# Energy absorption ability of buckyball C_{720} at low impact speed: a numerical study based on molecular dynamics

- Jun Xu
^{1}, - Yibing Li
^{2}, - Yong Xiang
^{3}Email author and - Xi Chen
^{1, 4, 5}Email author

**8**:54

**DOI: **10.1186/1556-276X-8-54

© Xu et al.; licensee Springer. 2013

**Received: **7 December 2012

**Accepted: **16 January 2013

**Published: **29 January 2013

## Abstract

The dynamic impact response of giant buckyball C_{720} is investigated by using molecular dynamics simulations. The non-recoverable deformation of C_{720} makes it an ideal candidate for high-performance energy absorption. Firstly, mechanical behaviors under dynamic impact and low-speed crushing are simulated and modeled, which clarifies the buckling-related energy absorption mechanism. One-dimensional C_{720} arrays (both vertical and horizontal alignments) are studied at various impact speeds, which show that the energy absorption ability is dominated by the impact energy per buckyball and less sensitive to the number and arrangement direction of buckyballs. Three-dimensional stacking of buckyballs in simple cubic, body-centered cubic, hexagonal, and face-centered cubic forms are investigated. Stacking form with higher occupation density yields higher energy absorption. The present study may shed lights on employing C_{720} assembly as an advanced energy absorption system against low-speed impacts.

### Keywords

Impact Energy absorption Buckyball Buckling## Background

Absorption of external impact energy has long been a research topic with the pressing need from civil[1, 2] to military needs[3, 4]. In particular, effective absorption of mechanical energy at low-impact speed, i.e., below 100 m/s is of great interest[5, 6]. As one of the major branches of fullerene family, the carbon nanotube (CNT) has demonstrated an outstanding mechanical energy dissipation ability through water-filled CNT[7], CNT forest and bundle[7], CNT/epoxy nanocomposites[8], CNT immersed in nonaqueous liquid[9], intercalating vertical alignment with aligned existing layered compounds[10], and sponge-like material containing self-assembled interconnected CNT skeletons[11], among others. The advantage lies within the CNTs’ intriguing mechanical properties, i.e., ultra-strong (Young’s modulus of 0.9 to 5.5 TPa[12–14] and tensile strength of 60 GPa[12]) and ultra-light, as well as the tube structure which buckles upon external loadings[15]. Both theoretical modeling[16–18] and experiments[19–21] have proposed that the energy dissipation density of CNTs could be on the order of 200 J/cm^{3}, about 1-2 order of magnitudes over traditional engineering material[1].

Naturally, another branch of fullerene family with a spherical shape, i.e., the buckyball, also possesses excellent mechanical properties similar to CNTs. Man et al.[22] examined a C_{60} in collision with a graphite surface and found that the C_{60} would first deform into a disk-like structure and then recover to its original shape. It is also known that C_{60} has a decent damping ability by transferring impact energy to internal energy[23, 24]. This large deformation ability under compressive strain of C_{60} was also verified by Kaur et al.[25]. For higher impact energy, Zhang[26] employed C_{60}/C_{320} to collide with mono/double layer graphene, and the penetration of graphene and the dissociation of buckyball were observed. Furthermore, Wang and Lee[27] observed a novel phenomenon of heat wave propagation driven by impact loading between C_{60} and graphene which was responsible for the mechanical deformation of the buckyball. Meanwhile, giant buckyballs, such as C_{720}, have smaller system rigidity as well as non-recoverable morphology upon impact, and thus they are expected to have higher capabilities for energy dissipation[28]. However, to the best knowledge of the authors, currently, only few studies about the mechanical behavior of giant buckyball are available[29–31].

To understand the mechanical behavior of C_{720} and investigate its energy absorption potential in this paper, the dynamic response of C_{720} is studied at various impact speeds below 100 m/s by employing molecular dynamics (MD) simulations. Firstly, the buckling behaviors under both low-speed crushing and impact are discussed and described using classical thin shell models. Next, 1-D alignment of C_{720} system is investigated to identify the influence of packing of the buckyball on unit energy absorption. Finally, 3-D stacking of C_{720} system is considered, where four types of packing forms are introduced and the relationship between unit energy absorption and stacking density are elucidated by an empirical model.

## Methods

### Computational model and method

_{720}is a spherical buckyball with diameter of 2.708 nm (where the van der Waals equilibrium distance is considered), volume of 7.35 nm

^{3}, and mass of 1.45 × 10

^{−20}g. C

_{720}with varying numbers and packing directions (both vertical and horizontal) are selected in this study. Computational cells from single buckyball to 3-D buckyball stacking system are illustrated in selected examples in Figure 1. In the scenario of the impact, the buckyball system subjects to the impact of a top rigid plate with incident energy

*E*

_{impactor}, and the initial impact speed is below 100 m/s; in the scenario of crushing, the top rigid plate compresses the buckyball system at a constant speed below 100 m/s. The bottom plate, which is rigid and fixed, serves as a receiver, and the force history it experiences could indicate the energy mitigation capability of the protective buckyball system. The buckyball is not allowed to slip with respect to the impactor and receiver plates. Both the impactor and receiver plates are composed of carbon atoms. The masses of the atoms are varied in the following simulation to set various loading conditions (varying impactor mass), while the interactions between the plates and buckyballs remain as carbon-carbon interaction.

where *ɛ*_{CC} is the depth of the potential well between carbon-carbon atoms, *σ*_{CC} is the finite distance where the carbon-carbon potential is zero, *r*_{
ij
} is the distance between the two carbon atoms. Here, L-J parameters for the carbon atoms of the buckyball${\sigma}_{\mathrm{\text{CC}}}=3.47\dot{\mathrm{A}}$ and *ε*_{CC} = 0.27647 kJ/mol as used in the original parametrization of Girifalco[33] and van der Waals interaction govern in the plate-buckyball interaction. A time integration step of 1 fs is used, and periodical boundary conditions are applied in the *x* *y* plane to eliminated the boundary effect.

### Single buckyball mechanical behavior

#### Atomistic simulation result

*F*and displacement

*W*are normalized as

*FR/Eh*

^{3}and

*W*/

*D*, respectively, where

*R*,

*h*,

*D*, and

*E*are the radius, effective thickness, diameter, and effective Young’s modulus of the buckyball, respectively. Considering that bending is involved during the buckyball compression,

*h*= 0.66 nm and

*E*= 5 TPa[34, 35]. Here a crushing speed at 0.01 m/s is employed to mimic quasi-static loading, because the normalized force-displacement curves are verified to be the same at various loading rates from 0.1 to 0.001 m/s in trial simulations. The force-displacement response under both quasi-static and a representative dynamic impact loading (with impact speed of 50 m/s and energy of 1.83 eV) are studied, as shown in Figure 2. Two obvious force-drops could be observed in low-speed crushing, while only one prominent force-drop exists in dynamic loading which is related to the less-evident snap-through deformation shape.

The entire compression process could be divided into four phases according to the *FR*/*Eh*^{3} ~ *W*/*D* curve, i.e., buckling (*W*/*D* < 10%), post-buckling (10% ≤ *W*/*D* < 30%), densification (30% ≤ *W*/*D* < 40%), and inverted-cap-forming phase (*W*/*D* > 40%). Upon the ricochet of the plate, the deformation remains as a bowl shape with great volume shrinkage. The stabilization of such a buckled morphology is owing to a lower system potential energy in the buckled configuration due to van der Waals interaction; similar energy dissipation mechanism in CNT network is also revealed by[36].

The derivative of curve undergoes a sudden change at the same *W*/*D* value but in two completely different loading rates, suggesting that the sudden force-drop points are highly dependent on the buckyball deformation rather than the loading rate. And theoretical insights may be obtained from the four-phase deformation.

#### Phenomenological mechanical models

Note that due to the property of *FR*/*Eh*^{3} ~ *W*/*D* curve, among the phases of compression process, those with significant reduction of force (Figure 2) are relatively unimportant for energy absorption and not included in the modeling effort. A three-phase model for low-speed crushing and a two-phase model for impact loading are proposed separately in the following sections.

#### Three-phase model for low-speed crushing (quasi-static loading)

- (1)
Phase I. Buckling phase

*h*= 0.066 nm compressed by

*F*with deformation of

*W*(with the subscript number denoting the phase number sketched in Figure 3), the force-deflection relation should be expressed as[39]

*G*=

*Ehc*

^{2}; the reduced wall thickness$c=h/\sqrt{12\left(1-{\nu}^{2}\right)}$ and

*ν*is the Poisson’s ratio. The linear deformation behavior continues until it reaches the critical normalized strain

*W*

_{b1}. Experimental results for bulk thin spherical shell show that the transition from the flattened to the buckled configuration occurs at a deformation close to twice the thickness of the shell[40]; while

*W*

_{b1}here is about 4

*h*, indicating a larger buckling strain in nanoscale structure.

*f*

^{*}≈ 2.95 should be expanded to Equation 2 as

_{720}under low-speed (or quasi-static) crushing.

- (2)
Phase II. Post-buckling phase

*W*

_{b1}, the flattened area becomes unstable and within a small region, the buckyball snaps through to a new configuration in order to minimize the strain energy of the deformation, shown in Figure 3. The ratio between the diameter and thickness of buckyball is quite large, i.e.,

*D*/

*h*≈ 36.5, and only a small portion of volume is involved thus the stretching energy is of secondary order contribution to the total strain energy. Hubbard and Stronge[41] developed a model to describe the post-buckling behavior of a thin spherical shell under compression based on Steele’s[42] model

where$K={\left(\frac{5}{4}\right)}^{2}{\left(\frac{8}{3\mathrm{\pi}}\right)}^{2}\sqrt{3\left(1-{\mathrm{\nu}}^{2}\right)}$. This nonlinear deformation behavior extends until it reaches the densification critical normalized strain *W*_{b2}. The value of *W*_{b2} could be fitted from the simulation data for C_{720} where *W*_{b2} ≈ 11*h*.

*F*

_{2}(

*W*

_{2}) ≈ 0, Equation 4 maybe further modified as

- (3)
Phase III. Densification phase

*γ*is a coefficient and

*n*is fitted as

*n*≈ 1.16. Considering the relationship[41, 42]

Therefore, Equations 3, 5, and 10 together serve as the normalized force-displacement model which may be used to describe the mechanical behavior of the buckyball under quasi-static loading condition from small to large deformation.

#### Two-phase model for impact

The mechanical behaviors of buckyball during the first phase at both low-speed crushing and impact loadings are similar. Thus, Equation 2 is still valid in phase I with a different *f*^{*} ≈ 4.30. The characteristic buckling time, the time it takes from contact to buckle, is on the order of *τ* ≈ 10^{− 1} ~ 10^{0} ns ~ *T* ≈ 2.5*R*/*c*_{1} ≈ 5.71 × 10^{− 5}ns, where *ρ* is the density of C_{720} and${c}_{1}=\sqrt{E/\rho}$. It is much longer than the wave traveling time; thus, the enhancement of *f*^{*} should be caused by the inertia effect[43].

*L*experiences little stretching strain, whereas the side wall bends with finite deformation, governing the total system strain energy

*M*is the bending moment.

*A*denotes the integration area. The

*h*

^{’}is the ‘enlarged’ thickness, the result of smaller snap-through phenomenon. Here,

*h*

^{’}≈ 1.40

*h*via data fitting. Substituting geometrical constraints and taking the derivative, the force-displacement relation becomes (for C

_{720}under 100 m/s impact)

Therefore, Equations 3 and 12 together provide a model to describe the mechanical behavior of the buckyball under dynamic loadings.

*α*owing to strain rate effect[44–46]. With the subscript representing the impact speed (in units of m/s), the correction factor

**c**=

*α*

_{40},

*α*

_{50},

*α*

_{60},

*α*

_{70},

*α*

_{80},

*α*

_{90}= [0.83, 1.00, 1.12, 1.14, 1.17]. Figure 5 illustrates the comparison between atomistic simulation and model (for impact speeds of 40 to 90 m/s), with good agreements.

## Results and discussion

### Buckyball assembly

In practice, buckyballs need to be assembled (shown in Figure 1) so as to protect materials/devices. Various stacking arrays are investigated as follows.

#### 1-D alignment buckyball system

_{ 720 }can be arranged both vertically and horizontally in a 1-D chain-like alignment. Figure 6 shows the mechanical behavior of a five-buckyball array subjecting to a rigid plate impact with impact energy and speed of 9.16 eV and 50 m/s respectively. Progressive buckling and bowl-shape forming behavior takes the full advantage of single buckyball energy absorption ability one by one and controls the force on the receiver within a relatively low value during first section of deformation (within

*W*/

*D*< 1.5) which provides cushion protections.

^{3}) are given in Figure 8, which shows that the UME and UVE are almost invariant regardless of buckyball number or arrangement. In Figure 8 the impact energy per buckyball is fixed as 1.83 eV; if the impact energy or speed changes, the value of UME or UVE alters; however, the result is still insensitive to buckyball number or arrangement. The major responsible reason is that the energy absorption ability of the system stems from the non-recoverable deformation of individual buckyball which is almost uniform.

#### 3-D stacking buckyball system

The packing density of a 3-D stacking system can be different than that of the 1-D system, and thus the performance is expected to vary. Four types of 3-D stacking forms are investigated, i.e., simple cubic (SC), body-centered cubic (BCC), face-centered cubic (FCC) (a basic crystal structure of buckyball[47]), and hexagonal-closed packing (HCP). The occupation density *η* _{
SC
} = *π*/6 ≈ 0.52,${\eta}_{\mathit{\text{BCC}}}=\pi \sqrt{3}/8\approx 0.68$,${\eta}_{\phantom{\rule{0.2em}{0ex}}\mathrm{\text{FCC}}}={\eta}_{\phantom{\rule{0.2em}{0ex}}\mathrm{\text{HCP}}}=\pi /3\sqrt{2}\approx 0.74$[48] for SC, BCC, FCC, and HCP, respectively. Convergence study indicates that the profiles of force-displacement curves as well as the energy absorption rate at increasing buckyball numbers at one computational cell keep the same. In this case, a fundamental unit, such as containing 2 × 2 × 3 buckyballs for SC arrangement is shown in Figure 1c.

*η*) have more space for system to comply and hence the impact force is smaller yet the displacement is larger. Consequently, FCC and HCP have the same energy absorption ability and that of BCC and SC are inferior.

*η*.

*Π*

_{m}= UME/(

*E*

_{impactor}/

*m*) and

*Π*

_{ v }= UVE/(

*E*

_{impactor}/

*V*

_{volume}) where

*V*

_{volume}is the volume of the buckyball and impact speed as$V=v/\sqrt{B/\rho}$ where

*B*= 34 GPa[49] is the bulk modulus of graphite. An empirical equation could be fitted as

*A*= 5.50,

*B*= −0.25,

*C*= 0.21, and

*D*= 25.0 with fitting correlation coefficient of 0.96 and

where *A* = 0.46, *B* = −1.94, *C* = 0.21, and *D* = 187.9 with fitting correlation coefficient of 0.96. These equations are valid for low-speed impact speed (below 100 m/s) on stacked C_{720} buckyballs. When the impact speed is fixed, the unit energy absorption linearly increases with the occupation density; under a particular spatial arrangement, the energy absorption ability increases nonlinearly with the impact speed.

## Conclusions

C_{720} as a representative giant buckyball has the distinctive property of non-recovery deformation after crushing or impact, which makes it capable of absorbing a large amount of energy. The mechanical behaviors of a single C_{720} under quasi-static (low-speed crushing) and dynamic impact are investigated via MD simulation and analytical modeling. By understanding the mechanism of mechanical behavior of individual C_{720}, the energy absorption ability of a 1-D array of buckyball system is studied. It is found that regardless of the direction of alignment and number of buckyballs, the unit energy absorption density is almost the same for low-speed impact. In addition, different 3-D stacking at various impact speeds and stacking forms are investigated. Explicit empirical models are suggested where packing density and impact speed may pose a positive effect on the unit energy absorption. This study may shed lights on the buckyball dynamic mechanical behavior and its application in energy absorption devices and inspire the related experimental work.

## Authors’ information

JX is a Ph.D. candidate in Department of Earth and Environmental Engineering at Columbia University, supported by the Presidential Distinguished Fellowship. His research interests are nanomechanics and energy-related materials. YL is a Professor in Department of Automotive Engineering at Tsinghua University. He has been awarded by the National Science and Technology Advancement Award (second prize) for twice. His major research interests are advanced energy absorption material. YX is a Professor in School of Energy Science and Engineering at University of Electronic Science and Technology of China. His research is focused on combinatorial materials research with emphasis on energy applications, particularly on thin film materials and devices, printed electronics, and power electronics. He has authored and co-authored more than 40 articles, with an *h*-index of 12. XC is an Associate Professor in Department of Earth and Environmental Engineering at Columbia University. He uses multiscale theoretical, experimental, and numerical approaches to investigate various research frontiers in materials addressing challenges in energy and environment, nanomechanics, and mechanobiology. He has published over 200 journal papers with an *h*-index over 30.

## Declarations

### Acknowledgments

The work is supported by National Natural Science Foundation of China (11172231 and 11102099), DARPA (W91CRB-11-C-0112), National Science Foundation (CMMI-0643726), International joint research project sponsored by Tsinghua University (20121080050), Individual-research founding State Key Laboratory of Automotive Safety and Energy, Tsinghua University (ZZ2011-112), and World Class University program through the National Research Foundation of Korea (R32-2008-000-20042-0).

## Authors’ Affiliations

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