Membranes with Functionalized

Nanomaterials : Current and Emerging

Research Trends in Membrane
Technology Suman Dutta
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MEMBRANES WITH
FUNCTIONALIZED
NANOMATERIALS
This page intentionally left blank
MEMBRANES WITH
FUNCTIONALIZED
NANOMATERIALS
Current & Emerging
Research Trends in
Membrane Technology
Edited by

SUMAN DUTTA
Department of Chemical Engineering, IIT(ISM), Dhanbad,
India

CHAUDHERY MUSTANSAR HUSSAIN

Department of Chemistry and Environmental Sciences,
New Jersey Institute of Technology (NJIT), Newark, NJ,
United States
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Contents

Contributors ix

1. Modern perspective in membrane technologies—Sustainable

membranes with FNMs 1
Mehrzad Zandieh, Abtin Ebadi Amooghin, and Hamidreza Sanaeepur
1.1 Introduction 1
1.2 Nanostructured membranes 2
1.3 Nano-engineered membranes 4
1.4 Several aspects of nanocomposite membranes 7
1.5 Applications of NEMs 10
1.6 Functionalization of nanoparticles in NEMs 19
1.7 Sustainability of membranes 27
1.8 Future perspective 29
1.9 Conclusions 30
References 31

2. Theoretical concepts of membrane-nanomaterial

composites 37
Deepshikha Datta, K.S. Deepak, Krishna Priyadarshini Das, and Bimal Das
2.1 Nanomaterials 37
2.2 Membranes 44
2.3 Membrane-nanomaterial composites 61
2.4 Conclusions 69
References 70

3. Candidates of functionalized nanomaterial-based

membranes 81
Deepshikha Datta, Krishna Priyadarshini Das, K.S. Deepak, and Bimal Das
3.1 Introduction 81
3.2 Nanomaterials 83
3.3 Potential of nanomaterials 84
3.4 Limitations of nanomaterials 85
3.5 Functionalized nanomaterials 85

v
vi Contents

3.6 Methods of nanomaterials functionalization 89

3.7 Different types of nanomaterials and additives used for making the
functionalized nanomaterial-based membrane 90
3.8 Carbon-based functionalized nanomaterials 91
3.9 Silica-based nanomaterials 103
3.10 Metallic inorganic nanomaterials 106
3.11 Organic nanomaterials 114
3.12 Application of functionalized nanomaterials 117
3.13 Conclusions 119
References 120

4. Fabrication of sustainable membranes with functionalized

nanomaterials (FNMs) 129
Jasir Jawad and Syed Javaid Zaidi
4.1 Introduction 129
4.2 Fabrication methods 131
4.3 Summary and future perspective 148
Acknowledgment 149
References 149

5. Sustainable membranes with FNs: Current and emerging

research trends 159
P. Das and Suman Dutta
5.1 Introduction 159
5.2 Fabrication techniques 161
5.3 Classification of different forms of nanomaterial-functionalized
membranes 163
5.4 Diverse applications of functionalized nanomaterials 165
5.5 Removal of different contaminants with functionalized nanomaterial
membranes 169
5.6 Pilot studies and industrial applications 173
5.7 Possibility of value-added product recovery 173
References 176

6. Sustainable membranes with functionalized nanomaterials

(FNMs) for environmental applications 185
Nur Hashimah Alias, Mohamad Nor Nor Azureen, Nur Hidayati Othman,
Fauziah Marpani, Woei Jye Lau, and Munawar Zaman Shahruddin

6.1 Introduction 185

 Contents vii

6.2 Limitations of membranes with functionalized nanomaterials (FNMs)

in environmental applications 187
6.3 Synthesis and modification of membranes with functionalized
nanomaterials (FNMs) 189
6.4 Future challenges for membranes with functionalized
nanomaterials (FNMs) 197
6.5 Conclusions 198
References 199

7. Sustainable membranes with FNMs for biomedical

applications 205
Zinnia Chowdhury, Sanjib Barma, Aparna Ray Sarkar, and Dwaipayan Sen
7.1 Introduction 205
7.2 Overview on membrane technology 206
7.3 Identification of sources for nanomaterial synthesis 220
7.4 Preparation of nanomaterials 222
7.5 Economic analysis for different methods 225
7.6 Functionalization of nanomaterials 226
7.7 Membrane modified with functionalized nanomaterials 234
7.8 Summary 240
References 240

8. Sustainable membranes with FNMs for energy generation

and fuel cells 245
K. Khoiruddin, G.T.M. Kadja, and I.G. Wenten
8.1 Introduction 245
8.2 Preparation of IEM containing FNMs 247
8.3 IEM/FNMs for fuel cell applications 255
8.4 IEM/FNMs in redox flow battery (RFB) 259
8.5 IEM/FNMs in reverse electrodialysis (RED) 263
8.6 Concluding remarks 267
References 268

9. Sustainable membranes with FNMs for pharmaceuticals

and personal care products 275
Maher Darwish, A.A. Abuhabi, and Hanan Mohammad

9.1 Introduction 275

9.2 PhACs in the environment 277
9.3 Methods to remove PhACs from water 283
9.4 Approaches of membrane functionalization 291
viii Contents

9.5 Functionalized NF membranes for PhACs removal 295

9.6 Nanocomposite membranes for PhACs removal 302
9.7 Conclusions 318
References 318

10. Challenges in commercialization of sustainable membranes

with FNMs 329
Putu Doddy Sutrisna
10.1 Introduction 329
10.2 Overview of important problems in liquid-based and gas-based
membranes 330
10.3 Functionalized nanomaterials-membranes 334
10.4 Challenges in synthesis and commercialization of mixed matrix and
nanocomposite membranes with functional nanomaterials 335
10.5 Conclusions 346
References 347

11. Membranes with FNMs for sustainable development 355

Deepshikha Datta, K.S. Deepak, and Bimal Das
11.1 Introduction 355
11.2 Functionalized nanomaterial acts as a silver bullet in the arsenal 357
11.3 Role of sustainable membranes with FNMs in modern society 360
11.4 Road map for sustainable development through FNM-based
membranes 377
11.5 Conclusions 378
References 379

12. Future prospects of sustainable membranes 389

Deepshikha Datta, K.S. Deepak, and Bimal Das
12.1 Introduction 389
12.2 Changing dynamics of the world 390
12.3 The path ahead 393
12.4 Conclusion 410
References 411

Index 419
Contributors

A.A. Abuhabi
Water Technology PhD Joint Programme Between Islamic University of Gaza IUG &
Al-Azhar University of Gaza AUG, Gaza, Palestine
Nur Hashimah Alias
Department of Oil and Gas Engineering, School of Chemical Engineering, College of
Engineering, Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia
Abtin Ebadi Amooghin
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak, Iran
Sanjib Barma
Department of Chemical Technology, University of Calcutta, Kolkata, West Bengal, India
Zinnia Chowdhury
Department of Chemical Technology, University of Calcutta, Kolkata, West Bengal, India
Maher Darwish
Department of Pharmaceutical Chemistry and Drug Control, Faculty of Pharmacy, Wadi
International University, Homs, Syria
Bimal Das
Department of Chemical Engineering, National Institute of Technology Durgapur,
Durgapur, India
Krishna Priyadarshini Das
Department of Material Science and Engineering, Indian Institute of Technology, Delhi,
India
P. Das
CSIR-Central Institute of Mining and Fuel Research, Dhanbad, Jharkhand, India
Deepshikha Datta
Department of Chemical Engineering, GMR Institute of Technology, Rajam, India
K.S. Deepak
Department of Chemical Engineering, National Institute of Technology Durgapur,
Durgapur, India
Suman Dutta
Department of Chemical Engineering, IIT(ISM), Dhanbad, India
Abtin Ebadi Amooghin
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak, Iran
Jasir Jawad
Centre for Advanced Materials, Qatar University, Doha, Qatar

ix
x Contributors

G.T.M. Kadja
Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Sciences,
Institut Teknologi Bandung, Bandung, Indonesia
K. Khoiruddin
Department of Chemical Engineering, Faculty of Industrial Technology, Institut Teknologi
Bandung, Bandung, Indonesia
Woei Jye Lau
Advanced Membrane Technology Research Centre (AMTEC), School of Chemical and
Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, Skudai, Johor,
Malaysia
Fauziah Marpani
Department of Oil and Gas Engineering, School of Chemical Engineering, College of
Engineering, Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia
Hanan Mohammad
Department of Pharmaceutical Chemistry and Drug Control, Faculty of Pharmacy, Wadi
International University, Homs, Syria
Mohamad Nor Nor Azureen
Department of Chemical Sciences, Faculty of Science & Technology, The National
University of Malaysia (UKM), Bangi, Selangor, Malaysia
Nur Hidayati Othman
Department of Oil and Gas Engineering, School of Chemical Engineering, College of
Engineering, Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia
Hamidreza Sanaeepur
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak, Iran
Aparna Ray Sarkar
Department of Chemical Engineering, Heritage Institute of Technology, Kolkata,
West Bengal, India
Dwaipayan Sen
Department of Chemical Engineering, Heritage Institute of Technology, Kolkata,
West Bengal, India
Munawar Zaman Shahruddin
Department of Oil and Gas Engineering, School of Chemical Engineering, College of
Engineering, Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia
Putu Doddy Sutrisna
Department of Chemical Engineering, University of Surabaya (UBAYA), Surabaya,
Indonesia
 Contributors xi

I.G. Wenten
Department of Chemical Engineering, Faculty of Industrial Technology, Institut Teknologi
Bandung, Bandung, Indonesia
Syed Javaid Zaidi
Centre for Advanced Materials, Qatar University, Doha, Qatar
Mehrzad Zandieh
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak, Iran
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CHAPTER 1

Modern perspective in membrane

technologies—Sustainable
membranes with FNMs
Mehrzad Zandieh, Abtin Ebadi Amooghin, and Hamidreza Sanaeepur
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak, Iran

1.1 Introduction
Separation technology has acquired significance in different industrial usages
[1]. Membrane technology is favored over other purification methods such
as disinfection or distillation owing to the absence of chemical additives,
energy yield, and the convenience of the technology [2]. In other words,
membranes suggest energy-effective processes versus available separation
processes [1]. Membrane technology renders a preferable operating effi-
ciency along with small energy and performance costs. A lot of effort has
been focused on making unique materials or structures with a higher capa-
bility to improve the membrane performance [3]. To attain membranes with
the best performance, different kinds of materials have been applied. Among
them, polymeric membranes suggest an extensive scope of molecular trans-
fer features with more straightforward methods and lower membrane pro-
duction costs [1]. Commercial membranes are mainly manufactured from
polymeric materials containing polysulfone and polyamides [2]. Neverthe-
less, polymeric membranes involve a challenge of choosing between selec-
tivity and permeability of penetrants. The focus to eliminate this challenge is
to combine excellent-performance particles like zeolites, metal-organic
frameworks, and nanoparticles such as porous layers or nanotubes in the
membrane; the presence of different nanoparticles augments the perfor-
mance of separation as well as physicochemical features of the membrane
[1,4]. A novel approach in the development of membranes is incorporating
nanomaterials that can improve the porosity, reactivity, and permeability of
the membranes. Considering this approach, various types of membranes can
be constructed, such as thin-film nanocomposite (TFN) membranes or
mixed matrix membranes (MMMs) [5]. Embedding nanomaterials in

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2 Membranes with functionalized nanomaterials

thin-film layer, high-performance TFN membranes have developed with

excellent physicochemical properties [6].
On the other hand, thin-film composite (TFC) membranes have excel-
lent potential due to their specific structure, a thin selective layer created on
the top of a porous supporting layer. These membranes are very versatile, as
they have an acceptable permeability (flux) simultaneous with excellent
selectivity (rejection). In addition, incorporating the nanoparticles in the
TFC membrane structure is a prevalent approach. Different nanoparticles,
like zeolites, titanium dioxide, and graphene oxide, have been effectively
embedded into the separating layer of TFC membranes [7]. Moreover,
porous organic polymers (POPs)—as a novel class of nanomaterials—can
be excellent candidates for making TFC with high performance [5]. On
the other hand, mixed matrix membranes (MMMs)—as another form of
nanostructured membranes—have superior selectivity and/or permeability
and excellent capability to overcome restrictions of polymeric membranes as
well as inorganic membranes [8]. The application of advanced functional
materials is developing to enhance MMMs’ performance as energy-efficient
substitutes for common membranes. Enhancing the facilitated transfer and
selective adsorption of a specified molecule via MMMs are the original
purposes of designing and developing functional materials for the prepara-
tion of these membranes. Excellent inherent permeability and selectivity
of advanced nanomaterials simultaneously with well mechanical features
of polymers result in excellent separation performance of MMMs compared
to a pristine polymer [9]. Today, modern functionalized MMMs are the
great candidates for the specific separations [10].

1.2 Nanostructured membranes

The manipulation of atomic and molecular interactions results in a correction
of macroscopic properties, leading to a fundamental reconstruction of material
features like optical, mechanical, and transfer phenomena. Macroscopic
adjustments can be ascribed to small size effects, interface effects, quantum size
effects, quantum tunneling effects, and so on. A nanostructured membrane
represents the internal and external nanostructures together since nano-based
characteristics can be in bulk or all over the membrane’s surface (Fig. 1.1) [11].
Pores with sizes ranging from 1 to 100 nm that permit particles and com-
pounds are separated according to their sizes are common structural ele-
ments that enable membranes to be categorized as nanostructures. In
addition, the incorporation of nanofillers in polymer matrixes puts the
 Modern perspective in membrane technologies 3

Fig. 1.1 Examples of tailor-made nanostructured membranes. (From E. Drioli, L.

Giorno, A. Gugliuzza, An introduction to nanostructured membranes for advanced
applications in strategic fields, in: E. Drioli, L. Giorno, A. Gugliuzza (Eds.), Functional
Nanostructured Membranes, first ed., Jenny Stanford Publishing, 2019, pp. 1–11. https://
doi.org/10.1201/9781351135115.)

membranes in the classification of nanostructures. The hierarchical texture

on the membrane surfaces is another reason to categorize it in the nanostruc-
tures. Block copolymers in combination with nanotubes, catalytic nanopar-
ticles, zeolites, or bio-combined compounds can be incorporated in the
polymer matrix or deposited onto the relevant surface to enhance the sep-
aration performance as well as decreasing energy and capital costs (Fig. 1.1)
[11]. The substantial allocation of nano-objects and complementary compo-
nents in confined spaces yields new tunable functions and advanced perfor-
mances that depend on intrinsic relationships between local structure,
transport, and surface properties. The source of transport phenomena con-
trolling the membrane permeability and selectivity depends on the activity at
nano levels. It is essential to enhance the structural complexity of nanostruc-
tured membranes since many species need to be arranged in complex
organizations that depend on the previous level of assembly. This applies
organizational principles and accurate control on various length scales [8].
In nano-porous membranes, the pores are considered structural constituent
4 Membranes with functionalized nanomaterials

sectors of the entire framework. This suggests that nano-porous membranes

are not related to inherent risks, such as toxicity, that arise in conventional
nanomaterials [11].

1.3 Nano-engineered membranes

In nanostructured membranes (NSMs), the word “nano” refers to the mem-
brane’s interior configuration. Nanoscience has created a way to manufac-
ture nano-added or nano-engineered membranes (NEMs), where the word
“nano” signifies NM-based membranes. Various kinds of nanomaterials
(NMs) that have been investigated in preparing membranes are illustrated
in Fig. 1.2. NEMs are applied to make reasonable adjustments to the mor-
phology, permeability, selectivity, physical, and chemical properties of
membranes to supply the following practical items [12]:
• enhanced selectivity via improving the membrane structure and surface
features;
• extensive usage of membranes in different separation processes;
• improved mechanical and thermal consistency NEMs, which can be cat-
egorized as follows:
(1) nanostructured membranes are prepared from a layer of NMs on
top of porous membrane substrate or fabricated as a freestanding
NM film; and
(2) nanocomposite membranes (NCMs), in which NMs are embedded
through a polymer binder (Fig. 1.3).
Moreover, NCMs are subclassified into:
(a) (1) thin film nanocomposite membranes (TFNCMs), where particles
are immobilized/entrapped within the top layer of the membrane;
(2)surface-coated TFNCMs, where NMs are coated onto the top sur-
face of an NCM; and (3) substrate-coated TFNCMs, where NMs are
located on a TFNCM support membrane; and
(b) MMMs in which NMs are embedded in the membrane matrix.
TMNCMs can be fabricated by employing an MMM or a conventional
nanostructured UF/MF membrane as the support [12].
TFC membranes are made by applying an ultra-thin selective layer on top of
a microporous substrate with the support of nonwoven fabric. The structure
of a totally fibrous membrane is known as a membrane of thin-film nanofi-
brous composite (TFNC). Applying nanofibrous scaffolds presents a novel
combination of interlinked pore structures with high porosity that makes
TFNC membranes more permeable than standard TFC membranes [13].
Fig. 1.2 Various kinds of nanomaterials for preparation of nano-engineered membranes. (From J.M. Gohil, R.R. Choudhury, S. Thomas, D.
Pasquini, S.-Y. Leu, D.A. Gopakumar, Introduction to nanostructured and nano-enhanced polymeric membranes: preparation, function, and
application for water purification, in: Micro and Nano Technologies, Elsevier, 2019, pp. 25–57. https://doi.org/10.1016/B978-0-12-813926-4.
00038-0. (Chapter 2))
6 Membranes with functionalized nanomaterials

Fig. 1.3 Different kinds of nano-engineered membranes. (From J.M. Gohil, R.R.
Choudhury, S. Thomas, D. Pasquini, S.-Y. Leu, D.A. Gopakumar, Introduction to
nanostructured and nano-enhanced polymeric membranes: preparation, function, and
application for water purification, in: Micro and Nano Technologies, Elsevier, 2019,
pp. 25–57. https://doi.org/10.1016/B978-0-12-813926-4.00038-0. (Chapter 2))

Developing an easy procedure for the fabrication of TFN membranes with

excellent antibiofouling and separation performance is very important.
Simultaneous formation of the polymer matrix and nanoparticles, which
is called in-situ hybridization, has many advantages and has been widely
employed in various composites [14]. These advantages are the creation
of an interpenetrating polymer network (IPN) between nanoparticles,
and better dispersity/compatibility of the nanoparticles in hybrid networks.
This procedure can also simplify the fabrication process of composite mem-
branes (Fig. 1.4) [14]. Fig. 1.4 shows an easy in-situ hybridization procedure
for the fabrication of membranes of Ag nanoparticle (AgNP)-incorporated
TFN (Ag-TFN) RO with excellent antibiofouling and separation perfor-
mance. AgNP has robust antibacterial activity and hydrophilic nature that
can improve water permeance and biofouling resistance of the prepared
membrane. This procedure is based on the possible multifunctional ability
of the materials commonly used in interfacial polymerization (IP). MPD
(m-phenylenediamine) monomer contains the main amine groups that are
applied to create a main PA network, and can be a reducing agent to gen-
erate AgNPs from an Ag precursor (silver nitrate, AgNO3). Sodium dodecyl
 Modern perspective in membrane technologies 7

NH2 Reduction AgNP=

MPD Ag+
NH2

SDS
Stabilization

COCI

TMC
CIOC COCI PA layer
IP reaction

PSF support Ag-TFN

Fig. 1.4 Fabrication of Ag-TFN membrane through in-situ hybridization. (From S. Jeon,
J.-H. Lee, Rationally designed in-situ fabrication of thin film nanocomposite membranes
with enhanced desalination and anti-biofouling performance, J. Membr. Sci. 615
(2020) 118542. https://doi.org/10.1016/j.memsci.2020.118542.)

sulfate (SDS), which is widely applied as a surfactant to facilitate IP, can also
be a stabilizer for AgNPs to improve their uniformity and dispersion [14].

1.4 Several aspects of nanocomposite membranes

The main purpose for preparing of the modified membrane is to improve
the effectiveness of the physicochemical properties and separation perfor-
mance. In this section, a summary of different nanoparticles used in the fab-
rication of composite membrane is provided [15].

1.4.1 TiO2
TiO2 is usually applied for the fabrication of nanocomposite membranes.
This metal oxide always improves the mechanical strength, hydrophilicity,
water permeability, and antifouling capability of a membrane. It also can
improve the antibacterial property of the membrane surface [15]. Wei
et al. [16] studied polyamide membranes of TFN nanofiltration prepared
through interfacial polymerization of piperazine and trimesoyl chloride
on a PES substrate using aminated titanium dioxide (APTES (3-aminopro-
pyltriethoxysilane)-TiO2). The results illustrated that a membrane contain-
ing 0.3 w/v% amine-functionalized TiO2 seriously improved the pure water
flux with a relatively high Na2SO4 rejection (>95%). This TFN membrane
revealed a separation factor of 477.89 with the NaCl to Na2SO4 ratio of
about 1:19.
8 Membranes with functionalized nanomaterials

1.4.2 Silver
Silver is a well-known antibacterial agent. Hence, this nanoparticle min-
imizes the biofouling of the membrane surface due to its antibacterial
nature. This nanoparticle annihilates the microorganisms present in differ-
ent effluents. Therefore, silver-incorporated composite membranes usu-
ally reveal better surface charge density, permselectivity, etc., in
comparison with typical membranes [15]. Maiphetlho et al. [17] evaluated
silver nanocomposite polymer inclusion membranes (PIMs) for trace metal
transports. A polyvinyl chloride/di-(2-ethylhexyl) phosphoric acid
(PVC-D2EHPA)-based PIM containing silver nanoparticles fabricated
to remove and measure the trace metals in contaminated water. The con-
tact angle results showed that the presence of AgNPs seriously modified the
hydrophilic/hydrophobic characteristics of fabricated membranes. On the
other hand, the membrane stability was reduced during the operations
with repeated cycles despite an improvement of hydrophilicity by incor-
porating of AgNPs.

1.4.3 SiO2
Silica is applied as an inherent semiconductor. Therefore, this nanoparticle
improves hydrophilicity, permeability, and selectivity of the membrane.
Thus, such a membrane can be mainly applied for the oil removal from water
and gas separation. In addition, different kinds of silica-based composite
membranes can be used in wastewater treatment [15]. Shakak et al. [18] have
synthesized polysulfone/polyvinylpyrrolidone/SiO2 nanocomposite ultra-
filtration membranes and evaluated the amoxicillin removal from water.
Ultrafiltration membranes were fabricated by the phase inversion method.
Nanoparticles of SiO2 were applied as a hydrophilic agent for modification
of membrane. The results achieved by contact angle and Fourier-transform
infrared spectroscopy (FTIR) analysis showed that the presence of hydroxyl
groups of SiO2 enhanced the membrane hydrophilicity. It was also found that
by increasing the SiO2 content, the spongiform and tear-like structure of the
membranes shifted to canal-shaped, finger-shaped, and macro-void struc-
tures. Moreover, increasing the SiO2 nanoparticle from 0 to 4 wt% caused
an increase in the separation performance of amoxicillin from 66.52% to
89.81%.
 Modern perspective in membrane technologies 9

1.4.4 Iron
FeO nanoparticle is a very suitable material for water purification due to its
high surface area, accessibility, magnetic property, cheapness, and hydro-
philic nature [13]. Copper removal was investigated by employing a poly-
ethersulfone (PES)-iron oxide composite nanofiltration membrane [19].
The highest copper removal was in the presence of 0.1 wt% iron oxide.
PES-iron oxide membrane treatment (reusability test) applying ethylene
diamine tetraacetic acid (EDTA) had the best performance (in copper
removal) at 0.1 wt% iron oxide [19]. FeO nanoparticles led to a consider-
able improvement in the removal of hydrophobic pollutants and antifoul-
ing for saline water treatment applications. At low FeO loading (0.05 wt%),
peeling type structure was observed, while 0.2 wt% FeO led to the seed-
like covered surface morphology. Excellent dispersion of FeO nanoparti-
cles and finger-like structure were observed in the cross-section of
membranes [20].

1.4.5 Zirconia
Zirconium oxide (zirconia or ZrO2) has been used in the preparation of dif-
ferent NCMs. In the case of membrane of PVDF ultrafiltration, suitable
changes in the membrane performance can be achieved via alterations to
the solvent of PVDF or by varying the ZrO2 content ratio of the PVDF/
ZrO2 mixture. ZrO2 has also been used with sulfonated polyetherketone
(PEK) to reduce the water and methanol permeabilities. This ability has
made the PEK/ZrO2 membrane a suitable candidate for utilization in appli-
cations related to fuel cells [13]. Noormohamadi et al. [21] studied the
hydrophilic properties of nanoparticles of ZrO2 and the role of nanoparticles
of iron oxide in increasing the porosity of polymer membranes. To achieve
this purpose, Fe3O4@ZrO2/PAN (polyacrylonitrile) nanocomposite mem-
brane was synthesized, and its performance was tested in decreasing biolog-
ical fouling of the membrane. Analysis of FTIR showed the functional
groups in nanoparticles of Fe3O4@ZrO2 and confirmed their presence in
the matrix of an Fe3O4@ZrO2/PAN NCM. Analysis of contact angle ver-
ified the role of nanoparticles of ZrO2 in increasing the hydrophilicity of
membrane by 51%, and analysis of porosimetry verified the role of nanopar-
ticles of iron oxide in improving porosity of the NCMs by 47%. Application
of 1 wt% of nanoparticles of Fe3O4@ZrO2 in the PAN membrane matrix
resulted in a 40% increase in water flux.
10 Membranes with functionalized nanomaterials

1.4.6 Copper
Ben-Sasson et al. [22] employed a procedure for inserting copper nanopar-
ticles (Cu-NPs) on the surface of a membrane of TFC polyamide reverse
osmosis. Cu-NPs were synthesized, resulting in particles with an average
radius of 34 nm. The positive charge of the Cu-NPs permitted an easy elec-
trostatic functionalization of the RO membrane with a negative charge. It
was found that functionalization of Cu-NPs had minimal effect on the trans-
port parameters of the membrane. After functionalization, the surface charge
of the membrane became positive. The functionalized membrane showed
significant antibacterial activity.

1.4.7 Clay
Clay is relatively cheap, environmentally friendly, and available in nature.
The most commonly embedded inorganic nanoparticles in the nanocompo-
sites come from a group of 2:1 phyllosilicates that contain a sheet silicate
structure. Hectorite, montmorillonite, and vermiculite are the most used
fillers for polymer-clay nanocomposites. They significantly enhance the
ability of filtration of membranes by adjusting the formation of macrovoids.
In addition, they can increase hydrophilicity, surface pores, and
porosity [13].

1.4.8 Other nanoparticles

Different NCMs can be fabricated using nonconventional nanoparticles
such as Fe3O4, Al2O3, ZnO, Ag2O, carbon nanotubes (CNTs), cellulose
nanocrystals (CNCs), graphene oxide, zeolites, MOFs, etc. [15]. Functiona-
lization of the NPs prohibits accumulating large NPs and develops other fea-
tures of the selective layer. Considering the hydrophilic groups like
carboxylic acid, amine, and sulfonic acid for NP functionalization, results
in TFN membranes with superior surface hydrophilicity and water perme-
ability. Functional groups of NPs can participate in interfacial polymeriza-
tion, producing covalent bonds with the PA matrix [23].

1.5 Applications of NEMs

The advancement of membranes with multifunctional characteristics and
minor consumption of energy and utilization of them for the elimination
of contaminants have been significant in membrane separations. Unification
of membrane and nanotechnologies has resulted in much progress in
 Modern perspective in membrane technologies 11

membrane configuration. This not only provides better control of the pore’s
shape of membranes but also improves the hydrophilicity and permeates flux
of the nanocomposite membrane. Therefore, nano-architectured mem-
branes are more “reactive” rather than just behaving as a physical barrier
for transferring the solutes. Incorporating nanofillers in polymeric mem-
branes leads to durable membranes, since it slows down the membrane foul-
ing procedure that has resulted in a restriction in industrial usages [24].

1.5.1 Adsorption
Some NEMs, which are synthesized based on nano CNT, metal oxides,
porous boron nitride, graphene, nanofibers, and zeolite, are applied for fil-
tration and adsorption of heavy metal ions, etc. High porosity and active
adsorption sites of these NMs facilitate the contaminant removal. For exam-
ple, nanofiber-based membranes present suitable separation properties to
remove the various trace amounts of pollutants from water by filtration
and adsorption, owing to their porosity and high surface area. From water
media, adsorbent could be captured through the chemical binding (owing to
the presence of various functional groups in NMs) or physical adsorption
(for example, due to the high surface area and porosity of NMs), or electro-
static attraction [12].

1.5.2 Water disinfection

Water disinfection technologies have been usefully combined according to
the membrane and nanomaterials. NEMs are highly efficient for water
disinfection via the killing/preventing of microorganisms and physical cap-
ture. Most of the NEMs fabricated for MF, NF, UF, and RO applications
are intended to develop antifouling properties by imparting hydrophilic/
antimicrobial properties to membranes. Molecular-level separation can be
possible by NF membranes, and hence it produces water free from any toxic
microorganisms [12].

1.5.3 Dissolved pollutants/salt ions removal by NF and RO

Removal of soluble salt ions from seawater and saline to make them drink-
able is one of the significant applications of NF membrane technology.
Commercial and laboratory NF membranes in hollow fiber and flat sheet
configurations are TFCMs fabricated by interfacial polymerization (IP).
NF membranes usually reject about 20%–80% of monovalent ions and
>95% of divalent ions with the same charge on the membrane’s surface.
12 Membranes with functionalized nanomaterials

NF is also used to remove the hardness in drinking water recycling as an

alternative to RO or as a pre-RO process [12]. The TFN membrane, as
a new generation of composite membrane, was explored in 2007 for the first
time to enhance the separation performance and overcome the trade-off of
selectivity-permeability of the TFC membrane in reverse osmosis applica-
tions. Incorporating a low content of zeolite into the polyamide (PA) layer
of the TFC membrane improved the water permeability of the final
membrane [13].

1.5.4 Gas separation

At an early step of the progress of NCMs, further studies have focused on the
interactions between the polymer matrix and the nanofiller and the changes
in the polymer matrix due to the presence of nanoparticles. The interfacial
adhesion properties can be known better by investigating the findings
achieved from experiments of gas permeation. The introduction of nanofil-
ler leads to some significant changes in the polymer matrix, such as: (1) rigid-
ification or tightening of polymer chains; (2) formation of tortuous paths;
(3) creation of intermediate cavities or microvoids at polymer-filler interface
as well as nonselective voids with distinctive properties; and (4) blockage of
nanoparticles’ pore openings [25]. Fig. 1.5 demonstrates the possible inter-
actions of penetrant molecules with the nanofillers and polymer matrix. Var-
ious possible ways for the gas transports can be explained as: (1) solution-
diffusion mechanism of gas transport in a conventional polymer membrane;
(2) small gases can diffuse easier via the interfacial microvoids; (3) larger mol-
ecules should be transferred through a tortuous path in the filler’s vicinity;
(4) pore size restricts the larger gas molecules penetration while small gases
can quickly utilize this diffusion path; and (5) the presence of functional
moieties or adsorptive sites that attract target gas and increase overall solu-
bility in the membrane [25].
It is significant to choose appropriate fillers related to the particle size, the
pore diameter, functional groups of surface, and affinity of the fillers to the
distinct gases in a gas mixture. Furthermore, the interaction of functional
groups of the nanofiller surfaces with gases like CO2 may increase perme-
ability in the MMMs for gas separation membranes [26]. According to fillers’
features in the membrane, gas transport can be increased via various routes.
Filler particles can improve the features of the continuous polymeric phase,
and hence change the general transport features. This is considerable for
CO2-inert particles that are appropriately dispersed in the polymer matrix,
 Modern perspective in membrane technologies 13

Fig. 1.5 A schematic view of the interaction of penetrant molecules with the polymer
matrix and nanofillers in a nanocomposite membrane. (From P.S. Goh, A.F. Ismail,
Structure and gas transport of nanocomposite membranes, in: Micro and Nano
Technologies, Elsevier, 2020, pp. 101–123. https://doi.org/10.1016/B978-0-12-819406-5.
00003-4. (Chapter 3))

where the fractional free volume (FFV) can be significantly increased, par-
ticularly for glassy polymers. Filler particles can change the dynamics or con-
formation of polymer chains near the particle surfaces, and consequently lead
to an increase in diffusion. Chemical modification (or functionalization) of
inorganic fillers has been applied to improve their scattering and separation
features [27].

1.5.5 Applications of NEMs in modern engineering sciences

1.5.5.1 NEMs in biotechnology
Membranes are extensively applied in biotechnology, with applications
ranging from bioproduct purification and laboratory filtration to use as a
component of bioreactors, biosensors, and biomedical devices. Nano-
engineered membranes, in addition to the function of the selective barrier,
show advanced and tailorable properties, which are provided by functional
groups of their nano-sized constituents [28]. High specific surface area and
the possibility to combine separation with other advanced functions make
membranes an optimal candidate for the development of hybrid systems.
Biomolecule-membrane hybrid systems are examples of NEMs.
A biomolecule is any molecule present in living organisms. Examples of bio-
molecules include large macromolecules such as proteins and nucleic acids,
and small molecules like metabolites. Biomolecules are nanoscale materials
14 Membranes with functionalized nanomaterials

with intrinsic structure and properties [28]. Nano-engineered membranes

using biomolecules, i.e., the biofunctionalized membranes, have been
employed in several biotechnological applications such as catalysis
(membrane-based bioreactors), analysis (biosensors), separations (affinity
membranes), and development of artificial organs. In bioreactors, the mem-
branes can be applied just as an external separation unit downstream of a tra-
ditional reactor including the biocatalyst, as in membrane bioreactors
(MBRs), or can be operated either as an internal site for the biocatalyst con-
finement or separation unit in biocatalytic membrane reactors (BMRs) [28].

1.5.5.2 NEMs in pharmaceutical applications

BMRs have been applied to produce amino acids, antibiotics, vitamins, anti-
cancer drugs, and so on. These devices mainly use enzymes or cells immo-
bilized on the membrane. In this field, BMR increases the yield and purity of
the downstream concerning to the interest component, enabling cost reduc-
tion in downstream purification. BMRs represent higher conversion rates
when a product inhibition or a reversible reaction happens [28].

1.5.5.3 NEMs in biomedical applications

Different types of synthetic paths have been applied for the surface modifi-
cation of polymeric membranes. Functionalized biomedical polymeric
membranes have shown excellent performance in the field of blood-
contacting, which has led to the dramatic development of many critical
medical applications such as blood purification, artificial limbs, and so on.
In blood-contacting fields, polymeric functionalized biomedical membranes
have shown outstanding performances and have fueled many diverse bio-
medical applications, such as blood purification, artificial organs, etc. Silk
is a potential biopolymer for different biomedical applications, especially
in the scaffold and regeneration membrane fields. Heparin-modified silk
can yield a surface with high hemocompatibility. For example, the excellent
anticoagulant activity of the heparin-coated graphene oxide (GO) makes it a
suitable candidate for the fabrication of GO-based composite membranes
with a blood compatible by the method of filtration. Many novel
heparin-functionalized nanomaterials with specific functionalities will be
developed in the future and used to prepare composite membranes with bio-
active materials [29]. In another example, Ioniță et al. [30] comparatively
evaluated novel combinations of three kinds of carbon nanomaterial mem-
branes (CNMs) with significant capability for biomedical usages. Biological
performance and excellent cytocompatibility illustrated by (i) cellulose
 Modern perspective in membrane technologies 15

acetate/ammonia functionalized graphene oxide (CA/GO), (ii) cellulose

acetate/ammonia functionalized carbon nanotubes (CA/CNT), and
(iii) cellulose acetate/CNT-GO membranes suggested that these materials
can be a novel type of composite membranes in different biomedical appli-
cations such as tissue regeneration and separation processes.

1.5.5.4 NEMs in food applications

Membrane technologies have several benefits in applications related to food
industries [28]. For example, the electrospinning technique is used for the
preparation of fibrous polymeric nonwoven membranes formed by polymer
fibers with nanometric diameters for application in active food packaging
systems and functional food. Bioactive compounds can be placed on the
nanofiber’s surface by adsorption to surface-functionalized nanofibers or
by physical adsorption [31]. As another example, cellulose nanostructures
have different applications in food packaging (including active packaging).
These nanostructures are applied as a reinforcement phase in nanocompo-
sites (as cellulose nanofibrils or cellulose nanocrystals). Cellulose nanostruc-
tures can be used as matrices for films—bacterial cellulose (BC), since it is
fabricated naturally—nanostructured membranes that could grow in a
medium including other biopolymers. They can be impregnated with other
components or be disintegrated into nanocrystals or nanofibrils [32]. In addi-
tion, films based on synthetic polymers and biopolymers have been used in
food packaging. Chitosan (CS) films are applied as materials in food pack-
aging because they have nontoxic and antimicrobial properties. Moreover,
polyvinyl alcohol (PVA) is a synthetic polymer and is nontoxic. In chitosan
functionalized poly(vinyl alcohol) (CS/PVA) membranes, the combination
of superior properties of PVA with chitosan is applied in food packaging due
to the excellent chemical properties and generation costs [33].

1.5.5.5 NEMs for biosensor development

A biosensor is an analytical device that provides specific analytical informa-
tion, applying a biological sensing element (bioreceptor) intimately related
with or integrated within a physicochemical transducer [34]. Nanostruc-
tured membranes, which are composed of various materials with different
porosity and geometry, have been widely applied in several medical and bio-
logical usages such as separation and sorting of biomolecules, analysis of sin-
gle molecules, sensing of ions and proteins, and immunoisolation and drug
delivery [34]. In biosensing applications, membrane technology offers mul-
tiple benefits. The high ratio of surface area to volume is an essential property
16 Membranes with functionalized nanomaterials

of nanostructured membranes. The increased pore surface can interact with

biomolecules that are trapped into the pores or flowing via the membrane,
providing a significant and often highly reactive surface area that enables
more effective detection of molecules on the sensing surface. Moreover,
compared with other nanostructures like nanotubes and nanowires, mem-
branes allow separating biomolecules according to their size, shape, charge,
and interactions with nanopores that increase the selectivity of the sensor.
They can be produced using different methods with high control in pore
size, pore-size distribution, pore location, nanoarchitecture, nano-patterns,
and the overall physical and chemical properties. In addition, surface
modification methods can be applied to achieve better biocompatibility
and antibiofouling capability to promote/control interaction with
biomolecules [34].
The increased surface area, together with the selective barrier properties
and the possibility of integration with both electrochemical and optical
detection techniques, allowed the nanostructured membranes applications
in many biosensing situations like glucose detection, nucleic acid detection,
bacteria, and virus detection for either diagnostics or environmental and
food analysis. The integration of nanostructured membranes in biosensor
design has various benefits regarding to sensitivity, response time, and lower
detection limits [34]. Microporous polyvinylidene fluoride (PVDF) mem-
branes, which were examined between multiple layers of nanomaterials
for continuous monitoring of glucose levels in vivo, were studied by Chen
et al. [35]. These membranes, which were prepared using the layer-by-layer
deposition method, were made by coating needle electrodes with polyani-
line nanofiber, platinum nanoparticles, glucose oxidase, and porous layers.
The purpose of the nanoparticles’ presence in conductive polyaniline nano-
fillers was to create a superior surface to volume ratio and electrocatalytic
activity for glucose enzyme. The glucose transport in the PVDF and
nano-sphere Nafion was limited, and the lifetime of in vivo measurements
was increased. In addition, the glucose biosensor showed a sensitivity of
0.23 μA/mM and a fast response time of less than 30 s. In addition, despite
maintaining biocompatibility with surrounding tissues, implant tests showed
an outstanding response to changes in blood glucose concentration. Further-
more, for rapid detection of pirimiphos-methyl in olive oil, an ultrasensitive
electrochemical biosensor based on electrospun blended chitosan-poly(vinyl
alcohol) nanofibrous enzymatically sensitized membranes was developed by
El-Moghazy et al. [36]. This biosensor showed a good performance with a
detection limit of 0.2 nm. Moreover, the biosensor was used in olive oil
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With thirteen little ones of her own, and living in a small and rather
an inconvenient coop, it was no wonder that she felt unwilling to
have any addition to her family. But she might have declined civilly. I
am afraid she was a sad vixen, for no sooner did she see the poor
duckling among her chickens, than she strode up to him, and with
one peck tore the skin from his head,—scalped him,—the old
savage! I rescued Jack from her as soon as possible, and dressed
his wound with lint as well as I could, for I felt something like a parent
to the fowl myself. He recovered after a while, but, unfortunately, no
feathers grew again on his head,—he was always quite bald,—which
gave him an appearance of great age. I once tried to remedy this evil
by sticking some feathers on to his head with tar; but, like all other
wigs, it deceived no one, only making him look older and queerer
than ever. What made the matter worse was, that I had selected
some long and very bright feathers, which stood up so bold on his
head that the other fowls resented it, and pecked at the poor wig till
they pecked it all off.
While Jack was yet young, he one day fell into the cistern, which had
been left open. Of course he could not get out, and he soon tired of
swimming, I suppose, and sunk. At least, when he was drawn up, he
looked as though he had been in the water a long time, and seemed
quite dead. Yet, hoping to revive him, I placed him in his old basket
of wool, which I set down on the hearth. He did indeed come to life,
but the first thing the silly creature did on leaving his nest was to run
into the midst of the fire, and before I could get him out, he was very
badly burned. He recovered from this also, but with bare spots all
over his body. In his tail there never afterwards grew more than three
short feathers. But his trials were not over yet. After he was full-
grown, he was once found fast by one leg in a great iron rat-trap.
When he was released, his leg was found to be broken. But my
brother William, who was then inclined to be a doctor, which he has
since become, and who had watched my father during surgical
operations, splintered and bound up the broken limb, and kept the
patient under a barrel for a week, so that he should not attempt to
use it. At the end of that time, Jack could get about a little, but with a
very bad limp, which he never got over. But as the duck family never
had the name of walking very handsomely, that was no great matter.
After all these accidents and mishaps, I hardly need tell you that
Jack had little beauty to boast of, or plume himself upon. He was in
truth sadly disfigured,—about the ugliest fowl possible to meet in a
long day’s journey. Indeed, he used to be shown up to people as a
curiosity on account of his ugliness.
I remember a little city girl coming to see me that summer. She
talked a great deal about her fine wax-dolls with rolling eyes and
jointed legs, her white, curly French lap-dog, and, best and prettiest
of every thing, her beautiful yellow canary-bird, which sung and sung
all the day long. I grew almost dizzy with hearing of such grand and
wonderful things, and sat with my mouth wide open to swallow her
great stories. At last, she turned to me and asked, with a curl of her
pretty red lips, “Have you no pet-birds, little girl?” Now, she always
called me “little girl,” though I was a year older and a head taller than
she. I replied, “Yes, I have one,” and led the way to the back-yard,
where I introduced her to Jack. I thought I should have died of
laughter when she came to see him. Such faces as she made up!
I am sorry to say, that the other fowls in the yard, from the oldest hen
down to the rooster without spurs, and even to the green goslings,
seemed to see and feel Jack’s want of personal pretensions and
attractions, and always treated him with marked contempt, not to say
cruelty. The little chickens followed him about, peeping and cackling
with derision, very much as the naughty children of the old Bible
times mocked at the good, bald-headed prophet. But poor Jack
didn’t have it in his power to punish the ill-mannered creatures as
Elisha did those saucy children, when he called the hungry she-
bears to put a stop to their wicked fun. In fact, I don’t think he would
have done so if he could, for all this hard treatment never made him
angry or disobliging. He had an excellent temper, and was always
meek and quiet, though there was a melancholy hang to his bald
head, and his three lonesome tail-feathers drooped sadly toward the
ground. When he was ever so lean and hungry, he would gallantly
give up his dinner to the plump, glossy-breasted pullets, though they
would put on lofty airs, step lightly, eye him scornfully, and seem to
be making fun of his queer looks all the time. He took every thing so
kindly! He was like a few, a very few people we meet, who, the uglier
they grow, the more goodness they have at heart, and the worse the
world treats them, the better they are to it.
But Jack had one true friend. I liked him, and more than once
defended him from cross old hens, and tyrannical cocks. But
perhaps my love was too much mixed up with pity for him to have felt
highly complimented by it. Yet he seemed to cherish a great affection
for me, and to look up to me as his guardian and protector.
As you have seen, Jack was always getting into scrapes, and at last
he got into one which even I could not get him out of. He one day
rashly swam out into the mill-pond, which was then very high, from a
freshet, and which carried him over the dam, where, as he was a
very delicate fowl, he was drowned, or his neck was broken, by the
great rush and tumble of the water. I have sometimes thought that it
might be that he was tired of life, and grieved by the way the world
had used him, and so put an end to himself. But I hope it was not so;
for, with all his oddities and misfortunes, Jack seemed too sensible
for that.

ELEGY.

Alas, poor lame, bald-headed Jack!

None mourned when he was dead,
And for the sake of her drowned drake
No young duck hung her head!

The old cocks said they saw him go,

Yet did not call him back,
For a death from hydropathy
Was a fit death for a quack.

The cockerels said, “Well, that poor fowl

Is gone,—who cares a penny?”
And guessed he found that last deep dive
Was one duck-in too many.

The heartless pullets saw him,

 Yet raised no warning cries,
As he swam o’er the dam,
And was drowned before their eyes!
Hector the Grey-Hound
 HECTOR, THE GREYHOUND.

Hector was the favorite hound of my brother Rufus, who was

extremely fond of him, for he was one of the most beautiful creatures
ever seen, had an amiable disposition, and was very intelligent. You
would scarcely believe me, should I tell you all his accomplishments
and cunning tricks. If one gave him a piece of money, he would take
it in his mouth and run at once to the baker, or butcher, for his dinner.
He was evidently fond of music, and even seemed to have an ear for
it, and he would dance away merrily whenever he saw dancing. He
was large and strong, and in the winter, I remember, we used to
harness him to a little sleigh, on which he drew my youngest brother
to school. As Hector was as fleet as the wind, this sort of riding was
rare sport. At night we had but to start him off, and he would go
directly to the school-house for his little master. Ah, Hector was a
wonderful dog!
A few miles from our house, there was a pond, or small lake, very
deep and dark, and surrounded by a swampy wood. Here my
brothers used to go duck-shooting, though it was rather dangerous
sport, as most of the shore of the pond was a soft bog, but thinly
grown over with grass and weeds. It was said that cattle had been
known to sink in it, and disappear in a short time.
One night during the hunting season, one of my elder brothers
brought a friend home with him, a fine, handsome young fellow,
named Charles Ashley. It was arranged that they should shoot ducks
about the pond the next day. So in the morning they all set out in
high spirits. In the forenoon they had not much luck, as they kept too
much together; but in the afternoon they separated, my brothers
giving their friend warning to beware of getting into the bogs. But
Ashley was a wild, imprudent young man, and once, having shot a
fine large duck, which fell into the pond near the shore, and Hector,
who was with him, refusing to go into the water for it, he ran down
himself. Before he reached the edge of the water, he was over his
ankles in mire; then, turning to go back, he sunk to his knees, and in
another moment he was waist-high in the bog, and quite unable to
help himself. He laid his gun down, and, fortunately, could rest one
end of it on a little knoll of firmer earth; but he still sunk slowly, till he
was in up to his arm-pits. Of course, he called and shouted for help
as loud as possible, but my brothers were at such a distance that
they did not hear him so as to know his voice. But Hector, after
looking at him in his sad fix a moment, started off on a swift run,
which soon brought him to his master. My brother said that the dog
then began to whine, and run back and forth in a most extraordinary
manner, until he set out to follow him to the scene of the accident.
Hector dashed on through the thick bushes, as though he were half
distracted, every few moments turning back with wild cries to hurry
on his master. When my brother came up to where his friend was
fixed in the mire, he could see nothing of him at first. Then he heard
a faint voice calling him, and, looking down near the water, he saw a
pale face looking up at him from the midst of the black bog. He has
often said that it was the strangest sight that he ever saw. Poor
Ashley’s arms, and the fowling-piece he held, were now beginning to
disappear, and in a very short time he would have sunk out of sight
for ever! Only to think of such an awful death! My brother, who had
always great presence of mind, lost no time in bending down a
young tree from the bank where he stood, so that Ashley could grasp
it, and in that way be drawn up, for, as you see, it would not have
been safe for him to go down to where his friend sunk. When Ashley
had taken a firm hold of the sapling, my brother let go of it, and it
sprung back, pulling up the young man without much exertion on his
part. Ashley was, however, greatly exhausted with fright and
struggling, and lay for some moments on the bank, feeling quite
unable to walk. As soon as he was strong enough, he set out for
home with my brother, stopping very often to rest and shake off the
thick mud, which actually weighed heavily upon him. I never shall
forget how he looked when he came into the yard about sunset. O,
what a rueful and ridiculous figure he cut! We could none of us keep
from laughing, though we were frightened at first, and sorry for our
guest’s misfortune. But after he was dressed in a dry suit of my
brother’s, he looked funnier than ever, for he was a tall, rather large
person, and the dress was too small for him every way. Yet he
laughed as heartily as any of us, for he was very good-natured and
merry. It seems to me I can see him now, as he walked about with
pantaloons half way up to his knees, coat-sleeves coming a little
below the elbows, and vest that wouldn’t meet at all, and told us
queer Yankee stories, and sung songs, and jested and laughed all
the evening. But once, I remember, I saw him go out on to the door-
step, where Hector was lying, kneel down beside the faithful dog,
and actually hug him to his breast.
When not hunting with his master Hector went with Albert and me in
all our rambles, berrying and nutting. We could hardly be seen
without him, and we loved him almost as we loved one another.
One afternoon in early spring, we had been into the woods for wild-
flowers. I remember that I had my apron filled with the sweet
claytonias, and the gay trilliums, and the pretty white flowers of the
sanguinaria, or “blood-root,” and hosts and handfuls of the wild
violets, yellow and blue. My brother had taken off his cap and filled it
with beautiful green mosses, all lit up with the bright red squaw-
berry. We had just entered the long, shady lane which ran down to
the house, and were talking and laughing very merrily, when we saw
a crowd of men and boys running toward us and shouting as they
ran. Before them was a large, brown bull-dog, that, as he came near,
we saw was foaming at the mouth. Then we heard what the men
were crying. It was, “Mad dog!”
My brother and I stopped and clung to each other in great trouble.
Hector stood before us and growled. The dog was already so near
that we saw we could not escape; he came right at us, with his
dreadful frothy mouth wide open. He was just upon us, when Hector
caught him by the throat, and the two rolled on the ground, biting and
struggling. But presently one of the men came up and struck the
mad dog on the head with a large club,—so stunned him and finally
killed him. But Hector, poor Hector, was badly bitten in the neck and
breast, and all the men said that he must die too, or he would go
mad. One of the neighbours went home with us, and told my father
and elder brothers all about it. They were greatly troubled, but
promised that, for the safety of the neighbourhood, Hector should be
shot in the morning. I remember how, while they were talking, Hector
lay on the door-step licking his wounds, every now and then looking
round, as if he thought that there was some trouble which he ought
to understand.
I shall never, never forget how I grieved that night! I heard the clock
strike ten, eleven, and twelve, as I lay awake weeping for my dear
playfellow and noble preserver, who was to die in the morning.
Hector was sleeping in the next room, and once I got up and stole
out to see him as he lay on the hearth-rug in the clear moonlight,
resting unquietly, for his wounds pained him. I went and stood so
near that my tears fell on his beautiful head; but I was careful not to
wake him, for I somehow felt guilty toward him.
That night the weather changed, and the next morning came up
chilly and windy, with no sunshine at all,—as though it would not
have been a gloomy day enough, any how. After breakfast—ah! I
remember well how little breakfast was eaten by any of us that
morning—Hector was led out into the yard, and fastened to a stake.
He had never before in all his life been tied, and he now looked
troubled and ashamed. But my mother spoke pleasantly to him and
patted him, and he held up his head and looked proud again. My
mother was greatly grieved that the poor fellow should have to die
for defending her children, and when she turned from him and went
into the house, I saw she was in tears; so I cried louder than ever.
One after another, we all went up and took leave of our dear and
faithful friend. My youngest brother clung about him longest, crying
and sobbing as though his heart would break. It seemed that we
should never get the child away. My brother Rufus said that no one
should shoot his dog but himself, and while we children were bidding
farewell, he stood at a little distance loading his rifle. But finally he
also came up to take leave. He laid his hand tenderly on Hector’s
head, but did not speak to him or look into his eyes,—those sad
eyes, which seemed to be asking what all this crying meant. He then
stepped quickly back to his place, and raised the rifle to his shoulder.
Then poor Hector appeared to understand it all, and to know that he
must die, for he gave a loud, mournful cry, trembled all over, and
crouched toward the ground. My brother dropped the gun, and
leaned upon it, pale and distressed. Then came the strangest thing
of all. Hector seemed to have strength given him to submit to his
hard fate; he stood up bravely again, but turned away his head and
closed his eyes. My brother raised the rifle. I covered my face with
my hands. Then came a loud, sharp report. I looked round and saw
Hector stretched at full length, with a great stream of blood spouting
from his white breast, and reddening all the grass about him. He was
not quite dead, and as we gathered around him, he looked up into
our faces and moaned. The ball which pierced him had cut the cord
in two that bound him to the stake, and he was free at the last. My
brother, who had thrown down his rifle, drew near also, but dared not
come close, because, he said, he feared the poor dog would look
reproachfully at him. But Hector caught sight of his beloved master,
and, rousing all his strength, dragged himself to his feet. Rufus bent
over him and called him by name. Hector looked up lovingly and
forgivingly into his face, licked his hand, and died. Then my brother,
who had kept a firm, manly face all the while, burst into tears.
My brother William, who was always master of ceremonies on such
occasions, made a neat coffin for Hector, and laid him in it, very
gently and solemnly. I flung in all the wild-flowers which Albert and I
had gathered on the afternoon of our last walk with our noble friend,
and so we buried him. His grave was very near the spot where he
had so bravely defended us from the mad dog, by the side of the
way, in the long, pleasant lane where the elm-trees grew.
 BOB, THE COSSET.

One cold night in March, my father came in from the barn-yard,

bringing a little lamb, which lay stiff and still in his arms, and
appeared to be quite dead. But my mother, who was good and kind
to all creatures, wrapped it in flannel, and, forcing open its teeth,
poured some warm milk down its throat. Still it did not open its eyes
or move, and when we went to bed it was yet lying motionless before
the fire. It happened that my mother slept in a room opening out of
the sitting-room, and in the middle of the night she heard a little
complaining voice, saying, “Ma!” She thought it must be some one of
us, and so answered, “What, my child?” Again it came, “Ma!” and,
turning round, she saw by the light of the moon the little lamb she
had left for dead standing by her bedside. In the morning it was
found that the own mother of “Bob,” (for we gave him that name,)
had died of cold in the night; so we adopted the poor orphan into our
family. We children took care of him, and though it was a great
trouble to bring him up by hand, we soon became attached to our
charge, and grew very proud of his handsome growth and thriving
condition. He was, in truth, a most amusing pet, he had such free
manners with every body and was so entirely at home everywhere.
He would go into every room in the house,—even mount the stairs
and appear in our chambers in the morning, sometimes before we
were up, to shame us with his early rising. But the place which of all
others he decidedly preferred was the pantry. Here he was, I am
sorry to say, once or twice guilty of breaking the commandment
against stealing, by helping himself to fruit and to slices of bread
which did not rightfully belong to him. He was tolerably amiable,
though I think that lambs generally have a greater name for
sweetness of temper than they deserve. But Bob, though playful and
somewhat mischievous, had never any serious disagreement with
the dogs, cats, pigs, and poultry on the premises. My sister and I
used to make wreaths for his neck, which he wore with such an
evident attempt at display, that I sometimes feared he was more vain
and proud than it was right for such an innocent and poetical animal
to be.
But our trials did not really commence until Bob’s horns began to
sprout. It seemed that he had no sooner perceived those little
protuberances in his looking glass, the drinking-trough, than he took
to butting, like any common pasture-reared sheep, who had been
wholly without the advantages of education and good society. It was
in vain that we tried to impress upon him that such was not correct
conduct in a cosset of his breeding; he would still persevere in his
little interesting trick of butting all such visitors as did not happen to
strike his fancy. But he never treated us to his horns in that way, and
so we let him go, like any other spoiled child, without punishing him
severely, and rather laughed at his sauciness.
But one day our minister, a stout, elderly gentleman, solemn-faced
and formal, had been making us a parochial visit, and as he was
going away, we all went out into the yard to see him ride off, on his
old sorrel pacer. It seems he had no riding-whip; so he reached up to
break off a twig from an elm-tree which hung over the gate. This was
very high, and he was obliged to stand on tiptoe. Just then, before
he had grasped the twig he wanted, Bob started out from under a
large rose-bush near by, and run against the reverend gentleman,
butting him so violently as to take him quite off his feet. My father
helped the good man up, and made a great many apologies for the
impiety of our pet, while we children did our best to keep our faces
straight. After our venerable visitor was gone, my father sternly
declared that he would not bear with Bob any longer, but that he
should be turned into the pasture with the other sheep, for he would
not have him about, insulting respectable people and butting
ministers of the Gospel at that rate.
So the next morning Bob was banished in disgrace from the house
and yard, and obliged to mingle with the vulgar herd of his kind. With
them I regret to say that he soon earned the name of being very bold
and quarrelsome. As his horns grew and lengthened, he grew more
and more proud of the consequence they gave him, and went forth
butting and to butt. O, he was a terrible fellow!
One summer day, my brother Charles and a young man who lived
with us were in the mill-pond, washing the sheep which were soon to
be sheared. I was standing on the bank, watching the work, when
one of our neighbours, a hard, coarse man, came up, and calling to
my brother, in a loud voice, asked if he had been hunting a raccoon
the night before. “Yes, Sir, and I killed him too,” answered my
brother. “Well, young man,” said the farmer, “did you pass through
my field, and trample down the grain?” “I crossed the field, Sir, but I
hope I did no great damage,” replied Charles, in a pleasant way.
“Yes, you did!” shouted the man, “and now, you young rascal, if I
ever catch you on my land again, day or night, I’ll thrash you!—I’ll
teach you something, if your father won’t!” As he said this, stretching
his great fist out threateningly toward my brother, he stood on the
very edge of the steep bank. Just behind him were the sheep,
headed by the redoubtable Bob, who suddenly darted forward, and,
before the farmer could suspect what was coming, butted him head
over heels into the pond! My brother went at once to the assistance
of his enemy, who scrambled on to the shore, sputtering and
dripping, but a good deal cooled in his rage. I suppose I was very
wicked, but I did enjoy that!
For this one good turn, Bob was always quite a favorite, with all his
faults, and year after year was spared, when worthier sheep were
made mutton of. He was finally sold, with the rest of the flock, when
we left the farm, and though he lived to a good old age, the wool of
his last fleece must long since have been knit into socks and
comforters, or woven into cloth,—must have grown threadbare, and
gone to dress scarecrows, or stop cellar-windows; or been all
trodden out in rag-carpets.
 ROBIN REDBREAST.

I must now, dear children, pass over a few years of my life, in which
I had no pets in whose history you would be likely to be interested.
 ROBIN REDBREAST
At the time of my possessing my wonderful Robin, we had left our
country home, my brothers were most of them abroad in the world,
and I was living with my parents in the pleasant city of R——. I was a
school-girl, between fifteen and sixteen years of age. That spring, I
commenced the study of French, and, as I was never a remarkably
bright scholar, I was obliged to apply myself with great diligence to
my books. I used to take my grammar and phrase-book to my
chamber, at night, and study as long as I could possibly keep my
eyes open. In consequence of this, as you may suppose, I was very
sleepy in the morning, and it usually took a prodigious noise and
something of a shaking to waken me. But one summer morning I
was roused early, not by the breakfast-bell, nor by calling, or
shaking, but by a glad gush of sweetest singing. I opened my eyes,
and right on the foot-board of my bed was perched a pretty red-
breasted robin, pouring out all his little soul in a merry morning song.
I stole out of bed softly, and shut down the window through which he
had come; then, as soon as I was dressed, caught him, carried him
down stairs, and put him into a cage which had hung empty ever
since the cat made way with my last Canary.
I soon found that I had a rare treasure in my Robin, who was very
tame, and had evidently been carefully trained, for before the
afternoon was over he surprised and delighted us all by singing the
air of “Buy a Broom” quite through, touching on every note with
wonderful precision. We saw that it was a valuable bird, who had
probably escaped, and for some days we made inquiries for its
owner, but without success.
At night I always took Robin’s cage into my chamber, and he was
sure to waken me early with his loud, but delicious, singing. So
passed on a month, in which I had great happiness in my interesting
pet. But one Saturday forenoon I let him out, that I might clean his
cage. I had not observed that there was a window open, but the bird
soon made himself acquainted with the fact, and, with a glad,
exulting trill, he darted out into the sunshine. Hastily catching my
bonnet, I ran after him. At first, he stayed about the trees in front of
the house, provokingly hopping from branch to branch out of my
reach, holding his head on one side, and eyeing me with sly,
mischievous glances. At last he spread his wings and flew down the
street. I followed as fast as I could, keeping my eye upon him all the
time. It was curious that he did not fly across squares, or over the
houses, but kept along above the streets, slowly, and with a
backward glance once in a while. At length, he turned down a narrow
court, and flew into the open window of a small frame-house. Here I
followed him, knocking timidly at the door, which was opened at once
by a boy about nine years old. I found myself in a small parlour, very
plainly, but neatly furnished. In an arm-chair by the window sat a
middle-aged woman, who I saw at once was blind. A tall, dark-eyed,
rather handsome girl was sitting near her, sewing. But I did not look
at either of these more than a moment, for on the other side of the
room was an object to charm, and yet sadden, my eyes. This was a
slight girl, about my own age, reclining on a couch, looking very ill
and pale, but with a small, red spot on each cheek, which told me
that she was almost gone with consumption. She was very beautiful,
though so thin and weary looking. She had large, dark, tender eyes,
and her lips were still as sweet as rose-buds. I think I never saw
such magnificent hair as hers; it flowed all over her pillow, and hung
down nearly to the floor, in bright, glossy ringlets.
At that moment she was holding the truant Robin in her white,
slender hands, crying and laughing over him, calling him her “dear
lost pet,” her “naughty runaway,” and a hundred other loving and
scolding names. I, of course, felt rather awkward, but I explained
matters to Robin’s fair mistress as well as I could. She looked
pleased, and thanked me warmly for the good care I had taken of the
bird. Then she made me sit down by her side, and asked my name,
and told me hers, which was Ellen Harper, and introduced me to her
mother, sister, and brother, all in the sweetest manner possible. We
got quite well acquainted, and talked like old friends, till Ellen’s
cough interrupted her. Then, as I rose to go, she made me promise
to come again very soon, and raised herself as though she would
kiss me before I went. Just as I bent down to press my lips to hers,
Robin, who, of his own accord, had taken possession of his old
cage, which had been left open for him, burst out into a sweet, merry
warble, full of the most astonishing trills and shakes. Then I felt that it
was well that we two should love one another.
After that, I went almost daily to see Ellen Harper. I carried her
books, I read to her, talked to her, and listened to her low gentle
voice, and looked down deep into her clear hazel eyes, till I grew to
love the sweet, patient girl more than I can tell. I think that she was a
most remarkable person. Her parents were quite poor, and she had
enjoyed few advantages; but she was far beyond me in scholarship
and reading. And then she was a true Christian, with a calm hope,
and a cheerful resignation; she seemed indeed to have given her
heart to God.
Ellen knew that she was dying; she knew that, young and fair and
beloved as she was, she had not long to stay in this bright, beautiful
world. But she did not fear, or complain, for she knew also that a kind
Father called her away, to a world far brighter and many times more
beautiful than ours. It was touching to see her trying to comfort her
sister Lucy, whose strength would sometimes give way as she saw
that slight form growing weaker every day; or her young brother
Willie, when he would leave his book, or his play, and come and lay
his face against her bosom and cry; or her father, when he would
come home from his work at night, and sit down beside his darling
child, and hold her thin, fair fingers in his great, brown hand, and say
no word, only sigh as though his poor heart was breaking; or her
mother, who was blind, and could not see the change in her “own
little Nellie,” as she called her, and so had to be told again and again
that she was failing fast. For all these dear ones, Ellen had words of
consolation, and they always felt stronger after she had talked with
them.
On some of those mornings when I went over to dress her beautiful
hair, which I dearly loved to do, she talked to me as an angel might
talk, I thought, and told me many sweet and holy things, which I shall
remember all the days of my life.
As long as she stayed with us, Ellen had great pleasure in her pet
Robin. She said that to her ear he always seemed to be singing
hymns, which was a great joy to her after she became too weak to
sing them herself.
Dear Ellen died at night. She had been very restless in the evening,
and at last said that, if she could lie in her mother’s arms, as she
used to lie when she was a little child, she thought that she could
sleep. So Mrs. Harper laid down beside her daughter, who nestled
against her bosom and slept. Ellen’s happy spirit passed away in
that sleep. But her mother was blind, and could not see when her
child was dead; and when her husband, fearing what had happened,
came near, she raised her finger and said, “Hush, don’t wake Nellie!”
The next morning, Lucy sent over for me to come and dress Ellen’s
hair for the last time. I found my friend looking very much as I had
always seen her, only with a sweeter smile, if possible, hovering
about her lips. She was lying on her couch, dressed in white muslin,
and with many flowers scattered around her. A vase of roses stood
on a stand at her feet, and over it hung the pretty cage of Robin, and
Robin himself was singing very sweetly, but in lower tones than
usual, as if he thought his young mistress was sleeping, and feared
to waken her.
They had cut away some of the hair from the back of Ellen’s head,
but around the forehead the familiar ringlets were all left. These I
dressed very carefully, though my tears fell so fast, I could scarcely
see what I was doing. I shall never forget the scene when the family
came into the parlour to look upon Ellen, after she had been laid out,
that morning. Lucy, sobbing and trembling, led her mother to the
couch. The poor woman felt in the air above the dead face a
moment, and said, “How I miss her sweet breath round me!” Then
she knelt down, and, with her arms flung over the body, swayed back
and forth, and seemed to pray silently. The father took those shining
curls in his hands, and smoothed them tenderly and kissed them
many times, while his great hot tears fell fast on the head of his child,
and on the rose-buds which lay upon her pillow, and seemed to give
a flush to her white, cold cheek.
I noticed that little Willie was the calmest of them all. He seemed to
have taken to heart the words of his sister, when she told him that
she was going into a better and happier life, where she would
continue to love him, and whither he would come, if he was good
and true in this life. So he did not grieve for her, as most children
grieve, but was quiet and submissive.
Ellen was buried in a beautiful cemetery a mile or two from the noise
and dust of the city. The morning after she had been laid there, I
went to plant a little rose-tree over her grave. I was somewhat
surprised to find Willie there, and with him Robin Redbreast, in his
pretty cage.
“Why have you brought the bird here, Willie?” I asked.
“Because,” said he, in a low, trembling voice, “I thought that, now
sister’s spirit was free, I ought not to keep her bird a prisoner any
longer.”
“That is right,” I said, for I thought that this was a beautiful idea of the
child’s.
So Willie opened the door of the cage, and out flew the Robin. This
time he did not alight on the trees, but mounted right up toward
heaven. There was a light cloud floating over us, and, as we stood
looking up after the bird, Willie seemed troubled to see that it passed
into this, and so was lost to our sight. “Ah,” he said, “I hoped he
would follow Nellie! but he has gone into the cloud, and sister’s soul,
I am very sure, passed away into the sunshine.”