Ultrafine Grain Overview

The Mechanical Properties of Nanostructured Materials

Yulin Lu and Peter K. Liaw
In this paper, the state-of-the-art progress in research on novel mechanical properties of nanocrystalline materials and carbon nanotubes is reviewed. There is evidence that the relation between the strength of nanocrystalline materials and grain size does not observe the classic Hall-Petch plot. Lowtemperature and high-strain rate superplasticity have been found in some nanocrystalline materials.Theoretical prediction and experimental data indicate that carbon nanotubes are materials with high stiffness, high strength, great toughness, and low density. There are already some application examples for novel mechanical properties of nanocrystalline materials and carbon nanotubes. INTRODUCTION Widespread attention has been paid lately to the potential for fabricating materials and/or devices with special properties by manipulating their microstructure at the atomic level. For decades, scientific efforts have emphasized phenomena at the macroscopic and atomic/molecular levels. However, phenomena at nanostructured levels (intermediate between macroscopic and molecular dimensions) have recently been found to exhibit unique properties that cannot be readily understood by either macroscopic or atomic/molecular models (Landauer relationship1 and quantum Hall effect,2 for example). New techniques are being developed to investigate the behavior of nanostructures. Nanostructured materials (NsMs) have a characteristic length scale of a few (typically 110) nanometers. This length scale could be a particle diameter [zero
12 10 100 15 5 d (nm)
qPd sCu xAg vFe qFe sNi xNi vCu wSe

w vv v v wv 8 w v w v wx sv sq xs 6 vq v qw w 4 s q w qqq qqs q q qq x vv s s s s 2 x x x x s s s x xx 0s 0.0 0.1 0.2 0.3 0.4 0.5 0.6 d1/2 (nm1/2) Figure 1. Hall-Petch plots for different nanocrystalline materials showing that hardness increases with decreasing grain size.15

dimensional (0-D)], width of a fiber or tube [one dimensional (1-D)], layer thickness [two dimensional (2-D)], or grain size [three dimensional (3-D)]. Scientific work on NsMs can be traced back more than 100 years ago to 1861, when the term colloid was coined by the British chemist, Thomas, to describe a solution containing 1 nm to 100 nm diameter particles in suspension.3 In 1930, the Langmuir-Blodgett method for fabricating nanolayer films was developed.3 By 1960, arc, plasma, and chemical-flame furnaces were utilized to produce submicron particles. C60 was found at Rice University in 1980,4 and, in 1991, a Japanese scientist, Iijima, first found carbon nanotubes, a 1-D NsMs, while conducting research on C60.5 The promising application potential for NsMs has piqued research interests. The first applications of NsMs were as catalysts and pigments.3 Reducing the grain size to several nanometers decreased the sintering temperature of ceramics. 6 The giant magnetoresistive (GMR) effect, which is expected to find widespread applications as magnetic recording read heads in the near future, was discovered in the late 1980s.7 WC/ Co composites are another near-term application for NsMs. Nanostructured WC/Co composites have been prepared with hardness values about twice that of conventional micrograined WC/Co, enhanced wear resistance, and improved cutting performance.8 Recently, tungsten-disulfide (WS2 ) nanotubes have been synthesized, and they show an enormous potential for novel surface probe microscope (SPM) tips.9 More applications of NsMs are expected to develop in the near future. This paper reviews the recent results of research on mechanical properties of nanocrystalline (nc) materials (one 3-D NsMs) and nanotubes (one 1-D NsMs). Readers who are interested in 0-D and 2D NsMs are directed to References 10 and 11, respectively. For nc materials, two phenomena (the strongest grain size and low-temperature superplasticity), are given special attention; for nanotubes, this paper will concentrate on the mechanical behavior of carbon nanotubes, a class of materials which are expected to form the technological base for the 21st century.

475 400 VPH 325 250 175

16.0 w

d (nm) Pd vv vv v v v q 0.30 d1/2 (nm1/2) q

6.25

Cu w q

100 0.20

0.25

0.35

0.40

Figure 2. Reverse Hall-Petch plots for nanocrystalline palladium and copper. The hardness tests were performed on a Leitz microhardness tester using a Vickers diamond pyramid indenter with a load of 0.2 kg.16

NANOCRYSTALLINE MATERIALS Bulk nc materials, a class of 3-D nanostructures, consist of equiaxed nanometer-sized (1100 nm) crystals. In these materials, because the interfacial region represents a significant fraction of a sample, mechanical parameters are dominated by the properties of surfaces and interfaces. The promising structural applications of nc materials have led to intense research of their mechanical properties in recent years. To a great degree, the mechanical properties of bulk nc materials have become an identifiable field in materials science because of the work of Gleiters research group.12 Although some novel mechanical properties that they found were caused by high porosity or other artifacts in the samples, their work has helped attract research interest into the nc materials field. As fabrication techniques develop, fully dense samples, which are critical for obtaining reliable data, are becoming available. The well-accepted intrinsic mechanical results are briefly summarized as follows: Elastic moduli of nanocrystalline materials are approximately the same as those for conventional grain size materials until the grain size becomes very small (e.g., <5 nm). In those cases, elastic properties are not very clear yet. The hardness and yield stress of nc materials increase with decreasing grain size until the smallest regime (e.g., < 20 nm), where negative Hall31

Hardness (GPa)

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Frequency (Arbitrary Units)

Petch slopes are observed for copper and palladium. Thus, the strongest grain size, i.e., the grain size with the greatest mechanical properties (hardness and yield stress), is observed for copper and palladium.13 High ductility in nc brittle ceramics or intermetallics at temperatures significantly less than 0.5 Tm (the melting temperature) has not been confirmed. For ductile metals (conventional-grained), the ductility decreases sharply as the grain size decreases into the <25 nm range.8 Superplasticity has been observed at lower temperatures and higher strain rates in some nc materials than their conventional-grained counterparts.14
4.0 1

The Strongest Grain Size Grain refinement is commonly known to improve the hardness and strength of conventional-grained materials (grain diameter, d > 1 m). The empirical HallPetch equation has been found to express this grain-size dependence of strength or hardness very well. In terms of yield strength and hardness, the expressions are = 0 + Kd1/2 and H = H0 + Kd1/2, respectively, where and H refer to the yield strength and hardness of the material, respectively, the subscript 0 relating to the material of infinite grain size; K and K are constants representing the grain boundary as an obstacle to the propagation of deformation; and d is the grain diameter. Nanocrystalline materials represent the ultimate in grain refinement. If these equations hold true down to grain sizes of a nanometer scale with the same value of K or K found at conventional grain sizes, significant strength increase should result. For example, if d is changed from 10 m to 10 nm, the strength increases about 30 times. Unfortunately, despite great strength improvements for all nc materials tested to date, no results have matched those predicted by the equations. Because limited fabrication techniques have limited the size of nc materials available, the most convincing results of the strength have been obtained through hardness tests. In most cases, hardness increases with decreasing grain size. The pure nc metals (10 nm grain size) can be 27 times harder than their coarsegrained (>1 m) counterparts. The results of hardness measurements are usually carried out as a function of grain size and plotted out in the form of a HallPetch curve. As shown in Figure 1, the trend of the curves is independent of the synthesis method, since the results from nanostructured materials fabricated by gas condensation, mechanical attrition, and electrodeposition are all similar.15 However, when grain size is very small (<20 nm), curves for different materials show various trends as grain size continues to decrease. Some have a normal Hall-Petch relation (positive slope), others show a zero slope (no obvious grain size dependence), and still others have a reverse Hall-Petch relation (negative slope).8 Figure 216 presents the negative Hall-Petch curve of nc copper and palladium. Because of the negative Hall-Petch curve found in nc copper and palladium with the smallest grain sizes (typically <10 nm), a critical grain size, where these materials have the highest strength, may exist as the grain size decreases from a micro-grained region to a nano-grained region. Schitz et al.17 tried to prove the reverse Hall-Petch relation using the molecular-dynamics technique. They conElongation to Failure (%)

20.0 15.0

10.0 5.0 0.0 1

q s qq q w w v sss ss s w x vq w s w x x sx ww x x q x 10 100 Grain Size (nm)

qCu [a] sCu [b,c] xCu [d] vCu [e] qCu [f] wCu/ZrC/O [g] qAl/Al6.4Zr [f] sAl-10Ti [h] xPd [b,c] vAg [c]

q x v

1,000

Figure 4. Plot of tensile ductility versus grain size for several metals and alloys.8

Dislocation Activity

Grain Boundary Sliding

True Stress zz (GPa)

3.0 2.0 1.0 0.0 0.0

Metals

Intermetallics Ceramics Decreasing Grain Size (Arbitrary Units)

1d = 6.56 nm (8 grains) 2d = 5.21 nm (16 grains) 3d = 4.13 nm (32 grains) 4d = 3.28 nm (64 grains) 2.0 4.0 6.0 Strain (%) 8.0 10.0

Figure 5. Schematic framework for the grain size dependence of dislocation activity and grain-boundary sliding contributions to the deformation behavior of the various classes of nanophase materials. The nature of its interatomic bonding determining the appropriate location for a particular material.15

a 4.0 Flow Stress (GPa)

Grain Size d (nm) 7.0 5.0 4.0

3.0

3.5

q q q q

3.0

2.5 0.3 b

0.4

0.5 d1/2 (nm1/2)

0.6

Grain Size d (nm) 7.0 1.3 Yield Stress (GPa) 1.2 1.1 1.0 0.9 0.3 q q q q 5.0 4.0 3.0

0.4

0.5 d1/2 (nm1/2)

0.6

c Figure 3. The effect of grain size on deformation. (a) The average stress in the direction of the stretch (zz) versus strain for each grain size, (b) the maximal flow stress and and (c) the yield stress as a function of grain size. The yield stress decreases with decreasing grain size, resulting in a reverse Hall-Petch effect.17

sidered a series of 3-D cubic crystals with a side of about 10 nm. Each crystal was assigned a grain size ranging from 3.3 nm to 6.6 nm. An interatomic potential model appropriate for copper was chosen as a starting point for the simulation, which amounted to a number of tensile tests.18 The crystal was stretched, the movement of individual atoms was calculated, and their positions were recorded. This way, the deformation (strain) could be observed at every step of the process. By considering the force of atoms acting upon each other, the mean stress (tension) was obtained for each step. Thus, one stress-strain curve was obtained for each simulated tensile test on each crystal. A series of stressstrain curves for crystals with different grain sizes is shown in Figure 3a. These curves show expected elastic and plastic regions, from which a yield stress and a flow stress were obtained for each curve. When the yield stress and flow stress were plotted out versus grain sizes, as shown in Figure 3b, a negative HallPetch relation was indicated. It was also found that the deformation results mainly from many small, independent slip events in the grain boundaries. In conventional-grained materials, dislocation activities account for the major part of the deformation. This suggests that the shift from a positive Hall-Petch plot to a negative one could be caused by competition between activities inside and between grains. With the grain size decreasing into the nanometer region, activities at the grain boundaries become JOM March 2001

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Stress (GPa)

more and more important. Note that although an interatomic potential for copper was used, this strongest grain size phenomenon is not necessarily unique to copper or palladium. The strongest grain sizes for other nc materials, which are still to be found, will eventually set a limit on how strong nc materials can become. Reduced Ductility Ductility, like strength, is predicted to increase as grain size decreases into the nanoscale regime. This expectation is based on experience with conventionalgrained materials, in which different grain sizes affect yield and fracture strengths. With the same decrease of grain size, the fracture strength increases more than the yield strength, and the materials become more ductile. However, experimental data have not verified this predicted trend. Instead, the yield stress has been found to increase faster than the fracture strength as grain size decreases. Thus, the ductility is reduced. The majority of mechanical tests is conducted on consolidated particulates, and so the ductility data obtained from these materials consist of two parts: intrinsic ductility and ductility controlled by flaws due to imperfect particulate bonding and porosity. Nieman et al.19 demonstrated that the perfection of powder compaction and surface finish greatly influenced the ductility data. For that reason, efforts were made to improve the gas condensation technique by decreasing the extent of flaws introduced by consolidation. Those efforts generated samples with densities greater than 98% of the theoretical density, but very limited ductility was still observed.20,21 Figure 48 is a plot of tensile ductility versus grain size for several metals and alloys. Although data are scattered, ductility clearly decreases when grain size decreases and becomes very limited when grain sizes are smaller than 25 nm.

c Figure 6. Schematic models for (a) armchair, (b) zigzag, and (c) chiral single-walled carbon nanotubes.30

Note that all these materials tested have a typical elongation of 4060% in the conventional-grained form. It is important to also note that the data in Figure 4 are obtained by tension testing, and the ductility from compression for similar materials can be much larger than that from tension. For example, for copper samples with a grain size of 20 nm prepared in the same synthesis chamber, the ductility by compression is 1218%, and by tension, less than 2%. Compression tests are known to be insensitive to porosity and imperfect interparticle bonding, while these flaws may lead to premature tensile failure, and thus, result in reduced ductility. This trend suggests that the flaw and porosity present in many nc samples might be partly responsible for the asymmetry of the results in compression and tension tests. However, such a large difference between compressive and tensile data also suggests that shear banding in the deformation process may also contribute to the disparity.8 In order to overcome the particledebonding problem of samples prepared by the powder-consolidation technique, Wang et al.22 performed some tensile and creep tests on nc nickel samples processed by electrodeposition, one of the so-called one-step processing techniques. That work suggests that two mechanisms, grain-boundary sliding and diffusion creep, are important in deformation of nc electrodeposited nickel. At high stress levels, the grain boundary may play a major role. But with the grain size decreasing into the smallest region, diffusion creep could become more of a factor. They also found that even for artifact-free nc materials, macroscopic tensile ductility was still very limited. This could result from mechanical instability, which may be inherent to the deformation behavior controlled by shear banding. Brittle fracture is the primary barrier to the application of intermetallics and ceramics in load-bearing situations. Based on the early results of ductile behavior of brittle nc ceramics at low temperatures (below 0.5 Tm, the melting point of the matrix), brittle ceramics or intermetallics might exhibit ductility if their grain sizes are refined into a nanometer region.12 This logic is based on the classic work done by Cottrell,23 which showed, for conventional materials, the fracture stress typically increased faster than the yield stress with decreasing grain size such that ductile/brittle transitions could occur. Schulson24 studied the grain-size dependence of ductility in NiAl at 673 K. He found that ductility was low and independent of grain size for samples with grain diameters >20 m, but ductility increases rapidly for grain sizes <20 m, as grain size decreases. He suggested that this could be because, in fine-

v
d
v w

w L + L w L v v

a
40 30 20 10 0 w vw w v w s w v ss v ss q ww s q w vs w vs s q s w v q w v wq q s s s q Four Different Nanotubes w ss q s 0 2 4 6 8 Strain (%) 10 12

b Figure 7. (a) A schematic showing the principle of the tensile-loading experiment. When the top cantilever is driven upward, the lower cantilever is bent upward by a distance d, while the nanotube is stretched from its initial length of L to L + L because of the force exerted on it by the AFM tips. The force is calculated as kd, where k is the force constant of the lower cantilever. The strain of the nanotube is L/L. (b) Plot of stress versus strain curves for individual MWNTs.44

grained materials, less stress was required to nucleate cracks than to propagate them, and additional strain hardening by the plastic flow would be needed to continue crack propagation. However, this behavior has not been verified in other intermetallics. Some interesting work done by Karch et al.25 indicated the apparent plastic behavior in compression of nc CaF2 at 353 K and nc TiO 2 at 453 K. Again, these results are not reproduced, and probably are not intrinsic data. Therefore, improved ductility in nc brittle ceramics or intermetallics at significantly less that 0.5 Tm has not been verified. Improved Superplasticity When tensile-tested at particular temperatures and strain rates, some polycrystalline materials become extremely elongated before failure by necking or fracture. This phenomenon is called superplasticity. The defining elongation is typically from 100% to >1,000%. Usually, a stable fine-grained microstructure and a temperature higher than 0.5 Tm are needed for superplasticity. The fabrication benefits of superplasticity are especially appealing to industrythe forming process can be used to produce components with complex shapes from materials that are hard to machine, such as metal-matrix composites and intermetallics. More widespread application of superplastic forming may develop if lower deformation temperatures can be attained. McFadden et al.14 presented observations of low-temperature superplasticity in nc nickel, a nc aluminum alloy (1420Al), and nc nickel aluminide (Ni3Al). The nc nickel was found to be superplastic at a temperature 743 K below the temperature previously attained. 33

2001 March JOM

This corresponds to 0.36 Tm, the lowest normalized superplastic temperature reported for any crystalline material. The nc Ni3Al was found to be superplastic at a temperature 723 K below the superplastic temperature in the microcrystalline regime. Lu et al.26 attained low-temperature superplasticity by rolling electrodeposited nc pure copper, causing a very high extensibility (elongation exceeding 5,000%) without a strain-hardening effect. In contrast, conventional coarse-grained polycrystalline copper would usually break after an extension of about 800%. Further Study Needed As noted in the previous discussion, one major problem with research on mechanical properties of nc materials is obtaining fully-densified samples without particle debonding. Another problem is the lack of understanding of the microscopic deformation and fracture mechanisms in nc materials. Extensive experimental and theoretical research is urgently needed to clarify these issues and to provide direction for optimizing property design. Some work has been done in this area. As shown in Figure 5, Siegel15 suggested a qualitative framework indicating that, as grain size decreases into nanometers, the frequency of dislocation activities decreases, while grain-boundary sliding increases. Which effect dominates depends upon the grainsize regime of the material and, most importantly, on the nature of its interatomic bonding.

Huang et al. suggested that mechanical twinning might be important in the deformation mechanisms of nc materials.27 Amorphous materials exhibit many of the same characteristics of deformation in nc materials, that is, shear banding, asymmetry between tensile and compressive behavior, and elastic-perfectly plastic behavior.28 However, deformation mechanisms are not clear in amorphous materials, either.28 Much more theoretical work is needed to fully understand the mechanical behavior of nc materials. CARBON NANOTUBE In 1991, while using a transmissionelectron microscope (TEM) to investigate C60, Iijima5 discovered a filament of carbon atoms several nanometers in diameter. These 1-D nanostructures, known now as carbon nanotubes (CNTs), are large macromolecules similar to a sheet of graphite (a hexagonal lattice of carbon) rolled into a cylinder and capped with half a fullerene at each end. Because of their unique structure and remarkable physical properties, CNTs have stimulated numerous theoretical and experimental research interests. Since their discovery, two kinds of tubes have been found: single-walled carbon nanotubes (SWNTs) with only one cylinder of an atomic layer, and multi-walled carbon nanotubes (MWNTs), with cylinders inside other cylinders. There are different types of SWNTs, and each type can be described by a chiral vector (n,m), where n and m

Figure 8. Uses for consolidated nanostructured hard materials: nanocomposite microtwist drill bit (top), compared to conventional products after wear for the same use time (courtesy of Nanodyne, Inc.).51

APPLICATIONS OF MECHANICAL PROPERTIES OF NANOSTRUCTURES

The past decade has seen many scientific and technological advances in the mechanical properties of nanostructures. These advances have led to some applications already, and many more are expected to come. Following are two application examples. Nanostructured hard materials are beginning to have commercial impact. Cemented carbide nanocomposites, such as WC/Co and TiC/Fe, are widely used in the manufacture of machine tools, drill bits, and wear parts. Refining the grain size of these nanocomposites has been found to lead to considerably enhanced hardness, fracture toughness, and wear resistance. For example, with WC/Co, mechanical properties can be greatly improved if the WC and Co phases of nanosize are interconnected to form a three-dimensional nanostructure. Traditionally, WC/Co products are produced by a process of three steps, i.e., mechanically mixing powders of the Wc and Co phases, cold pressing, and sintering. The difficulty here is to uniformly mix ultrafine WC and Co powders by mechanical means. This difficulty limits the WC grain size attainable in the final sintered product to about 300 nm. Recently, some chemical methods have been developed for producing pre-mixed powders at the nanoscale level. In one such method,51 the first step is to produce a homogeneous precursor powder by mixing tungsten and cobalt salts using a spray-drying technique. Then, by fluid-bed thermochemical conversion (pyrolysis, reduction, and carburization), the precursor powder is transformed into the desired product powder of a nanophase WC/Co, in which, typically, the WC particle size is about 30 nm to 40 nm. To inhibit the grain growth of WC, phases are sintered in a liquid state, and small amounts of a graingrowth inhibitor, such as VC, are added. These powders are used to manufacture high-performance parts, such as microtwist drills used for drilling holes in printed circuit boards. As illustrated by the drill bits in Figure 8,51 the nanostructured drills perform much better than the conventional products. Carbon nanotubes can be ideal for scanning force microscopy (SFM) and scanning tunneling microscopy (STM) tips.36 The resolution that a SFM or STM can achieve depends on the sharpness of its microscopical tips. Although conventional tips can sometimes achieve a sub-nanometer resolution by controlling the position of the macroscopic probe to sub-angstrom accuracy and designing sensitive-detection schemes, one problem remains: The sharpness of the tips deteriorates quickly. Dai et al.36 has reported initial successes in using individual carbon nanotubes several microns in length as probe tips in SFM and STM. A typical, mounted MWNT probe is shown in Figure 9.36 Using a soft acrylic adhesive 110 nm thick, MWNTs have been bonded to the side of the tip of a conventional silicon cantilever. When the MWNT tip is crashed into a hard surface, it can snap back to its original straight position when it is withdrawn. It serves as a compliant spring, which can moderate the impact of each tap on the surface. Because of their high strength and flexibility, carbon nanotubes can survive direct impact with the surfaces investigated. Also, because of their metallic conductivity, carbon nanotubes can serve as tips for STM.

are integers. One particular vector (n, m) represents a particular diameter of the tube and a particular rolling-up direction from a graphite sheet (for detail, please see D. Tomneks nanotube site, Reference 29). The SWNTs can be grouped into three categories: armchair (n, n), zigzag (n, 0), and chiral [all other vectors except (n, n) and (n, 0)]. These three types of SWNTs are shown in Figure 6. 30 SWNTs are interesting examples of a 1-D periodic structure along the axis of the nanotube. Carbon nanotubes appear to possess remarkable electronic properties, with about 1/3 of the nanotubes being metallic and 2/3 being semiconducting, depending on the fiber diameter and chiral angle between the nanotube axis and the zigzag direction.3134 Because of their novel electrical properties, carbon nanotubes represent a new building block for nanoelectronics. Carbon nanotubes may also possess novel mechanical properties.35 Although the in-plane C-C bond in graphite is extremely strong, graphite is not utilized to make structural components because of the weak bond between sheets. When the sheet is rolled up into a fiber form, a carbon nanotube results. It is possible to exploit the enormous strength associated with sheets of graphite in this fiber geometry. Mechanical Properties The elastic properties of SWNTs have been a hotly disputed area in recent years. On the whole, SWNTs have better stiffness than steels, and cannot be easily broken. For example, if pressure is applied to its tip, the CNT will bend without plastic deformation inside. When the force is removed, the CNT will restore to its original state. 36 However, these effects are rather difficult to quantify because CNTs are too small to manipulate. An exact numerical value has not been agreed upon yet. The Youngs modulus (Y) of conventional materials varies from a few GPa to up to 600 GPa for the hardest materials, such as diamond and SiC. Carbon nanotubes could have values of Y even larger than these, given that the in-plane C-C bond in graphite is one of the strongest chemical JOM March 2001

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bonds known in nature (the elastic constant of graphite along the basal plane can be as high as 1.06 TPa37). In 1997, Gao, Cagin, and Goddard III38 reported their results calculated from the second derivatives of the potential. They found that a (10,10) armchair tube had a modulus of 640.30 GPa, a (17,0) zigzag tube had a modulus of 648.43 GPa, and a (12,6) tube had a value of 673.94 GPa. In 1999, using tight-binding calculations, Hernndez and Rubio39 indicated that the Youngs modulus was dependent on the size and chirality of the SWNT, ranging from 1.22 TPa for the (10, 0) and (6, 6) tubes to 1.26 TPa for the large (20, 0) SWNT. However, using first principal calculations, they obtained a value of 1.09 TPa for a generic tube. These results demonstate that the difference in calculation methods leads to various results. Treacy et al.,40 who provided the first hard evidence of a high Y value for CNTs, monitored the amplitude of the thermal oscillations of the free tips of anchored MWNTs in a range of temperatures (from approximately 300 K to 1,100 K) in a TEM. The modulus was calculated from the amplitude of vibration in the photograph at different temperatures. The mean value of Y for MWNTs was estimated to be 1.8 TPa, but the data for individual nanotubes ranged from 0.4 TPa. to 4.15 TPa. Krishnan et al.41 also used this technique to determine the value of Y for SWNTs. Their reported value, 1.25 TPa, is much closer to the expected value for graphite along the basal plane, and is probably a more realistic figure than that obtained by Treacy, Ebbesen, and Gibson.40 The thermal vibration technique has some limitations. First, for reliable TEM detection, the thermally-excited vibrations cannot be either too large or too small. This restricts the size (diameter and length) of samples. Second, this approach cannot evaluate strength and toughness. Wong et al.42 used a different method: exerting a distortion on the freestanding part of an anchored nanotube using an atomic force microscope (AFM). The force exerted on the tip was recorded by AFM when the nanotube was being pushed out of its equilibrium position. These authors reported a value of 1.28 TPa for MWNTs, which agrees with the results of Krishnan et al.41 for SWNTs. The similarity of the measured Y values for SWNTs and MWNTs indicates that the stiffness of nanotubes is essentially a consequence of the strength of the C-C bond in the graphite sheets. The interaction between different walls in MWNTs has only a small effect on their mechanical properties. Ruoff and his research group43,44 obtained the first tensile stress-strain curve of MWNTs, as shown in Figure 7. An individual MWCNT was picked up, po2001 March JOM

References
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Figure 9. A typical MWCNT tip bonded on a commercial silicon AFM tip.36

sitioned on a nanometer scale, firmly attached, and tensile loaded until it broke. The firm attachment of a nanotube onto the AFM tips is critical. The electron beam was focused onto the MWNT where it was loosely attached by the relatively weak van der Waals forces to the cantilever tips. Doing this caused residual hydrocarbon gases in the electron microscope to be decomposed and to build up a small carbonaceous deposit creating the strong attachment that held the nanotubes in place during the experiment. Their results showed that the Y value of SWNTs lay close to 1 TPa. The maximum tensile strength was approximately equal to 30 GPa. Other groups, such as Salvetat et al.45 and Muster et al.46 , have also experimented to determine the mechanical properties of nanotubes. All these works confirmed that nanotubes indeed have exceptional stiffness along the axial direction. In addition, many direct observations of the flexibility4749 of nanotubes provided evidence of their capability to sustain large strains without collapse or failure. The large variation of the data from different groups seems to suggest that the elastic modulus depends on the diameter and shape of the CNT. CNTs that investigators are working on are not uniform, leading to different results. However, work by Forr et al.50 suggested that this conclusion might not be the case. They argued that the SWNT and MWNT perform differently. The Y value of MWNT did not strongly depend on the diameter; rather, the value had something to do with the amount of disorder in the nanotube walls. In contrast, the Y value for SWNT did depend on the diameter; an individual tube had a modulus of about 1 TPa, while bundles (or ropes) of 15 nm to 20 nm in diameter had a modulus of about 100 GPa. It has been suggested29 that the difference of the Y value is due to the authors various interpretation of the nanotube walls thickness. For example, the CNT would have a much lower Y value if the tube was considered a solid cylinder not a hollow one. The thinner the nanotube wall, the higher the modulus becomes.

For more information, contact P.K. Liaw, University of Tennessee at Knoxville, Materials Science and Engineering Department, 427-B Dougherty Engineering Building, Knoxville, Tennessee 37996; (865) 974-6356; fax (865) 9744115; e-mail pliaw@utk.edu.

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