Fuel 83 (2004) 845–850

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The effect of demineralisation on a lignite surface properties

Julien Starcka, Philippe Burga,*, Denise Cagnianta, Juan M.D. Tascónb,
Amelia Martinez-Alonsob
a
Laboratoire de Thermodynamique et d’Analyses Chimiques, UFR Sciences, Université de Metz, 1 Boulevard Arago,
Technopôle 2000, 57078 Metz Cedex3, France
b
Instituto Nacional del Carbón, C.S.I.C., Apartado 73, Oviedo 33080, Spain
Received 16 May 2003; revised 22 October 2003; accepted 30 October 2003; available online 28 November 2003

Abstract
The preparation of active carbons from nitrogen-enriched lignites was previously described by the authors. This study is carried on with the
aim of investigating the role played by the mineral matters of lignites on the process and on the properties of the resulting active carbons.
First, the effect of demineralisation by strong acids on the surface chemical properties of the lignite sample was studied. The XRD and FT-IR
analysis showed that carbonates (calcite, dolomite) are totally removed, and the main remaining mineral matter constituents are well
crystallized quartz besides a small amount of sulphates (bassanite). The changes in the surface chemistry properties were investigated by
FT-IR spectroscopy, Boehm’s titration method and LSER modelling. All these methods pointed out the increase of the acidic character of
the surface of the lignite after demineralisation.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Lignite; Demineralisation; Surface properties; Linear solvation energy relationship

1. Introduction hereafter. Thus, the inorganic constituents of lignites can

The aim of this work is to study the influence of
demineralisation by strong acids (HCl, HF) on the surface
chemical properties of a lignite sample in connection with
its use as active carbon precursor.
From a general point of view, lignites are cheap and
abundant carbonaceous materials but they contain large and
variable amounts of mineral matter whose presence can
influence negatively their processing or the applications of
the resulting activated carbons. The origin, nature and
methods of identification of these mineral matters have been
recently reviewed by Vassilev and Tascón [1]. During the
last decade, a number of papers have been published about
their effect and the influence of their removal on several
aspects of lignite properties and their relevant processing for
active carbon preparation. Some examples are given
* Corresponding author. Address: Laboratoire de Thermodynamique et
d’Analyses Chimiques, UFR Sciences, Université de Metz, 1 Boulevard
Arago, Technopôle 2000, 57078 Metz Cedex 03, France. Tel.: þ 33-387-
547-435; fax: þ 33-387-547-462.
E-mail addresses: burg@sciences.univ-metz.fr (P. Burg), tascon@
incar.csic.es (J.M.D. Tascón).
0016-2361/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2003.10.023
exert a catalytic action during the gasification process. Their
removal results in a reduction in the gasification rate [2], an
increase in the activation energy [3] and changes in the
surface area development of the carbons [3]. It was shown
that the mineral matter contained in the chars produced from
25 lignite samples (DTA investigation) increases catalyti-
cally the rate of combustion [4,5]. In the same view, the high
reactivity of a calcium rich lignite was assigned to the high
calcium content of its ash, which acts catalytically [6].
An acidic treatment, by HCl or HCl/HF, was generally
applied for the demineralisation process, the interest
being essentially focused on the mineral analysis and the
thermochemical properties of the products. However, the
effect of these acid treatments on the organic part of
the lignite was not investigated. It was only pointed out
(by elemental analysis of the initial and demineralised
lignite) that the acid treatment did not change the carbon
content of the sample [2].
Besides gasification and combustion, lignites can be used
as active carbon precursors with adsorbent properties and it
is well known, in this case, that the surface chemical
properties play a significant role. In this regard,
846 J. Starck et al. / Fuel 83 (2004) 845–850

the preparation of active carbon adsorbents from nitrogen the ability of the sorbent to interact through n- and p-
enriched lignites as precursors was recently described by electrons, s is a measure of the dipolarity/polarizability of
some of us [7,8]. the studied phase, a is the hydrogen-bond basicity, b is the
Our objective is now to consider the effect of the mineral hydrogen-bond acidity, and, l is an evaluation of the
matter on our procedure and to compare the properties of the dispersion interactions.
active carbons prepared from the same sample of lignite, The r-; s-; a-; b- and l- coefficients thus obtained on the
before and after its demineralisation. The first step of this lignite samples, before and after demineralisation, will point
study, described here, concerns the effect of the out the influences of the mineral matter and of the surface
demineralisation on the lignite surface properties. The chemistry on their molecular interaction abilities and,
demineralisation treatment was carried out successively by among them, acidity and basicity.
HCl and HF in an original apparatus described in the
experimental part. The identification of the mineral matter
of the two samples, raw lignite (RL) and demineralised 2. Experimental
lignite (DL), was made by FT-IR spectroscopy and XR
refractometry carried out on the residues of the low 2.1. Materials
temperature ashing (LTA) treatment. The application of
the Boehm’s titration method [9 –11] provides an estimation The starting raw lignite sample was prepared from a
of the acidic sites and of the total basicity of the two Polish lignite (Lubstov mine). After crushing and sieving,
samples. The modification of the surface chemistry thus the size of the sample was between 150 and 250 microns.
evidenced has a significant influence on the molecular The elemental analysis is given in Table 1.
interactions developed by the samples and on their
adsorbent properties. The linear solvation energy 2.2. Demineralisation
relationship (LSER) modelling [12,13] has been applied to
point out these interactions. Indeed, among the different The removal of the inorganic constituents was accom-
approaches in the characterisation of carbonaceous plished by washing the RL sample with HCl and HF acid
materials used as adsorbents of gaseous compounds, the solutions (5N). By this treatment, as described in the
LSER equation coupled with inverse gas chromatography is International Norm ISO 602– 1983, the ash content of a
an efficient method of investigation of the surface chemistry lignite sample can be reduced from 22.1 to 0.14% [3]. The
of these materials [14]. This equation can be written as procedure used in this work is also inspired by this norm. It
follows can be applied to a large amount of sample, until 100 g. A
special apparatus (cf. Fig. 1) was designed to this end, which
log10 ðSPÞ ¼ c þ rR2 þ spH H H
2 þ aSa2 þ bSb2 þ l log10 L
16
allows the use of these strong acids with security and with
ð1Þ not too much handling.
The apparatus developed in collaboration with the
where SP is a gas –solid partition coefficient at infinite Carbon Lorraine Society (Pagny-sur-Moselle (France)) is
dilution ðKc Þ of a solute on the adsorbent used as stationary made in Armylorw (steel overlayed with Teflonw (PTFE)).
phase. Kc values are obtained by the Elution by The heating is achieved by a heating ribbon, wound
Characteristic point method (ECP) [15]. To obtain the round the reactor. Taking into account its great thermal
adsorbent coefficients, several solutes with miscellaneous inertia, the temperature obtained inside the reactor is only
chemical properties are injected in a classical gas 40 8C instead of 50 –60 8C according to the norm.
chromatograph where the column is filled with the solid The total weight of the apparatus is about 30 kg.
sorbent, here RL or DL. For HCl treatment the conditions are: 100 g RL, 1 l of
As shown in Eq. (1), R2 ; pH 2 ; Sa2 ; Sb2 and log10 L are
H H 16
5N HCl, 100 ml ethanol (used as wetting agent), stirring
the known properties of a solute, also called solute at about 40 8C during 30 h. After vacuum filtration,
descriptors. They come from thermodynamic measure- washing with warm distilled water is carried out until
ments, except R2 : R2 [16] and pH 2 [17] represent the molar
excess of refraction and the dipolar/polarizability par- Table 1
ameters, respectively. SaH 2 ; and Sb2 are the hydrogen
H Elemental analysis of lignite samples
bond acidity and basicity parameters [12], respectively,
Samples Ash (%) C (%) H (%) N (%) O (%)* S (%)
and L16 is the gas –liquid partition coefficient of the solute
on n-hexadecane [18].All these solute descriptors were RL 6.15 55.64 5.20 0.65 37.92 0.59
obtained at 298 K. Then, the LSER equations are treated by DL (HCl/HF) 0.16 62.36 5.55 0.74 29.99 1.36
multiple linear regression analysis. This statistical treatment DL (HCl) 3.4 65.79 5.47 0.85 27.38 0.51
leads to the calculation of the parameters characterizing the *by difference. Results are given daf. The elemental analyses were
studied material, which are symbolized in Eq. (1) by r-; s-; made by the ‘Service Central de Microanalyses—CNRS (Vernaison-
a-; b-; and l-coefficients, at a given temperature, where r is France)’.
 J. Starck et al. / Fuel 83 (2004) 845–850 847

The mineralogical composition was established by XRD

in a Siemens D 5000 diffractometer using CuKa (step
size:0.0158, step time 2 s) and FT-IR spectroscopy.
The FT-IR spectra were obtained on a Nicolet mod.
Magna 450 spectrometer working in transmission/absorp-
tion, using pellets in KBr (13 mm diam.) with a sample
concentration of 1 wt% and drying under vacuum during
12 h at 393 K. The assignments of the FT-IR bands are
presented in Table 2.

2.4. FT-IR: spectra of the RL and DL samples

These spectra are determined by micro-FT-IR on a

Bruker IFS 55 apparatus coupled with a multipurpose
microscope Bruker IR equipped with a liquid nitrogen-
cooled MCT detector. The objective used was a reflachro-
mat with a magnifying power of 15. The experimental
specifications were :analysed zone size: 60 mm, 64
accumulations (32 s), diamond cell (Spectra Tech. Inc.).The
spectra are presented in Fig. 2.

2.5. Boehm’s titration

The Boehm’s method [9] often described in the literature,

Fig. 1. Scheme of the demineralisation apparatus. 1–reactor with stirring
rod and thermometer; 2 –filter in PTFE; 3–filter support in graphite
with holes; 4–sluice gate overlayed with PTFE; 5– vacuum filtration
device; 6–draining gate.
for example in the cases of activated carbons [10], and
oxidized porous carbons [11], was applied in this work to
RL and DL as follows: weighed amounts of the lignite
sample ( ø 1.00 g) were placed in 50 ml vials of the
following solutions: 0.5N NaOH and 0.178N Na2CO3,
0.102N NaHCO3 or 0.5N HCl. The vials were sealed and
allowed to equilibrate with agitation for 24 h at room
temperature. After filtration, the liquids were titrated with

no reaction with AgNO3; then, washing with acetone is

done. The residue is dried under vacuum at 60 8C.
Table 2
For HF treatment the conditions are: 100 g of HCl-
Assignments of the FT-IR bands in the LTAs of lignite samples ðn in cm21)
demineralised lignite, 200 ml of 5N HF, stirring at about
40 8C during 23 h, then treated as above. RL DL(HCl) DL(HCl–HF) Assignments
This protocol is used if a sample of DL (HCl) must be
submitted to analysis In the other case, the treatment with 3606 – – SO224 (bassanite)
3432 3421 3400 H2O (gypsum)
HF follows immediately the one with HCl
2922 2922 2922 traces-CH (stretching)
2850 2850 2850 traces-CH (stretching)
2.3. LTA analysis: mineralogical composition of the ashes 1690(shoulder) – – H2O (gypsum)
1625 1628 1628 SO224 .(bassanite)

The LTA treatment was carried out on RL and DL 1483 – – dolomite

1435 – – calcite
samples in a Technics Plasma mod.200-E reactor. 1388 – – nitrates
The ashing conditions were: plasma activation by micro- 1157 1164 1154 Si–O (quartz),
wave (2450 GHz), 150 W radiofrequency power, 100 Pa SO224 (bassanite)
oxygen pressure, and 1.0000 g sample mass (four 1099 1093 1082 Si–O (quartz)
portions being oxidised simultaneously).The samples 868 – – calcite, dolomite
799 798 798 Si–O (quartz)
were spread on Petri boats in glass (75 mm diameter) 778 781 777 Si–O (quartz)
with an ashing time of 4-h periods with intermediate – 694 695 Si–O (quartz)
stirring and spreading of the samples. The treatment is 663 – 679 SO224 (bassanite)
repeated until constant weight showing the total gasifica- 605 597 595 SO224 (bassanite-anhydrite)

tion of the organic matter, the mineral matter being only 516 514 527 Si–O (quartz)
468 464 463 Si–O (quartz)
remaining.
848 J. Starck et al. / Fuel 83 (2004) 845–850
Fig. 2. Micro-infrared spectroscopic results. RL in bold line, DL in thin line.
either H2SO4 or NaOH, respectively. The results are given
in Table 3.
2.6. LSER analysis
2.6.1. Gas – solid chromatography
The Kc values at infinite dilution, for each injected solute,
were calculated from the linear part of the isotherms
obtained by the ECP method. The latter allows one to
calculate Kc values from chromatographic data, which were
determined using a Shimadzu GC14 gas chromatograph.
The detector was a catharometer and the flow-rate was
fixed at 20 ml/min of helium gas (99.995% of purity).
The materials under study were filled in teflon tubing of
2.1 mm internal diameter and fifty centimeters long. The
chromatographic columns so obtained were conditioned
overnight at 160 8C to remove impurities. Then, for the
experiments, the oven of the chromatograph was fixed at
110 8C.
Fifteen solutes were injected to characterize each
lignite sample. They were selected for their volatility,
and to cover a wide range of descriptor values. They
were also chosen to minimize inter-correlations between
these values in an aim to well-test each type of
molecular interaction. Their characteristics are given in
Table 4.
2.6.2. Computational
All the chromatographic measurements are collected
using an Hercule 2000 interface and treated with Diamir
software (JMBS, Inc.) on a personal computer. All the
statistical calculations, more particularly the Multiple
Linear Regression Analysis were performed using Minitab
software (Minitab Inc.).
3. Results and discussion
The discussion will point out the efficiency of the
demineralisation process and the influence of the treatment
by strong acids on the surface properties of the studied
lignite.
3.1. Efficiency of the demineralisation procedure-Analyses
of the mineral matter
Starting from 30 g of RL, treated in the conditions
described in the Experimental Part, 24.3 g of DL (HCl) were
obtained (81% yield). About 2 g were taken away for
analyses and the remaining (22.3 g) were treated by HF
giving rise to 20.8 g of DL (HCl/HF) (90% yield). The
global yield is about 70%.
The contents of mineral matter (residues of LTA
analyses after four treatments of 4 h each) were 3.40% for
DL(HCl) and 0.16% for DL (HCl/HF), versus as much as
6.15 for RL. This indicates a global good efficiency in spite
of the low temperature used of 40 8C. Nevertheless, it is
interesting to point out the significant role of the treatment
temperature since in an experiment carried out with HCl in a
plastic vessel during 12 h at 55– 60 8C the amount of
mineral matter was about 0.98%.
By using a three steps procedure (washing successively
l h at room temperature with 5N HCl, 22N HF,and 12N
HCl), the ashes of a lignite sample are reduced from 27 to
around 1% [19]. The identification of the mineral matter is
summarized in Table 2.
Carbonates, sulphates and quartz are the main mineral
constituents identified in the LTA residues. Those present in
the raw lignite are carbonates (calcite and dolomite), sulphates
(bassanite and gypsum) quartz and nitrates. Bassanite (stable
form of calcium sulphate at 150 8C, the approximate
temperature of the LTA treatment) and nitrates are seldom
Table 3
Results of the Boehm’s method (in mmol/g)
RL DL (HCl– HF) D
Carboxylic acids 1.50 1.07 20.43
Lactones 1.02 1.58 þ 0.56
Phenols 2.25 3.4 þ 1.15
Basicity 1.25 0.05 21.20
 J. Starck et al. / Fuel 83 (2004) 845–850 849

Table 4
Molecular probes descriptors and results obtained on the raw and demineralised lignite

Molecular probes R2 pH
2 SaH
2 SbH
2 log10L 16 Raw lignite Demineralised lignite

Kc Log10Kc Kc log10Kc

n-hexane 0 0 0 0 2.668 0.0325 21.4881 0.0641 21.1931

n-heptane 0 0 0 0 3.173 0.0708 21.1500 0.1434 20.8435
n-octane 0 0 0 0 3.677 0.1541 20.8122 0.3207 20.4939
n-nonane 0 0 0 0 4.182 0.3357 20.4741 0.7173 20.1443
n-decane 0 0 0 0 4.686 nd – 1.6044 0.2053
Butan-2-ol 0.217 0.36 0.33 0.56 2.338 0.1234 20.9087 nd –
1-nitropropane 0.242 0.95 0 0.31 2.894 nd – 1.3944 0.1444
Chloroform 0.425 0.49 0.15 0.02 2.48 nd – 0.1241 20.9062
Carbon tetrachloride 0.458 0.38 0 0 2.823 nd – 0.0643 21.1918
Toluene 0.601 0.52 0 0.14 3.325 0.2643 20.5779 0.1731 20.7617
Benzene 0.610 0.52 0 0.14 2.768 0.1323 20.8784 0.1748 20.7575
Thiophene 0.687 0.57 0 0.15 2.819 0.4132 20.3838 nd –
Cyclohexane 0.305 0.1 0 0 2.964 nd – 0.0639 21.1945
Dipropylether 0.008 0.25 0 0.45 2.954 0.0607 21.2168 nd –
Pentan-2-one 0.143 0.68 0 0.51 2.755 0.4086 20.3887 nd –
Butanol 0.224 0.42 0.37 0.48 2.601 0.3917 20.4070 3.0754 0.4879
Propanol 0.236 0.42 0.37 0.48 2.031 nd – 1.7664 0.2471
Trifluoroethanol 0.015 0.6 0.57 0.25 1.224 0.1977 20.7040 0.2821 20.5496
Hex-1-ene 0.078 0.08 0 0.07 2.572 0.0703 21.1530 nd –
Acetone 0.179 0.7 0.04 0.49 1.696 nd – 0.9103 20.0408
Ethyle acetate 0.106 0.62 0 0.45 2.314 0.1879 20.7261 nd –

found in coals. Their finding could be explained either by the The decrease of carboxylic acid amounts corresponds
dehydration of gypsum (at about 100 8C) or by an interaction nearly to the increase of the amounts of lactones.
between alkaline-earth ions with acidic gas (NOx, SOx) arising The increase in phenol groups evidenced by the IR
from oxidation of nitrogen and sulphur organic species. spectra is confirmed by the increase of free phenols,
After acidic treatments, the carbonates are completely another part of the phenols being linked in the lactone
removed. The mineral species are mainly quartz besides groups. Therefore, it is assumed that the demineralization
some residues of calcium sulphates. Qualitatively there are process has released acidic and phenol groups linked to
no fundamental differences between the spectra of DL (HCl) calcium, these groups being in good position to give rise
and DL (HF– HCl) samples. The X-ray diffractograms to lactones.
showed that quartz is well crystallised which can explain its At the same time, the basicity decreases also
resistance to the HCl – HF treatment. dramatically.
Then it becomes evident that the acid treatment modified
3.2. Influence of the acidic treatment on the functional significantly the surface chemistry of the lignite sample and
groups of the lignite very likely the molecular interactions that it is able to
develop as well as its adsorbent properties.
FT-IR spectroscopy and the Boehm’s method point out
the main functional groups and their modification during 3.3. LSER modelling
acid treatment.
The main changes between the two spectra, presented in The LSER equations obtained for the RL and DL
Fig. 2 for RL and DL (HCl – HF) samples, appear between samples are the following
1800 and 1200 cm21 Raw lignite (RL)
The band at 1710 cm21,assigned to carbonyl/carboxyl
log10 ðKc Þ ¼ 22:82 þ 1:27pH H
2 þ 1:15Sa2 þ 0:531log10 L
16
groups as in lactone, carboxylic acid, which is only a
shoulder of the band at 1620 cm21, increases dramatically ð2Þ
after demineralisation. SD ¼ 0.177, r ¼ 0:900; F ¼ 13:41; n ¼ 14:
The band at 1620 cm21, assigned to aromatic CyC, is Demineralized lignite (DL) by HCl – HF
amplified by an increase of phenol groups content which
corresponds to the increase of intensity in the field of C – O log10 ðKc Þ ¼ 22:76 2 802R2 þ 0:554pH H
2 þ 0:934Sa2
linkage around 1410 – 1310 cm21.These interpretations are
þ 2:70SbH
2 þ 0:615log10 L
16
ð3Þ
in agreement with the results of the Boehm’s method
presented in Table 3. SD ¼ 0.129, r ¼ 0:984; F ¼ 53:82; n ¼ 15:
850 J. Starck et al. / Fuel 83 (2004) 845–850
where SD is the standard deviation of the regression, r is
the correlation coefficient between measured and calculated
log10ðKc Þ values, F is the Fischer-statistic and n is the
number of injected probes.
From a statistical point of view, based on Eqs. (2) and (3),
the results are satisfactory with r values of 0.900 – 0.984.
Moreover, F values are those expected for this type of
material [20].
In the case of the RL sample the number of molecular
interactions is restricted to dispersion ðl ¼ 0:531Þ and
attraction for compounds with acidic character ða ¼ 1:15Þ:
After demineralisation, the molecular interactions are
more developed and indicate a pronounced attraction for
compounds with basic character ðb ¼ 2:70Þ which is in
agreement with the results of the Boehm’s titration
The acidic character of the surface chemistry of the
demineralised lignite can augur a greater reactivity
towards nitrogenated compounds like urea or ammonia
(ammoxidation reaction).
4. Conclusion
The purpose of this study was to point out the influence
of the treatment with the strong acids (HCl –HF) used in the
demineralisation process on the surface chemistry proper-
ties of a lignite sample. The efficiency of the described
procedure is good, though the temperature is lower than the
one generally used. The analyses of the LTA residues before
and after acid treatment, show the total removal of
carbonates (calcite and dolomite), quartz being the main
mineral remaining besides some calcium sulphates (bassa-
nite). FT-IR spectroscopy and Boehm’s titration indicate
that the amount of organic species, such as carboxylic acids
and phenols, partially linked to calcium, increase after acid
treatments giving rise to lactones. These modifications in
the amount of the functional groups have repercussion in the
molecular interactions, as it can be seen by the LSER
modelling, the surface chemistry of the lignite sample
becoming more acid.
The adsorbent properties against VOCs, and the
reactivity against nitrogenated targets, could be interest-
ingly modified by the demineralisation process.
Acknowledgements
The authors wish to thank gratefully the ‘Société
Carbone Lorraine’ (Pagny sur Moselle, France) for the
design and set up of the demineralisation apparatus. The
authors also thank Dr Pierre Faure of the G2R/UMR 7566
(CNRS, Nancy) for the micro infrared spectroscopy
measurements. This work was supported by CNRS and
the Polish Academy of Sciences (PAN) in the frame of the
‘Jumelage: Matériaux carbonés et catalytiques pour l’envir-
onnement’.
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