Accepted Manuscript

Measurement of tortuosity of porous Cu using a diffusion diaphragm cell

Kaikan Diao, Liping Zhang, Yuyuan Zhao

PII: S0263-2241(17)30448-7
DOI: http://dx.doi.org/10.1016/j.measurement.2017.07.014
Reference: MEASUR 4854

To appear in: Measurement

Received Date: 25 July 2016

Revised Date: 7 June 2017
Accepted Date: 11 July 2017

Please cite this article as: K. Diao, L. Zhang, Y. Zhao, Measurement of tortuosity of porous Cu using a diffusion
diaphragm cell, Measurement (2017), doi: http://dx.doi.org/10.1016/j.measurement.2017.07.014

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 Measurement of tortuosity of porous Cu using a diffusion
diaphragm cell

Kaikan Diao, Liping Zhang and Yuyuan Zhao

School of Engineering, University of Liverpool, UK

Abstract

Open-cell porous metals have many potential applications, such as heat exchangers and flow
batteries, due to good permeability for fluid flow. Porous metals manufactured by space
holder methods have controllable porous structure, but the fluid pathways and channels are
tortuous. The tortuosity can directly influence the fluid permeability and turbulence, which in
turn affect the performance of the porous metal. This paper measured the tortuosity of porous
Cu, manufactured by Lost Carbonate Sintering (LCS), directly by a diffusion method using a
diaphragm cell. The tortuosity of the samples with pore sizes 250-1500 µm and porosities
0.56-0.84 was in the range of 1.33-1.78. It decreased with porosity and increased with pore
size. The measured values were comparable to those reported in literature, obtained by the
acoustic absorption method.

Key words: Lost carbonate sintering; porous copper; tortuosity; diffusion

1. Introduction

In the last few decades, porous metals have attracted considerable attention in both academia
and industry, because of their unique mechanical, thermal and chemical properties 1-3. Open-
cell porous metals, in particular, have many potential applications involving fluids such as
heat exchangers 4,5, porous electrodes for batteries 6,7 and wastewater treatment 8, because
they have high effective surface area 9 and good fluid permeability 4,5.

Tortuosity of a porous medium characterizes the convoluted pathways, or channels, formed

by pores through the porous medium. It is defined as the ratio of the average length of
pathways between two points to the straight-line distance between the points in the porous
medium 10. A large tortuosity is caused by the decreased area of available cross-section and

1
increased path length 11. Tortuosity is an important property of porous metals influencing
fluid related behaviour, including diffusion 11, permeability 12 and dynamic specific surface
area 13.

X-ray computed tomography (CT) and acoustic absorption methods are commonly used to
measure the tortuosity of porous media. X-ray CT scan can generate a 3D image from a large
series of 2D radiographic images and the tortuosity can be calculated from the 3D image 14.
The pathways in the porous metals manufactured by the space-holder methods, however,
involves both primary and secondary pores, the latter of which are difficult to be detected by
X-ray CT. As a result, the X-ray CT method can lead to significant errors in the
measurements. The acoustic method is an indirect method for the estimation of the tortuosity
from the acoustic absorption curves of the porous medium 15-18. It is based on the movement
of air in the pathways in the porous medium. Because gases can access pathways that liquids
cannot flow through, the acoustically estimated tortuosity is not always useful for porous
media intended for applications involving fluid flow. The diffusion method is a direct method
for measuring tortuosity, because the tortuosity is the ratio of the average pore length for the
major flow or diffusion pathway to the length of the porous medium along flow or diffusion
axis 10.

This paper carried out direct measurements of the tortuosity of porous Cu samples
manufactured by the Lost Carbonate Sintering (LCS) process using a diaphragm cell based
on the diffusion of NaCl in water through the porous structure.

2. Experimental

Porous Cu samples with different porosities (0.55-0.85) and pore sizes (250-425 µm, 425-710
µm, 710-1000 µm and 1000-1500 µm) were manufactured by the LCS process via the
dissolution route. The details of the manufacturing process were reported elsewhere 19,20. The
samples were cut into circular discs of 48 mm in diameter and 10 mm in thickness by an
EDM machine (WMT ONA E250), with a precision better than 0.1 mm. Before tortuosity
measurements, the samples were cleaned in 10% HCl solution and then soaked in distilled
water in order to obtain a clean surface and to ensure that water penetrates all pores or
channels.

2
Fig. 1 shows a schematic diagram of the purpose-built diaphragm cell used for the tortuosity
measurement, based on the diffusion of NaCl in water through the porous Cu sample. It
consisted of two compartments, with the top compartment initially filled with pure distilled
water and the bottom compartment initially filled with 1.75 mol/L NaCl aqueous solution.
The circular porous Cu sample sat in the middle of the cell between the two compartments.
The circumferential side of the sample was sealed by PTFE and PVA tapes, so that the solute
(NaCl) can only diffuse through the porous Cu sample from the bottom compartment to the
top compartment. To minimise the concentration difference within the top and bottom
compartments, the two compartments were stirred by two stirrers at 60 rpm using two
rotating magnets placed outside the two ends of the cell. Two pieces of No.1 Filter paper
were used to cover both sides of the porous Cu sample to prevent forced flow within the
sample due to stirring in the compartments.

Electric motor with

rotating magnet for
stirring

Magnetic
stirring bar

Filter paper

Acrylic tube
Porous Cu sample

Fig. 1 Schematic of the diaphragm cell used in the tortuosity measurement and a photograph
showing a typical porous Cu sample.

3
The tortuosity of the porous sample can be obtained from the effective diffusion coefficient
measured by the diaphragm cell, with respect to the standard diffusion coefficient 11:

(1)

where De is the effective diffusion coefficient and Do is standard diffusion coefficient of

NaCl in water. The effective diffusion coefficient of NaCl in water through the porous Cu
sample can be determined by 21:

(2)

where De is the effective diffusion coefficient; l, A and Ԑ are the thickness, cross-sectional
area and porosity of the porous sample, respectively; V is the volume of the compartment; c is
the solute concentration in the compartment; and t is the time duration between the initial and
final measurements of the solute concentrations in the two compartments. The first subscripts
b and t designate bottom and top compartments, and the second subscripts i and t designate
the initial and final measurements, respectively.

The diffusion experiment was conducted in an incubator (Thermo Scientific, USA) at a

constant temperature of 25 °C for 72 hours. The concentration of the solution in either of the
two compartments after the diffusion experiment was measured by quantifying the amount of
solute in the solution. This was achieved by heating 50 ml of the solution in a furnace at
220°C to evaporate the water and crystallise the NaCl. Specifically, the solution was poured
into a small beaker contained in a large beaker, which was then covered with a lid and placed
in the furnace to prevent any loss of solute through splashing and ensure that all of the solute
remained in the two-beaker cell. The weight of the crystallised NaCl was measured by an
electronic balance, from which the molar concentration of the solution was obtained.

For calibration purposes, an experiment was carried out with no sample between the two
compartments. An acrylic tube, 50 mm inner diameter and 10 mm length, both sides covered
with two pieces of No.1 Filter paper, was used instead to effect a straight channel. The
effective diffusion coefficient under this condition was measured to be 1.474×10-5 cm2/s
(±0.03×10-5 cm2/s), which is very close to the standard diffusion coefficient of NaCl in water
(1.481×10-5 cm2/s) 20, confirming the validity of the experimental setup. The errors of the

4
tortuosity measurements were estimated to be around 2.5% to 4.7%, based on the analysis of
propagation of uncertainty 22.

3. Results and Discussion

Fig. 2 shows the measured values of tortuosity as a function of porosity and pore size. In the
porosity range 0.56-0.84 and pore size range 250-1500 µm, the tortuosity measured by the
diffusion method is in the range of 1.33-1.78. These values are somewhat lower than the
values obtained by the acoustic absorption method (1.36-2.42) for LCS porous Cu with
approximately same pore size and porosity ranges 12. The difference is likely due to the
different fluids used in these two methods. The LCS porous Cu contains secondary pores,
which can be easily accessed by air but more difficult by liquids.

Fig. 2 shows that the tortuosity of the porous Cu samples increased with pore size and
decreased with porosity and a linear relationship exists between tortuosity and porosity for
samples with the same pore size. The results agreed well with a correlation between
tortuosity and porosity developed for porous materials with a porosity range from 0.5 to 1 by
solving the flow equations using the Lattice Gas Automata method 23:

(3)

where Ƭ is tortuosity, p is a fitting parameter and Ԑ is porosity.

Fig. 3 shows the values of the fitting parameter, p, obtained by fitting the experimental results
to Eqn. 3, as a function of pore size. It is shown that the fitting parameter increased nearly
linearly with pore size. In other words, the tortuosity increases with pore size and it decreases
more rapidly with increasing porosity for samples with a large pore size.

The effects of porosity and pore size on tortuosity can be explained by the distinctive
structure of the LCS porous metals. The number of windows connecting the primary pores in
LCS porous metals is determined by the number of contacts between the pore former
particles, i.e., K2CO3 particles, which decreases with pore size and porosity 4. A smaller
number of windows means longer channels for fluid flow through the porous metal, leading
to increased tortuosity.

5
 2.2

1.8

Torotusity
1.6

1.4

1.2

1
0.5 0.6 0.7 0.8 0.9 1
Porosity

Fig. 2 Variations of tortuosity with porosity for samples with different pore sizes:

( 250-425 µm, 425-710 µm, 710-1000 µm, 1000-1500 µm).

2.5

1.5
P

0.5

0
0 500 1000 1500
Pore size, µm

Fig. 3 Variation of fitting parameter, p, with pore size.

Conclusions

A diaphragm cell method based on the diffusion of NaCl has been developed and used to
measure the tortuosity of porous Cu samples. The tortuosity of the LCS porous Cu samples
with different pore sizes (250-1500 µm) and porosities (0.56-0.84) was in the range of 1.33-
1.78. The tortuosity decreased with porosity and increased with pore size. The relationship
between tortuosity and porosity was found to be in agreement with the correlation reported by
Koponen et al23.

6
Acknowledgments

This work has been supported by the Engineering and Physical Sciences Research Council
(Grant No. EP/N006550/1). The data file for the figures in this paper may be accessed at
http://datacat.liverpool.ac.uk/id/eprint/164.

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