.S. Department of Defense specicationbased uids. The primary capabilities of this type of nanomaterials are: heat transfer due to the control of the design parameters described previously and higher lubricicity due to a lower friction coefcient. Typical applications are engine coolants for all types of engines both military and domestic. The anticipated benets are: downsizing engine blocks, redesign of engine systems, higher durability of engine components, shorter engine downtime, and lower operation costs. Type 3 nanomaterials are nanolubricant greases based on uids and greases: BP 166 Durecene oil and military specications-based greases. The primary capabilities of these nanomaterials are also twofold, as described previously. However, in this case the carbon nanotube load is much higher typically, between 1 vol.% and 6 vol.%. The carbon nanotube load in the previous two types of nanomaterials is typically between 0.05 vol.% and 0.5 vol.%. Applications of the nanolubricant greases include high-stress contact gears for rotary craft. In this case, the anticipated benets are higher torque transmitted, less heat generated, more heat dissipated, longer ight duration, and longer life of the metallic components. This article presents results from the rst generation of nanomaterials (heat transfer nanouids and nanolubricants) only. Proprietary data including pending patent applications is not included. Production of Nanouids in Synthetic and Mineral Oils Nanouids were produced in two oil systems: a commercial diesel oil
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(Shell Rotella 15W-40) and synthetic poly--olen oil with 5 wt.% succinimide dispersant. The commercial oil was initially tested to determine the direct applicability of nanotube additives, with the synthetic oil providing a model system to gain a fundamental understanding of nanouids. The mixing was performed by various schemes of high-shear homogenization with sonication assistance. Enhanced dispersion by preliminary dispersal in volatile solvents such as toluene or chloroform, which act as compatibilizers for nanotubes with the oil, was also carried out. Various protocols were evaluated as well as sample preparation of the nanotubes (drying, degassing, pretreatment with dispersant, and various addition sequence methods). The total mixing energy was always monitored. As a screening tool to help evaluate architectural thermal property changes as a function of nanotube type, mixing energy, loading, and various processing methods, the thermal conductivity testing was used. More than 100 uids were designed and manufactured in laboratory amounts of approximately 100 mL each. In addition, bulk quantities of selected HTNFs were manufactured for advanced testing. For dynamic ow conditions and in-situ engine testing, increased sample distribution, and as deliverables, larger volumes (500 mL to 1 L) of preferred nanouids in synthetic oil base were prepared. One of the preferred sets was designed under the following specications: High thermal conductivity (TC) SWNT nanouid which was still uid at room temperature (RT) High TC SWNT nanogrease which was paste-like at RT High TC MWNT nanouid which was still uid at RT High TC MWNT nanogrease which was paste-like at RT Based on these specications the following sample set was manufactured with the following compositions: SWNT nanouid1.0 vol.% HiPco puried SWNT nanogrease2.0 vol.% HiPco raw MWNT nanouid3.0 vol.% VGCF annealed High TC MWNT nanogrease

1.50 1.40 1.30 1.20 1.10 1.00 0.0

TC Ratio

0.2

0.4 0.6 0.8 Nanotube (vol. %) 1.0 1.2

Figure 20.The hot-disc thermal conductivity ratio of SWNTs in 15W-40 oil as a function of loading.

1.50 1.40 TC Ratio 1.30 1.20 1.10 1.00 0

Non Vortexed Vortexed Poly. (Vortexed) Poly. (Non Vortexed)

y = 0.3446x2 + 0.1022x + 0.9919 R2 = 0.9934

y = 0.1167x + 0.1288x + 0.9976 R2 = 0.9979 0.2 0.4 0.6 0.8 1 1.2 NT Loading (vol.%)
2

Figure 21. The effect of architecture of HTNFs on the thermal conductivity of the rst generation of HTNFs.

6.6 vol.% VGCF annealed Single-wall nanotube nanouids were prepared by rst pre-dispersing ovendried nanotubes in chloroform using 15 min. of homogenization and 5 min. of sonication. This was followed by adding the appropriate amount of poly--olen oil+5 wt.% dispersant to achieve nal volume percent. The chloroform was removed by closed distillation with mechanical stirring. Final drying was done under heated dynamic vacuum until the odor of chloroform could no longer be detected. Multi-walled nanotube nanouids were prepared by the slow addition of oven-dried VGCF with homogenization. An additional 15 min. of homogenization was performed. For higher loading, the nanotubes were added in 1 vol.% increments with a 3 min. homogenization until the desired nanogrease consistency was achieved. Physical Properties of Nanouids The thermal decomposition properties of base heat transfer uids and developed heat transfer nanouids based on of the Shell SAE 15W-40 diesel oil and the BP Amoco DS-166 oil in argon and air were measured by thermal gravimetric analysis (TGA) and compared with each other. The 15W-40 oil began to decompose around 200C with total
39

decomposition occurring at about 500C. Again, a triplicate measurement was made using 1020 mg of sample to ensure accuracy of the results. The TGA data of SWNTs, diesel oil, and 1 vol.% solutions of SWNTs in diesel oil showed some of their properties. Two conditions were used: the inert argon atmosphere and the oxidizing environment of air in order to examine thermal degradation characteristics and the effect of oxidation on thermal degradation. The SWNTs showed enhanced thermal properties. This is due to their decomposition temperature occurring at a much higher temperature when compared to diesel oil and the nanouid. As was expected, the diesel oil began to decompose at around 200C. The nanouids, however, showed signicant increases in their thermal decomposition when compared to the base oils. The TGA results show that the presence of nanotubes in oil does not lead to very large changes in the degradation temperature of the oil, but that these changes are signicant. This research also shows that appropriate methods for processing the nanotubes in the oils can be developed in order to provide for increased thermal conductivity without degrading the oil (these results do not include the use of functionalization at this time). Fourier Transform Infrared Spectroscopy A number of the nanouids were analyzed by Fourier transform infrared spectroscopy (FTIR). The study of some of the key FTIR spectra and their com-

parison with those of the base oils show that the nanotubes lead to alterations in the spectra, and that specic bonding groups can be identied. Typical results are shown in Figures 17, 18, and 19. There are spectral changes in three regions: >3,500, ~2,300, and <1,800 cm1. Differences appear in the spectra as a function of processing mode (sonication and homogenization) and with the addition of various nanotubes. The changes due to the nanotubes may be related to their purication condition. Fourier transform infrared spectroscopy shows that some peaks change with the use of homogenization and also change with the presence of the SWNTs. The changes associated with the presence of nanotubes may be inuenced by the way the nanotubes were processed since they bring additional chemistry with them according to their purication. THERMAL MEASUREMENTS OF NANOFLUIDS AND NANOLUBRICANTS Heat Transfer Nanouids Based on Rotella 15W-40 Oil Various mixing methods of dispersing various types of nanotubes in 15W-40 diesel oil were quickly screened. The rst series of nanouids tested for TC were produced by adding SWNTs to 15W-40 with the appropriate dispersant, followed by 10 min. homogenization and 5 min. sonication with a probe-type sonicator. The nanouids appeared as very homogeneous black uids, with somewhat higher viscosity at room temperature. The TC values were measured repeat-

Thermal Conductivity Ratio (ko/kf)

3.00 2.50 2.00 1.50 1.00 0

MWNT Rao MWNT Rao, Type II

0.2 0.4 0.6 0.8 Vol.(%) 1 1.2

a 3.0 Thermal Conductivity Ratio (ko/kf) (%) 2.5 2.0 1.5 1.0 0.0 0.2

0.4 0.6 0.8 1.0 Volume Fraction (%)

1.2

b Figure 22. (a) The effect of MWNT load on the thermal conductivity of BP Amoco DS-166 oil. (b) For comparison, is the original publication result by Choi and co-workers.

Table II. Hot Disk Thermal Conductivity of Nanotubes Loaded in 15W-40 Oil Data Summary Sample ID 15W-40-0 15W-40-.25 15W-40-.50 15W-40-1.00 NT vol.% 0.000 0.250 0.500 1.000 Th. Cond. 0.147 0.161 0.172 0.215 TC/TC_o 1.000 1.098 1.170 1.461 Th. Diff. 0.111 0.120 0.121 0.173 Sp. Ht. 1.331 1.340 1.424 1.257 Probe Depth 3.579 3.725 3.826 3.871

Table III. Thermal Conductivity of Bulk Nanouids Nano Material SWNT Nanouid SWNT Nanogrease MWNT Nanouid High TC MWNT Nanogrease Nanolubricant 1 Nanolubricant 2 Composition 1.0 vol.% HiPco puried 2.0 vol.% HiPco raw 3.0 vol.% VGCF annealed 6.6 vol.% VGCF annealed 0.175 HiPco ESD grade, B&S SAE 30 0.175 HiPco ESD grade, B&S BP 166 TC Ratio 1.53 1.85 1.97 3.32 1.22 1.35

edly to obtain precision statistics. The results are summarized in Table II and depicted in Figure 20. These are averaged data values from four to six measurements of each suspension under similar conditions. The thermal conductivity statistical standard deviation averaged 0.004. The TC increase is somewhat non-linear with nanotube loading with a substantial increase of >45% with only 1 vol.% nanotube additive. A series of experiments addressing the effects of various types of nanotubes, loading, effect of intense mixing on base oil, and dispersion on thermal conductivity were performed. The nanouid inventory developed by the authors provides a detailed description of the samples that were prepared and evaluated. The images of the raw materials used show that the challenge for SWNTs is the adequate breakdown of the interconnected network of nanoropes into a well-dispersed system, followed by further exfoliation of individual nanotubes from the nanoropes. The nanoropes may contain up to 100 individual nanotubes. Detailed research in the solution properties of SWNT indicate that dispersed nanotubes can readily aggregate (super ropes) depending on the uid system. In this study, without the use of additional dispersant or functionalization of the nanotubes to maintain their separation, a similar phenomenon was
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3.00 2.75 2.50 2.25 2.00 1.75 1.50 1.25 1.00 0.75 Base Oil SWNT, Mixed SWNT, SWNT, SWNT, SW Mixed + Mixed + Pre-Disp. HiPco Homog Homog In Raw + Sonic Toluene Vacuum Drip Processing/NT SWNT Raw, Mixed MultiWall Rao MultiWall Rao Type II Carbon Black

Poly--Olen (BP Amoco DS 166) Oil Batches of test uid of 5 wt.% succinimide (Chevron Oronite 1107) in synthetic poly--olen oil (BP Amoco DS-166) were prepared and used throughout all further blending. Suspensions were prepared from a master batch of 1 vol.% of MWNT, puried SWNTs (HiPco), raw HiPco, and as-produced SWNTs (plasma). Nanouids reproducing the work of Choi et al. were prepared using a similar source of MWNTs (A. Rao at Clemson University) and the same oil/additive ingredients. Suspensions of 1.0 vol.%, 0.5 vol.%, and 0.25 vol.% were prepared as described in 5 wt.% succinimide/poly-alpha-olen. Results are shown in Figure 22, which shows for comparison the original publication result by Choi and co-workers. At 1% volume, even higher TC improvement (175% vs. 160%) is achieved than formerly reported. After an investigation of the MWNTs supplied by Rao and those used by Choi, it was learned that Type 2 were the MWNTs most similar to that used by Choi and co-workers. No nanouids were produced at lower loadings to accurately relate the non-linear behavior. The thermal conductivity of bulk quantities of nanouids, designed and manufactured for advanced testing, was

TC Ratio

Figure 23. The effect of processing parameters and nanotube type on the thermal conductivity of HTNFs.

observed and its effect on thermal conductivity. The data in Figure 21 shows a SWNT nanouid system where highpurity HiPco was pre-dispersed in chloroform, added to 15W-40 oil, and the solvent removed by low heated evaporation. Upon sitting, the sample showed a 25% decrease in TC with 1 vol.% loading along with the same nonlinear behavior. Upon re-dispersion by a desktop vortexer or test-tube shaker, the same sample then showed a substantial increase to 45% TC improvement. Signicant loose agglomeration prior to initial testing is most likely to have occurred. The continued use of commercial oil (15W-40) nanouids led to concerns of complications of the many additives used in the oil formulations. This was especially noted in viscosity, as well as visual and odor changes in the nature of the nanouids with intensive sonication. The base oil typically comprises only about <75 wt.% of the formulation, with >25 wt.% additives such as wear/corrosion inhibitors (zinc thioalkylphosphates), detergents, viscosity modifiers, and thermal stabilizers. To focus on the contributions of nanotubes and separate interferences, a new set of uids was used based on a synthetic poly--olen (BP Amoco DS -166) oil with a single dispersant. Several dispersion factors were identied. It was observed with the commercial diesel oil that the state of nanotubes before mixing affected the thermal conductivity. In addition, the following observations were made: Nanotubes that had agglomerated
2005 December JOM

during aqueous processing and purication were more difcult to disperse. They produced lower thermally conductive suspensions for the same mixing energy. As-produced plasma-arc materials (containing about 2530% SWNTs) gave higher TC uids than puried (>90%) perhaps due to the agglomeration issues. The agglomeration of the puried SWNTs can be overcome by predispersing them in a polar solvent (such as CHCl3) and then blending the suspension into the oil. With higher concentrations, some reagglomeration may occur.
104

0.5% Acid Treat SWNT 103 0.5% Rao SWNT 102 0.5% MER SWNT 10 1 101 102 0 5 10 15 20 25 30 Shear Rate (Pa) 105

Viscosity (Pa)

Figure 24. The viscosity versus shear rate with 0.5% MER SWNT, 0.5% acidtreated CNI ESD SWNT, and 0.5% Rao MWNT in BP166. 35

Figure 25. The viscosity versus shear rate with BP166, 1% CNI ESD SWNT, and 1% Carbolex SWNT in BP166.

104 1% CNI ESD SWNT 1% Carbolex SWNT 103 BP166 102 10 1 101 102 0 5 10 15 20 25 30 35 Shear Rate (Pa)

Viscosity (Pa)

40

41

Table IV. Shape Factor A for Common Filler Types Filler Type Aspect Ratio 1 1 2 4 6 10 15 Ratio A 2 1.50 1.58 2.08 2.80 4.93 8.38 2 L/D (a) 0.5(b)

Cubes Spheres Random Fibers Random Fibers Random Fibers Random Fibers Random Fibers Uniaxially Oriented Fibers Uniaxially Oriented Fibers

(a) in ber axis, (b) transverse to ber axis

also carried out. The results are shown in Table III. Effect of Processing Variables In the rst generation of HTNFs with SWNT nanofluids, the largest TC improvements were achieved with raw HiPco materials (60% at 1 vol.%), though considerably lower than MWNT results described. This was not expected, as the SWNTs have lower defects and thus, higher inherent thermal conductivity, which should impart a greater contribution to the overall TC. Furthermore, with the raw HiPco having very high interconnectivity, it was difcult to readily disperse them, often resulting in thick pastes, not the desired free-owing uids. Based on the characteristics of the nanotubes used, it was surmised that the following issues are at play: Strong van der Waals attractions among the more nely nanostructured carbons is not allowing adequate dispersion, but rather forming a loose intertwined template that adsorbs the oil and signi-

cantly increases the viscosity. Minimal exfoliation of the individual nanotubes from the nanoropes does not take advantage of the smaller dimensions, and hence colloidal stability. There is a strong propensity to reagglomerate, creating large volumes of non-lled, thermal insulative domains, thereby reducing the overall TC. The very high surface area of SWNTs may have a signicant amount of adsorbed water and gases providing a thermal barrier interface and minimizing thermal transfer from the matrix to the conductive tubes. Aggregation and bundling also reduce the interaction contact surface area with the oil matrix, dropping the effective thermal transfer rate. As this study was originally focused on the manufacture of SWNT nanouids, a series of experiments was performed to address issues that concentrated on nanotube sample preparation and processing. Typical results are summarized in Figure 23. Typical levels of the thermal conductivity increments are: nanomaterials Type 1, 60%; Type 2, 175%; and Type 3, 243%. Rheology The effect of the shear rate on the viscosity of HTNFs and nanolubricants based in the BP166 at room temperature (gap = 150) was investigated. Typical results show that the viscosity decreases sharply with increasing shear rate as

Table V. Maximum Packing Fraction of Selected Fillers Particle Shape Spheres Spheres Spheres Spheres Spheres Spheres Irregular Fibers Fibers Fibers Fibers Packing Order Hexagonal close Face-centered cubic Body-centered cubic Simple cubic Random loose Random close Random close 3-D random Uniaxial hexagonal close Uniaxial simple cubic Uniaxial random m 0.7405 0.7405 0.60 0.524 0.601 0.637 ~0.637 0.52 0.907 0.785 0.82

presented in Figures 24 and 25. This conrms the lubricating potential of these nanolubricants. These properties are currently being measured at room temperature and at two elevated temperatures, 100C and 150C, respectively, in order to understand the performance/ architecture relationships at appropriate working conditions for each specic nanolubricant. Modeling of Heat Transfer Nanouids Performance This research conrms that the rule of mixtures is not adequate to describe the carbon nanotube contributions to thermal conductivity. Thus, a new approach was developed based on the morphologies of the agglomerates of the carbon nanotubes observed and on the Nielsen Model for conductive llers in a matrix. These observed morphologies are represented schematically in Figure 26. It is assumed that nanotubes in suspension would not remain straight and rigid, but would be in a dynamic folded state, thereby providing an effective agglomerate of various aspect ratio (L/D) shapes. This model is based on Einsteins viscosity model and can be represented by the following equation: K 1 + A B 2 = k1 1 B 2 The physical meaning of these parameters is: K = thermal conductivity of the binary system; A quanties the particle shape; k1 = thermal conductivity of the base uid; k2 = thermal conductivity of carbon nanotubes; 2 = volume loading of carbon nanotubes.
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Figure 26. A schematic of typical morphologies observed in the dispersion of SWNT agglomerates.

42

B=

k 2 / k1 1 k 2 k1 + A 2

= 1+ 1- m 2 m 2 m = maximum packing efciency The constants A and m are calculated in Tables IV and V, respectively. This model can be used to explore various factors that can affect thermal conductivity of nanouids such as L/D of the nanotube agglomerate, decoupled orientation effects (along ber axis, Kl, transverse to ber Ktrans), along with overall volume loading. An Excel program was written to investigate these relations. An example of the output is shown in Figure 27. It is interesting to note that there are non-linear portions to the model, which may assemble to link to general non-linear behavior observed by Choi and co-workers. Further model development synergistic with experimental nanouid production is in progress. The degree of dispersion achieved in all three types of nanomaterials has been very good. However, microstructural observations by optical microscopy, SEM, and TEM show that most of the carbon nanotubes are present in the form of agglomerates and not as single individual nanotubes. This is consistent with the values obtained by particle size analysis and is in excellent agreement with the results predicted by the model.

The degree of stability achieved has been very good in Type 1 and Type 3, and good in Type 2 of the nanomaterials described. It is expected that the overcoming of some of the most important challenges as described will result in further considerable advances in both the degree of dispersion and degree of stability and thus the effectiveness of these HTNFs and nanolubricants. CONCLUSIONS Carbon nanotubes, both SWNTs and MWNTs, and VGCFs have been found to considerably increase the thermal conductivity of many heat transfer uids such as mineral and synthetic oils, water, water/ethylene glycol mixtures, and other commercial heat transfer uids such as antifreeze. Prior functionalization and mixing in appropriate solvents, followed by homogenization and sonication were some of the methods used to achieve various levels of dispersion of carbon nanotubes in these uids. A 175% increase in the thermal conductivity was obtained for 1 vol.% load. Increments of 243% have been achieved at 6% loads with considerable increase in the viscosity. The thermal conductivity levels obtained varied considerably with the type of carbon nanotube used, the load, and the processing route. More aggressive mixing protocols lead to the alteration of the additives in the commercial heat transfer uids. Carbon nanotubes are believed to contribute to the thermal conductivity of HTNFs through Brownian motion and through a tridimensional network formation within the uid. The preliminary evaluation of the viscosity of heat transfer nanouids and other dynamic properties show that these uids have the potential to nd a place in many applications such as engine cooling systems, oil coolers, and heat pumps to signicantly improve their thermal and lubricating performance. ACKNOWLEDGEMENTS This work is supported by the U.S. Army Research Laboratory, Aberdeen Proving Ground, under Cooperative Agreement number DAAD19-02-2-0011. The authors acknowledge the collabora-

tion of Professor E.V. Barrera of Rice University, and the support from Carbon Nanotechnology, Inc., and Professors A. Rao, Clemson University, and S. Jin, University of California at San Diego for providing some of the carbon nanotubes for this project. The authors also want to acknowledge B. Rostro, D. Rebsom, and H. Hong for doing some of the measurements.
References
1. J.C. Maxwell, A Treatise on Electricity and Magnetism, 2nd edition (Wotton-under-Edge, U.K.: Clarendon Press, 1881). 2. R.L. Hamilton and O.K. Crosser, I and EC Fundamentals, 1 (3) (1962), p. 187. 3. U.S. Choi, Developments and Applications of NonNewtonian Flows, eds. D.A. Siginer and H.P. Wang, Vol. 231/MD-Vol.66 (New York: American Society of Mechanical Engineers, 1995), p. 99. 4. J.A. Eastman et al., Enhanced Thermal Conductivity Through the Development of Nanouids, Mater. Research. Soc. Symp. Proc. 457 (Warrendale, PA: MRS, 1997), pp. 311. 5. S. Lee et al., Measuring Thermal Conductivity of Fluids Containing Oxide Nanoparticles, Journal of Heat Transfer, 121 (1999), pp. 280289. 6. J.A. Eastman et al., Anomalously Increased Effective Thermal Conductivities of Ethylene GlycolBased Nanouids Containing Copper Nanoparticles, Appl. Phys. Lett., 78 (6) (2001), pp. 718720. 7. H. Masuda et al., Netsu Bussei (Japan), 4 (1993), pp. 227233. 8. S.U.S. Choi et al., Anomalous Thermal Conductivity Enhancement in Nanotube Suspensions, Appl. Phys. Lett., 79 (14) (2001), pp. 22522254. 9. S. Iijima, Nature (London), 354 (1991), p. 56. 10. J. Horne, M. Whitney, and A. Zettl, Synth. Met., 103 (1999), p. 2498. 11. S. Berber, Y.K. Kwon, and D. Tomanek, Phys. Rev. Lett., 84 (2000), p. 4613. 12. J. Hilding et al., Dispersion of Carbon Nanotubes in Liquids, Dispersion Science and Technology, 24 (1) (2003), pp. 141. 13. Y. Sabba and E.L. Thomas, High-Concentration Dispersion of Single-Wall Carbon Nanotubes, Macromolecules, 37 (2004), pp. 48154820. 14. C. Richard et al., Supramolecular Self Assembly of Lipid Derivatives on Carbon Nanotubes, Science, 300 (2003), pp. 775778. 15. S. Niyogi et al., Ultrasonic Dispersions of Singlewalled Carbon Nanotubes, J. Phys. Chem. B, 107 (2003), pp. 87998804. 16. M.F. Islam et al., High Weight Fraction Surfactant Solubilization of Single-Wall Carbon Nanotubes in Water, Nanoletters, 3 (2) (2003), pp. 269273. F.D.S. Marquis is with the Department of Materials and Metallurgical Engineering at the South Dakota School of Mines and Technology in Rapid City, South Dakota. L.P.F. Chibante is with NanoTex Corporation in Houston, Texas. For more information, contact F.D.S. Marquis, South Dakota School of Mines andTechnology, Department of Materials and Metallurgical Engineering, Rapid City, SD 57701; (605) 394-1283; fax (605) 394-3369; e-mail fernand.marquis@sdsmt.edu.

L/D = 100 4.0 L/D = 50 3.5 L/D = 10 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.00 0.02 0.04 0.06 0.08 0.10 0.12 Volume Loading

Figure 27. The effect of loading and architectural parameters (aspect ratio) on the thermal conductivity of nanomaterials with carbon nanotube agglomerates.

TC Ratio

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