Recent Trends in - leseprobe.buch.de fileMay 3, 2012 10:41 World Scientiﬁc Review Volume - 9in x...

Recent Trends in Surface and Colloid

Science

Statistical Science and Interdisciplinary Research

Series Editor: Sankar K. Pal (Indian Statistical Institute)

Description:

In conjunction with the Platinum Jubilee celebrations of the Indian Statistical

Institute, a series of books will be produced to cover various topics, such as

Statistics and Mathematics, Computer Science, Machine Intelligence, Econometrics,

other Physical Sciences, and Social and Natural Sciences. This series of edited

volumes in the mentioned disciplines culminate mostly out of significant events —

conferences, workshops and lectures — held at the ten branches and centers of

ISI to commemorate the long history of the institute.

Vol. 4 Advances in Multivariate Statistical Methods

edited by A. SenGupta (Indian Statistical Institute, India)

Vol. 5 New and Enduring Themes in Development Economics

edited by B. Dutta, T. Ray & E. Somanathan

(Indian Statistical Institute, India)

Vol. 6 Modeling, Computation and Optimization

edited by S. K. Neogy, A. K. Das and R. B. Bapat


Vol. 7 Perspectives in Mathematical Sciences I: Probability and Statistics

edited by N. S. N. Sastry, T. S. S. R. K. Rao, M. Delampady and

B. Rajeev (Indian Statistical Institute, India)

Vol. 8 Perspectives in Mathematical Sciences II: Pure Mathematics

edited by N. S. N. Sastry, T. S. S. R. K. Rao, M. Delampady and

B. Rajeev (Indian Statistical Institute, India)

Vol. 9 Recent Developments in Theoretical Physics

edited by S. Ghosh and G. Kar (Indian Statistical Institute, India)

Vol. 10 Multimedia Information Extraction and Digital Heritage Preservation

edited by U. M. Munshi (Indian Institute of Public Administration,

India) & B. B. Chaudhuri (Indian Statistical Institute, India)

Vol. 11 Machine Interpretation of Patterns: Image Analysis and Data Mining

edited by R. K. De, D. P. Mandal and A. Ghosh


Vol. 12 Recent Trends in Surface and Colloid Science

edited by Bidyut K. Paul (Indian Statistical Institute, India)

Rhaimie - Recent Trends in Surface.pmd 5/3/2012, 4:13 PM1

N E W J E R S E Y • L O N D O N • S I N G A P O R E • B E I J I N G • S H A N G H A I • H O N G K O N G • TA I P E I • C H E N N A I

World Scientific

Platinum Jubilee Series

Editor

Bidyut K. PaulIndian Statistical Institute, India

Guest Editor

Satya P. MoulikCentre for Surface Science, India

Series Editor: Sankar K. Pal

Statistical Science and Interdisciplinary Research — Vol. 12

Recent Trends in Surface and Colloid

Science

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

For photocopying of material in this volume, please pay a copying fee through the Copyright

Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to

photocopy is not required from the publisher.

ISBN-13 978-981-4299-41-1

ISBN-10 981-4299-41-3

All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means,

electronic or mechanical, including photocopying, recording or any information storage and retrieval

system now known or to be invented, without written permission from the Publisher.

Copyright © 2012 by World Scientific Publishing Co. Pte. Ltd.

Published by

World Scientific Publishing Co. Pte. Ltd.

5 Toh Tuck Link, Singapore 596224

USA office: 27 Warren Street, Suite 401-402, Hackensack, NJ 07601

UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE

Printed in Singapore.

RECENT TRENDS IN SURFACE AND COLLOID SCIENCE

Statistical Science and Interdisciplinary Research — Vol. 12

Rhaimie - Recent Trends in Surface.pmd 5/3/2012, 4:13 PM2

May 3, 2012 10:41 World Scientific Review Volume - 9in x 6in 00˙bidyutmaster/Chp. 0

Foreword

The Indian Statistical Institute (ISI) was established on 17th December,

1931 by a great visionary Professor Prasanta Chandra Mahalanobis to pro-

mote research in the theory and applications of statistics as a new scientific

discipline in India. In 1959, Pandit Jawaharlal Nehru, the then Prime Min-

ister of India introduced the ISI Act in parliament and designated it as an

Institution of National Importance because of its remarkable achievements

in statistical work as well as its contribution to economic planning.

Today, the Indian Statistical Institute occupies a prestigious position

in the academic firmament. It has been a haven for bright and talented

academics working in a number of disciplines. Its research faculty has done

India proud in the arenas of Statistics, Mathematics, Economics, Computer

Science, among others. Over eighty years, it has grown into a massive

banyan tree, like the institute emblem. The Institute now serves the na-

tion as a unified and monolithic organization from different places, namely

Kolkata, the headquarters, Delhi, Bangalore, Chennai and Tezpur four cen-

ters, a network of five SQC-OR Units located at Mumbai, Pune, Baroda,

Hyderabad and Coimbatore, and a branch (field station) at Giridih.

The platinum jubilee celebrations of ISI have been launched by Hon-

orable Prime Minister Dr. Manmohan Singh on December 24, 2006, and

the Government of India has declared 29th June as the “Statistics Day” to

commemorate the birthday of Professor Mahalanobis nationally.

ProfessorMahalanobis, was a great believer in interdisciplinary research,

because he thought that this will promote the development of not only

Statistics, but also the other natural and social sciences. To promote in-

terdisciplinary research, major strides were made in the areas of computer

science, statistical quality control, economics, biological and social sciences,

physical and earth sciences.

The Institute’s motto of ‘unity in diversity’ has been the guiding prin-

ciple of all its activities since its inception. It highlights the unifying role

of statistics in relation to various scientific activities.

v


vi Foreword

In tune with this hallowed tradition, a comprehensive academic pro-

gramme, involving Nobel Laureates, Fellows of the Royal Society, and other

dignitaries, has been implemented throughout the Platinum Jubilee year,

highlighting the emerging areas of ongoing frontline research in its various

scientific divisions, centres, and outlying units. It includes internatinal and

national-level seminars, symposia, conferences and workshops, as well as

series of special lectures. As an outcome of these events, the Institute is

bringing out a series of comprehensive volumes in different subjects under

the title Statistical Science and Interdisciplinary Research, published by

World Scientific Publishing, Singapore.

The present volume titled Recent Trends in Surface and Colloid Sci-

ence is the twelfth one in the series. It has twenty two chapters, written

by eminent scintists from different parts of the world, dealing with various

aspects of the subjects, for example, modern concept on colloidal stabil-

ity, mixed micellar and mixed protein-surfactant systems, microemulsion

and related systems with special reference to fundamental phenomena and

wide applications in nanoscience and nanotechnology, drug delivery, reac-

tion medium, biocatalysis and enzymatic reactions, photochemistry. The

volume provides a state-of-the-art in significant developments and advances

that have been made in the field of surface and colloid science over the past

decades in a comprehensive manner.

The volume will serve as a fountain-head for further exciting develop-

ments in this field, and will be useful to students, researchers and practi-

tioners.

Thanks to the contributors for their excellent research contributions and

to volume editors, Dr. Bidyut K. Paul and Professor S.P. Moulik (guest

editor) for their sincere effort in bringing out the volume nicely. Thanks

are also due to World Scientific for their initiative in publishing the series

and being a part of the Platinum Jubilee endeavor of the Institute.

February, 2012

Kolkata Sankar K. Pal

Series Editor and

Former Director, ISI


Preface

Colloid and surface science is a fascinating interdisciplinary field in sci-

ence, where modern development and knowledge of physics, chemistry, bi-

ology, material science, pharmacy, engineering etc. have been extensively

exploited and adopted, with ample scope of fundamental research and ex-

tensive potentials for applications. The progress of research in this impor-

tant field has been remarkable throughout the world during the last four

decades, and it has developed for the benefit of the society and people all

over the world. This volume contains extended version of some articles

presented at International Symposium on Recent Trends in Surface and

Colloid Science (ISSCS), in addition to the contributions made by some of

the members of the International Advisory Committee of this International

Symposium. With a summary of recent advances in this multifaceted field,

the chapters of this volume provide critical information to enrich the liter-

ature by presenting the basic concepts of organized systems in relation to

their practical significance. It would be a potential addition to the litera-

ture and also should be of interest to beginners as well as experts working

in the field of colloid and surface science.

In the first chapter, Kunz and Bostrom have proposed an efficient but

physically well-based modified DLVO theory considering specific ion effects

around water profiles near colloidal surfaces and molecular dynamics sim-

ulation. The new appraoch is expected to be useful to explain specific

ion adsorption on electrode surfaces. In the second chapter, electrokinetic

theories in suspensions of soft particles (particle surfaces containing ion-

penetrable polyelectrolyte layers) have been critically reviewed by Ohshima.

In the reviewing process, electrokinetic phenomena viz., electrophoresis,

electroosmosis, streaming potential and sedimentation potential have been

summarized. In the subsequent chapter, phase diagram analysis of an evap-

orating emulsion comprising water, linalool and a commercial surfactant,

Laureuth 4 has been presented by Friberg and Aikens. Based on an equi-

librium between the vapor and emulsion, variations in the fractions of com-

vii


viii Preface

pounds and phases have been determined. The process has been found to

be influenced by the relative humidity. In Chapter 4, Thaker, Sengupta

and Sengupta discussed on the stability of an emulsion system containing

NaOH with aging. The presence of NaOH has been found to influence both

viscosity and salinity of the system. Increased internal phase volume has

affected the viscosity but not the emulsion salinity. Aging has influenced

the droplet size distribution. In Chapter 5, the work of Moulik and Mitra

entails enthalpy of micellization determined by van’t Hoff procedure and by

direct calorimetry on a number of ionic and nonionic surfactant systems.

The results do not agree, the discripencies are more for ionic systems than

nonionics. This anomaly arises because of the basic differences between

the two evaluation methods; while the van’t Hoff procedure is a differen-

tial approach, the calorimetry is an integral approach. The first method

evaluates only the enthalpy of micellization whereas the second measures

the total heat produced in the system, micellization or otherwise. In the

next chapter, the salt free binary cataionic system of hexadecyltrimethy-

lammonium octylsulfonate has evidenced a miscibility gap for the formal

lamellar phase, as presented by Silva, Marques and Olsson. Coexistance

of a swollen and a collapsed lamellar phase has been observed in a two-

phase region with linear swelling in each phase. Increase of temperature

has caused a vesicle-to-micelle transition of the system. A theoretical cell

model has been proposed to provide insight to the observed miscibility gap

in the system. In Chapter 7, Miller and coworkers have proposed models for

quantitative analysis of the adsorption layer formed from mixed solutions

comprising proteins and surfactants for understanding the hydrodynamics,

adsorption kinetics and dilational rheology. The procedure used was drop

shape analysis using a capillary pressure tensiometer. The findings are

encouraging and needs analysis by way of improved theories and better ex-

perimentations. Factors that affect mixed aggregation of surfactants have

been summarized by Schulz in Chapter 8. The interaction parameter, β in

regular solution theory has been separated into βph (interaction between

polar head groups) and βcore (interaction of amphiphile tails in the micellar

core); thus β = βph + βcore. The role of various factors like differences in

chain lengths, steric constraints, presence of double bond on the β has been

also discussed. In Chapter 9 Chanda, Singh and Ismail have focused on the

micellization of the surfactant AOT in the presence of both sodium chloride

(NaCl) and sodium salicylate (NaSl). The counter-ion binding in 0.02 mol

dm−3 NaCl has been found to increase two fold which did not occur in the

presence of NaSl. It is considered that at 0.02 mol dm−3 NaCl both the


Preface ix

aggregation number and micellar polarity of AOT suddenly change. The

shape of the micelle has also been expected to change. In the subsequent

chapter, the results on clouding and solubilization of the amphiphilic drug,

promazine hydrochloride in presence of additives, viz., alkanols, sugars and

amino acids have been presented by Kabir-Ud-Din and coworkers. The re-

sults have been analyzed in the light of drug aggregation and modification

of the physico-chemistry of the medium by the additive effects. The in-

fluence of the amide urea on surfactant self-assembly in solution has been

reviewed by Souza, Alvarez and Politi in Chapter 11. An attempt has been

made to rationalize this effect in the light of electrostatic interaction as well

as hydrophobic repulsion wherein the increase in the dielectric permittivity

by urea has a role to play. In Chapter 12, Romsted presented a model for

the role of ion-pair formation at the micellar interface by way of counter-

ion binding in the sphere-to-rod transition of ionic micelles and potentially

other structural transitions of different types of association colloids. The

merits and demerits of the model has been presented in view of its future

applications. The review article of Xenakis (Chapter 13) describes uses

of microemulsions and related systems to immobilize lipase and causing

favourable catalytic esterification of fatty acids. The catalytic activity of

lipase remains effective when the external organic solvent is replaced by

supercritical CO2. The stability of lipase and its reusuability have been

assessed and presented. The review article of Gupta comprises an overview

of different types of nanoscale colloidal drug delivery systems in Chapter

14. The advantages and disadvantages of these systems have been high-

lighted with relevant examples. Nanoscale self-assemly of gelatin molecules

and clusters spread on hydrophilic surface has been discussed by Bohi-

dar and Gupta using AFM technique in Chapter 15. The nano-structured

assemblies formed compact fractal objects resulting from a diffusion lim-

ited aggregation process. Koetz and coworkers have reported on water

soluble polymers which can modify w/o microemulsions and used as tem-

plates for the synthesis of nanoparticles. The system poly (diallydimethyl

ammonium chloride, PDADMAC) incorporated into inverse microemulsion

(water / toluene / heptanol / sulfobetaine) droplets can be successfully used

as template for the formation of spherical BaSO4 nanoparticles in Chapter

16. Addition of nonionic polymer, polythylene glycol in water / toluene /

SDS / polyampholytes, can produce nanorods of BaSO4 in the template.

Uptake of nickel oxide in water / AOT / isoctane w/o microemulsion has

been discussed by Nassar and Husein in Chapter 17. Nanoparticle uptake

increased with increasing AOT and precusor salt concentration. Maximum


x Preface

uptake occured at water to AOT mole ratio, R = 3.0. The particle size

increased with increasing [AOT] and [precursor salt] due to intermicellar

nucleation and growth. Synthesis and size dependent photocatalytic be-

havior of luminescent semiconductor quantum dots, viz., CdS and CdTe

have been presented and discussed in Chapter 18 by Saha and coworkers.

The methods of preparation and catalytic efficacies of the materials have

been presented with physicochemical justifications. Possible development

of fluorescence-based nonoparticle sensors has been discussed. The arti-

cle of Das, Sarkar and Chattopadhyay deals with a fluorometric strategy

to enhance the efficiency of a quencnching-based cationic fluorosensor for

Cu2+ by several order of magnitude in Chapter 19. This strategy is con-

sidered to be applicable for physiochemical fluids for detecting trace metal

ions like Cu2+. According to Mejuto and coworkers, the nanodroplets in

microemulsion can act as scalable microreactors in which synthesis of mate-

rials and dynamics of reactions, can be studied (Chapter 20). This chapter

deals with pseudophase approach to study the transnitrosation reactions

in microemulsion media. The role of interface between water and oil has

been proposed to be vital. In Chapter 21, Sinha and Tarafdar have focused

on the introduction of electric field for the formation of gel of synthetic

clay, laponite. Rapid gel formation at the anode has been observed, which

is slow in the absence of the electric field. The structure and properties

of these gels are reported to be different in the two conditions. The final

chapter by (Nandi) Ganguly and coworkers describes molecular association

(dimerization etc.) of cinnamic acid molecules that exists in the crystalline

form by intermolecular hydrogen bonding. Positron annihilation spectro-

scopic and DSC studies with varying temperature, have been conducted to

understand the changes in the molecular structure in the crystalline phase.

At the end, our pleasant task of thanking those who helped in many

and different ways to bring this volume to fruition. First of all we express

our heart felt gratitude towards the contributors, who are internationally

renowned researchers, of this volume. In total, 62 individuals from 11

countries contributed to this volume. We are also grateful to members

of the organizing committee for their constant encouragement. Our special

thanks are due to the reviewers for their valuable comments, as peer-review

is a requirement to preserve the highest standard of publication. We also

express our gratitude to the Indian Statistical Institute Platinum Jubilee

Core Committee and the series editor for giving us opportunity to edit this

volume. Finally, the help of Mr. Dibyendu Bose to prepare the camera-

ready version is sincerely acknowledged with thanks and appreciation. Our


Preface xi

appreciation goes to both Rhaimie B. Wahap and Hwee Yun Tan for their

excellent job done on the production of this edited volume.

Bidyut Kumar Paul

Editor

Satya Priya Moulik

Guest Editor


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Contents

Foreword v

Preface vii

1. Specific Ion Effects in Colloid and Surface Science:

A Modified DLVO Approach 1

Werner Kunz and Mathias Bostrom

2. Electrokinetics in a Suspension of Soft Particles 11

Hiroyuki Ohshima

3. Relative Humidity and Evaporation of a Simple Fragrance

Emulsion 25

Stig E. Friberg and Patricia A. Aikens

4. Aging and Stability of W/O Emulsions with NaOH in

Aqueous Phase 39

Rujuta Thaker, Bina Sengupta and Ranjan Sengupta

5. Energetics of Micelle Formation: Non Agreement between

the Enthalpy Change Measured by the Direct Method of

Calorimetry and the Indirect Method of van’t Hoff 51

Satya P. Moulik and Debolina Mitra

6. Unusual Phase Behavior in a Two-Component System 69

Bruno F.B. Silva, Eduardo F. Marques and Ulf Olsson

xiii


xiv Contents

7. Mixed Proteins/Surfactants Interfacial Layers as Studied by

Drop Shape Analysis and Capillary Pressure Tensiometry 85

V.S. Alahverdjieva, D.O. Grigoriev, A. Javadi, Cs. Kotsmar,

J. Kragel, R. Miller, V. Pradines and A.V. Makievski

8. Factors Affecting Mixed Aggregation 105

Pablo C. Schulz

9. Micellization Characteristics of Sodium Dioctylsulfosuccinate:

An Overview 131

S. Chanda, O.G. Singh and K. Ismail

10. Phase Separation Study of Surface-Active Drug Promazine

Hydrochloride in Absence and Presence of Organic Additives 143

Kabir-ud-Din, Mohammed D.A. Al Ahmadi,

Andleeb Z. Naqvi and Mohd. Akram

11. Effect of Urea on Surfactant Aggregates: A Comprehensive

Review 155

Silvia M.B. Souza, E.B. Alvarez and Mario J. Politi

12. Specific Ion-Pair/Hydration Model for the Sphere-To-Rod

Transitions of Aqueous Cationic Micelles. The Evidence from

Chemical Trapping 171

Laurence S. Romsted

13. Biocatalytic Studies in Microemulsions and Related Systems 199

Aristotelis Xenakis

14. Colloidal Dispersions for Drug Delivery 207

Syamasri Gupta

15. Nanoscale Self-Organization of Polyampholytes 231

H.B. Bohidar and Amarnath Gupta

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