Mechanical Properties of

Methane & Propane Hydrate

The problem is to estimate the elastic and plastic properties of a

hydrocarbon-water hydrate deposit forming in a condensate pump at
approx 1100psi, 55oF (13oC). The particular mixture of methane and
propane is stable at 635psi, 63.5oF (44bar, 17.5oC).
Estimation of mechanical properties is attempted using Prof. Ashby's
"Isomechanical Classes of Materials" technique whereby:
1 Materials are grouped by bond-type (and length) and
crystal structure into classes (e.g. fluorite-structured
transition metal oxides)

2 The parameters that control the mechanisms of plasticity

for each material are normalised in a physically-sensible
manner (e.g. stress/shear-modulus, or
activation-energy/R.melting-temperature)

3 Within each class the normalised parameters have very

similar values, and the mean values can be used as a good
estimate of the properties of other materials of the same
class for which detailed measurements are not available,
e.g.(Tm/GoK).dG/dT below.

This is described in Ch.18 of Frost & Ashby's "Deformation Mechanism

Maps", Pergamon Press, 1982.
Thermophysical Properties
For the structure II hydrates, with approx. 18 moles of water per
propane molecule, the bond-type and length is almost identical to that
of water-ice, i.e. it is hydrogen-bonded. The strength of hydrogen
bonds are weakly dependent on bond-orientation, so several different
crystal structures are possible for water-ice. However, ice I, II and III
have broadly similar mechanical properties so it appears that the
detailed crystal structure does not have a great effect on the strength
of the material.
Thus it appears very likely that the hydrates fall into the same
isomechanical class as water-ice because the bonding is very similar,
although the crystal structure is different. The density of hydrate at
0.78 x 10-3 kg/cm3 is low compared to that of water ice so it is to be
expected that the elastic properties will be similarly reduced, simply on
a basis of the number of H- bonds per unit volume. Therefore it seems
sensible to estimate the fundamental elastic moduli of hydrate to be
78% of that of ice.
(A few of the carbon atoms of the hydrocarbon might participate in H-
bonding, so some of this reduction in density may be due to the
different atomic masses of carbon and oxygen, at most (17.9+3)*16 to
(17.9*16 + 3*12), i.e. propane-hydrate is 96% the mass it would be if
the carbons were replaced by oxygens, so this effect is insignificant.)
(continued)
The normalised parameter which is most useful in correlating the
mechanical properties of materials in the same class is the melting
temperature. There is no melting data available for hydrate, only
decomposition data. An alternative normalision can be obtained from
the energy of formation divided by the gas constant R, the result of
which which has dimensions of temperature:
Heat of Formation
water 188.0 kJ/mol
hydrate 195.3 kJ/mol (188 + 7.54)
Hf/R
water 22.62 K
hydrate 23.50 K
This also leads to a first-guess estimate of a melting point for the
hydrate of 10.6oC, we know this is too low since it must be above the
measured decomposition temperature of 17.5OC, but it is reassuringly
close, evidence that ice and hydrate are in fact iso-mechanically
similar.
The shear modulus of water ice at OoK is 4.04 GPa. The modulus drops
approximately linearly with temperature at a rate of 3.75 x10-3 GPa.K-1,
so the shear modulus at the melting point (273 K) is 3.01 GPa
(extrapolating to 300K would make it 2.91 GPa). The important
normalised parameter is the dimensionless rate of modulus decrease:
(Tm/GoK).dG/dT which for ice is -0.254.
If we take the 0oK shear modulus for hydrate to be 78% of 4.04 GPa we
get 3.15 GPa at 0 K. Using the same rate of modulus decrease:
(Tm/GoK).dG/dT) of -0.254, and using a melting point of 18oC (291K), we
get a shear modulus at 13oC of 2.36 GPa. However an ounce of
experiment is worth a ton of theory and this value should be treated as
the gross estimate that it is.
(On the phone I just quoted the extrapolated 300K value for water-ice of 2.91 GPa.)
(continued)
Plasticity Properties
The important thing about ice, and by extrapolation hydrates, is that it
is immensely strong, much stronger at temperatures close its melting
point than any other class of material (strength being considered
normalised with respect to the moduli). Ice also has a plasticity
mechanism not found in any other material: dislocation glide controlled
by proton-hopping. However this high strength should not blind us to
the fact that we are dealing with a material at over 90% of its melting
point and that therefore its strength is strongly affected by thermal
activation and hence extremely time-dependent.
It is difficult to measure the elastic moduli except by ultrasonic
methods, any slowly applied stress just causes the material to creep.
Conventional mechanical testing machines are usually used to impose
strain rates of about 0.001 per second, "quasistatic" strengths (at 10-
6
/s) will be perhaps only 20% of the testing-machine measured
strength. Wang's data gives approx. 4.7 MPa dropping to around 1 MPa
for quasistatic loading. Conversely, a very rapid explosive shock
(about 100/s) will "see" a much higher strength, perhaps a factor of 10
higher (see Goodman, Frost & Ashby's paper). Thus the slow buildup of
a deposit will be dominated by the "slow" strength, but a pre-existing
plug could withstand a much higher pressure for a very short period of
time.
These strengths for ice could be crudely scaled by the ratio of the
shear moduli for ice and hydrate, i.e. hydrate would be only about 80%
as strong. Clearly the scatter and the rate-dependence of the data for
ice mean that estimates of strength could be at best within a factor of
3 of the real values.
Philip Sargent Feb.3rd 1989
To: Dr. John E. Arregger
J.E.Arregger & Co. Ltd.
16A King Street
Twickenham TW1 3SN
(01)-891-1242
enc.
Ch18 of Frost & Ashby,
Acta Met. 43 665-695, Goodman, Frost & Ashby
short paper by Sinha
1 page from Wang 1982.