Industrial Crops & Products 133 (2019) 325–332

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Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

Natural fibre-nanocellulose composite filters for the removal of heavy metal T

ions from water
⁎
Andreas Mautnera, , Yosi Kwawa,b, Kathrin Weilanda, Mlando Mvubuc, Anton Bothac,
⁎
Maya Jacob Johnc,d,e, Asanda Mtibec, Gilberto Siqueiraf, Alexander Bismarcka,g,
a
Institute of Materials Chemistry & Research, Polymer & Composite Engineering (PaCE) Group, University of Vienna, Währinger Str. 42, 1090 Wien, Austria
b
Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom
c
Polymers and Composites Competence Area, Materials Science and Manufacturing, CSIR, Port Elizabeth, South Africa
d
Department of Chemistry, Faculty of Science, Nelson Mandela University, Port Elizabeth, South Africa
e
School of Mechanical, Industrial and Aeronautical Engineering, University of the Witwatersrand, Johannesburg, South Africa
f
Applied Wood Materials Laboratory, Swiss Federal Laboratories for Materials Science and Technology (EMPA), Dübendorf, Switzerland
g
Department of Mechanical Engineering, Faculty of Engineering and the Built Environment, University of Johannesburg, South Africa

A R T I C LE I N FO A B S T R A C T

Keywords: Contamination of fresh water sources with heavy metal ions constitutes a serious threat to drinking water safety.
Cellulose nanofibrils Treatment of water in order to remove these contaminants, e.g. copper ions, is thus an important task, usually
Copper ions performed by utilizing adsorbents or continuous membrane/filter processes. In particular combinations of these
Flax fibres processes, i.e. adsorption or ion-exchange membranes/filters, are potential solutions in this regard. Thereby,
Agave fibres
materials derived from renewable resources constitute an environmentally benign alternative to traditional
TEMPO-oxidation
Adsorption filter
adsorption membrane/filter materials. For example, anionic TEMPO-oxidized cellulose nanofibrils (TCNF) were
demonstrated to have high affinity towards heavy metal ions but nanopaper membranes made thereof suffer
from low permeance and hence limited performance. To achieve high permeance and efficient adsorption of
metal ions utilizing pure nanopapers has still not been possible. However, decorating a porous natural fibre
substrate with TCNF should allow for high adsorption capacity towards Cu2+ together with high water per-
meance. We here present natural fibre-nanocellulose composite filters derived from flax and agave fibres, ex-
tracted e.g. from tequila residues, decorated with TCNF. The performance of these filters was determined with
respect to their permeance and adsorption capacity for copper. It was shown that this new type of filter derived
from industrial crop residues is capable of adsorbing high amounts of Cu(II) ions during a continuous filtration
process with very high permeances enabled by their highly porous nature.

1. Introduction plants (Angelova et al., 2004), manure or soil eventually contaminating

Among the most utilized heavy metals is copper, which is used in a
wide variety of industries due to its excellent properties (Camarillo
et al., 2010; Lambert et al., 2014), for example high ductility as well as
electrical and thermal conductivity (Samuelsson and Björkman, 2014).
Unfortunately, during mining and production processes as well as ap-
plication, including pulp, paper and paper board manufacture, and in
the fertilizer industry (Gupta, 1998; Wan Ngah et al., 2002), copper
ions do leak into water streams subsequently being further distributed
and contaminating fresh water sources (Akar et al., 2009; Bilal et al.,
2013). Copper is also used as nutrient supplement for animals or as
fungicide for plants, which can result in accumulation of copper in
ground water sources (Tegoni et al., 2014).
Even though copper is an essential element for the human body
(Bilal et al., 2013; Fraga, 2005), a very high intake of copper poses
serious implications (Shannon et al., 2008). Adverse effects of copper in
living organisms include accumulation in the liver potentially causing
Wilson’s disease, which leads to neurological and psychiatric defects
(Araya et al., 2001; Zamani et al., 2007). Accordingly, the intake of
copper for humans should not exceed 5 mg d−1, as suggested ex-
emplarily by the European Commission (European-Comission, 2003)
and reinforced by the World Health Organization (WHO) guidelines,
which stipulate that the concentration of copper in drinking water
should be below 2 mg L−1 (WHO, 2004).

⁎
Corresponding authors at: Institute of Materials Chemistry & Research, Polymer & Composite Engineering (PaCE) Group, University of Vienna, Währinger Str. 42,
1090 Wien, Austria.
E-mail addresses: andreas.mautner@univie.ac.at (A. Mautner), alexander.bismarck@univie.ac.at (A. Bismarck).

https://doi.org/10.1016/j.indcrop.2019.03.032
Received 17 December 2018; Received in revised form 11 March 2019; Accepted 12 March 2019
Available online 22 March 2019
0926-6690/ © 2019 Elsevier B.V. All rights reserved.
A. Mautner, et al.
Copper removal from water is usually achieved by various pro-
cesses, such as chemical precipitation (Chen et al., 2009; Fu and Wang,
2011), ion-exchange or adsorption (Akar et al., 2009; Feitoza et al.,
2014; Jain et al., 2016; Wan Ngah et al., 2002; Zhu and Li, 2015). In
this regard, bioadsorbents (Bansal et al., 2014; Davis et al., 2003; Deng
et al., 2013; Hokkanen et al., 2013; Ramos et al., 2016; Şen et al., 2015;
Shaheen et al., 2013) or low-cost adsorbents derived from industrial or
agricultural waste streams (Castaldi et al., 2015; Romero-Cano et al.,
2016) have recently received increased attention but often suffer from
limited adsorption efficiencies (Cretescu et al., 2015; Komkiene and
Baltrenaite, 2016; Oo et al., 2009).
Recently, cellulose nanofibrils (CNF) (Klemm et al., 2011) that can
also be derived from industrial crops or side streams (García et al.,
2016; Jonoobi et al., 2012; Mathew et al., 2014; Tibolla et al., 2017),
were introduced as adsorbent material for various kinds of ions in static
media (Božič et al., 2014; Hokkanen et al., 2013; Jin et al., 2013; Karim
et al., 2014; Liu et al., 2015, 2014; Pei et al., 2013; Sehaqui et al., 2014;
Yu et al., 2013a, b). Cellulose nanopapers prepared from CNF
(Henriksson et al., 2008; Lee et al., 2012; Sehaqui et al., 2010) were
also utilized in membrane processes (Mautner et al., 2014; Metreveli
et al., 2014), with adsorption membranes being most recently demon-
strated (Karim et al., 2017; Mautner et al., 2017, 2016b). Yet, these
nanopapers were too dense to allow for high water permeance and
hence efficiency. However it could be anticipated that decorating a
substrate of conventional natural fibres with charged nanocellulose
would allow for high permeance while providing sufficient contact area
for dissolved ions to adsorb during water passage through the filter.
Here we present an approach that takes advantage of a natural
adsorbent material utilized to impregnate a substrate of natural fibres
(flax and agave). The originality and novelty of this study lies in the fact
that adsorption on TEMPO-CNF was not performed on the nanofibrils
alone in static mode, as in common adsorption studies (Isobe et al.,
2013; Liu et al., 2016; Sehaqui et al., 2014), but while water containing
copper ions permeates a highly porous filter. The agave fibres were
chosen as their fibre diameters are big and vary much thus affecting
their packing efficiency. This qualifies them as appropriate substrate for
a filter-application in which high porosity and accordingly perme-
ability/permeance is required. A non-woven was prepared from a
mixture of flax and agave fibres and decorated with anionic TEMPO-
oxidized cellulose nanofibrils providing high negative net surface
charge, which is beneficial for the adsorption of positively charged
heavy metal ions. Substrates prepared from cotton and viscose fibres
served as reference substrate material. Applicability of these natural
fibre-nanocellulose composite filters was to be demonstrated by per-
meance tests and adsorption studies.
2. Materials & methods
2.1. Materials
Agave, flax, cotton and viscose fibres were provided by the CSIR
(Port Elizabeth, South Africa). The agave (extracted from agave leaves)
and flax fibres were obtained from local plantations in the Eastern Cape
Province and North West Province, respectively. Never-dried elemental
chlorine-free bleached softwood (Picea abies and Pinus spp.) pulp,
obtained from Stendal (Berlin, Germany), was used for the production
of CNF by disintegration in a disc mill MKCA 6-2 (Masuko Sangyo Co.,
Ltd., Japan) (Mautner et al., 2018). The chemical composition of the
pulp was 81.3% cellulose, 12.6% hemicellulose and 0.3% ash (Josset
et al., 2014). (2,2,6,6-Tetramethylpiperidin-1-yl)oxy (TEMPO) oxidized
CNF (TCNF) were provided by EMPA (Dübendorf, Switzerland)
(Weishaupt et al., 2015). NaCl, NaOH (99.6%), HCl (37%), Murexide
and CuCl2 were purchased from Sigma-Aldrich. Ethylenediamine tet-
raacetic acid (EDTA) was purchased from W. Neuber’s Enkel (Wien,
Austria). All chemicals were used as received without further pur-
ification. Deionized water (Elga PureLab, High Wycombe, UK) was used
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Industrial Crops & Products 133 (2019) 325–332
in all process steps.
2.1.1. Characterization of TEMPO-CNF
The zeta (ζ)-potential of TCNF was determined at a concentration of
0.1 wt.-% using a Zetasizer NanoZS instrument (Malvern, UK) by
monitoring the electrophoretic mobility at pH 6. The charge content of
TEMPO-CNF was determined by conductometric titration of 0.15 g (dry
weight) TEMPO-CNF suspended in water (60 mL + 5 mL 0.01 M NaCl
solution), which was magnetically stirred for 15 min. The starting pH
was set to 2.8 by addition of 0.1 M HCl and then titrated with 0.04 M
NaOH solution at a rate of 0.05 mL min−1 up to a pH of 11. During the
titration pH and conductivity were recorded. Nitrogen adsorption
measurements were performed using a Micrometrics system to char-
acterize the specific surface area (SSA) of TEMPO-CNF at −77 K. The
sample for SSA determination was prepared by supercritical drying.
Prior to measurements, an aqueous suspension of TEMPO-CNF was
solvent exchanged to ethanol, followed by solvent exchange to liquid
CO2 using a Quorum Critical Point Dryer. This suspension was super-
critically dried at a temperature of 37 °C and a pressure of 100 bar.
Scanning electron microscopy (FEI Nano SEM 230) of dried TEMPO-
CNF was performed to investigate the morphology of TEMPO-CNF at an
accelerating voltage of 5 kV and a working distance of 5 mm.
2.2. Preparation of the substrates and filters
2.2.1. Non-woven substrates fabrication
The needle-punched non-woven substrates were produced by
blending the flax/agave (FA) and cotton/viscose (CV) fibres at ratios of
50/50 by weight. The fibres were first blended manually and then the
pre-blended fibres passed through a roller carding machine
(BefamaTex, Poland) twice to enhance blending and to ensure a
homogeneous mixing of fibres. After the second pass through the car-
ding machine, the layered web (batt) is allowed to pass through into the
needle-punching unit (Dilo DI-LOOM OD-II 6, Germany), which was
operated at 5 mm depth of needle penetration, a stroke frequency of the
needling loom of 400 min−1 and 1.7 to 2.2 m s−1 conveyor belt speed.
The needle-punched fabrics were then passed through an Aquajet
(Fleissner, Germany) for pre-wetting at 5 bars of water jet pressure and
3 m s−1 conveyor belt speed, before the application of the nanocellu-
lose finish (filter preparation), which was applied onto the non-woven
fabrics as explained in Section 2.2.2 below.
2.2.2. Filter preparation
Filters were prepared by impregnating the produced natural fibre
non-woven substrates with 5, 10, 20, 25, 50 g m−2 (gsm) of CNF and/or
TCNF, respectively. Circles of the substrates (125 mm diameter) were
placed in a Büchner-Funnel and pre-determined amounts of suspensions
(0.1 wt.-%) of CNF or TCNF were filtered through them to achieve the
grammage required; e.g. 156.25 mL of a 0.1 wt.-% suspension of CNF
was required to load the substrate with 10 gsm CNF. Three-component
filters were prepared by filtering TCNF on top of unmodified CNF. The
wet filter cakes were partially dried at room temperature between
blotting papers (3 MM Chr, VWR, Lutterworth, UK) for 5 min to absorb
excess water, subsequently sandwiched between sheets of greaseproof
paper and metal plates (∼1.25 kg), followed by drying in an oven at
120 °C overnight (16 h). The amount of the dry weight of nanocellulose
added to the substrate is presented in gsm along with the sample code
and the filter thickness in Table 1. The thickness of the filters varied
depending on the processing steps and attachment of the various types
of nanocellulose. For low loadings, in particular of CNF, the thickness
decreased, however, not significantly, due to the pressing and con-
solidation step. By attaching larger amounts of CNF the filter thickness
increased, as expected.
A. Mautner, et al.
Table 1
Sample code of the filters and amounts of (T)CNF deposited on natural fibre
substrates.
Sample Code CNF [gsm] TEMPO-CNF [gsm] Thickness [mm]
FA – – 1.85 ± 0.16
FA_5-50 5 50 1.62 ± 0.06
FA_10-50 10 50 2.11 ± 0.36
FA_20-50 20 50 2.14 ± 0.19
CV – – 1.44 ± 0.05
CV_5-50 5 50 1.41 ± 0.15
2.3. Characterization of the substrates and filters
2.3.1. Morphology of substrates and filters by Scanning Electron
Microscopy
The morphology of the substrates and filters was assessed by
Scanning Electron Microscopy (SEM) performed on a JCM-6000 (JEOL
GmbH, Eching, Germany) table-top SEM operating at an accelerating
voltage of 15 kV. Prior to imaging, samples were fixed onto SEM stubs
using carbon tabs and gold coated for 1 min at 30 mA using a sputter
coater (JFC-1200, JEOL GmbH, Eching, Germany).
2.3.2. Air permeability of the non-woven substrates
The air permeability of the non-woven substrates was analyzed
according to ISO 9237 1995 (E) with a Textest FX 3300 IV at 100 Pa on
a sample area of 20 cm2. At least 8 measurements were performed on
each sample and the result [mm s−1] presented as the average thereof.
2.3.3. Surface charge of the filters
In order to characterize the surface charge of the filters, the ζ-po-
tential was determined by streaming potential measurements (SurPass,
Anton Paar, Graz, Austria). The substrates were packed in a cylindrical
cell (15 mm diameter) and the ζ-potential measured between pH 10 and
2. The pH was changed by titration of 0.05 mmol L−1 NaOH and HCl,
respectively. The filters were analyzed in an adjustable gap cell with a
gap width of 230 μm between pH 10 and 2. From the streaming po-
tential or current, respectively, the ζ-potential was calculated using the
Smoluchowski relationship. Results of the measurements were plotted
as function of pH.
2.3.4. Tensile properties of nanopapers
Tensile tests were performed using an Instron universal test frame
(Model 5969 Dual Column Universal Testing System, Instron,
Darmstadt, Germany) equipped with a 1 kN load cell at 25 °C and 50%
relative humidity with a crosshead displacement speed of 1 mm min−1
and a gauge length of 20 mm. Dry and wet tests were performed on at
least 5 rectangular (5 × 40 mm2) specimens cut from the prepared
filters. Prior to each test the thickness of each test specimen was mea-
sured at 5 different spots using a digital micrometer (705–1229, RS
components, Corby, UK). Wet tests were performed after soaking the
samples for 30 min in deionized water (Saito and Isogai, 2007). All of
the filters are porous materials, hence a comparison of the tensile
strength [MPa] would not be valid. For a fair comparison, the paper
tensile strength [N/m] after Tappi T 494 om-96 was used. Here, the
maximum load is related to the width of the sample, thus allowing for a
comparison of the load bearing capacity of the filters.
2.3.5. Pure water permeance of the filters
The permeance of pure water was tested in a dead-end cell HP4750
(Sterlitech, Kent, USA) with 1 bar nitrogen head pressure. Discs with a
diameter of 49 mm were cut from the filters and installed on a porous
stainless steel support plate of the cell. The cell was filled with 250 mL
of deionized water and the pressure applied. The volume of permeate
fractions permeating the filters in a certain time interval was de-
termined and used to calculate the permeance [L m−2 h−1 MPa−1] for
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Industrial Crops & Products 133 (2019) 325–332
an active filtration area of 1460 mm2. Permeance tests were performed
until the variation was less than 2% within one hour of testing for low
permeance filters or 4 tests of 250 mL (full dead end cell) in the case of
high permeance filters, respectively.
2.3.6. Dynamic adsorption of copper ions during filtration tests
Continuous adsorption tests of copper ions were conducted using a
dead-end cell HP4750 (Sterlitech, Kent, USA). Discs of the filters with
49 mm diameter were cut and installed on the stainless steel support
plate of the cell. Solutions of 0.1 mM CuCl2, corresponding to
6.35 mg L−1, were filled into the cell and 1 bar nitrogen head pressure
applied. Fractions of permeate were taken and their concentration
analyzed by colorimetric titration with EDTA against Murexide. From
the difference of copper concentrations between the permeate fractions
and the starting solution (c(Cu2+)) and the fraction volume (Vfract) the
amount of copper adsorbed qA [mg m−2] (Eq. (1)) was calculated in
relation to the unit filtration area (A = 1460 mm2). qA was then plotted
as function of the filtration volume and the maximum qA,max used for
the calculation of the adsorption capacity qe [mg g−1] (Eq. (2)) per unit
mass (G(TCNF)) of the active adsorption agent (TEMPO-CNF, 50 [g
m−2]).
c (Cu2 +)
qA = [mg m−2]
A ∙ Vfract (1)
qA, max
qe = [mg g−1]
G(TCNF ) (2)
3. Results & discussion
3.1. Preparation of substrates and filters
The approach to manufacture adsorption filters was to decorate
natural fibre non-woven substrates with TEMPO-oxidized cellulose
nanofibrils bearing a high negative charge (carboxyl group content =
1.1 mmol g−1, ζ-potential = −72 mV), which should facilitate efficient
adsorption of heavy metal ions. Agave fibres were selected because they
are commonly extracted from an industrial side stream, e.g. from te-
quila production. In order to facilitate the production of non-wovens,
rigid agave fibres had to be blended with more flexible flax fibres. The
non-woven substrates were prepared by a needle-punching process in a
non-woven pilot plant. As reference material a mixture of industrial
fibres (cotton and viscose) was utilized. The resultant fibre structures
are shown in Fig. 1. It is apparent that the flax-agave (FA) substrate
consisted of a wide range of fibre (bundle) diameters (10 to 50 μm and
bundles up to 500 μm), whereas the industrial fibre substrates (cotton-
viscose, CV) were composed of more uniform, thinner fibres (5 to
15 μm). This also provided for apparent higher porosity of the FA
substrate. Even though FA substrates were considerably heavier and
thicker than CV, having a three times higher grammage (G), their
higher porosity was also confirmed by air permeability tests that re-
sulted in higher air permeability of FA substrates (Table 2).
The active ingredient of the filter enabling adsorption of copper ions
was (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO)-oxidized CNF
(TCNF). The fibril diameter (SEM image see Supporting Information
Fig. S1) and specific surface area were about 10 nm and 252 m2 g−1,
respectively, and the carboxyl group content 1.1 mmol g−1.
Unmodified CNF were prepared by grinding softwood pulp with a disc
mill. These CNF had fibril diameters of about 30 to 50 nm. Filters were
prepared by a filtration process adapted from a previous study (Fortea-
Verdejo et al., 2016) without densification to allow for the creation of a
porous filter rather than a compacted structural fibre preform for
composite applications. Suspensions containing various amounts and
types, respectively, of CNF were deposited onto the natural fibre sub-
strates and consolidated. Initially, it was tried to directly decorate the
natural fibre substrates with TEMPO-CNF. Unfortunately, due to the
A. Mautner, et al. Industrial Crops & Products 133 (2019) 325–332

Fig. 1. Representative SEM images (magnification: 50×) of non-woven flax-agave blend (left) and cotton-viscose (right) filter substrates.

Table 2
Dimensions of natural fibre (bundles): fibre (bundle) diameters, grammages and
air permeabilities of FA and CV substrates.
Sample Fibre (bundle) diameter G [gsm] Air Permeability [mm s−1]
[μm]

FA 10-50 (up to 500) 570 ± 180 1040 ± 290

CV 5-15 170 ± 20 550 ± 100

small fibril diameters (about 10 nm), the fibrils passed the substrate
without being retained. Hence, a different approach was designed and
tested. Unmodified CNF were used to provide anchor sites onto which
the TEMPO-CNF would attach. First, in order to determine the optimal
amount of CNF to form this anchor, various amounts unmodified CNF Fig. 3. Permeances of flax-agave (full green diamond) and cotton-viscose (open
were deposited to the substrates. Pictures of these composites with blue circle) substrates with 0–50 gsm of unmodified CNF as function of the
50 gsm CNF are shown in Fig. 2. amount of CNF added. Note: the error bars (< 2%) are too small to be no-
It was observed that for high grammages of unmodified CNF ticeable in this graph.
(50 gsm), a dense film was created on the substrate sealing it, which
was anticipated to result in very low permeances. This was confirmed
permeability (Table 2). Accordingly, higher grammages of the anchor
by permeance tests (Fig. 3). For low amounts of unmodified CNF added,
CNF could be realized for the flax-agave substrates.
the permeance of the impregnated substrates, which was above
Subsequently, three component composite structures were prepared
100,000 L m−2 h−1 MPa−1 for both FA and CV, respectively, remained
by first applying 5 gsm CNF onto CV and 5, 10 and 20 gsm CNF onto FA,
at large unaffected. However, particularly in the case of CV substrates,
respectively. On top of these anchors, 50 gsm of TEMPO-CNF were
already when applying a 10 gsm coating we observed a drastic decrease
deposited. SEM images of these filters are shown in Fig. 4. The porous
of the permeance. A permeance of 8 L m−2 h−1 MPa−1 was measured
structure of the substrates can still be observed but also CNF were
for CV coated with 50 gsm of CNF, which is comparable to permeances
present not only at the surface but also throughout and within the filter
of stand-alone nanopapers composed of the same grammage (Mautner
impregnating the substrate. This was considered beneficial as the active
et al., 2015). This trend was, however, not present for the flax-agave
adsorption agent would be better available for the adsorption of heavy
substrates for these had a higher porosity as proven by their higher air

Fig. 2. Representative SEM images (magnification: 100×) of non-woven flax-agave (left) and cotton-viscose (right) filter substrates coated with 50 gsm of un-
modified CNF.

328
A. Mautner, et al.
Fig. 4. Characteristic SEM images (magnification: 100×) of non-woven flax-agave (left) and cotton-viscose (right) filter substrates coated with 5 gsm of unmodified
CNF and 50 gsm TCNF.
metal ions than when coated as dense layer on the surface of the sub-
strates.
Tensile properties of the filters were measured both in wet and dry
conditions. Paper tensile strengths of about 1200 N m−1 and 1700 N
m−1 were determined for FA and CV filters, respectively. This is com-
parable to the tensile properties of common membranes and filters
prepared from renewable resources (Karim et al., 2016, 2014; Mautner
et al., 2019, 2016a). The wet strength decreased to 700 N m−1 and
600 N m−1 for FA and CV filters, respectively, which accounts to a
retention of 60% and 35% of the original strength. This high strength in
wet conditions outperforms current pure nanocellulose filters, which
often retain merely 5% of their original dry strength (Karim et al.,
2016). This high strength in wet conditions is due to the inter-
penetrating, hierarchical (nano- and microscale) structure of the non-
woven filters in which the CNF act as water stable binder between
natural fibres. Water stability is a result of the hornification of the
(T)CNF during hot consolidation at 120 °C.
In order to verify the suitability of these filters in the application of
metal cation adsorption, the surface charge as expressed by the ζ-po-
tential was analyzed (Fig. 5). Whereas for the FA substrate only a
moderately negative ζ-potential (plateau at high and moderate pH
about −10 mV), similar to values reported in literature (Baltazar-y-
Jimenez and Bismarck, 2007b; Bismarck et al., 2002, 2001, 2000;
Cadena et al., 2009), was found, the filters decorated with TEMPO-CNF
had greatly reduced ζ-potential (plateau at about −60 mV), which
should facilitate metal-ion adsorption (Liu et al., 2014; Sehaqui et al.,
2014). Thus the ζ-potential of the composite filter was close to that of
pure TCNF, which was −72 mV. The much higher negative ζ-potential
of the composite filter compared to the pure substrate indicates a high
concentration of carboxylic acid groups on the surface of the fibres/
Fig. 5. ζ-potential = f(pH) of the FA non-woven (open circle) and FA im-
pregnated with 20 gsm CNF and 50 gsm TCNF (full circle).
329
Industrial Crops & Products 133 (2019) 325–332
fibrils, thus facilitating adsorption of positively charged metal ions. The
isoelectric point (i.e.p.) was at pH 2.3 for the natural fibre substrate,
and thus lower as compared to pH 2.8 for flax fibres (Camano et al.,
2014) and 3.4 for agave fibres reported in literature (Baltazar-Y-
Jimenez and Bismarck, 2007a,b). Upon decoration with TCNF the i.e.p.
remained unchanged at pH 2.3. This was due to the same class of
functional groups (carboxylic groups) being responsible for the forma-
tion of the electrochemical double layer, and thus charge in both the
fibre substrates and TEMPO-CNF. Typically, the i.e.p. of TEMPO-CNF in
suspension is found just below pH 2 (Liu et al., 2016; Mautner et al.,
2014), whereas in the form of nanopaper it is about 2.7 (Mautner et al.,
2018). Thus, for in the present filter TEMPO-CNF is neither in the form
of isolated particles nor of a fully consolidated paper, this intermediate
i.e.p. can be expected.
3.2. Permeance and rejection properties of the filters
The performance of natural fibre-nanocellulose composite filters
was evaluated in terms of their water permeance as well as adsorption
of Cu2+. In order to achieve high efficiency, it is important that the
filters not only adsorb a high amount of copper ions as expressed by
their adsorption capacity qe [mg g−1], but also a high water permeance
is required. Currently, most nanocellulose membranes or filters achieve
good adsorption capacities but suffer from low permeance. Thus the
approach of this study was to enable good adsorption properties also at
high permeance. The permeance was tested in a dead-end cell by ap-
plying nitrogen head-pressure and taking the time for 250 mL (full cell)
to pass the filter. The measurements were repeated at least four times or
until a stable permeance was achieved, i.e. the permeance of four
consecutive measurements varied by less than two percent. The results
of these measurements are shown in Fig. 6. It was found that the ap-
plication of TEMPO-CNF onto the substrate already decorated with
unmodified CNF had only a minor influence onto the permeance of the
filters (compare Fig. 3). Permeances of more than 100,000 L
m−2 h−1 MPa−1 were found, which is more than 1000 times higher
than the permeance of pure nanocellulose papers (Mautner et al.,
2015). The TEMPO-CNF did apparently not form a dense layer on top of
the substrate as confirmed by SEM images (Fig. 4), which would sig-
nificantly reduce the permeance, but were rather attached to the un-
modified CNF on the natural fibres within and throughout the substrate.
Furthermore, it is important to stress that these high permeances were
achieved already at a driving pressure of only 1 bar! Hence an effective
filtration process at low pressures and thus low energy input is feasible
with this type of filter.
The adsorption behavior of the all-cellulose composite filters was
assessed by dynamic filtration tests with Cu(II) ion solutions. 0.1 mM
solutions were used, corresponding to 6.35 mg L−1 and thus
A. Mautner, et al.
Fig. 6. Permeances of flax-agave (full green diamond) and cotton-viscose (open
blue circle) filters with 50 gsm of TEMPO-CNF deposited on various amounts of
unmodified CNF. Note: the error bars (< 2%) are too small to be noticeable in
this graph.
Fig. 7. Adsorption per unit area qA [mg m−2] of Cu(II) ions on FA (top) and CV
(bottom) filters with various amounts of unmodified CNF and TCNF as function
of the filtration volume. No (T)CNF (open black square), 5 gsm CNF & 50 gsm
TCNF (yellow triangle), 10 gsm CNF & 50 gsm TCNF (blue diamond), 20 gsm
CNF & 50 gsm TCNF (green square). Note: the error bars (< 4%) are too small
to be noticeable in this graph.
representing a highly copper contaminated water source containing
more than 3 times the amount of Cu ions that are considered to be safe
(WHO, 2004). The amount of Cu adsorbed during passage of the solu-
tion through the filter was determined by colorimetric titration by re-
lating the difference between the permeate concentration and the start
concentration to the active filtration area. In Fig. 7, the amount [mg] of
Cu adsorbed per unit area [m2] of FA filters and CV-reference filters as
function of the permeate volume [mL] is shown.
We found that the amount of unmodified CNF used to anchor TCNF
impacted the amount of copper that could be adsorbed due to enabling
better availability of the active adsorption agent (TCNF) for the ad-
sorption of heavy metal ions. In the beginning of the measurement a
330
Industrial Crops & Products 133 (2019) 325–332
Table 3
Amount of Cu(II) ions adsorbed qA,max and adsorption capacity qe of FA and CV
filters.
Sample Code qA,max [mg m−2] qe [mg g−1]
FA 0 0.0
FA_5-50 630 31.4
FA_10-50 980 49.0
FA_20-50 1285 64.3
CV 0 0.0
CV_5-50 1090 54.5
rapid uptake of copper was observed, which levelled off during the
experiments for the filters became saturated. Cumulative values of more
than 1200 mg m−2 Cu were found to be adsorbed on FA filters, which is
appreciably (factor > 3) more than filters completely prepared from
anionic CNF were capable of (Mautner et al., 2016a). This value cor-
responds to adsorption capacities of more than 60 mg g−1 of active
adsorption agent (TEMPO-CNF). These adsorption capacities are at
least on par with those recently reported for other biosorbents prepared
from industrial crops (Oo et al., 2009; Ramos et al., 2016; Romero-Cano
et al., 2016) and much higher than for modified flax (Marshall et al.,
2007). However, the process demonstrated here works continuously,
which is beneficial over traditional sorbent materials that are used
batch-wise. For CV, only one type of CNF filter was applied for higher
amounts of unmodified CNF caused significantly reduced permeance.
Nevertheless, 1100 mg m−2 copper ions adsorbed corresponding to
55 mg g−1 adsorption capacity were found for a CV filter in which 5
gsm CNF acted as anchor for the TEMPO-CNF. The combination of very
high permeances and high amounts of copper being adsorbed makes
these filters a potential alternative for the treatment of water sources
for heavy metal ions (Table 3).
As-produced filters, as well as filters after permeance tests and Cu
adsorption, respectively, are shown in Fig. 8. It is apparent that the
filtration tests did not affect the structure and integrity of the filters.
This does not only indicate that they are stable enough under wet
conditions, as proven also by the retention of the tensile strength, but
also to withstand water permeating them. Furthermore, in particular for
CV filters, the success of continuous adsorption of Cu is demonstrated. A
green haze on the filters signals the presence of Cu2+ on the filters.
Unfortunately, this is not so obvious in the case of FA filters due to their
natural brownish color. However, still a slight variation of the color can
be distinguished between filters permeated with water (Fig. 8B
(center)) and those (Fig. 8B (right)) that were to filter Cu2+.
4. Conclusions
Natural fibre-nanocellulose composite filters were prepared from
flax and agave fibres and various types of cellulose nanofibrils (CNF).
Cotton/viscose substrates were used as reference material. These filters
were prepared by depositing first an anchor of unmodified CNF onto the
substrates and subsequently attaching anionic TEMPO-CNF. SEM
images confirmed successful preparation of these composite filters. The
ζ-potential of the composite filters was significantly reduced by the
addition of TEMPO-CNF as compared to the pure substrates, which
indicates highly negative surface charge enabling adsorption of metal
ions. Due to the previous optimization of the unmodified CNF anchor,
the permeance of three component composite filters was kept at about
100,000 L m−2 h−1 MPa−1, thus being a factor of 1000 higher as for
nanopapers made from pure nanocellulose. Ultimately, more than
1200 mg m−2 copper could be adsorbed on these filters. This corre-
sponds to an adsorption capacity of more than 60 mg g−1 for the active
adsorption agent TEMPO-CNF. The combination of very high per-
meance already at only 1 bar of driving pressure together with high
adsorption capacity allows for highly effective application of these fil-
ters in heavy metal removal from aqueous solution.
A. Mautner, et al.
Fig. 8. Filters from CV_5-50 (A) and FA_10_50 (B) after production (left), after permeance test (centre) and after filtration of Cu2+ (right).
Funding
This work was supported by the OeAD [grant number WTZ ZA 03/
2017] and NRF [grant number 106135]. Funding from University of
Warwick and Erasmus+ for Yosi Kwaw and University of Vienna for
Andreas Mautner is also acknowledged.
Acknowledgements
We thank Haydon Whitebooi for his help with the non-woven
manufacture and Anja Huch of EMPA for SEM imaging.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.indcrop.2019.03.032.
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