Italian pharmacy online: cialis senza ricetta medica in farmacia.
Available online at www.sciencedirect.com
Chemical Physics Letters 447 (2007) 316–319
He intercalated C60 solid under high pressure
Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho,
Received 26 July 2007; in ﬁnal form 19 September 2007
In situ synchrotron X-ray diﬀraction measurement of solid C60 under high pressure up to about 26 GPa was performed using He gas
as pressure transmitting medium. This is the ﬁrst study to precisely investigate the structural property of the He intercalated C60 underhigh pressure in a few tens GPa range. It was found that the He intercalated C60 solid is much less compressible than the pure C60 solid.
The bulk modulus of the He intercalated C60 solid is determined to be B0 = 35.1 (6.0) GPa. The eﬀect of hydrostaticity on the deforma-tions of unit cell and C60 molecule is also discussed.
Ó 2007 Published by Elsevier B.V.
est. Although many experimental investigations on the ful-lerene polymers have been performed, the formation
Fullerenes have attracted much attention not only from
mechanism of the fullerene polymers has not yet been clar-
an academic point of view for their extraordinary molecu-
lar structures, but also from an industrial point of view for
In order to elucidate the formation mechanism of the
their unique physical and chemical properties. For exam-
fullerene polymers and the elastic property of the C60 mol-
ple, the elastic property of the C60 molecule is quite inter-
ecule, it is very important to investigate the structural
esting because its bulk modulus is calculated to be
change of fcc–C60 under high pressure. In fact, many exper-
greater than 700 GPa which signiﬁcantly exceeds that of
iments concerning the high pressure behavior of C60 have
already been done . However, since only restricted exper-
High pressure and high temperature (HPHT) treatments
imental techniques and a small sample space are allowed
of solid C60 (fcc–C60), in which C60 molecules are bound
for high pressure experiments, it has not been very easy
together by weak van der Waals forces, produce a variety
to get high resolution structural data under high pressure.
of polymerized C60 phases known as ‘fullerene polymers’
On the other hand, experimental techniques to investigate
The polymerized fullerenes consists of hybrid net-
ﬁne structures under pressure have recently undergone sig-
works of sp2 and sp3 carbon atoms and are classiﬁed as a
niﬁcant advances. For example, synchrotron radiation and
new family of crystalline carbon Therefore, they are
a 2-dimensional detector (e.g., imaging plate, CCD detec-
expected to have diﬀerent properties from those of the
tors, etc.) make it possible to get high resolution diﬀraction
other carbon phases such as graphite, diamond, fcc–C60,
data of small powder sample. Using noble gases as the
and carbon nanotubes. Recently, it was reported that C60
pressure transmitting media expands the upper pressure
molecules in peapods also polymerize by compression at
limit applicable for hydrostatic pressure experiments. Due
room temperature and it has been attracting much inter-
to the above mentioned experimental advances, it hasnow become possible to obtain high resolution diﬀractiondata up to a few tens GPa. However, in the case of C60,
one must pay attention to the choice of the pressure trans-
Corresponding author. Fax: +81 52 735 5221.
E-mail address: (S. Kawasaki).
mitting medium, because some noble gases with small
0009-2614/$ - see front matter Ó 2007 Published by Elsevier B.V.
S. Kawasaki et al. / Chemical Physics Letters 447 (2007) 316–319
atomic sizes can penetrate in the lattice of C60 solid. Schir-ber et al. and Pintschovius et al. pointed out the
penetration of He and Ne gases into the C60 lattice. They
also investigated the eﬀect of the penetration on the high
pressure behavior of the solid C60. However, their experi-
ments are limited to the low pressure range below 1 GPa
and the lattice volume change due to the intercalation is
quite small. Therefore, the structural property of the noble
still not known. In this study, we report the results of the
in situ synchrotron XRD measurements of solid C60 under
high pressure up to about 26 GPa using He gas as the pres-
The in situ XRD measurements of fcc–C60 (>99.99%)
under high pressure were performed using a diamond anvil
cell at the beam line BL-10XU of SPring-8. Two kinds ofexperiments were carried out: one used He gas as the pres-sure transmitting medium and the other used a 4:1 mixtureof methanol and ethanol. For convenience, the former and
the latter experiments are abbreviated Exp-He and Exp-
M + E, respectively. The pressure was determined by the
ruby ﬂuorescence method. The XRD patterns were
observed using an imaging plate detector.
a and b show the changes in the XRD patterns of
the fcc–C60 in Exp-M + E and Exp-He as a function of
pressure, respectively. Comparing a and b, no extra
diﬀraction peak can be observed by the penetration of Hegas and all the diﬀraction lines can be indexed by cubic lat-
tice. Since the alcohols mixture of methanol:ethanol = 4:1
used in Exp-M + E (does not freeze up to about
10 GPa, it has been reported to be possible to perform a
hydrostatic pressure experiment up to its solidiﬁcation
pressure using this mixture It was also observed in
Fig. 1. Changes in XRD patterns of fcc–C60 (a) in alcohol mixture, and
the present study (that the full width at half max-
(b) in He gas pressure transmitting medium.
imum (FWHM) of the observed 2 2 0 diﬀraction peakabruptly increased from about 10 GPa ) probablydue to the nonhydrostatic eﬀect. In the FWHM val-
lecular bonding, the ratio a/RC changes with pressure and
ues were determined by ﬁtting the observed data with a
the accidental absence of the 2 0 0 line is eliminated at high
pseudo voight function. On the other hand, in the Exp-
pressure. In other words, the relative intensity of the 2 0 0
He experiment, no remarkable change in the FWHM of
peak at high pressure expresses the degree of the change
of the a/RC ratio from ambient pressure. Therefore, the dif-
Another important diﬀerence between and b is
ference in the relative intensity of the 2 0 0 peak in Exp-He
the relative intensity of the 2 0 0 diﬀraction peak at about
and Exp-M + E indicates that the compression behaviors
the same pressure. Although in both a and b, the
of the C60 molecule and/or fcc lattice diﬀers in the two
2 0 0 peak can be observed at high pressure, the peak in
Exp-M + E appears at a pressure lower than that in the
shows the lattice constant a determined by the
Exp-He. The scattering factor of the 2 0 0 peak position,
observed diﬀraction patterns of the two kinds of experi-
which is determined by the ratio of the lattice constant a
ments. The pressure dependence of the a values of Exp-
and the molecular radius RC, is accidentally almost 0 at
M + E is in good agreement with previous reports, especially
atmospheric pressure. However, since the intramolecular
with Duclos’s experiment in which the same alcohols
bonds are signiﬁcantly less compressible than the intermo-
mixture pressure transmitting medium was used. By ﬁtting
S. Kawasaki et al. / Chemical Physics Letters 447 (2007) 316–319
penetration of He into the C60 lattice. By applying the sameanalysis method as in the case of Exp-M + E, the B0 and B0
values of the He intercalated C60 solid are determined to be35.1 (6.0) GPa and 4.1 (1.1), respectively.
The main reason why the 2 0 0 diﬀraction peak of Exp-
M + E appeared at a lower pressure than that of Exp-Heis probably due to the diﬀerence in the lattice compressibil-ity mentioned above. If the pressure deformation of the C60
molecule diﬀers in Exp-M + E and Exp-He, it would be an
another possible explanation for the anomaly of the 2 0 0peak. The deformation can be analyzed using the relativediﬀraction intensities. In , the relative intensities ofthe 2 0 0 peak in the two experiments to the 1 1 1 and 2 2 0diﬀraction peak intensities are plotted as a function of
the lattice constant a. The solid curves in are the
curves calculated using the following conditions: the C60
molecular scattering factor can be approximated by the
Fig. 2. FWHM of 2 2 0 peaks as a function of pressure. Solid circles and
0th order spherical Bessel function, and the radius of the
open diamonds correspond to Exp-M + E and Exp-He, respectively.
molecule is ﬁxed at 0.35 nm. Therefore, the solid lines indi-cate the relative intensities when the deformation of C60molecule does not occur and only the lattice shrinks bycompression.
Although the relative intensities I2 0 0/I1 1 1 and I2 0 0/I2 2 0
signiﬁcantly diﬀer in Exp-He and Exp-M + E as a functionof the pressure and b), those plotted as a function
of a do not show any remarkable diﬀerence at least in the
˚ . In the case of Exp-He, since both the
Fig. 3. Lattice constant a as a function of pressure. Solid circles and open
diamonds correspond to Exp-M + E and Exp-He, respectively. Solid linesare ﬁtting curves using Birch–Murnaghan’s equation of state.
the relative unit cell volume change (V =V 0 ¼ a3=a3, where V
0 are unit cell volume and lattice constant at ambient
pressure, respectively) with pressure to the Birch–Murna-
ghan’s equation of state (P = 1.5B0[(V/V0)À7/3 À (V/V0)À5/3][1 + 0.75(B0 À 4)((V/V
and its ﬁrst pressure derivative B0 are determined to be
15.8 (1.7) GPa and 6.4 (0.4), respectively. These values are
B0 = 5.3 (0.6). It should be noted that the B
Fig. 4. Relative intensities of I2 0 0 to (a) I2 2 0 and (b) I1 1 1 as a function of
of the present Exp-M + E agree fairly well with Horikawa’s
the lattice constant a. Solid circles and open diamonds correspond to Exp-
M + E and Exp-He, respectively. The solid lines denote the lines simulated
which was performed using a multianvil press with no liquid
with a spherical shell model (see text in detail). The errors were estimatedfrom the ﬁtting errors. Some error bars are within the data marks.
pressure transmitting medium. On the other hand, the pres-
Pressures are: A (0.1 MPa), B (5.5 GPa), C (10.6 GPa), D (15.0 GPa), E
sure change of the lattice constant a derived from Exp-He is
(18.6 GPa), a (0.1 MPa), b (2.1 GPa), c (5.2 GPa), d (10.3 GPa), e
more gentle than that of Exp-M + E probably because of the
(14.4 GPa), f (18.0 GPa), g (22.0 GPa), h (25.9 GPa).
S. Kawasaki et al. / Chemical Physics Letters 447 (2007) 316–319
I2 0 0/I1 1 1 and I2 0 0/I2 2 0 data points (the data at 22.0 GPa
the pure C60 solid (B0 = 15.8 GPa). Diﬀraction intensity
and 25.0 GPa are missing in because the 1 1 1 dif-
analysis revealed that the intensity ratio (e.g., I2 0 0/I2 2 0)
fraction peak could not be detected at those pressures
deviates from the isotropic lattice compression model at
(b)) are in good agreement with the calculation, it
about 10.6 GPa in the case of the experiment using the
is indicated that the C60 molecules of Exp–He do not
alcohol mixture as the pressure transmitting medium. It
deform very much even at high pressure. Although this is
indicates that the C60 molecular shape begins to deform
probably due to the good hydrostaticity of the He pressure
transmitting medium, it should be also considered that theintercalated He might protect C60 from deformation. Onthe other hand, the I
2 0 0/I1 1 1 and I2 0 0/I2 2 0 data of Exp-
M + E disagree with the calculation curves on the left sides
 R.S. Ruoﬀ, A.L. Ruoﬀ, Nature 350 (1991) 663.
 Y. Iwasa, Science 264 (1994) 1570.
be due to the molecular deformation caused by a nonhy-
 M. Nu´n˜ez-Regueiro, L. Marques, J.-L. Hodeau, O. Bethoux,
drostatic shear stress at high pressure. In Exp-M + E, a
M. Perroux, Phys. Rev. Lett. 74 (1995) 278.
liquid pressure transmitting medium was used. However,
 V.D. Blank, S.G. Buga, G.A. Dubitsky, N.R. Serebryanaya, M.Yu.
since within the experimental errors, the obtained bulk
Popov, B. Sundqvist, Carbon 36 (1998) 319.
 X. Chen, S. Yamanaka, K. Sako, Y. Inoue, M. Yasikawa, Chem.
modulus coincides with the value of Horikawa’s experi-
ment, which was performed with a solid pressure transmit-
 C. Goze, F. Rachdi, L. Hajji, M. Nu´n˜ez-Regueiro, L. Marques,
ting medium, the hydrostaticity should not be perfect and
J.-L. Hodeau, M. Mehring, Phys. Rev. B 54 (1996) R3676.
the nonhydrostatic components may not be negligible.
 S. Kawasaki, Chem. Phys. Lett. 418 (2006) 260.
 T. Horikawa, K. Suito, M. Kobayashi, A. Onodera, Phys. Lett. A287
 S.J. Duclos, K. Brister, R.C. Haddon, A.R. Kortan, F.A. Thiel,
 J.E. Schirber, G.H. Kwei, B. Morosin, Phys. Rev. B 51 (1995)
This is the ﬁrst time that the precise structural property
 L. Pintschovius, O. Blaschko, G. Krexner, N. Pyka, Phys. Rev. B 59
of the He intercalated C60 solid under high pressure in a
 G.J. Piermarini, S. Block, J.D. Barnett, J. Appl. Phys. 44 (1973)
few tens GPa range has been investigated. It was found
 H. Horikawa, T. Kinoshita, K. Suito, A. Onodera, Solid State
0 = 35.1 GPa) is much less compressible than that of
WELLNESS INSIDER AUSGABE 19 Vitalität für den Mann - ein Leben lang Von den zahlreichen Kräutern, die das menschliche Wohlbefinden steigern, gibt es einige, die ganzbesonders für den männlichen Körper und seine Bedürfnisse geeignet sind. Zusammen mit Geheimnissen aus der traditionellen chinesischen Medizin entstand daraus SuperMale FormulaTM von Platinum, die Wellness Formel
Curriculum Vitae Habibolah Khazaie Personal History: • Birth: 1971.03.21, Kermanshah, Iran • Marital Status: Married • Address: Farabi Hospital, Sleep Research Center, Department of Psychiatry, Kermanshah University of Medical Sciences, Dolatabad Blvd, PO box: 6719851151, Kermanshah, Iran. • Phone: +98-918-8332426 (Cell Phone) • Email: firstname.lastname@example.org