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Barrer, R.M. and Edge, A.V., : Gas hydrates con-
taining argon, krypton and xenon: kinetics and
energetics of formaion and equilibria. Proc. R. Soc.
Lond. , .
Gudmundsson, J.S. and Borrehaug, A., : Frozen
hydrate for transport of natural gas. Proceedings
of nd International Conference on Gas Hydrates,
.
Hiruta, A., Snyder, G.T., Tamaru, H. and Matsumoto,
R., : Geochemical constraints for the forma-
tion and dissociation of gas hydrate in an area of
high methane flux, eastern margin of the Japan
Sea. Earth and Planetary Science Letters, ,
.
Jin, U., Nagao, J., Hayashi, J., Shimada, W., Ebinuma,
T. and Narita, H., : Observation of Xe hydrate
growth at gas-ice interface by microfocus X-ray
computed tomography. J. Physical Chemistry C,
, .
Kanda, H., Uchida, K., Nakamura, K. and Suzuki, T.,
: Economics and energy requirements on nat-
ural gas ocean transport in form of natural gas
hydrate (NGH) pellets. Proceedings of the Fifth
International Conference on Gas Hydrates,
.
:
.
Maruyama, M., : Roughening transition of prism
faces of ice crystals grown from melt under pres-
sure. Journal of Crystal Growth, , .
Ohmura, R., Matsuda, S., Uchida, T., Ebinuma, T. and
Narita, H., : Clathrate hydrate crystal growth
in liquid water saturated with a guest substance:
Observations in methane water System. Crystal
Growth & Design, , .
Servio, P. and Englezos, P., : Morphology of met-
hane and carbon dioxide hydrates formed from
water droplets. AIChE J., , .
Shimada, W., Jin, S., Takeya, S., Nagao, J., Ebinuma,
T. and Narita, H., : In situ observation of gro-
wth and dissociation of Xe clathrate hydrate on
ice. Proceedings of the Fifth International Confer-
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TO HIMADA AGAO
BINUMA ARITA
ence on Gas Hydrates, . Tanaka, R., Sakemoto, R. and Ohmura, R., : Crys-
Sloan, E.D. Jr. and Koh, C.A., : Clathrate hydrtate tal growth of clathrate hydrates formed at the
of natural gases. rd edition, CRC Press, . interface of liquid water and gaseous methane,
: ethane or propane: variations in crystal morphol-
ogy. Crystal Growth & Design, , .
. Uchida, T., Ebinuma, T., Kawabata, J. and Narita, H.,
Takaoki, T., Hirai, K., Kamei, M. and Kanda, H., : : Microscopic observations of formation pro-
Study of natural gas hydrate (NGH) carriers. Pro- cesses of clathrate-hydrate films at an interface
ceedings of the Fifth International Conference on between water and carbon dioxide. J. Crystal Gro-
Gas Hydrates, . wth, , .
Masato I , Wataru S *, Jiro N ,
Takao E and Hideo N
: We carried out “in situ” observation of the growth of the Xe clathrate hydrate crystal on
an ice surface at various pressures and temperatures. Xe hydrate nucleated and grew along the ice
surface. The growth morphology changed with an increase in excessive pressure as follows:
polygonal, middle type and circular. The analysis of growth rate and morphology indicated layer by
layer growth at excess pressure below . MPa. At excess pressures below . MPa, the growth of
the Xe hydrate would be controlled by the formation of a screw dislocation. The growth mechanism
changed to adhesive growth at excess pressure above . MPa, because of roughening, and the
corresponding growth morphology changed to circular.
) Graduate School of Science and Engineering for Education, Earth Sciences,
University of Toyama, Gofuku, Toyama .
) Graduate School of Science and Engineering for Research, Earth Sciences,
University of Toyama, Gofuku, Toyama .
* Corresponding author
) National Institute of Advanced Industrial Science and Technology, AIST,
Tsukisamu-Higashi , Sapporo .
Abstract
Growth morphology and mechanism of Xe clathrate hydrate crystal
on ice surface
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