Chapter 30

THERMODYNAMICS OF FLUIDS IN
MESOPOROUS MEDIA
Application to capillary pumped loops and loop heat
pipes

A. H. Reis
Departm ent of Ph ysics, Uni versity of Evora
R ua Rom iio Ramalho 59, 7000-67 1 Euora, Por tugal

1. Introduction
The pore size range of t he mesop orous medi a is ty pically 2- 50 nm. These
sizes are found in inorganic xerogels, e.g alumina and silica powders,
porous glasses and pillar ed or non-pillared clays. They are also found
in meso-structurat ed materials of t he M41S-typ e t hat have an orde red
pore system , see Beck et al. [2]. A great variety of pore st ructures
can be found in mesop orous materials: crystalline (mainly hexagon al),
polyhedral , lam ellar , pillared , nan otubes (carbo ns), 'hairy t ubes ' , etc.,
see Bejan et at. [3] .
Mesop orous materials can take up rela ti vely large amounts of gas
condensed on the inn er sur face (adso rpt ion) and may have also it s void
space partially or to tally filled wit h a liquid phase (sor ption).
Gas adsorpt ion on the pore inner surface of mesoporous materials
t akes place at low sub-saturation P / P, < 0.3. As the gas pressure in-
creases, the narrowest pores first and then all the pores become progress-
ively filled with t he liquid ph ase. Pore filling develops in a wide pressure
rang e 0.3 < P/ P, < 1 un til all the pores become com pletely filled closely
before t he saturation pr essure. In a porous material in equilibrium with
a gas at temperature T and sub-sat ur ation P/ P, pores with wid th lower
than d are complete ly filled wit h the liquid ph ase of density PL following
t he Kelvin equation

P ( 4')'cos () ) (30.1)
Ps = exp - dpLRgT '

465
D.B. Ingham et al. (eds.) , Emerging Technologies and Techniqu es in Porous Media, 465--475.
© 2004 Kluwer Academic Publ ishers. Printed in the Netherlands.
466 EMERGING TECHNOLOGIES AND TECHNIQUES

e
where "( stands for surface tension, is the liquid -solid contact angle
and Rg is the specific gas constant. The pore size range of mesoporous
materials is defined as the same for the range of application of t he Kelvin
equation. In these materials the surface tension of the liquid -fluid inter-
faces is as important as pressure and gravity forces and t herefore cannot
be neglected.
Usually, the amo unt of fluid within a porous material at a given temp-
erature is represented by the respective adsorption/desorption isotherms
as t hat represented in Figure 30.1, which is a type IV isotherm, see Gregg
and Sing [6].
The plateau at the end of t he isotherm (close to P/ P, = 1) corres-
ponds to comp lete pore filling. Adsorption isot herms of different fluids
in the same material coincide at this plateau provided that the amount
adsorbed is expressed in terms of the equivalent volume of the liquid
phase (Gurvitsch rule), see Gregg and Sing [6]. Desorption isotherms of
many mesoporous materials do not coincide entirely with the resp ective
sorption isotherms, showing a hysteresis loop in the part corresponding
to pore filling, see Figure 30.l.
The high internal surface area enables a wide range of applications of
mesoporous media. These materials ar e used as catalysts, in separation
processes (e.g. pressure swing adsorption and thermal swing adsorption
processes), in electronics (e.g. tantalum capacitors) and also in heat
transfer devices, e.g. adsorption heat pumps, capillary pumps, loop
heat pipes.

100

80

z
OIl 60
;§ Desorption - j - Adsorption
t=
~
40
0
c,
20

0
0 0.2 0.4 0.6 0.8
PIPs

Figure SO.l . Typical adsorption isotherm of a gas in a mesoporous material exhibit-

ing adsorption/desorption hysteresis.
THERMODYNAMICS IN MESOPORO US MEDIA 467

2. Pore scale hydrodynamics

Mass flux within un saturated porous media is a pro cess that involves
at least two of the following ph ases: gas , adsorbe d phase and liquid
ph ase. At low sub-sa t uration mass transport develops through adsorp-
tion/desorption processes that involve ph ase-change ent halpies that are
usu ally high er than condensation ent halpies. At int ermedi ate and high
sub-saturation mass t rans port occurs mainl y by evaporation at some li-
quid vapor int erface followed by vapor t ransport and conde nsat ion on
t he next int erface followed by t ransport in t he liquid ph ase. Heat and
mass flows are st rongly coupled since lat ent heat is carried by the vapor
between the int erfaces. The forces driving these fluxes are the pressure
and temp erature grad ients exist ing within t he materials.
Curved liqu id-vapor interfa ces in thermodyn ami c equilibri um within
the pores exhibit pre ssure differences between liquid and vapor according
to the Youn g-Lapl ace equa tion
p _ P _ 4, cos (J
(30.2)
v L - d

For wetting fluids, t he contact angle is smaller t han 90°, whi ch means
that the pressure in the liquid is sm aller t han the gas (vapor) pr essure
wh ile for non-wet ting fluids t he opposite occurs since (J > 90°.
Liquid-vapor equilibrium is ass umed t o exist at the interface and
therefore the Clausius-Clapeyron equa t ion relates t he pr essure to tem-
p erature as follows:

P = Po exp [- '~; (~ - ~o) ] , (30.3)

where (Po, To) is a reference state and hLV is t he liquid-vapor ph ase-

change ent halpy.
By definin g t he dimensionless t emperature as T * = (Rg/hLV)T and
d imensionless pore diam et er d* = (phLVh cos (J)d, and t aking int o ac-
count the equat ions (30.1) and (30.3), t he vapor pressure in equilibrium
with liquid at a cur ved interface becomes

P = Po exp [-~
T*
(1 +~ ) + ~] .
d* To
(30.4)

For differences in temperature such that t:..T*/ T* « 1, the vap or pres-

sure difference between two successive menisci 0: and (3, see Figure 30.2,
is given by

PO' - P{3 1 ( 4) 1 ( 4 ) (30.5)

(P) >:::; T~ 1+ d~ - T; 1 + d:X '
468 EMERGING TECHNOLOGIES AND TECHNIQUES

Solid

Liquid a T~ d'o
Po
Liquid

Vapor

Solid

Figure 30.2. Liquid and vapor within a pore. P ressure and t emperature of t he vapor
in equilibrium with the liqu id dep ends on the radius of cur vat ure of t he interface.

wher e (P) st ands for the average pr essure of the vapor within the pore.
This equation shows how the pressure difference within t he pores, which
is a driving force for fluid flow, is influenced by temp erature and pore
width. Equation (30.5) indicates that when vapor is in mechanic al equi-
librium, i.e. at null vapor pressure difference between successive menisci,
the resp ective temp erature ratio gives
Ta*
(30.6)
T*
(3

On t he other hand , when the vapor is in thermal equilibrium, i.e. at

null te mpera t ure difference between successive menisci , t he pressure dif-
ference is given by

r; - P(3
(P) ;:::; T*
4(1d~ - d:X1) ' (30.7)

which is th e Young-Lapl ace equation. Equations (30.6) and (30.7) show

that unless the width of t he pores containing the menisci are equal,
thermal and mechanical equilibrium will never exist together.
Figure 30.3 illustrates how t he pressur e difference behaves in some
ran ges of relative tempera t ure and pore widths and shows th at the tem-
perature and pressure gradients may have eit her the same , or the op-
posite direction depending on the relative pore width ratio. As vapor
flows against pr essure gradient , Figur e 30.3 shows that the vapor must
flow in the dire ction of the temp erature gradient when Pa - P(3 > 0 and
T~ /T; < 1 or when Pa - P(3 < 0 and T~ /T; > 1 and must flow against
the temperature gradient when Pa - P(3 < 0 and T~ /T; < 1 or when
i; - P(3 > 0 and T~ /T; > 1.
THERMODYNAMICS IN MESOPORO US MEDIA 469
d~ / diJ =
. -- - - - - - - - - - - - - - - - - - - - - - - - ' , 2 5
10
1.2
2

0.8 I
0.8
~ 0.4
I

~ o -t-"""------::::""~'--_=.......,:=------------1

-0.4

- 0.8 + - - -- ---,.------ -- - - - - , - - - - - - --1

0.98 1.02 1.04

Figure 30.3. Relative vapor pressure between menisci a and j3 as a funct ion of t he
t emperature ra tio for variou s por e diam et er ra tios, where TJ = 0.055 and d~ = 100.

In short, internal geometry plays a role as important as that of tem-

perature when defining equilibr ium vap or pressure within porous media.
This is why we can have count less adsorpt ion isotherms matchin g t he
same vapor pr essure. As a prac tical consequ ence, th e pore size distri-
bution of a mesoporous material can be obtain ed from gas or vapor
ad sorption isotherms. Another pr actical consequence is that adsorption
isotherms, which are constitutive relations between mass concentration,
pressure and temperature, may be helpful when dealing with heat and
mass fluxes within mesoporous mat erials, see Reis and Rosa [12] .

3. Capillary pumped loops (CPL) and loop heat

pipes (LHP)
One of the approaches to enhance cooling of small spaces involves th e
use of capillary pumped loops (CPL) and loop heat pipes (LHP) . The
CPL consists of sealed t ubes connecting a heat sour ce, the evaporator
whose major part is a porous wick, with a heat sink , the condenser, see
Figure 30.4. The liquid phase of the working fluid circulates in the CPL
utilizing t he capillary pr essure gradient develop ed in the porous wick.
Vapor pressure in the evaporat or must be high er t han in t he condenser
in order to keep th e syste m work ing.
The circulatin g fluid evaporates at th e evapora t or where heat is ab-
sorbed and t hen is transferre d by th e vapor in the form of latent heat
to the condenser where is released .
Although the total mas s of th e working fluid is constant within the
loop , t he amount of liquid ph ase decreases with the heat load . T he
470 EMERGING TECHNOLOGIES AND TECHNIQUES

ReseMJU
Porou, Evopaolor Compensatim
w ick charnb: I

t Vap:n

Figure 30.4. Schematic diagram of a Figure 30.5. Schematic diagram of a

capillary pumped loop , CPL (major loop heat pipe, LHP (major parts) .
parts).

function of the reservoir is to provide enough liquid to keep the wick

wet.
The LHP works in way similar to CPL but differs in the arrangement
of its components, see Figure 30.5. The major difference is that in the
LI-IP there is a compensation chamber, embodied in the evaporator, that
has the same function as the reservoir. This design has some advantages
since it makes the system more compact and avoids the piping system
that in the CPL connects the reservoir to the loop .
Although these systems may seem easy to operate some undesired
phenomena might happen, e.g. bubble formation in the compensation
chamber, wick dry out and interface (meniscus) oscillation. Kamotani [7]
and Ku [9] showed that interfacial oscillations can reduce by 90 per cent
the maximum heat transport capability of CPLs. Kaya and Hoang [8]
studied the use of a primary and a secondary wick within the evaporator
in order to prevent wick dry out. Muraoka et at. [11] investigated the
replacement of the usual tube condenser by a porous wick in order to fix
condenser pressure.
Choosing the working fluid depends upon the application. Although
water and ammonia are among the most common, several other fluids
have been tried . Chandratilleke et at. [4] analyzed nitrogen, neon, hydro-
gen and helium as working fluids that enable LHP working temperatures
as low as 70 K , 28 K, 15 K and 4 K, respectively. With the purpose of en-
hancing heat load and temperature range, Zhang [14] suggested the use
of new working fluids, which have positive variation of surface tension
with temperature.
The driving force that maintains the liquid circulating inside the loop
is the capillary pressure pumping head, t:J..PdL, at the evaporator that
must balance all pressure losses along the liquid line, i.e.
(30.8)
where tlPdL is given by equation (30.2) whenever the pressure is constant
along the vapor line, tlPw is the pressure loss in the wick that is the
THERMODYNAMICS IN MESOPORO US MEDIA 471

major pressure loss in the whole system, tlPL stands for the pressure
drop du e to flow of the liquid and tlPg = -pgtl z is t he pressure drop
in the liquid du e to gravity.
The Dar cy- Weisb ach equation gives t he pressure drop in a channel of
length L and width d du e t o hydrodynamic effects as follows:
2
tlP =
w
fF:..d pv2 .
.
(30.9)

where f = 64/Re for laminar flow, see White [13, p . 338], and p and v
st and for the fluid density and average fluid velocity, resp ectively. If d,
A w and E denote the wick charac te rist ic pore width , wick area and wick
porosity, resp ectiv ely, t hen the liquid flow rate per pore is of t he order
of PLvd 2 and the number of pores in the wick sur face is of t he ord er
of A w E2 / 3d - 2 . If TnL denot es the liquid flow rate within the wick, then
equation (30.9) may be written as follows:
32//LL .
tlPw = 2/3 2 Tn L· (30 .10 )
A wE d
In a simil ar way, within t he piping system the pressure drop in t he liquid
is given by
32//LLL .
tlPL = D 4 TnL , (30 .11)
where D is the diam et er of t he piping syste m and the subscript L stand
for liquid. As D f d ;» 1, by insp ection of equa t ions (30.9)-(30.11) we can
confirm that the major pressure drop occurs in t he evaporat or and is du e
to the flow within t he wick. Reducing L might minimize the pressure
drop in the wick but t he wick channels have to have a length suitable t o
prevent wick dr y out . These aspects are examples of the import an ce of
pore sh ap e for wick design.
If the wick channels are complete ly filled with liquid and if the hydro-
static pressure tlPg = pgtl z is neglect ed , e.g. a loop in the horizont al
plane, and tak ing into account equat ions (30.8), (30.10) and (30.11),
then the mass flow rate in the liquid ph ase must comply with the in-
equa lity
. ~ A w E2/ 3 , cos e d/ D
TnL ~ 8//L L/ D + D-2 A wE2/ 3 (d / D)2 (L L/ D) ' (30.12)
which sets a limit for the wick pumping capability that dep ends upon
the wick po re ratio d/ D , and upon t he ratios LL / D and L / D.
Vapor flows between t he evaporat or and the condenser under the pres-
sure difference

tlPd
v
~ (P) ~
T*
c
(1 + ~) - .l. (1 + ~)l '
D* T*e d'
(30.13)
472 EMERGING TECHNOLOGIES AND TECHNIQUES

where we used equat ion (30.5), D* = (PLhLV h cosO)D and the sub-
scripts c and e st and for condenser and evaporator, resp ectively. In a
way similar to the liquid flow, the driving force for the vapor flow must
be higher than, or equal to , t he pressure drop along the vapor line, i.e.
32v v L v .
t:lPdv ;?: D 4 m v, (30.14)

where the subscript v means vapor. Using equat ions (30.13) and (30.14),
we obtain the following:
4
m s:: (Pv) hLVD [~ (1 _ Tc ) + _1 (1 _ Tc D)] (30.15)
v '" 8v vLv 4 T; D* T; d '
which sets a limit for t he vapor transfer rate between t he evaporator and
the condenser, which dep ends upon the wick por e ratio d/ D and upon
the ratio between condenser and evapora t or temp eratures. It is import-
ant to note that the same liquid flow rate can correspond to count less
vapor flow rat es. Nevertheless , st abl e operations occur when t he vapor
mass flow rat e equals th e liquid mass flow rate, i.e.
(30.16)
Stabl e operation points for t he temp erature rat ios 0.92, 0.95 and 0.98
are represented in Figur e 30.6 as a function of the pore wick load, L / D ,
t hat measures the height of liquid in the wick pores in units of pip e
diamet er , see also Figure 30.7.
In Figure 30.6 the points above the stable operation cur ve corres pond
to excess of vapor flow rate while the points below correspond to insuf-
ficient vapor flow. Wick dr y out may occur when the vapor flow rate
becomes higher than t he liquid flow ra te. The syst em self-adjusts the
perform an ce to some exte nt around the stable operation cur ve. As the
temp erature ratio increases the height L of liquid in the wick lowers, in
ord er to redu ce the internal resistan ce of the wick to liquid flow. How-
ever, as the difference between evapora t or and condenser temperature
becomes higher and higher t hen complete wick dr y out may be achieved
as it occurs close to mv = 0.05 kg/ s for the case represent ed in the Fig-
ure 30.6. Liao and Zhao [10] have verified experimentally the effect of
wick load L / D upon heat t ransfer rate.
Other asp ects of loop two-phase flow have not been considered here .
One of the most intriguing is that the operation of CPLs in space (low
gravity) has generally been unabl e to match ground-based performance
due to liquid slug formation in the vapor return line, see Allen et al.
[1]. Capill ary fingering limits also the operating ran ge of the CPLs, see
Figus et al. [5].
THERMODYNAMICS IN MESOPOROUS MEDIA 473

0.1.,- -- --------------------- - ,
0.01 Liquid
Vapor

I
0.001 =1 - - ----1k - - -
TriTe = 0.92
7~ (Te = 0.!J5
----'- '----'-- - - - - - -"--- - +- - - ---j

0.00011==~~====~===~~::~~~==~~
o 0.01 0.02 0.03 0.04 0.05
L(D

Figure 30.6. Mass flow rates be tween t he evapor at or and t he condenser as a function
of t he wick load L ID . Stable ope ra tion corresponds to points whe re the vapor mass
flow rate curves meet the liquid mass flow rat e cur ve. The curve corresponding to
stable op erations coincide with the liquid flow rate cur ve. The curves correspond to
water (around 290 K) as working fluid and t o wick porosity E = 0.5 , relative pore
width diD = 10- 6 and shape factor A wd - 2 = 10, pip e di am eter D = 0.01 m and
length of vapor and liquid lines L; = LL = 1 m. The heat transfer rate is between
394 W at TciT e = 0.98 and 2800 W at 'I'c I'I'e = 0.92.

Vapor

D
Liquid

Figure 30.1. Schematic diagram of the wick with the me nisci attached to the upper
side of the channels.

4. Conclusions
T he ana lysis of two-phase flow in mesoporous media has made clear t hat
surface te nsion effects have to be considered in t he calculations. One of
t he master equations here is t he Kelvin equation (30.1) t hat combines
wit h t he Cla usius-Clapeyron equation (30.3) to give t he equ ilibriu m
vapor pressure wit hin t he pores. Depending upon the pore widt h, the
equilibri um vapor pressure is always lower t han the bulk equilibri um
474 EMERGING TECHNOLOGIES AND TECHNIQUES

temperature as shown by equation (30.5). The other master equation

is the Young-Laplace equation (30.2) that describes the pressure drop
between the liquid and vapor at an interface.
The pressure drop at liquid-vapor interfaces (menisci) is a driving
force for fluid flow, while the temperature difference between menisci
lead to a vapor pressure difference that is a driving force for vapor flow.
Capillary pumped loops (CPL) and loop heat pipes (LHP) take advant-
age of both effects in order to drive evaporating!condensing cycles that
transfer heat from a source to a sink . CPL and LHP systems act upon
the same basic evaporating cycle, the key element being the evaporator,
which is a porous wick that connects to a tube condenser through a
piping system.
The operating conditions of the basic evaporating!condensing cycle
have been analyzed and it was found that a stable operation, which
occurs when the liquid flow rate equals the vapor flow rate, depends
on the ratio between temperatures at the condenser, Te , and at the
evaporator, Ts, Excessive heat load on the evaporator can lead to wick
dry out as shown in the Figure 30.6.
Several other aspects like interfacial instability, low-gravity perform-
ance and capillary fingering that have not been considered here are also
very important in CPL and LHP operation.

References
[1] Allen , J. S., Hallinan, K. P. and Lekan, J. (1998) . A study of the fundamental
operations of a capillary driven heat transfer device in both normal and low
gravity. Amer. lnst. Phys . Conf. Proc. , 420, 471-7. Woodbury, New York .
[2] Beck, J . S., Vartuli, J . C., Roth, W. J., Leonowitz, M. E. , Kresge, C. T .,
Schmitt, K. D., Chu, C. T . W ., Olson, D. H., Sheppard , E. W ., McCullen,
S. B., Higgins , J. B. and Schlenker, J. L. (1992). A new family of mesoporous
molecular sieves prepared with liquid crystal templates. J. Amer. Chem . Soc.,
114, 10834-43.
[3] Bejan, A., Dincer, I., Lorente, S., Miguel , A. F . and Reis , A. H. (2004). Por-
ous and complex flow structures in modern technologies. Springer-Verlag, New
York.
[4] Chandratilleke, R., Hatakeyama, H. and Nakagome, H. (1998) . Development
of cryogenic loop heat pipes. Cryogenics, 38, 263-9.
[5] Figus, C., Le Bray, Y., Bories, S. and Prat, M. (1999) . Heat and mass transfer
with phase change in a porous structure partially heated: continuum model
and pore network simulations. Int. J. Heat Mass Transfer, 42, 2557-69.
[6] Gregg, S. J. and Sing , K. S. W. (1982) . Adsorption, surface area and porosity
(2nd edn). Academic Press, London.
[7] Kamotani, Y . (1999). Thermocapillary flow und er microgravity-experimental
results. Adv . Space Res. , 24, 1357-66.
TH ERMOD Y NAMICS IN MESOPORO US MEDIA 475

[8] Kaya , T . and Hoan g, T . (1999). Mathemat ical modeling of loop heat pip es and
experimental valid ation . J . Tti ermoplujs. Heat Transfer , 13, 3 1 4~20 .
[9] Ku, J . (1999). Op er at ing characteristics of loop heat p ipes . Proceedings of the
29th intern ati onal confe rence oj envi ronmental systems, Denver , CO . P ap er no .
981212.
[10] Liao, Q. and Zhao , T . S. (1999) . Evapora t ive heat tran sfer in a ca pilla ry st ruc-
ture heated by a grooved block. J. Thermophus. Heat Transfer, 13, 1 26~33 .
[11] Muraoka , 1., Ramos, F . M. and VI assov , V . V . (2001). Analysis of t he oper a-
tional charac teristics an d limits of a loop heat pip e wit h por ous eleme nt in the
conde nser. Int . J. Heat Mass Transfer', 25 , 2287- 97.
[12] Reis, A. H. and R osa , R. (2002) . Sorption isot herms as a fun d am ental t ool
for the analysis of coupled heat and mass fluxes in porous medi a. Proceedings
of the first interna tio nal conference on applicati ons of porous m edia, J erb a ,
Tunis ia .
[1:1] White, F . M. (1999 ). Fluid mec hanics (4t h ed n ). McGraw-Hill , New York .
[14] Zhan g, N. (2001). Innovati ve heat pi pe sys te ms using a new working fluid . Int .
Com m. Heat Mass Transfer, 28 , 1025- 33.