Membranes: Materials, Simulations,

and Applications 1st Edition Alfredo

Maciel-Cerda (Eds.)
Visit to download the full and correct content document:
https://textbookfull.com/product/membranes-materials-simulations-and-applications-1
st-edition-alfredo-maciel-cerda-eds/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Biota Grow 2C gather 2C cook Loucas

https://textbookfull.com/product/biota-grow-2c-gather-2c-cook-
loucas/

Biomembrane Simulations Computational Studies of

Biological Membranes 1st Edition Max L. Berkowitz
(Editor)

https://textbookfull.com/product/biomembrane-simulations-
computational-studies-of-biological-membranes-1st-edition-max-l-
berkowitz-editor/

Nanomaterial and Polymer Membranes. Synthesis,

Characterization, and Applications 1st Edition Tawfik
Abdo Saleh

https://textbookfull.com/product/nanomaterial-and-polymer-
membranes-synthesis-characterization-and-applications-1st-
edition-tawfik-abdo-saleh/

Biomimetic Lipid Membranes Fundamentals Applications

and Commercialization Fatma N. Kök

https://textbookfull.com/product/biomimetic-lipid-membranes-
fundamentals-applications-and-commercialization-fatma-n-kok/
Nanofiber Membranes for Medical Environmental and
Energy Applications 1st Edition Ahmad Fauzi Ismail
(Editor)

https://textbookfull.com/product/nanofiber-membranes-for-medical-
environmental-and-energy-applications-1st-edition-ahmad-fauzi-
ismail-editor/

Introduction to Stellar Structure 1st Edition Walter J.

Maciel (Auth.)

https://textbookfull.com/product/introduction-to-stellar-
structure-1st-edition-walter-j-maciel-auth/

Biopolymer Membranes and Films: Health, Food,

Environment, and Energy Applications 1st Edition
Mariana Agostini De Moraes (Editor)

https://textbookfull.com/product/biopolymer-membranes-and-films-
health-food-environment-and-energy-applications-1st-edition-
mariana-agostini-de-moraes-editor/

Polymeric membrane synthesis, modification, and

applications electro-spun and phase inverted membranes
First Edition Das

https://textbookfull.com/product/polymeric-membrane-synthesis-
modification-and-applications-electro-spun-and-phase-inverted-
membranes-first-edition-das/

Fundamentals and applications of magnetic materials 1st

Edition Krishnan

https://textbookfull.com/product/fundamentals-and-applications-
of-magnetic-materials-1st-edition-krishnan/
Alfredo Maciel-Cerda Editor

Membranes
Materials, Simulations, and Applications
Membranes
Alfredo Maciel-Cerda
Editor

Membranes
Materials, Simulations, and Applications
Editor
Alfredo Maciel-Cerda
Instituto de Investigaciones en Materiales
Universidad Nacional Autónoma de México
Mexico City, Mexico

ISBN 978-3-319-45314-9 ISBN 978-3-319-45315-6 (eBook)

DOI 10.1007/978-3-319-45315-6

Library of Congress Control Number: 2016954200

© Springer International Publishing Switzerland 2017

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,
broadcasting, reproduction on microfilms or in any other physical way, and transmission or information
storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology
now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
editors give a warranty, express or implied, with respect to the material contained herein or for any errors
or omissions that may have been made.

Printed on acid-free paper

This Springer imprint is published by Springer Nature

The registered company is Springer International Publishing AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
Foreword

The Fifth National Congress of the Society of Membrane Science and Technology
was held in Mexico City on June 15, 16, and 17 of 2015. The best papers presented
at that meeting have been peer-reviewed and are collected in this volume. This com-
pilation covers a broad range of contemporary topics in the field of membrane sci-
ence and technology ranging from materials and processes to simulations.
Polymers and ceramics are the most widely used materials by the invited authors
for the production of membrane systems to separate chemical species. Different
commercial polymers, both modified and new synthetic polymers, have been tested
in the manufacture of membranes, such as poly(ether amides), polyhydrotriazine,
and polysulfones. Regarding ceramic membranes used by the authors include sul-
fated TiO2–ZnRO2 membranes, liquid membranes supported on alumina, and cata-
lytic membranes based on mixed cerium and cobalt oxides.
The contributions in the theoretical field begin with Dr. Joel Fried of the
University of Louisville, whose work focuses on high-performance computer simu-
lation of ion transport through nanochannels assembled bilayer membrane, for med-
ical and engineering applications. Other theoretical works discuss pulsatile flow in
reverse osmosis and filtration obtaining parameters as the tortuosity parameter and
three-dimensional modeling and simulation of multilayer membrane spacers.
A global ongoing concern is the contamination and pollution of aquifers by the
industrial activity and the domestic and municipal usage. Another major concern
that goes hand in hand with the first is the demand for water. In places where seawa-
ter is the only source of water available, desalination processes become highly
important to provide service and agriculture water. In this field, the reader will find
works addressing membrane biofouling in desalination process, photo oxidation in
the rejected flux, and cleaning strategies for a membrane bioreactor. In the field of
gas processing, a technical and economical design was studied for sweetening natu-
ral gas through membranes. This collection also includes two new development
projects in membranes.
We hope that the sum of these contributions will be of interest to the reader, since
its validity and new approaches set new priorities for future study.

v
vi Foreword

We thank the Mexican National Council on Science and Technology

(CONACYT), the National Autonomous University of Mexico (UNAM), and the
Mexican Institute of Petroleum (IMP) for their support. We are deeply grateful to
the authors and the reviewers for voluntarily contributing to the efforts that brought
to fruition of this work.

The Editor
Contents

Part I Polymer Synthesis for Membranes

1 Poly (Hexahydrotriazine) Membranes Prepared
by Coupling Reaction Between Diamines and Aldehydes ................... 3
Luis Fernando Alcocer-Márquez and Joaquín Palacios-Alquisira
2 Preparation and Characterization of Hybrid Membranes
Based on Poly(Ether-b-Amide) .............................................................. 11
Héctor Iván Meléndez-Ortiz, Griselda Castruita-de León,
Yibran Perera-Mercado, Jesús Alfonso Mercado-Silva,
Bertha Puente-Urbina, Sandra García-Rodríguez,
and Luis Alfonso García-Cerda
3 Preparation of Membranes Based on Polysulfone (PSU)
and Graphene Oxide (GrO) by Electrospinning .................................. 23
Yareni Aguilar-Costumbre, Juliette A. Lambert,
Miguel A. Meléndez-Lira, and Vladimir A. Escobar-Barrios

Part II Ceramic Membranes

4 Sulfated TIO2–ZRO2 Membrane as Synthesized
by Sol–Gel Method: Application in the Olefin Oligomerization ........ 33
M. Torres-Rodríguez, L. López-Pérez, M. Gutiérrez-Arzaluz,
and V. Mugica-Álvarez
5 CO2/N2 Separation in Postcombustion Processes by Means
of Alumina-Supported Ionic Liquid Membranes ................................ 41
Cinthia E. Sánchez-Fuentes, Natalya V. Likhanova,
Miguel Torres Rodríguez, Diego Guzmán-Lucero,
Juan Navarrete Bolaños, Diana Gómora-Herrera,
and Octavio Olivares-Xometl

vii
viii Contents

6 Synthesis of Catalytic Membranes for the Oxidation

of Organic Pollutants in Wastewater .................................................... 51
M. Gutiérrez-Arzaluz, V. Mugica-Álvarez, and M. Torres-Rodríguez

Part III Theoretical Approaches

7 Ion Transport Through Biomimetic Nanochannel Membranes ......... 61
Joel R. Fried
8 Synergies Between Pulsatile Flow and Spacer Filaments
in Reverse Osmosis Modules .................................................................. 67
Gustavo Adolfo Fimbres-Weihs and Jesús Álvarez-Sánchez
9 Obtaining the Tortuosity Factor as a Function of Crystallinity
in Polyethylene Membranes ................................................................... 77
L.F. del Castillo, S.I. Hernández, and V. Compañ
10 Three-Dimensional Modeling and Simulation of Multilayer
Spacers for Spiral Wound Membrane Modules ................................... 87
Luis Mario González Rodríguez and Fernando Tiscareño Lechuga

Part IV Applications of Membranes

11 Biofouling Studies on Thin Film Composite Membranes
for Reverse Osmosis Desalination Processes ........................................ 99
Griselda Evelia Romero-López, Jesús Alvarez-Sánchez,
Sergio de los Santos-Villalobos, and Gustavo Adolfo Fimbres-Weihs
12 Photo-Oxidation Treatment of the Reject Stream
of a Nanofiltration Membrane System .................................................. 105
Alma Chávez Mejía, Abraham Chávez Velasco,
Paloma Zaragoza Sánchez, and Blanca Jiménez Cisneros
13 Cleaning Strategies for a Membrane Bioreactor to Produce
Permeate with a Quality Suitable for Indirect Reuse .......................... 113
Alma Chávez Mejía, D. González-Tenorio, and B. Jiménez-Cisneros

Part V Design of Membrane Processes

14 Effect of the Transport Properties on the Design
of a Plant and on the Economy of the Sweetening Process
of Natural Gas Using Membranes ......................................................... 125
Jorge F. Palomeque Santiago, Diego Javier Guzmán Lucero,
and Javier Guzmán Pantoja
Contents ix

Part VI Forum on New Laboratories for Membrane Preparation

15 Fouling Modeling and Optimization of Membrane
Module Design for Brackish and Seawater Desalination
in the Mexican Pacific Coast: Project Description and Progress ....... 135
Gustavo Adolfo Fimbres-Weihs, Jesús Álvarez-Sánchez,
and Eulises Villegas-Álvarez
16 Research on Polymer Membranes and Teaching Performed
in UNAM Campus Morelia .................................................................... 145
Joel Vargas

Index ................................................................................................................. 149

Contributors

Yareni Aguilar-Costumbre Instituto Potosino de Investigación Científica y

Tecnológica, San Luís Potosí, San Luís Potosí, Mexico
Jesús Álvarez-Sánchez Department of Water and Environmental Sciences,
Instituto Tecnológico de Sonora, Ciudad Obregon, Sonora, Mexico
Juan Navarrete Bolaños Instituto Mexicano del Petróleo, Ciudad de México,
Mexico
L. F. del Castillo Departamento de Polímeros, Instituto de Investigaciones en
Materiales, Universidad Nacional Autónoma de México UNAM, Ciudad
Universitaria, México, Mexico
Alma Chávez Mejía Instituto de Ingeniería, Universidad Nacional Autónoma de
México, Mexico City, Ciudad de México, Mexico
Abraham Chávez-Velasco Instituto de Ingeniería, Universidad Nacional
Autónoma de México, Mexico City, Mexico
V. Compañ Departament de Termodinàmica Aplicada, Universitat Politècnica de
Valencia, Valencia, Spain
Vladimir A. Escobar-Barrios Instituto Potosino de Investigación Científica y
Tecnológica, San Luís Potosí, San Luís Potosí, Mexico
Gustavo Adolfo Fimbres-Weihs Department of Water and Environmental
Sciences, Instituto Tecnológico de Sonora, Ciudad Obregón, Sonora, Mexico
Cátedras, CONACyT - Instituto Tecnológico de Sonora, Ciudad Obregon, Sonora,
Mexico
Joel R. Fried Department of Chemical Engineering, University of Louisville,
Louisville, KY, USA

xi
xii Contributors

Cinthia E. Sánchez-Fuentes Posgrado en Ciencias e Ingeniería de Materiales,

Universidad Autónoma Metropolitana Azcapotzalco, Ciudad de México, Mexico
Luis Alfonso García-Cerda Centro de Investigación en Química Aplicada,
Saltillo, Coahuila, Mexico
Sandra García-Rodríguez Centro de Investigación en Química Aplicada, Saltillo,
Coahuila, Mexico
Diana Gómora-Herrera CIITEC, Instituto Politécnico Nacional, Ciudad de
México, Mexico
D. González-Tenorio Instituto de Ingeniería, Universidad Nacional Autónoma de
México, Mexico City, Ciudad de México, Mexico
M. Gutiérrez-Arzaluz Area de Quimica Aplicada, Universidad Autonoma
Metropolitana, Unidad Azcapotzalco, Ciudad de Mexico, Mexico
Diego Javier Guzmán-Lucero Instituto Mexicano del Petróleo, Ciudad de
México, Mexico
S. I. Hernández Unidad Multidisciplinaria de Docencia e Investigación-Juriquilla,
Facultad de Ciencias, Universidad Nacional Autónoma de México UNAM,
Juriquilla, Querétaro, Mexico
Blanca Jiménez-Cisneros Instituto de Ingeniería, Universidad Nacional Autónoma
de México, Mexico City, Ciudad de México, Mexico
Juliette A. Lambert CIATEC, León, Guanajuato, Mexico
Fernando Tiscareño Lechuga Departamento de Ingeniería Química, Instituto
Tecnológico de Celaya, Celaya, Guanajuato, Mexico
Griselda Castruita-de León CONACyT-Centro de Investigación en Química
Aplicada, Saltillo, Coahuila, Mexico
Natalya V. Likhanova Instituto Mexicano del Petróleo, Ciudad de México,
Mexico
L. López-Pérez Area de Quimica Aplicada, Universidad Autonoma Metropolitana,
Unidad Azcapotzalco, Ciudad de Mexico, Mexico
Luis Fernando Alcocer-Márquez Departamento de Fisicoquímica, Facultad de
Química, UNAM, Ciudad Universitaria, México, DF, Mexico
Miguel A. Meléndez-Lira CINVESTAV-IPN, Ciudad de México, DF, Mexico
Héctor Iván Meléndez-Ortiz CONACyT-Centro de Investigación en Química
Aplicada, Saltillo, Coahuila, Mexico
Jesús Alfonso Mercado-Silva Centro de Investigación en Química Aplicada,
Saltillo, Coahuila, Mexico
Contributors xiii

V. Mugica-Álvarez Area de Quimica Aplicada, Universidad Autonoma

Metropolitana, Unidad Azcapotzalco, Ciudad de Mexico, Mexico
Octavio Olivares-Xometl Facultad de Ingeniería Química, Benemérita
Universidad Autónoma de Puebla, Puebla, Puebla, Mexico
Joaquín Palacios-Alquisira Departamento de Fisicoquímica, Facultad de
Química, UNAM, Ciudad Universitaria, México, DF, Mexico
Javier Guzmán Pantoja Instituto Mexicano del Petróleo, México, DF, Mexico
Yibran Perera-Mercado Centro de Investigación en Química Aplicada, Saltillo,
Coahuila, Mexico
Bertha Puente-Urbina Centro de Investigación en Química Aplicada, Saltillo,
Coahuila, Mexico
Luis Mario González Rodríguez Departamento de Ingeniería Química, Instituto
Tecnológico de Celaya, Celaya, Guanajuato, Mexico
Unidad Profesional Interdisciplinaria de Ingeniería Campus Zacatecas, Instituto
Politécnico Nacional, Blvd. del Bote S/N Cerro del Gato Ejido La Escondida, Col.
Ciudad Administrativa, Zacatecas, Zacatecas, Mexico
Miguel Torres Rodríguez Universidad Autónoma Metropolitana Azcapotzalco,
Depto. de Ciencias Básicas, Ciudad de México, Mexico
Griselda Evelia Romero-López Dirección de Recursos Naturales, Instituto
Tecnológico de Sonora, Ciudad Obregón, Sonora, Mexico
Jorge F. Palomeque Santiago Instituto Mexicano del Petróleo, México, DF,
Mexico
Sergio de los Santos-Villalobos Dirección de Recursos Naturales, Instituto
Tecnológico de Sonora, Ciudad Obregón, Sonora, Mexico
Cátedras CONACyT, Consejo Nacional de Ciencia y Tecnología, Ciudad de México,
Mexico
M. Torres-Rodríguez Area de Quimica Aplicada, Universidad Autonoma
Metropolitana, Unidad Azcapotzalco, Ciudad de Mexico, Mexico
Joel Vargas Instituto de Investigaciones en Materiales, Unidad Morelia,
Universidad Nacional Autónoma de México, Morelia, Michoacán, Mexico
Eulises Villegas-Álvarez Departamento de Ciencias del Agua y Medio Ambiente,
Dirección de Recursos Naturales, Instituto Tecnológico de Sonora, Ciudad Obregón,
Sonora, Mexico
Paloma Zaragoza-Sánchez Instituto de Ingeniería, Universidad Nacional
Autónoma de México, Mexico City, Ciudad de México, Mexico
 Part I
Polymer Synthesis for Membranes
Chapter 1
Poly (Hexahydrotriazine) Membranes
Prepared by Coupling Reaction Between
Diamines and Aldehydes

Luis Fernando Alcocer-Márquez and Joaquín Palacios-Alquisira

1.1 Introduction

The industrial use of membranes for gas separation has been known for more than
30 years. Membranes are used for nitrogen production from air, hydrogen recovery,
ammonia manufacturing, hydrocarbon processing, and carbon dioxide elimination
from natural gas sources, among other applications [1–4]. Commercial membranes
are derived from polymer systems that show packed rigid chains to create small inter-
molecular empty spaces and improve selectivity upon separating gases. However,
they may present low gas permeability rendering the separation process slow.
Microporous materials containing organic compounds are a kind of polymers offer-
ing high gas permeability. In order to provide good selectivity, the polymers must be
highly rigid. Permeability and selectivity, as well as intrinsic microporosity, are
directly related to the rigidity of the polymeric chains in the membrane [5]. To
achieve this condition, a high fractional free volume (FFV) is needed; this feature can
be obtained by cross-linked microstructures like those generated from polycondensa-
tion reactions. In our case, the polycondensation reaction between diamines and
paraformaldehyde monomers produced a cross-linked structure by forming rings of
three diamine monomers connected by methylene groups, a typical architecture that
can be tested in gas separation with a good selectivity–permeability balance.
A polyhydrotriazine thermosetting polymer was synthesized using 4,4′-oxydianiline
(ODA) and formaldehyde, Fig. 1.1. This polymer has shown good properties for
membrane preparation with a thermal stability up to 300 °C, appropriate rigidity,
and processability [6, 7]. In this project, new polymeric membranes were synthesized
using different diamines and paraformaldehyde by a traditional heating activation.
It has been found that microwave-assisted reactions improved efficiency in triazine
synthesis rendering high yields and short reaction times [8].

L.F. Alcocer-Márquez • J. Palacios-Alquisira (*)

Departamento de Fisicoquímica, Facultad de Química, UNAM, Ciudad Universitaria,
México D.F. 04510, Mexico
e-mail: polylab1@unam.mx

© Springer International Publishing Switzerland 2017 3

A. Maciel-Cerda (ed.), Membranes, DOI 10.1007/978-3-319-45315-6_1
4 L.F. Alcocer-Márquez and J. Palacios-Alquisira

N N N
O
O

O
2.5 equiv. N
O N H
CH2O NMP
O
H
200°C N
H2 N N
NH2 NMP, 50°C -H2O,NMP N N N
30 min
Hemiaminal O O
4,4'-Oxydianiline O Dynamic
(ODA) Polyhexahydrotriazine
Covalent Network
(PHT)
N (HDCN) N

Fig. 1.1 Polymerization reaction scheme between oxydiamines and paraformaldehyde

1.2 Materials and Methods

1.2.1 Materials

All the reagents were used as obtained from Sigma-Aldrich. This includes 4,4′-oxy-
dianiline (ODA, 95 %, A); 4,4′-(4,4′-isopropylidenediphenyl-1,1′-diyldioxy)diani-
line (BAPPP, 98 %, B); 4,4′-(hexafluoroisopropylidene)bis(4-phenoxyaniline)
(BAPPH, 97 %, C); 2,3,5,6-tetramethyl-1,4-phenylenediamine (4MPD, 99 %, D);
4,4′-(1,1′-biphenyl-4,4′-diyldioxy)dianiline (BAPB, 97 %, E); 4,4′-(hexafluoroiso-
propylidene)dianiline (6F-diamine, 98 %, F); paraformaldehyde (PFA, 97 %); and
N-methyl-2-pyrrolidone (NMP, 99.5 %) as a solvent.

1.2.2 Membrane Synthesis by Conventional Heating

Technique

The polymeric membranes were prepared by using PFA–ODA (MA1), PFA–BAPPP

(MB1), PFA–BAPPH (MC1), PFA–4MPD (MD1), PFA–BAPB (ME1), and PFA–
6F-diamine (MF1). The polymeric membranes were synthesized following the same
procedure. As an example, for the synthesis of MB1: 0.80 g (2 mmoL) of BAPPP,
0.15 g (5 mmoL) of PFA, and 3.5 mL of NMP solvent (corresponding to 80 %w)
were placed in a 20-mL vial and stirred for 15 min at 50 °C, until a homogenous
solution was obtained. A soft N2 gas stream was fed to the vial for 30 s. Then, the
solution was poured over a 15 × 15 cm glass plate, which was then placed in an
electric oven. The reaction system was heated at 40–50 °C for 1 h. Then, the tem-
perature was gradually increased from 50 to 200 °C in a 1-h time period. The reac-
tion system was held at 200 °C for one additional hour. The membrane was allowed
to cool down overnight. Then, the membrane edges were trimmed, and the polymer
film was immersed in deionized water. See Table 1.1.
1 Poly (Hexahydrotriazine) Membranes Prepared by Coupling Reaction Between… 5

Table 1.1 Aromatic diamines in the polymerization reaction

Key Diamine Bridge group (X)
A ODA O

n
B BAPPP H3C CH3

O O
n

C BAPPH F F F F
F F

O O
n

D 4MPDa NH2

NH2

E BAPB NH3

O O

n
F F F
F 6F-Diamine F

F F

a
Base structure with no bridge group

1.2.3 Membrane Composition

1.2.4 Membrane Characterization

1.2.4.1 Solubility

Solvents with increasing dielectric constants were used for the solubility tests. In 10-mL
test tubes, 0.1 g of the polymeric membrane sample and 1 mL of solvent were kept
at room temperature for 24 h in order to monitor the observed solubility.
6 L.F. Alcocer-Márquez and J. Palacios-Alquisira

1.2.4.2 FTIR

For the FTIR analysis, we used film samples in an FTIR/FIR Spectrum 400,
Perkin–Elmer spectrophotometer, in the range of 4000–400 cm−1, in attenuated
total reflectance (ATR) mode.

1.2.4.3 Thermal Analysis

Differential scanning calorimetry, DSC, and thermogravimetric tests were carried out
in a Mettler Toledo 851e instrument. The selected conditions were, heating program
of 1 °C/min in an inert dry nitrogen atmosphere.

1.2.4.4 Density Determination

The density of membrane samples was obtained at room temperature using four mis-
cible solvents: n-pentane, dichloromethane, dichloroethane, and trichloromethane.
In a 15-mL graduated cylinder containing the polymeric sample and a high-density
solvent, a low-density solvent was added dropwise with a burette, until the mem-
brane sample was floating freely at the middle of the graduated cylinder. By consid-
ering the density value of each solvent, the corresponding density of the final solution
was calculated. The density of mix solvents was considered to be equal to polymer
density.

1.2.4.5 Permeability Estimation

To estimate the permeability, the following equation was used, P = A*exp(−B/

FFV). This equation is based on the FFV of the polymer. The equation also con-
siders the membrane density, the molecular weight of structural unit Mo, and the
Van der Waals volume of structural unit Vw, see Ref. [9] for a more complete
explanation.

1.3 Results and Discussion

1.3.1 Conventional Heating Synthesis

By using the synthesis method explained above, according to Table 1.1, diamines A,
B, C, E, and F produced good polymers when reacted in a 2:5 molar ratio
(diamine:PFA), in the presence of 80 %w of NMP as a solvent, under the tempera-
ture and time specified above in the reaction conditions. The obtained membranes
are clear materials with yellowish coloration, low flexibility, and brittleness. When
diamine (4MPD) is added to our experiments, a poor membrane is obtained;
1 Poly (Hexahydrotriazine) Membranes Prepared by Coupling Reaction Between… 7

the polymerization reaction produced a brown powder of low molecular weight.

A possible explanation is that being the amine groups sterically hindered in the
4MPD polymer, a high molecular weight polymer was difficult to obtain.

1.3.2 Polymer Solubility Tests

The solubility of the polymers was determined using the following solvents: THF,
1,2-dichloropropane, ethyl–methyl–ketone, n-propanol, N-methyl pyrrolidone, nitro-
benzene, DMF, and DMSO. All solvents tested are polar, and the polymers obtained
from the diamines A, B, C, E, and F were not soluble in any of these substances. This
is a clear evidence of the high molecular reticulation achieved in the structure of the
obtained polymers. The solubility of the polymers prepared based on monomers C
and F was also tested in chloroform and other halogenated hydrocarbon compounds,
but these polymers were insoluble as well. The polymer prepared by using 4MPD
was soluble in DMSO, DMF, and n-pentanol due to its low molecular weight.

1.3.3 FTIR Analysis

FTIR tests were conducted in all the membrane samples. The analysis showed bands at
2850 cm−1 corresponding to the –CH2– methylene group. This was expected due to the
formation of a new bond between the formaldehyde and the amine group. Other peaks
corresponding to the –CH2– methylene group appeared at 1470–1450 cm−1: these were
assigned to vibrations known as methylene scissoring and are generally present in
cyclopentane and cyclohexane molecules. This is an important observation because it
indicates the formation of the desired hexahydrotriazine network. A relevant finding
was the presence of a band at 1230 cm−1 that was assigned to the tertiary amines in the
polymer network. The peak at 3400 cm−1 corresponding to –NH2– primary amine
group was not observed in the spectra of tested membranes.

1.3.4 Thermal Analysis

Differential scanning calorimetry (DSC) and thermogravimetric (TGA) tests were

carried out in a Mettler Toledo thermoanalyzer. Most of the membranes prepared had
a fairly similar thermal behavior, see Table 1.2. We found that the glass transition
temperature (Tg) for each sample is around 200 °C. The polymers with a more flexible
chain structure had the lowest Tg values, due to the presence of the ether groups in the
molecules. The degradation temperatures (Td) have a similar behavior to that of the Tg
temperatures, since the most rigid polymer chains correspond to high Td values, 280
8 L.F. Alcocer-Márquez and J. Palacios-Alquisira

Table 1.2 Glass transition temperature (Tg), degradation temperature (Td), and density of selected
sample membranes
Samplea T1 (°C) Tg (°C) Td (°C) ρ (g/cm3)
MA2 91.25 180.00 ~220 1.2994
MB1 122.80 198.69 ~210 1.2359
MC1 100.76 199.19 ~280 1.4260
MD2 117.93 200.11 ~240 –
ME1 89.17 173.00 ~200 1.2450
MF1 147.32 202.36 >300 1.4110
a
Sample identification, M membrane and letters A, B, C, D, E, and F correspond to the diamine and
experiment number

and 300 °C accordingly, while the more flexible chain polymers have Td temperatures
around 240 °C. See Table 1.2. T1 is the temperature corresponding to a first mass loss
caused by the presence of small amounts of impurities.

1.3.5 Density Determination

The densities of the obtained polymeric samples were determined at 20 °C by the

flotation method in a set of trichloromethane and n-pentane solutions with different
compositions. Densities between 1.22 and 1.43 g/cm3 were evaluated. See Table 1.2.
The fluorine-containing polymers showed the highest densities due to their high
crystallinity and molecular weight. Our density values were confirmed by pycnom-
etry determined at 20 °C.

1.3.6 Estimation of Fractional Free Volume and Membrane

Permeability

For all our materials, the estimated FFV values were between 0.1927 and 0.1202.
Based on this data, the permeability and selectivity to certain gases were evaluated
too. The values are similar to those in other polymers previously reported [9–11],
see Table 1.3. Polymers formed from diamines with more voluminous bridge groups
(X) showed larger FFV values as expected due to the larger volumes occupied by
these groups. The estimated permeabilities (P) show the same trend in values; how-
ever, as the FFV increases, the theoretical selectivities PCO2/PCH4 and PO2/PN2
decrease, as expected. See Table 1.3.
Figure 1.2 shows the effect of the Ln (FFV) on the Ln (P) permeability. As
expected, the higher the FFV values are, the Ln (P) permeability increases from
1.281 to 4.32 (Barrers).
1 Poly (Hexahydrotriazine) Membranes Prepared by Coupling Reaction Between… 9

Table 1.3 Gas permeability Permeability (Barrer) Selectivity

Membrane
and selectivity for selected
sample CH4 CO2 CO2/CH4
synthesized membranes
MB1 0.036 1.364 37.397
MC1 0.106 3.517 33.241
MC2 0.049 1.789 36.157
MC3 0.313 9.217 29.486
MC4 0.313 9.217 29.486
ME1 0.154 4.905 31.893
MF1 0.254 7.659 30.173
MF2 0.754 20.159 26.750
MF3 0.402 11.522 28.678
MF4 0.672 18.210 27.091

5
Ln (P)
4.5 Barrer
4 (x10^-2)
3.5
3
2.5
2
1.5
1
0.5
0
-2.2 -2.1 -2 -1.9 -1.8 -1.7 -1.6 -1.5
Ln (FFV)

Fig. 1.2 Effect of Ln (FFV) on Ln (P), permeability to CH4

1.4 Conclusions

Five new polymeric materials were prepared by reacting aromatic diamines and
paraformaldehyde. Insoluble membrane samples were obtained using a molar ratio
of 2:5 diamine/PFA. By conventional heating activation, polymeric membrane
products were prepared with high molecular weight. Only one polymer was obtained
as a fine powder. The polymeric compounds were characterized by FTIR, DSC,
solubility, and density tests. The molecular weights could not be determined due to
the insolubility of the highly reticulated materials.
10 L.F. Alcocer-Márquez and J. Palacios-Alquisira

References

1. Guiver, M. D., & Lee, Y. M. (2013). Polymer rigidity improves microporous membranes.
Science, 339, 284–285. doi:10.1126/science.1232714.
2. Seva, M. J. (2013). Poliimidas aromaticas de alta rigidez intrinseca para procesos de separa-
ción de gases. Ph.D. thesis, UAM, Madrid, España.
3. Bernardo, P., et al. (2009). Membrane gas separation: A review/state of the art. Industrial and
Engineering Chemistry Research, 48, 4638–4663.
4. Bernardo, P., & Ckarizia, G. (2013). 30 years of membrane technology for gas separation.
Chemical Engineering Transactions, 32, 1999–2004.
5. Calle, M., et al. (2010). Design of gas separation membranes derived of rigid aromatic poly-
imides. Polymers from diamines containing di-tert-butyl side group. Journal of Membrane
Science, 365, 145–153.
6. García, J. M. (2014). Recyclable, strong thermosets and organogels via formaldehyde conden-
sation with diamines. Science, 344, 732–735. doi:10.1126/science.12514841.
7. Carta, M., et al. (2013). An efficient polymer molecular sieve for membrane gas separations.
Science, 339, 303–307. doi:10.1126/science.1228032.
8. Dandia, A. (2004). Green chemical synthesis of fluorinated 1,3,5-Triaryl-S-Triazines in
medium under microwaves as potential antifungal agents. Journal of Fluorine Chemistry, 125,
1273–1277.
9. Paul, J. Y., & Paul, D. R. (1997). Correlation and prediction of gas permeability in glassy
polymer membrane materials via a modified free volume based group contribution method.
Journal of Membrane Science, 125, 23–29.
10. Hong-Ling, L. V., Bao-guo, W., & Ying, K. (2009). Prediction of solvent diffusivities in amor-
phous polymers by free-volume theory: Group contribution and PALS methods. Polymer
Journal, 41(12), 1049–1054.
11. Shuzen, Q. (2015). Preparation and characterization of matrimid/P84 blend films. Masters
Degree thesis, China University of Petroleum, Beijing.
Chapter 2
Preparation and Characterization of Hybrid
Membranes Based on Poly(Ether-b-Amide)

Héctor Iván Meléndez-Ortiz, Griselda Castruita-de León,

Yibran Perera-­Mercado, Jesús Alfonso Mercado-Silva,
Bertha Puente-Urbina, Sandra García-Rodríguez,
and Luis Alfonso García-Cerda

2.1 Introduction

In the recent decades, there has been an increased interest in developing materials
for achieving the separation of certain gases of industrial interest such as carbon
dioxide (CO2) and hydrogen sulfide (H2S) from natural gas (CH4) or oxygen (O2)
from nitrogen (N2). Polymer membranes play an important role in gas separation
because of their advantages such as low energy costs, environmental friendliness,
and simplicity compared to conventional methods such as aqueous amine scrubbing,
cryogenic distillation, or pressure swing adsorption [1–4]. However, a major drawback
of polymer-based membranes has been the naturally counteracting permeability and
selectivity. It means that the membranes with high permeability usually present a low
selectivity and vice versa. Therefore, the development of new membrane materi-
als with improved permeability, selectivity, and stability is required to overcome this
drawback and increase the process efficiency for industrial applications.
One strategy for improving membrane selectivity and permeability involves the
introduction of inorganic materials into the polymer matrix [5–7]. A variety of inor-
ganic fillers have been explored such as zeolites, carbon molecular sieves, mesopo-
rous silica, metal oxide, carbon nanotubes, metal organic frameworks, and, more
recently, graphene [8]. The resulting materials, also called mixed matrix membranes
(MMMs), have the advantage of combining the benefits of both phases: thermal
resistance of inorganic fillers with the desirable mechanical properties, low price,
and good processability of polymers. The inorganic fillers which are dispersed in

H.I. Meléndez-Ortiz (*) • G. Castruita-de León

CONACyT-Centro de Investigación en Química Aplicada, Blvd. Enrique Reyna
Hermosillo 140, Saltillo 25294, Coahuila, México
e-mail: hector.melendez@ciqa.edu.mx
Y. Perera-Mercado • J.A. Mercado-Silva • B. Puente-Urbina
S. García-Rodríguez • L.A. García-Cerda
Centro de Investigación en Química Aplicada, Blvd. Enrique Reyna
Hermosillo 140, Saltillo 25294, Coahuila, México

© Springer International Publishing Switzerland 2017 11

A. Maciel-Cerda (ed.), Membranes, DOI 10.1007/978-3-319-45315-6_2
12 H.I. Meléndez-Ortiz et al.

Fig. 2.1 Chemical Nylon 12 PTMO

structure of poly(ether-b-­
amide) (PEBAX® 2533) O

H
H N C11H22 C O C4H8 OH

X 1-X

X=0.2

polymer matrix change the membrane properties, allowing improved separation

performance, compared to unfilled polymer membrane.
The aim of this work is the preparation of MMMs based on poly(ether-b-amide)
(PEBA) copolymer and mesoporous silica MCM-48 previously modified with
3-aminopropyltrimethoxysilane (APS). PEBA copolymer, best known under the
trademark PEBAX®, is a relatively new family of thermoplastic elastomers with
unique physical and processing properties. The unique nature of these materials has
been attributed to the combination of linear chains of rigid polyamide segments inter-
spaced with flexible polyether segments [9–11]. The high polarity difference between
hard and soft segments and the development of a three-dimensional hydrogen-­bonding
network between the amide units lead to a microphase separated morphology [12].
Membranes made from PEBA copolymers exhibit good permselectivity as well as
excellent chemical separation and pervaporation applications because the hard phase
provides high selectivity and mechanical strength and the soft one offers high perme-
ability due to the great chain mobility of the ether linkage (Fig. 2.1) [13].
On the other hand, MCM-48 silica is found to be attractive for potential applica-
tion in membranes for gas separation due to its three-dimensional interconnected
cubic pore structure which is less prone to pore blocking than the unidimensional
hexagonal arrangement in MCM-41 silica. Also, mesoporous silica MCM-48
shows fascinating properties as tunable pore sizes, uniform mesopores, and high
surface area. There are some reports about the preparation of MMMs based on
PEBA copolymers and some fillers such as silica [14, 15], zeolites [16, 17], multi-
walled carbon nanotubes [18, 19], and polyoctahedral oligomeric silsesquioxanes
[20]. However, as far as we know, there is no report about the preparation of MMMs
of PEBA with amine-modified MCM-48 silica. The modification of MCM-48 with
compounds containing amine groups could be useful for either to improve the
filler–polymer interface compatibility or to facilitate the transport of CO2 [15, 21,
22]. The motivation of this work is to gain insight into the effect of incorporation of
amine-modified MCM-48 upon the thermal properties, morphology, as well as gas
separation performance of the prepared hybrid membranes. MMMs of PEBA and
APS-modified MCM-48 silica were successfully prepared using the methodology
reported in this work. The previous modification of MCM-48 with the amine
organosilane improved the interaction with the PEBA matrix. The gas separation
performance of pristine PEBA membranes was improved with the addition of the
inorganic material.
2 Preparation and Characterization of Hybrid Membranes Based… 13

2.2 Experimental Section

2.2.1 Materials

Poly(ether-b-amide) (PEBAX® 2533) in pellet form was obtained from Arkema, and
chloroform 99 % (CH3Cl) from J. T. Baker was used in the preparation of MMMs.
Tetraethylorthosilicate 98 %, TEOS, and cetyltrimethylammonium bromide 98 %,
CTAB, were supplied from Aldrich. Deionized water was obtained from a system of
two ionic interchange columns in a Cole-Parmer Instrument. Ethanol 99 % from J. T.
Baker and aqueous ammonia solution 29 %, NH4OH, from Fermont were used to
prepare mesoporous MCM-48 materials. In addition, 3-­aminopropyltrimethoxysilane
(APS) 97 %, APS, (Aldrich), isopropanol 99 % (Aldrich), and toluene 99 % (J. T.
Baker) were used to modify the mesoporous MCM-48 silica.

2.2.2  ynthesis and Functionalization of MCM-48

S
Mesoporous Silica

MCM-48 was synthesized and functionalized as previously reported by our research

group [23]. Briefly, 6.8 g of TEOS was added to a solution containing 5.2 g of
CTAB, 240 g of H2O, 100 mL of ethanol, and 24 mL of NH4OH. Then, the solid
product was dried at room temperature and further calcined at 540 °C. The modifi-
cation of the calcined MCM-48 silica was carried out by adding the silica material
to a mixture containing APS and toluene. The reaction mixture was vigorously
stirred under reflux for 15 h and then the solid was washed with isopropanol.

2.2.3 Preparation of the APS-MCM-48/PEBA Membranes

Flat PEBA and APS-MCM-48/PEBA membranes were prepared to evaluate its gas
separation performance. To prepare the pristine PEBA membranes, polymeric pel-
lets were dissolved at 35 °C in chloroform (10 wt%) to obtain an appropriate viscos-
ity for casting the solution. To prepare MMMs based on PEBA and APS-MCM-48,
some parameters were evaluated in order to obtain membranes for gas separation
studies. The parameters evaluated were the amount of modified silica, solution vis-
cosity, sonication, and stirring time. Thus, MMMs were fabricated as follows: APS-­
MCM-­48 silica (2.5–10 wt% with respect to the total content of PEBA) was
dispersed in 1 mL of CHCl3 containing a small amount of PEBA (0.02 g) by using
an ultrasonic processor for 5 min and then sonicated in an ultrasonic bath for 10 min.
After that, 3 mL of a PEBA solution (10 wt% polymer in CHCl3) was added under
vigorous stirring to the solution containing dispersed APS-MCM-48 silica, and the
resulting solution was magnetically stirred at 35 °C for 24 h. It is worthy to mention
14 H.I. Meléndez-Ortiz et al.

that no evaporation of CHCl3 was observed during the preparation of polymer

solutions. Before the membrane casting, three intervals of sonication of 15 min
were carried out to ensure a well-dispersed solution. Subsequently, the homoge-
neous solution was poured on a plain glass surface and left overnight covered with
a glass cover at room temperature for natural and slow evaporation. After that,
MMMs were heated at reduced pressure to remove the solvent remaining within the
membrane. The treatment took place in a vacuum oven at intervals of temperature
of 10 °C from 30 to 60 °C for 8 h each. Membrane thicknesses were measured by a
Digimatic Micrometer 0–30 mm (accuracy ± 1 mm).

2.2.4 Characterization

MCM-48 silica was characterized by X-ray diffraction (XRD) using a SIEMENS

D5000 diffractometer with CuKα radiation. The diffraction data were recorded in the
2θ range of 2–10°. Nitrogen adsorption–desorption isotherm was obtained on
Quantachrome AS1Win equipment at −196 °C. Before the experiments, the mesopo-
rous material was degassed under vacuum at 120 °C. The specific surface area of the
sample was calculated using a Brunauer–Emmett–Teller (BET) method, and the pore
size distribution was calculated using desorption branches of nitrogen isotherms and
a method according to Density Functional Theory (DFT). Transmission electron
microscopy (TEM) was performed using an HRTEM Titan operated at 300 kV.
MMMs were characterized by Fourier transform infrared spectroscopy (FT-­IR) by
using a Nicolet Magna 550 spectrophotometer, equipped with a Universal ATR sam-
pling accessory. TGA studies were carried out using a TGA Q500 apparatus (TA
Instruments, New Castle, DE) under nitrogen flow. The morphology of MMMs was
examined using a scanning electron microscope JEOL JSM-7401F.

2.2.5 Permeability Measurements

Gas permeability coefficients for three pure gases, methane (CH4), carbon dioxide
(CO2), and nitrogen (N2), were measured at 35 °C and 2 atm using a variable pres-
sure permeation cell. The permeability (P, Barrer, and 1 Barrer = 10−10 cm3 (STP)
cm/(cm2 s cmHg)) was determined by the time-lag method under steady-state con-
ditions according to the next equation:

V l R N é ( dp / dt ) ù
P= ê ú (2.1)
ART ë Dp û

where V is the inferior volume of the permeation cell (cm3), l is the membrane thickness
(cm), T is the temperature (K), A is the effective membrane area (cm2), Δp is the
2 Preparation and Characterization of Hybrid Membranes Based… 15

pressure of the superior volume of permeation cell (mmHg), dp/dt is the increase of
the pressure with respect to time (mmHg s−1), RN is the molar volume of gas at con-
stant temperature and pressure (22,415 cm3 (STP) cmHg mol−1 K−1), and R is the
universal constant of gases (62,634 cm3 (STP) cmHg mol−1 K−1). Ideal gas separa-
tion factors (α) were calculated from the ratio of pure gas permeability coefficients
using the following equation:

a A / B = PA / PB (2.2)

where PA and PB are gas permeability coefficients of the pure gases A and B,
respectively.

2.3 Results and Discussion

2.3.1 Characterization of Amine-Modified MCM-48 Silica

The powder XRD patterns of the pristine and amine-modified mesoporous silica
MCM-48 are shown in Fig. 2.2a. The XRD diffractogram for bare MCM-48 silica
displayed reflection peaks at 2θ values of 2.7 (211) and 3.1 (220) and signals between
4.5 and 5.8 corresponding to the planes (321), (400), (420), (332), (422), and (431)
which are characteristics for this silica. After modification with APS, the XRD pat-
terns of MCM-48 did not show significant changes which indicated that the struc-
ture of MCM-48 was preserved after modification. However, the peaks between 4.5
and 5.8 disappeared. This behavior indicated the pore filling of MCM-48 silica by
APS but not changes in the mesostructure [24]. The FT-IR spectra of pristine and
amine-modified MCM-48 are shown in Fig. 2.2b. MCM-48 silica exhibited a signal
at 3741 cm−1 assigned to the O–H bond of the silanol groups, a band at 1058 cm−1
due to Si–O–Si stretching vibration, and a peak at 800 cm−1 corresponding to the
bending vibration for the bond Si–O–Si. On the other hand, the FT-IR spectrum of
APS-MCM-48 showed a signal at 1560 cm−1 assigned to the NH2 scissor from APS
[25]. Also, it can be seen that the band of Si–O–H (3740 cm−1) disappeared in the
spectrum of APS-MCM-48 which evidences the covalent grafting of APS on MCM-­
48 silica. Figure 2.2c shows the pore size distribution of MCM-48 and APS-­
MCM-­48. The average pore size was estimated to be 2.2 and 1.5 nm for MCM-48
and APS-MCM-48, respectively. After modification, the surface area and pore vol-
ume decreased from 1912 to 450 m2/g and from 0.876 to 0.245 m3/g, respectively,
due to the pore filling effect of APS. Thermogravimetric analysis (TGA) was used to
determine the amount of APS grafted onto the inorganic material (Fig. 2.2d).
Unmodified MCM-48 silica was stable in the temperature range from 30 to 750 °C,
while APS-MCM-48 showed a weight loss of 3 % before 100 °C due to desorption
of moisture. Also, it was observed a small weight loss between 110 and 170 °C
probably due to the loss of NH3 from APS and then a main weight loss in the tem-
perature range of 200–600 °C due to chemical decomposition of the grafted APS.
16 H.I. Meléndez-Ortiz et al.

(a) (211)
(b)
3741 MCM-48 800

Transmittance (a.u.)
Intensity (a.u.)

(220)
MCM-48
1560
APS-MCM-48

APS-MCM-48 1058

2 3 4 5 6 7 8 9 10 4000 3500 3000 2500 2000 1500 1000

2q (Degrees) Wavelength (cm )
-1

(c) 1.8 (d)

100
1.5
dV/dr (cm /g-nm)

MCM-48

Weight (%)
1.2 MCM-48
90
3

0.9 APS-MCM-48
0.6 80

0.3 APS-MCM-48
0.0 70
0 2 4 6 8 10 12 100 200 300 400 500 600 700

Pore diameter (nm) Temperature (°C)

Fig. 2.2 Characterization of unmodified and modified MCM-48 silica: (a) X-ray powder diffraction
pattern, (b) FT-IR spectroscopy, (c) particle size distribution, and (d) thermogravimetric study

2.3.2 MMMs Characterization

2.3.2.1 FT-IR Spectroscopy

PEBA copolymer consists of both flexible poly(tetramethylene oxide) (PTMO)

segments and rigid polyamide segments (nylon 12). The FT-IR spectrum of pristine
PEBA showed signals at 3295 and 1645 cm−1 due to the stretching vibrations of
the N–H bond and the C = O bond from polyamide segment, respectively (Fig. 2.3).
The strong bands at 2935 and 2859 cm−1 correspond to the stretching vibration of
the C–H bond from methylene groups. In addition, the peaks at 1733 and 1108 cm−1
represent the O–C = O and C–O–C stretching vibrations, respectively. The FT-IR
spectrum obtained for APS-MCM-48/PEBA hybrid membrane is very similar to
that for the pristine PEBA copolymer. However, it can be observed a weak band at
1160 cm−1 probably due to the Si–O–Si from MCM-48 silica.

2.3.2.2 SEM Studies

The morphology of the prepared membranes was investigated using scanning electron
microscopy (SEM). The cross-sectional SEM images of pristine PEBA and APS-
MCM-48/PEBA membranes at different amounts of amine-modified filler are
2 Preparation and Characterization of Hybrid Membranes Based… 17

Fig. 2.3 FT-IR spectra for:

(a) pristine PEBA
membrane and (b) (a)
APS-MCM-48 (10 %)/ 1733
3295
PEBA membrane 1645

Transmittance (a.u.)
2859

2935 1108

(b)

1160

4000 3500 3000 2500 2000 1500 1000

Wavelength (cm-1)

shown in Fig. 2.4. Pristine PEBA membrane showed a smooth morphology free of
voids with some small roughness areas. On the other hand, the SEM images for
hybrid membranes showed that the spherical APS-functionalized MCM-48 silica
particles were uniformly dispersed throughout PEBA matrix in a concentration
range of 2.5–10 wt%. The APS-functionalized MCM-48 particles were completely
surrounded by polymer matrix and no voids were formed, as shown in Fig. 2.4b–e,
suggesting that the grafted APS on the external surface of MCM-48 silica enhanced
the filler–polymer interface compatibility.

2.3.2.3 Thermal Properties

The study of the thermal properties, especially the stability and decomposition
processes of the membrane materials, is important for understanding and eventually
improving their gas separation performance. TGA of pristine PEBA membrane
showed that there was no weight loss up to 350 °C indicating that the solvent was
removed with the treatment at 60 °C (Fig. 2.5). Above this temperature, the PEBA
copolymer starts to dramatically decompose until 470 °C due to the main chain scis-
sion. Similar behavior was observed for APS-MCM-48/PEBA membranes at differ-
ent contents of modified silica. However, a slight decrease in the thermal stability
was observed, and it was more evident when the content of silica was increased.
This could be related to a disruption caused by the silica particles in the rigid polyamide
domains. The remaining weight loss allowed the verification of the nominal wt%
loading of the amine-modified MCM-48 present in the corresponding MMM, i.e., 0,
4.7, and 9.0 wt% residual contents for nominal 0, 5, and 10 wt%, respectively.
DSC studies were carried out in a temperature range of 20–250 °C. The DSC
thermograms of pristine PEBA and hybrid PEBA membranes with different con-
tents of APS-MCM-48 are shown in Fig. 2.6. The DSC thermogram of pristine
18 H.I. Meléndez-Ortiz et al.

Fig. 2.4 Cross-sectional SEM images for (a) pristine PEBA membrane and MMMs with different
contents of APS-MCM-48: (b) 2.5 %, (c) 5 %, (d) 7.5 %, and (e) 10 %. Magnification × 20,000

PEBA only showed one endothermic transition at 139 °C. This transition is due to
the melting of the polyamide domains [9, 20]. Even after the incorporation of APS-­
MCM-­48, this peak transition was visible, and its shape remained unchanged.
However, a slight decrease of this transition to lower temperature was observed
with increasing filler loading. This may be due to a disruption caused by the silica
particles in the rigid polyamide domains as it was observed in TGA results.
Another random document with
no related content on Scribd:
between the leaves. These gillbearing appendages can be flapped to
and fro, and they seem to be at times held apart by the flabellum, a
spatulate process which Patten and Redenbaugh regard as a
development of the median sensory knob on the outer side of the
coxopodite of the last pair of walking limbs.
Limulus has no trace of
Malpighian tubules, structures
which seem often to develop only
when animals cease to live in
water and come to live in air. The
Xiphosura have retained as
organs of nitrogenous excretion
the more primitive nephridia, or
coxal glands as they are called, in
the Arachnida. They are redbrick
in colour, and consist of a
longitudinal portion on each side
of the body, which gives off a lobe
opposite the base of the pedipalps
and each of the first three walking
legs—in the embryo also of the
chelicerae and last walking legs,
but these latter disappear during
development. A duct leads from
Fig. 155.—Diagram of the first gill of
Limulus, from the posterior side,
the interior of the gland and
showing the distribution of the gill- opens upon the posterior face of
nerve to the gill-book (about natural the last pair of walking legs but
size). After Patten and Redenbaugh. 1, one.
Inner lobe of the appendage; 2, outer The nervous system has been
lobe of appendage; 3, median lobe of
appendage; 4, gill-book; 5, neural nerve
very fully described by Patten and
of the ninth neuromere; 6, internal Redenbaugh, and its complex
branchial nerve; 7, gill-nerve; 8, nature plays a large part in the
median branchial nerve; 9, external ingenious speculations of Dr.
branchial nerve. Gaskell as to the origin of
Vertebrates. It consists of a stout
ring surrounding the oesophagus
and a ventral nerve-cord, composed—if we omit the so-called fore-
brain—of sixteen neuromeres. The fore-brain supplies the median
and the lateral eyes, and gives off a median nerve which runs to an
organ, described as olfactory by Patten, situated in front of the
chelicerae on the ventral face of the carapace. Patten distinguishes
behind the fore-brain a mid-brain, which consists solely of the
cheliceral neuromere, a hind-brain which supplies the pedipalps and
four pair of walking legs, and an accessory brain which supplies the
chilaria and the genital operculum. This is continued backward into a
ventral nerve-cord which bears five paired ganglia supplying the five
pairs of gills and three pairs of post-branchial ganglia; the latter are
ill-defined and closely fused together. As was mentioned above, the
whole of the central nervous system is bathed in the blood of the
ventral sinus.
The sense-organs consist of the olfactory organ of Patten, the
median and lateral eyes, and possibly of certain gustatory hairs upon
the gnathobases. The lateral eyes in their histology are not so
differentiated as the median eyes, but both fall well within the limits
of Arachnid eye-structure, and their minute anatomy has been
advanced as one piece of evidence amongst many which tend to
demonstrate that Limulus is an Arachnid.
Both ovaries and testes take the form of a tubular network which is
almost inextricably entangled with the liver. From each side a duct
collects the reproductive cells which are formed from cells lining the
walls of the tubes, and discharges them by a pore one on each side of
the hinder surface of the genital operculum. As is frequently the case
in Arachnids the males are smaller than the females, and after their
last ecdysis the pedipalps and first two pairs of walking legs, or some
of these appendages, end in slightly bent claws and not in chelae. Off
the New Jersey coast the king-crabs (L. polyphemus) spawn during
the months of May, June, and July, Lockwood states at the periods of
highest tides, but Kingsley[217] was never “able to notice any
connexion between the hours when they frequent the shore and the
state of the tide.” “When first seen they come from the deeper water,
the male, which is almost always the smaller, grasping the hinder
half of the carapace of the female with the modified pincer of the
second pair of feet. Thus fastened together the male rides to shallow
water. The couples will stop at intervals and then move on. Usually a
nest of eggs can be found at each of the stopping-places, and as each
nest is usually buried from one to two inches beneath the surface of
the sand, it appears probable that the female thrusts the genital plate
into the sand, while at the same time the male discharges the milt
into the water. I have not been able to watch the process more closely
because the animals lie so close to the sand, and all the appendages
are concealed beneath the carapace. If touched during the
oviposition, they cease the operation and wander to another spot or
separate and return to deep water. I have never seen the couples
come entirely out of the water, although they frequently come so
close to the shore that portions of the carapace are uncovered.”[218]
Fig. 156.—A view of the nervous system of Limulus from below.
(About natural size.) After Patten and Redenbaugh.

The carapace is represented as transparent. The appendages have

been removed, but the outlines of the left entocoxites (6) have
been sketched in. The positions of the abdominal appendages are
indicated by the external branchial muscles (17), the branchial
cartilages (19), the tendinous stigmata (18), and the abdominal
endochondrites (21). In the cephalothorax (1) all the tergo-coxal
and plastro-coxal muscles have been dissected away, leaving the
endosternite (11) with the occipital ring exposed. One of the left
tergo-proplastral muscles (4) and the left branchio-thoracic
muscles (16) are represented. The longitudinal abdominal muscles
are also seen. All the muscles of the right side have been omitted
except the haemo-neural muscles (23), of which the last two are
represented upon the left side also. At the base of the telson the
flexors (29) and extensors (27) of the caudal spine are represented
as cut off near their insertions. The sphincter ani (26), levator ani,
and occludor ani (25), and their relations to the anus (28), are
shown.

The oesophagus runs forward to the proventriculus (3). From this

the intestine (20) passes posteriorly.

The brain lies upon the neural side of the endosternite, and the
ventral cord (22) passes back through the occipital ring. The
neural nerves are cut off, but the left haemal nerves and those
from the fore-brain (12) are represented entire.

The first pair of neural nerves go to the chelicerae. The second to

sixth pairs go to the next five cephalothoracic appendages, which
are represented by the entocoxites (6). The seventh pair of neural
nerves go to the chilaria, and the eighth pair to the operculum.
The neural nerves from the ninth to the thirteenth arise from the
abdominal ganglia and innervate the five pairs of gills.

From the fore-brain a median olfactory nerve (9) and two lateral
ones (8) pass forward to the olfactory organ; a median eye-nerve
(2) passes anteriorly and haemally upon the right of the
proventriculus (3) to the median eyes; and a pair of lateral eye-
nerves pass to the lateral eyes (15).

The first haemal nerve, or lateral nerve, follows the general course
of the lateral eye-nerve, but continues posteriorly far back on to
the neural side of the abdomen.

The haemal nerves of the hind-brain radiate from the brain to the
margins of the carapace, and each one passes anterior to the
appendage of its own metamere. The integumentary portions
divide into haemal and neural branches, of which the haemal
branches (5) are cut off. Each haemal branch gives off a small
nerve which turns back toward the median line upon the haemal
side of the body.

The haemal nerves of the accessory brain pass through the

occipital ring to the sides of the body between the operculum and
the sixth cephalothoracic appendage. The seventh innervates the
posterior angles of the cephalothorax, the eighth the opercular
portion of the abdomen. The next five haemal nerves arise from
the five branchial neuromeres, pass out anterior to the gills to the
sides of the abdominal carapace, and innervate the first five spines
upon the sides of the abdomen.

The first post-branchial nerve innervates the last abdominal

spine; the second post-branchial nerve and one branch of the
third post-branchial innervate the posterior angles of the
abdomen and the muscles of the telson; and the caudal branch of
the third post-branchial nerve innervates the telson.

Intestinal branches arise from all the haemal nerves from the sixth
to the sixteenth, and pass to the longitudinal abdominal muscles
and to the intestine.

Cardiac nerves arise from all the haemal nerves from the sixth to
the thirteenth. Six of the cardiac nerves communicate with the
lateral sympathetic nerve (24), which innervates the branchio-
thoracic muscles (16).

Two post-cardiac nerves arise from the first two post-branchial

nerves, and passing to the haemal side anastomose with a branch
from the last cardiac nerve, and innervate the extensors (27) of the
telson and the epidermis behind the heart.

1, Cephalothorax; 2, median eye-nerve; 3, proventriculus; 4, tergo-

proplastral muscles; 5, haemal branch of integumentary nerve; 6,
entocoxites; 7, 2nd haemal nerve; 8, right olfactory nerve; 9,
median olfactory nerve; 10, intestine; 11, endosternite; 12, fore-
brain; 13, origin of 4th neural nerve; 14, lateral nerve; 15, lateral
eye; 16, branchio-thoracic muscles; 17, external branchial muscles;
 18, tendinous stigmata; 19, branchial cartilages; 20, intestine; 21,
abdominal endochondrites; 22, ventral cord; 23, haemo-neural
muscles; 24, lateral sympathetic nerve; 25, occludor ani; 26,
sphincter ani; 27, extensors of telson; 28, anus; 29, flexors of
telson; 30, lateral projections of abdomen; 31, nerves of spines;
32, external branchial muscles.

The developing ova and young larvae are very hardy, and in a little
sea-water, or still better packed in sea-weed, will survive long
journeys. In this way they have been transported from the Atlantic to
the Pacific coasts of the United States, and for a time at any rate
flourished in the western waters. Three barrels full of them
consigned from Woods Holl to Sir E. Ray Lankester arrived in
England with a large proportion of larvae alive and apparently well.
According to Kishinouye, L. longispina spawns chiefly in August
and between tide-marks. “The female excavates a hole about 15 cm.
deep, and deposits eggs in it while the male fertilises them. The
female afterwards buries them, and begins to excavate the next
hole.”[219] A line of nests (Fig. 157) is thus established which is always
at right angles to the shore-line. After a certain number of nests have
been formed the female tires, and the heaped up sand is not so
prominent. In each “nest” there are about a thousand eggs, placed
first to the left side of the nest and then to the right, from which
Kishinouye concludes that the left ovary deposits its ova first and
then the right. Limulus rotundicauda and L. moluccanus do not bury
their eggs, but carry them about attached to their swimmerets.
The egg is covered by a leathery egg-shell which bursts after a
certain time, and leaves the larva surrounded only by the
blastodermic cuticle; when ripe it emerges in the condition known as
the “Trilobite larva” (Fig. 158), so-called from a superficial and
misleading resemblance to a Trilobite. They are active little larvae,
burrowing in the sand like their parents, and swimming vigorously
about by aid of their leaf-like posterior limbs. Sometimes they are
taken in tow-nets. After the first moult the segments of the meso-
and metasoma, which at first had been free, showing affinities with
Prestwichia and Belinurus of Palaeozoic times, become more
solidified, while the post-anal tail-spine—absent in the Trilobite larva
—makes its first appearance. This increases in size with successive
moults. We have already noted the late appearance of the external
sexual characters, the chelate
walking appendages only being
replaced by hooks at the last
moult.
Fig. 157.—The markings on the sand
made by the female Limulus when
depositing eggs. Towards the lower end
the round “nests” cease to be apparent,
the king-crab being apparently
exhausted. (From Kishinouye.) About
natural size.

Fig. 158.—Dorsal and ventral view of the last larval stage (the so-
called Trilobite stage) of Limulus polyphemus before the
appearance of the telson. 1, Liver; 2, median eye; 3, lateral eye; 4,
last walking leg; 5, chilaria. (From Kingsley and Takano.)

Limulus casts its cuticle several times during the first year—
Lockwood estimates five or six times between hatching out in June
and the onset of the cold weather. The cuticle splits along a “thin
narrow rim” which “runs round the under side of the anterior
portion of the cephalic shield.”[220] This extends until it reaches that
level where the animal is widest. Through this slit the body of the
king-crab emerges, coming out, not as that of a beetle anteriorly and
dorsally, but anteriorly and ventrally, in such a way as to induce the
unobservant to exclaim “it is spewing itself out of its mouth.” In one
nearly full-sized animal the increase in the shorter diameter of the
cephalic shield after a moult was from 8 inches to 9½ inches, which
is an indication of very rapid growth. If after their first year they
moult annually Lockwood estimates it would take them eight years to
attain their full size.
The only economic use I know to which Limulus is put is that of
feeding both poultry and pigs. The females are preferred on account
of the eggs, of which half-a-pint may be crowded into the cephalic
shield. The king-crab is opened by running a knife round the thin
line mentioned on p. 275. There is a belief in New Jersey that this
diet makes the poultry lay; undoubtedly it fattens both fowls and
pigs, but it gives a “shocking” flavour to the flesh of both.

CLASSIFICATION.

But five species of existing King-crabs are known, and these are
grouped by Pocock into two sub-families: (i.) the Xiphosurinae, and
(ii.) the Tachypleinae. These together make up the single family
Xiphosuridae which is co-extensive with the Order. The following is
Pocock’s classification.[221] The names used in this article are printed
in italic capitals.

Order Xiphosura.

Family 1. Xiphosuridae.

Sub-Fam. 1. Xiphosurinae.

This includes the single species Xiphosura polyphemus (Linn.) (=

Limulus polyphemus, Latreille), “which is said to range from the
coast of Maine to Yucatan.”

Sub-Fam. 2. Tachypleinae.

Genus A. Tachypleus includes three species: (i.) T. gigas, Müll. (=

Limulus gigas, Müll., and L. moluccanus, Latreille), widely
distributed in Malaysia; (ii.) T. tridentatus, Leach (= L. tridentatus,
Leach, and L. longispina, Van der Hoeven), extending from British
North Borneo to China and Southern Japan; and (iii.) T. hoeveni,
Pocock (= L. moluccanus, Van der Hoeven), found in the Moluccas.
Genus B. Carcinoscorpius with one species, C. rotundicauda
(Latreille) (= L. rotundicauda, Latreille). It occupies a more
westerly area than T. gigas or than T. tridentatus, having been
recorded from India and Bengal, the Gulf of Siam, Penang, the
Moluccas, and the Philippines.
With regard to the affinities of the group it is now almost
universally accepted that they are Arachnids. The chief features in
which they differ from other Arachnids are the presence of gills and
the absence of Malpighian tubules, both being features associated
with aquatic life. As long ago as 1829 Straus-Dürckheim emphasised
the points of resemblance between the two groups, and although the
view was during the middle of the last century by no means
universally accepted, towards the end of that epoch the painstaking
researches of Lankester and his pupils, who compared the King-crab
and the Scorpion, segment with segment, organ with organ, tissue
with tissue, almost cell with cell, established the connexion beyond
doubt. Lankester would put the Trilobites in the same phylum, but in
this we do not follow him. With regard to the brilliant but, to our
mind, unconvincing speculations as to the connexion of some
Limulus-like ancestor with the Vertebrates, we must refer the reader
to the ingenious writings of Dr. Gaskell,[222] recently summarised in
his volume on “The Origin of Vertebrates,” and to those of Dr. Patten
in his article “On the Origin of Vertebrates from Arachnids.”[223]

Fossil Xiphosura.[224]

Limulus is an example of a persistent type. It appears first in

deposits of Triassic age, and is found again in the Jurassic,
Cretaceous, and Oligocene. In the lithographic limestone of
Solenhofen in Bavaria, which is of Upper Jurassic age, Limulus is
common and is represented by several species. One species is known
from the Chalk of Lebanon, and another occurs in the Oligocene of
Saxony. No other genus of the Xiphosura appears to be represented
in the Mesozoic and Tertiary deposits, but in the Palaeozoic
formations (principally in the Upper Silurian, the Old Red
 Sandstone, and the Coal
Measures) several genera have
been found, most of which differ
from Limulus in having some or
all of the segments of the
abdomen free; in this respect they
resemble the Eurypterida, but
differ from them in the number of
segments. In Hemiaspis (Fig. 159,
A), from the Silurian, the
segments of the abdomen are
Fig. 159.—A., Hemiaspis limuloides, divisible into two groups
Woodw., Upper Silurian, Leintwardine,
Shropshire. Natural size. (After (mesosoma and metasoma) in the
Woodward.) B., Prestwichia (Euroöps) same way that they are in
danae (Meek), Carboniferous, Illinois, Eurypterids; the first six
× ⅔. (After Packard.) segments have broad, short terga,
the lateral margins of the sixth
being divided into two lobes,
probably indicating the presence of two fused segments; the last
three segments are narrower and longer than the preceding, and at
the end is a pointed tail-spine. In Belinurus (Fig. 160) from the
Carboniferous, the two regions of the abdomen are much less
distinct; there are eight segments, the last three of which are fused
together, and a long tail-spine. In Neolimulus, from the Silurian,
there seems to be no division of the abdomen into two regions, and
apparently all the segments were free. On the other hand, in
Prestwichia (Carboniferous), all the segments of the abdomen, of
which there appear to be seven only, were fused together (Fig. 159,
B).
In the Palaeozoic genera the median or axial part of the dorsal
surface is raised and distinctly limited on each side, so presenting a
trilobed appearance similar to that of Trilobites. In Neolimulus,
Belinurus, and Prestwichia, lateral eyes are present on the sides of
the axial parts of the carapace, and near its front margin median eyes
have been found in the two last-named genera.
In nearly all the specimens of Palaeozoic Xiphosura[225] which have
been found nothing is seen but the dorsal surface of the body; in only
a very few cases have any traces of the appendages been seen,[226]
but, so far as known, they appear
to have the same general
character as in Limulus.
Aglaspis, found in the Upper
Cambrian of Wisconsin, has been
regarded as a Xiphosuran. If that
view of its position is correct,
then Aglaspis will be the earliest
representative of the group at
present known. Other genera of
Palaeozoic Xiphosura are
Bunodes, Bunodella, and
Pseudoniscus in the Silurian;
Protolimulus in the Upper
Devonian; and Prolimulus in the
Permian.

Fig. 160.—Belinurus reginae, Baily,

Coal Measures, Queen’s Co., Ireland, ×
1. (After Woodward).
 EURYPTERIDA

BY

HENRY WOODS, M.A.

St. John’s College, Cambridge, University Lecturer in Palaeozoology.
 CHAPTER XI
ARACHNIDA (CONTINUED)—
DELOBRANCHIATA = MEROSTOMATA
(CONTINUED)—EURYPTERIDA

Order II. Eurypterida.

The Eurypterida or Gigantostraca are found only in the Palaeozoic

formations. Some species of Pterygotus, Slimonia, and Stylonurus
have a length of from five to six feet, and are not only the largest
Invertebrates which have been found fossil but do not seem to be
surpassed in size at the present day except by some of the
Dibranchiate Cephalopods. All the Eurypterids were aquatic, and,
with the possible exception of forms found in the Coal Measures, all
were marine. The earliest examples occur in the Cambrian deposits,
and the latest in the Permian; but although the Eurypterids have
thus a considerable geological range, yet it is mainly in the Silurian
and the Old Red Sandstone that they are found, the principal genera
represented in those deposits being Eurypterus, Stylonurus,
Slimonia, Pterygotus, Hughmilleria, Dolichopterus, and Eusarcus.
From the Cambrian rocks the only form recorded is Strabops;[227] in
the Ordovician the imperfectly known Echinognathus[228] and some
indeterminable fragments have alone been found. In the
Carboniferous deposits Eurypterus and Glyptoscorpius occur, and
the former survived into the Permian.[229]
Fig. 161.—Eurypterus fischeri, Eichw. Upper Silurian, Rootziküll,
Oesel. Dorsal surface. a, Ocellus; b, lateral eye; 2–6, appendages
of prosoma; 7–12, segments of mesosoma; 13–18, segments of
metasoma; 19, tail-spine. (After Holm.)
 The Eurypterid which is best known is Eurypterus fischeri (Figs.
161, 162), which is found in the Upper Silurian rocks at Rootziküll in
the Island of Oesel (Gulf of Riga). In the Eurypterids from other
deposits the chitinous exoskeleton has been altered into a
carbonaceous substance, but in the specimens from Oesel the chitin
is perfectly preserved in its original condition; and since these
specimens are found in a dolomitic rock which is soluble in acid, it
has been possible to separate the fossil completely from the rock in
which it is embedded, with the result that the structure can be
studied more easily and more thoroughly than in the case of
specimens from other localities. Consequently Eurypterus
fischeri[230] may, with advantage, be taken as a type of the
Eurypterida.
The general form of the body (Fig. 161) is somewhat like that of a
Scorpion, but is relatively broader and shorter. On the surface of
many parts of the exoskeleton numerous scale-like markings are
found (Figs. 162, 163).[231] The prosoma or cephalothorax consists
of six fused segments covered by a quadrate carapace with its front
angles rounded. This bears on its dorsal surface two pairs of eyes—
large kidney-shaped lateral eyes and median ocelli (Fig. 161, b, a).
The margin of the dorsal part of the carapace is bent underneath to
form a rim which joins the ventral part of the carapace.
On the ventral surface of the prosoma (Fig. 162) six pairs of
appendages are seen, of which only the first pair (the chelicerae) are
in front of the mouth. The chelicerae are small, and each consists of a
basal joint and a chela, the latter being found parallel to the axis of
the body; they closely resemble the chelicerae of Limulus. The
remaining five pairs of appendages are found at the sides of the
elongate mouth, and in all these the gnathobases of the coxae are
provided with teeth at their inner margins and were able to function
in mastication, whilst the distal part of each appendage served as an
organ of locomotion. The posterior part of each coxa is plate-like and
is covered (except in the case of the sixth appendage) by the coxa of
the next appendage behind. A small process or “epicoxite” is found at
the posterior end of the toothed part of the coxae of the second,
third, fourth, and fifth pairs of appendages. The second appendage
consists of seven joints, whilst the remaining four consist of eight
joints; none of these appendages end in chelae. The second, third,[232]
and fourth pairs of appendages are similar to one another in
structure, but become successively larger from before backwards.
These three pairs are directed radially outwards; each consists of
short joints tapering to the end of the limb, and bearing spines at the
sides and on the under surface, and also a spine at the end of the last
joint.
Fig. 162.—Eurypterus fischeri, Eichw. Upper Silurian, Rootziküll,
Oesel. Restoration of ventral surface; 1–6, appendages of
prosoma; m, metastoma. Immediately posterior to the metastoma
is the “median process” of the genital operculum. (After Holm.)
 The fifth appendage is longer than the fourth and is directed
backwards; its second and third joints are short and ring-like; the
others (fourth to eighth) are long and similar to one another, each
being of uniform width throughout; the last joint is produced into a
spine on each side, and between these two is the movable end-spine;
the other joints do not bear long spines as is the case in the three
preceding pairs of appendages.
The sixth appendage is much larger and stronger than the others,
and like the fifth, is without long spines. The coxa is large and
quadrate; the second and third joints are short, like those of the fifth
appendage; the fourth, fifth, and sixth joints are longer and more or
less bell-shaped; the seventh and eighth joints are much larger than
the others and are flattened.
The metastoma (Fig. 162, m) is an oval plate immediately behind
the mouth; it covers the inner parts of the coxae of the sixth pair of
appendages, and represents the chilaria of Limulus. But, unlike the
latter, it is not a paired structure; nevertheless the presence of a
longitudinal groove on its anterior part renders probable the view
that it is derived from a paired organ.[233] The front margin of the
metastoma is indented and toothed. On its inner side in front is a
transverse plate, the endostoma, which is not seen from the exterior,
since the front margin of the metastoma extends a little beyond it.
Behind the prosoma are twelve free segments, of which the first six
form the mesosoma (Fig. 161, 7–12). The tergum on the dorsal
surface of each segment is broad and short, the middle part being
slightly convex and the lateral parts slightly concave; the external
margin is bent under, thus forming a narrow rim on the ventral
surface. The tergum of each segment overlaps the one next behind.
The segments increase in breadth slightly up to the fourth segment,
posterior to which they gradually become narrower.
On the ventral surface the segments of the mesosoma bear pairs of
plate-like appendages, each of which overlaps the one behind like the
tiles on a roof. On the posterior (or inner) surfaces of these
appendages are found the lamellar branchiae, which are oval in
outline (Fig. 165, d). Between the two appendages of the first pair is a
median process which is genital in function; this pair are larger than
the other appendages, and cover both first and second segments, the
latter being without any appendages, and they represent the genital