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Bubble and Foam Chemistry
This indispensable guide will equip you with a thorough understanding of the complete
field of bubbles and foaming chemistry. Assuming only basic theoretical background
knowledge, the book provides you with

• a straightforward introduction to the principles and properties of bubbles, foams and

foaming surfactants underpinning the key ideas about why foaming occurs, how it can
be avoided and how different degrees of antifoaming can be achieved;
• the latest test methods, including laboratory and industry-developed techniques;
• details on a range of differents kinds of foams, from wet detergents and food foams to
polymeric, material and metal foams which connect theory with real-world applica-
tions and recent developments in foam research.
Combining academic and industrial viewpoints, this book is the definitive stand-alone
resource for researchers, students and industrialists working on foam technology,
colloidal systems in the field of chemical engineering, fluid mechanics, physical
chemistry and applied physics.

Robert J. Pugh is a Visiting Professor at Nottingham Trent University. He is an active

member of the foams community and has over 30 years experience in industry and
university, having worked as a foam specialist for Dow Chemical and Unilever
Research. He has also worked as a Professor at the Institute for Surface Chemistry,
Stockholm, and at Luleå University, Sweden, and has acted as a consultant for Akzo
Nobel, Nestlé, GlaxoSmithKline, Procter and Gamble, and Arizona Chemicals.
Professor Pugh has co-authored and edited two previous books in the field of surface
and colloid science and authored several highly cited review papers on the topic of foams
and foaming.
Bubble and Foam Chemistry
ROBERT J. PUGH
Nottingham Trent University
University Printing House, Cambridge CB2 8BS, United Kingdom

Cambridge University Press is part of the University of Cambridge.

It furthers the University’s mission by disseminating knowledge in the pursuit of
education, learning and research at the highest international levels of excellence.

www.cambridge.org
Information on this title: www.cambridge.org/9781107090576
© Robert J. Pugh 2016
This publication is in copyright. Subject to statutory exception
and to the provisions of relevant collective licensing agreements,
no reproduction of any part may take place without the written
permission of Cambridge University Press.
First published 2016
Printed in the United Kingdom by TJ International Ltd. Padstow Cornwall
A catalogue record for this publication is available from the British Library
Library of Congress Cataloging-in-Publication Data
Pugh, Robert J., 1942–
Bubble and foam chemistry / Robert J. Pugh, Nottingham Trent University.
Cambridge : Cambridge University Press, [2016] | Includes bibliographical
references and index.
LCCN 2016023274 | ISBN 9781107090576 (alk. paper)
LCSH: Surface chemistry. | Suspensions (Chemistry) | Foam. | Bubbles.
LCC QD506 .P844 2016 | DDC 541/.33–dc23
LC record available at http://lccn.loc.gov/2016023274
ISBN 978-1-107-09057-6 Hardback
Cambridge University Press has no responsibility for the persistence or accuracy of
URLs for external or third-party internet websites referred to in this publication,
and does not guarantee that any content on such websites is, or will remain,
accurate or appropriate.
 Contents

Preface page xiii

Acknowledgments xvi
List of symbols xvii

1 Basic principles and concepts 1

1.1 Introduction 1
1.2 The physics and chemistry of foams and foaming 7
1.3 The wetness and dryness of foams 9
1.4 Capillary pressure and the Laplace–Young equation 11
1.5 Plateau rules and pentagonal dodecahedral structures 12
1.6 Foam structures produced from bubbles with narrow size
distributions 16
1.7 Foam structures produced from bubbles with wide size distributions 21
1.8 Surface-active agents are needed to stabilize bubbles and wet foams 23
1.8.1 The adsorption of chemical surfactants at the air/water
interface 23
1.8.2 The purity of chemical surfactants in foaming 27
1.8.3 Other types of surface-active materials 28
1.9 Surface tension and surface energy 29
1.10 Gibbs adsorption and Gibbs elasticity 31
1.11 Methods of measuring surface tension 34
1.11.1 Maximum bubble pressure technique 38
1.11.2 Overflow cylinder technique 38
1.11.3 Oscillating jet technique 41
1.12 Foamability and foam stability 41
1.12.1 Surface tension, foamability and foam stability 45
1.12.2 Combining foamability with foam stability 47
1.13 Transition from wet to dry foams 48

2 The nature and properties of foaming surfactants 54

2.1 The formation of self-assemblies from pre-micellar surfactant species 54
2.1.1 Self-association in weakly hydrolysable soaps and fatty acids 56
2.1.2 Solubility and the Krafft point 59
vi Contents

2.2 Geometric packing of surfactant molecules in the interface and the critical
packing parameter 60
2.3 Phase behavior of more concentrated surfactant formulations 62
2.4 The influence of the Critical Packing Parameter on foaming 63
2.5 The influence of surfactant solubility on foaming 64
2.6 Anionic surfactants 64
2.7 Nonionic surfactants 65
2.8 Weak hydrolysable fatty acids 66
2.9 Mixed surfactants 68
2.10 The influence of the CMC on foaming 69
2.11 Foaming above the CMC: the influence of the stability of the micellar
self-assemblies 71
2.12 Influence of structure on foaming and low-foaming surfactants 75
2.13 The application of the HLB (hydrophile–lipophile) balance concept to
foaming 78
2.14 Temperature effects on surface tension and foaming 80

3 Soap bubbles and thin films 84

3.1 Introduction and early studies 84
3.2 20th-century studies on thin liquid films 86
3.3 Experimental techniques for investigating free horizontal circular liquid
films 87
3.3.1 The conventional Scheludko/Exerowa thin film balance 87
3.3.2 The porous plug film holder to measure disjoining isotherms
and surface forces in thin films 89
3.3.3 The bike wheel microcell film holder 90
3.3.4 The Nikolov/Wasan film balance for measuring drainage and film
thickness of curved foam films 91
3.4 Drainage of horizontal thin films 92
3.5 Drainage of vertical thin films 96
3.6 Disjoining pressure isotherms obtained from porous plug experiments 99
3.7 Intermolecular forces are the reason that thin films are stable 99
3.8 The physical chemistry of black films 104
3.9 Rupture mechanism of free microscopic horizontal foam films 105
3.10 Rupture of films between bubbles under dynamic conditions 106
3.11 Importance of fundamental studies on foam films 107

4 Processes in foaming 112

4.1 Overview of processes 112
4.2 Ascent of bubbles in liquids 113
4.2.1 Influence of nonionic surfactants 115
4.2.2 Influence of ionic surfactant 118
4.2.3 Bubbles bouncing from the interface 119
 Contents vii

4.2.4 Influence of impact velocity at the interface 120

4.2.5 The detection of surface-active contaminants in water 122
4.3 Drainage of foams 122
4.3.1 Forced, free and pulsed drainage 124
4.3.1.1 Forced drainage 124
4.3.1.2 Free drainage 127
4.3.1.3 Pulsed drainage 127
4.3.2 Influence on interfacial properties 127
4.3.3 Experimental approaches 128
4.3.4 Influence of foam film type 128
4.4 Disproportionation (Ostwald ripening) 130
4.4.1 Experimental methods with foams 132
4.4.2 Experimental methods with thin films 133
4.4.3 Models and theories 134
4.4.3.1 Diffusion theory 135
4.4.3.2 Energy barriers (nucleation theory and fluctuation of
holes) 136
4.4.3.3 Freely standing film 137
4.4.3.4 Density fluctuations and accessible area 138
4.4.4 Experimental results 138
4.5 Coupling disproportionation with drainage 144
4.6 Depletion of surfactant from solution 146
4.7 Humidity and evaporation 147

5 Generation of bubbles and foams 155

5.1 Introduction 155
5.2 The adsorption of surfactant on the freshly generated bubbles 155
5.3 Bubble size and distribution 156
5.4 Overview of foam generation techniques 158
5.5 Mechanical methods 159
5.5.1 High-intensity agitation (cavitation) 160
5.5.2 Rotary stirring in food processing 161
5.5.3 Rotary stirring in mineral processing 165
5.5.4 Shaking or successive flipping 168
5.5.5 Pouring and plunging jet methods 170
5.5.5.1 Static plunging jet 170
5.5.5.2 Continuous plunging jet 171
5.6 Growing bubbles from single orifices, frits and gas injection 173
5.6.1 Detachment of a bubble from single orifices 174
5.6.2 Growing bubbles using frits 176
5.6.3 Co-injection 177
5.6.4 Monodispersed bubbles and microfluidic foams 177
5.7 Nucleation of gas bubbles 180
viii Contents

5.7.1 Nucleation of bubbles in champagne and other beverages 181

5.7.2 Dissolved air and column flotation 184
5.8 In situ generation of foams by chemical reactions 186
5.9 Gas generation by electrolysis 188

6 Coalescence of bubbles in surfactant solutions 194

6.1 The formation, break-up and coalescence of bubbles in surfactant
solutions 194
6.2 The role of surface tension gradients in coalescence 196
6.3 Relationship between elasticity and critical transition
concentration Ct 198
6.4 Experimental studies on bubble coalescence 199
6.4.1 Bubble swarm and single bubbles 199
6.4.2 2D Bubble rafts 199
6.4.3 Coalescence at the moment of bubble creation 200
6.4.4 Freely rising single bubble using a laser detector 202
6.4.5 Growing bubbles from adjacent nozzles 205
6.5 Coalescence in aqueous solution of electrolytes 209
6.6 Influence of bubble approach velocity on bubble coalescence 212
6.7 Influence of temperature on coalescence 215

7 The stability/instability of bubbles and foams 220

7.1 Overview 220
7.2 Classification of the stability of foams 222
7.2.1 Unstable (transient) foams 222
7.2.2 Metastable foams 223
7.2.3 High-stability foams 223
7.2.4 Ultrastable foams 223
7.3 Reversing the stability of foams 223
7.3.1 pH-responsive foams 224
7.3.2 Temperature-responsive foams 225
7.3.3 Gas-responsive foams 226
7.4 Gibbs–Marangoni effect 227
7.5 Interfacial rheology 227
7.5.1 Dilational surface viscoelasticity 229
7.5.2 Theories and models 231
7.5.3 Experimental techniques for measurement of elasticity
and surface viscosity 232
7.5.4 Oscillating bubble methods 233
7.5.5 Experimental studies of elasticity and surface viscosity 235
7.6 Stability control agents 236
7.6.1 Single surfactant systems, pH, electrolyte and specific ion
effects 237
 Contents ix

7.6.2 Mixtures of surfactants, foam builders/boosters 238

7.6.3 Polymer/surfactant mixtures 240
7.6.4 Condensed shells 244
7.6.5 Nanopatterning 244
7.6.6 Hydrophobins 244
7.6.7 Control of gas diffusion 246
7.6.7.1 Gas type and foam type 247
7.7 Interfacial rheology and gas permeability 249
7.8 Stability by increase in bulk viscosity 252
7.9 Stability control in aerated food systems 252
7.10 Stratification 253
7.10.1 Hole formation and the diffusion osmotic mechanism 254
7.10.2 Reversible stratification behavior in nonionic surfactants 257
7.10.3 Stratification in charged surfactant systems 258
7.10.4 Stratification in polydispersed systems 259
7.11 Stabilization by liquid crystals 261
7.12 Stabilization by emulsion and pseudo-emulsion films 263

8 Particle-stabilized foams 269

8.1 Introduction 269
8.2 History of particle-stabilized foam systems 271
8.3 Established processes 271
8.4 Fundamentals of collision, contact angles, attachment/detachment 273
8.5 Measurement of attachment time between bubble and particle 275
8.6 Relationship between attachment force and contact angle 275
8.7 Detachment of particles from bubbles 277
8.8 Surface tension of films of attached particles 278
8.9 Interactions between neighboring particles attached to the interface 280
8.10 Key parameters influencing the interactions between bubbles and
particles 283
8.11 Steric barriers 284
8.12 Experimental studies relating contact angle and wetting on particle
attachment and stability 286
8.13 Janus particles 289
8.14 The influence of concentration, surface charge and state of
agglomeration 290
8.15 Simple models of interactions between droplets (bubbles) coated with
particles 291
8.16 Models of packing, agglomeration and bridging of particles 293
8.17 Particle/surfactant and particle/polymer mixtures 294
8.17.1 Surface tension measurements of particle/surfactant
mixture 296
8.17.2 Gel films 297
x Contents

8.18 Diffusive disproportionation and shrinkage of particle-laden foams 298

8.19 Drainage with film containing particle/surfactant mixtures 300
8.20 Super particle stabilized foams generated by a magnetic field 302
8.21 Preparation of stabilized monodispersed bubbles with particles 302

9 Foaming in non-aqueous liquids 307

9.1 Introduction 307
9.2 Hydrocarbon-type surfactants 308
9.3 Polymethylsiloxane and fluoroalkyl-type surfactants 309
9.4 Phase separation from partially immiscible liquids 312
9.5 Lamellar liquid crystals, surfactant solid particles and lipid phases 314
9.6 Bulk viscosity 322
9.7 Inorganic electrolytes in non-aqueous liquids 322
9.8 Interfacial charge in non-aqueous systems 324
9.9 Defoaming in non-aqueous solutions 325
9.10 Thin film studies with non-aqueous and ionic liquids 325

10 Antifoaming and defoaming 331

10.1 Background and types of antifoamers and defoamers 331
10.2 Physico-chemical mechanisms 334
10.2.1 Droplets and oil lenses: spreading coefficient (Sc), entry
coefficient (Ec) and bridging coefficient (Bc) 334
10.2.2 Emulsified droplets and pseudo-emulsion films 338
10.2.3 Effects of disjoining pressure on the stability of the
pseudo-emulsion film 338
10.3 Experimental studies 340
10.4 Surface tension gradients, viscosity and drainage 341
10.5 Superspreading 342
10.6 Influence of the interfacial and micellar aggregates 342
10.7 Particles 344
10.8 Cloud-point antifoamer: block copolymers 347
10.9 Fatty alcohol antifoamers: melting point, gel layers and droplet
rigidity 347
10.10 Precipitation effects 349
10.11 Mixtures of particles and oils 351
10.12 Fast and slow antifoamers and the film trapping technique 353
10.13 Critical entry pressure for foam film rupture 356
10.14 Influence of the hydrophobicity of solid particles on Ec 358
10.15 Influence of the pre-spread oil layer on Ec 360
10.16 Ageing effects with chemical antifoamers 360
10.17 Physical methods of defoaming 362
10.17.1 Ultrasonics 363
 Contents xi

10.17.2 Suppression of foam by the adjustment of the vessel

wettability 367

11 Bubble size measurements and foam test methods 372

11.1 Introduction 372
11.2 Bubble size measurements 374
11.2.1 Direct 2D imaging 374
11.2.2 Optical fiber probe analysis 376
11.2.3 X-ray tomographic imaging 378
11.2.4 Nuclear magnetic resonance imaging and terahertz
spectroscopy 380
11.2.5 Ultrasonic imaging 380
11.2.6 Multiple light scattering and back scattering 381
11.3 Bubbly liquids and foam test methods 382
11.3.1 Whipping, shake tests and the Bartsch test method 383
11.3.2 Rotor mixer tests 383
11.3.3 Ross–Miles (pour test) 383
11.3.4 Bikerman test (sparging in a cylindrical column) 385
11.4 Test methods under controlled pressure 388
11.4.1 Time of deviation (tdev) and time of transition (ttr) 388
11.4.2 Head space and pressure drop test methods 391
11.5 Electrical conductivity test method (the Foam Scan apparatus) 392
11.6 Measurement of bubbles lifetimes and free microscopic films 394
11.7 Measurement of foam stability in the presence of antifoams/
defoamers 397
11.8 Measurement of antifoaming/defoamer performance in washing
machines 399
11.9 Comparison of different laboratory foaming test methods 401

12 Bubble and foam chemistry – new areas of foam research 405

12.1 Antibubbles 405
12.2 Foaming research under microgravity 408
12.3 Particle-stabilized foams at high temperatures: metal and material
foams 410
12.4 Foams in nature and bio-surfactants 413

Index 420
Preface

The aim of this book is to provide a comprehensive, well-structured insight into the
physical chemistry of liquid foams which can be used by both academics and
industrialists. Liquid foams may occur naturally or by design and may be desirable
or undesirable. Generally, there is a multitude of complex causes of foaming and
antifoaming and the text is structured to give clarity to the field by providing an up-to-
date, state-of-the-art guide explaining the chemistry of real foam systems. It is hoped
that the reader will achieve a reasonably clear understanding of why foaming occurs,
how it can be measured and how it can be prevented. As the use of foams spans
different disciplines, some introductory aspects of physics, chemical engineering and
material science of foams are included but this is relatively easy to follow. This book
is orientated toward the descriptive rather than the theoretical and contains many
diagrams. It is also a rich source of information and references, arranged in a way
which the reader should find useful and also provides an historical prospect to the area
of foams and foaming.
The most popular academic books dealing solely with foams include the classics
Foams by J. J. Bikerman (1973), published by Springer-Verlag, Berlin and The
Physics of Foams by D. Weaire and S. Hutzler (1999), published by Clarendon
Press, Oxford. Both of these books ran into several updated editions but considerable
advancements in the field have been made since their publication. Other early texts
are Foams and Biliquid Foams-Aphrons by F. Sebba (1987), published by Wiley and
the two books – Antifoaming (edited by P. Garrett, 1993) and Foams (edited by R. K.
Prud’homme and S. A. Kahn, 1996) – published in the Surfactant Science Series
(Marcel Dekker). These are fairly well-read books but are essentially a collection of
viewpoints which describe many varied aspects of foaming and antifoaming science.
Foam and Foam Films by D. Exerowa and P. M. Kriglyako (1997), published by
Elsevier in the Studies in Interfacial Science Series, has been well received but
presents a strongly fundamental text with the main emphasis on thin films. More
recently is the book Foam Engineering, edited by P. Stevenson (2012) and published
by Wiley, covers rheology, flow and foam processing and is aimed toward the
chemical engineering community. Another recent book, Foams Structure and
Dynamics (2013) edited by a group of French scientists and published by Oxford
University Press, was directed toward the Physics community.
There are many other books available but they are multi-authored, specialist texts
edited by engineers, chemists, chemical engineers or physicists. They usually include an
xiv Preface

ad hoc assortment of specialist research or review papers focused on foams or foaming

within specific areas. For example, an early book by Schraum (1994) covered the oil
industry and E. Dickenson and coworkers edited several books on the food industry
which included chapters on food foams. Another multi-authored book, Foamspex, came
out as a European Union project and covers the large-scale applications and modeling of
foam spreads and extinguishment aspects of firefighting foams. This was published by
SP Sweden (the Swedish National Testing and Research and Fire Technology Institutes)
in 2001. Other texts on polymer foam systems are more specialized, for example,
Polymer Foam Handbook, edited by N. J. Mills and published by Elsevier (2007) and
Handbook of Polymeric Foams and Foam Technology, edited by D. Klemper and
coworkers and published by Hanser (2004).
This book is a single-authored, comprehensive text which gives a current and
coherent picture of foam chemistry. The book will probably be of most interest to
senior undergraduate and graduate students of physical chemistry, chemical engineer-
ing, surface and colloid chemistry, life sciences and applied physics. It is also aimed at
scientists and engineers in industry who frequently encounter foams under practical
conditions. In these cases, the presence, absence and nature of foam can determine the
economic and technical success of the process. Although some prerequisite scientific
knowledge is expected from the reader, only the bachelor’s level in sciences is needed
to adequately understand the principles presented. In fact, the book could prove to be
of interest to less academic amateur scientists, for example, with interests in the
brewing of beer.
The book contains twelve chapters. Chapter 1 outlines the most important proper-
ties of foams and their uses in everyday situations. The physical and chemical aspects
of foams and foaming are reviewed and the main features of wet and dry foams are
described. Surface active agents and the relevant basic thermodynamics are also
introduced. Chapter 2 describes the nature and properties of chemical foaming
surfactants together with their role in stabilizing bubbles. Chapter 3 is an important
chapter from a fundamental viewpoint since it covers soap films, which are the basic
structural elements in foams, and it reviews the role of the intermolecular forces
which define the stability of thin films. Techniques for measurement of the stability
and draining of foam films are also discussed. In Chapter 4, an overview of the
different types of processes in foaming is presented. These include the ascent of
bubbles in liquids, the drainage of liquids through foams and the diffusion of gas
through the foam, humidity and evaporation. Chapter 5 covers the generation of
foams and includes a range of methods used both in laboratory and in industry. In
Chapter 6, the coalescence of bubbles and techniques for measuring the coalescence
process are described. Coalescence of bubbles in solutions of different types of
inorganic electrolytes is reviewed in light of recent experiments in which the bubble
approach speed is taken into consideration. Chapter 7 discusses the classification of
bubble and foam stability and the different types of stabilization mechanisms which
can operate. In addition, the various types of additives which can be used in stabiliza-
tion of foam systems are summarized.
 Preface xv

In Chapter 8, the historic background of particle stabilized foams is presented

together with their use in established processes such as deinking and flotation. The
role of contact angle, particle shape, charge, detachment forces, capillary pressure
and the influence of the formation of different types of particle networks is discussed.
Chapter 9 covers foaming in non-aqueous liquids, which is less commonly encoun-
tered in non-aqueous fluids than in water-based media, but it is an important topic to
consider. It occurs in a wide range of industrial processes – for example, during the
processing of crude oils, drilling fluids, lubricants, solvent (base cleaners), etc.
Chapter 10 covers defoaming and antifoaming. Problems are caused by foaming
throughout a range of industrial processes – for example, in the production and
processing of paper, pharmaceuticals, materials, textiles, coatings, crude oils, wash-
ing, leather, paints, adhesives, lubrication, fuels, heat transfer fluids, etc. and in the
processing of food and beverages such as sugar beet, orange and tomato juice, beer,
wine and mashed potatoes. The different types of antifoaming additives used to
prevent formation and destruction of foams are classified and also the physical
chemical mechanisms involved. Foam test methods are described in Chapter 11,
including both laboratory and industrially developed techniques. Finally, in Chapter
12, several new developments in the area of foam research are reviewed. This
includes the growth and stability of foams in microgravity and mechanisms involved
in the production of metal foams at high temperature, which have the potential to be
used in the automobile and aircraft industries. In addition, foaming in the environ-
ment is documented (natural waters, sea waters and polluted waters). Insects, mam-
mals and reptiles produce stable foams from bio-surfactants or surface active proteins
which have complex structures.
Acknowledgments

I would like to thank the following people: first of all, my family for their patience and
constant love and support during our worldwide travels; secondly, I would like to
acknowledge my earlier teachers including Ron Ottewill (Bristol University, UK),
Fred Fowkes (Lehigh University, USA) and Joe Kitchener (Imperial College, UK) as
well as my students. Special thanks to Maud Norberg, who was deeply involved in
creating the beautiful illustrations. Finally, I would like to thank my colleagues at (a) the
Max Planck Institute for Colloids and Interfaces, Potsdam/Golm, Germany, (b)
Newcastle University, NSW, Australia, (c) the University of Geneva, Switzerland and
(d) Nottingham Trent University, UK, for providing me with a refuge during the period
from 2010 to 2015, following my retirement from the Institute for Surface Chemistry,
YKI, Stockholm, Sweden. Special thanks also to Chris Hamlett (at Nottingham
Trent University) and Sheila Brooks for critically reading through these chapters and
correcting the text.

R. J. Pugh
Symbols

A surface area of foam or foam film

Ai Initial area of foam film
As cross-sectional area of foam film
Af area of liquid film
a activity of solute
ah effective head group area of surfactant
ac condensation coefficient
Bc film breaking coefficient
B, B1, B3, B4 proportionality constants
C concentration
Cs surfactant concentration in solution
Cel electrolyte concentration in solution
Cel,cr critical electrolyte concentration
Cb concentration of black spot formation
CNBF critical surfactant concentration for Newton black film formation
Ce equilibrium surfactant concentration of Newton black film stability
Cmax maximum surfactant concentration (for bubble coalescence)
CPB transitional electrolyte concentration (Prince and Blanch)
D diffusion coefficient of surfactant molecules in bulk solution
Dg diffusion coefficient of gas from a shrinking bubble
Df diffusion coefficient of gas
Deff effective diffusion coefficient of gas
Dw diffusion coefficient of gas through aqueous core of thin film
Ds surface diffusion coefficient
Dν coefficient of vacancy diffusion in an amphiphile bilayer
d bubble diameter
deq bubble equivalent diameter
dv bubble vertical diameter
dh bubble horizontal diameter
dx small change in distance caused by stretching liquid film
Eg Gibbs coefficient of surface elasticity
Ea activation energy
Ec entry coefficient
Eg generalized entry coefficient
xviii List of symbols

E* complex dilational visco-elastic modulus

E0 real part of E* (storage modulus)
E 00 imaginary part of E* (the loss modulus)
F force
Fb buoyancy force
Fs force associated with surface tension
Fc capillary attachment force during bubble nucleation
Fp foam production under sparging
Fp⃰ foam production under agitation
Gad adsorption energy
G Gibbs coefficient of elasticity
Hi initial foam height
Hr residual foam height
Hf foam height
Hequ equilibrium foam height (Bikerman test)
Hof immersion depth of orifice tube
Hog Oswald coefficient of gas solubility
h thickness of liquid foam film
hi initial thickness of foam film
ht final thickness of foam
htr transitional thickness of foam film
hF height of foam as defined in test method
hs height of solution as defined in test method
hst thickness change due to loss of stability
hm minimum film thickness for bubble coalescence
hw thickness of aqueous thin film core
hml thickness of adsorbed monolayer adsorbed on thin film
hw equivalent thickness of a liquid film
hcr critical thickness of film rupture
hcr,bl critical thickness of film rupture via black spots formation
J diffusion and transfer of soluble surfactant to bubble interface
Js flow of surfactant along surface of bubble
Kn equilibrium constant for dissociation of mono-species into aggregates
K gas permeability
Km diffusion coefficient
Kf electro-conductivity of foam
Ks specific conductivity of foam
Kdc ratio of foam drainage time to coarsening time (tdr/tc)
kf gas permeability of monoatomic and diatomic atoms
k no dimensionless permeability
ko coefficient of background permeability
kml diffusion coefficient of single surfactant monolayer
ks specific electrical conductivity of bulk solution
kf electroconductivity of foam
 List of symbols xix

Kc dimensionless number (PB permeability)

keff effective coefficient of gas transfer
Lpb Poisson border length (foam structure)
L length of foam train (permeability model)
lt length of foam film
lc length of surfactant hydrocarbon chain
Nf number of flips in Hele-Shaw cell
n number of bubbles
nf intervening films in foam train model (standing diffusion model)
P pressure
Pl liquid pressure
Pg gas pressure
PB Laplace pressure in Plateau borders
Pc capillary pressure
Pcmax maximum value of the capillary pressure
Pf packing parameter for solid particles at bubble surface
Ql liquid flow rate
Qg gas flow rate (cm3/s)
Rb radius of bubble
Rpb Poisson Boltzman curvature (foam structure)
Rt radius of shrinking bubble
Rf radius of film curvature
rb radius of bubble or a microscopic film
requiv equivalent sphere radius
ro radius of orifice
rf film radius
Rg radius of gyration
So solubility of gas in liquid
Sc spreading coefficient
T absolute temperature
Tc cycle of period 1/f
Td drainage time of thin liquid film between two discs
TTR Threshold of entry barrier
t time
td coalescence time (MTR theory)
ts thin film stability time
tb thin film breakage time
tin thin film inertia time
tatt attachment time (particle and bubble interaction)
ti induction time (particle and bubble interaction)
tr thin film rupture time (particle and bubble interaction)
ttpc three-phase contact time (particle and bubble interaction)
tp bubble transition or persistence time (coalescence)
tdev time of deviation (foam test methods)
xx List of symbols

ttr time of transition (foam test methods)

t1/2 half-life of foam (foam test methods)
tdr drainage time
tc foam coarsening time
V volume of gas
Vb volume of bubble
Vo initial foam volume
Vi initial volume of foam
ΔV F change if foam volume (foam test methods)
ΔV S change in volume of drained liquid (foam test methods)
Vh volume of hydrocarbon chain
Vend final volume of foam produced (surfactant depletion experiments)
Vd foam decay rate
Vsgf superficial gas flow rate
VL liquid drainage velocity
Vab bubble approach velocity
VRe Stefan–Reynolds drainage rate between two discs
VFD forced drainage velocity
Kp bubble persistence constant
jg superficial gas flow (humidity and evaporation)
KH Hilgenfeldt ratio of drainage time to coarsening
v liquid flow velocity
Vav average approach velocity between two bubbles
Vbrs bubble rise velocity
Vch bubble approach velocity (Chester Hofman)
Vk bubble approach velocity (Klaseboer)
Vy1, Vy1 bubble approach velocity (Yaminsky)
Vcav critical bubble approach velocity
U average rate of foam decay
Ug superficial gas flow rate (m/s)
Uterm terminal velocity of bubble
Umax maximum velocity of bubble
Ud foam decay rate
W work
We Weber number
Wcr critical value of Weber number
W volume % liquid content of foam (foam test methods)
Wl volume % liquid content of foam (conductivity test methods)
Wl width of liquid inlet channel in microfluidic cell
Wg width of gas inlet channel in microfluidic cell
x, y coordinates in direction to the interface
z coordinate normal to the interface
β dynamic contact angle
Γ adsorption, surface concentration
 List of symbols xxi

Γ∞ maximum adsorption, surface concentration

Γ surface excess (adsorbed)
ΓR relative adsorption
Γmax maximum amount of coverage of surfactant
γ surface or interfacial tension
γo surface or interfacial tension of a pure solvent system
γdyn dynamic surface tension
γequ equilibrium surface tension
η dynamic viscosity
ηd surface dilational viscosity
ηsh surface shear viscosity
ηd viscosity of dispersion
ηo viscosity of liquid matrix
1/κ Debye screening length
λ characteristic tube width to bubble radius
Π disjoining pressure
Πel electrostatic component of the disjoining pressure
Πvw van der Waals component of the disjoining pressure
Πst steric component of the disjoining pressure
Πosc oscillatory component of the disjoining pressure
ρ1 density of liquid
ρg density of gas
ρR ratio density (wet and dry foam)
∑ Bikermann unit of foaminess
τ micellar break-up time
τ1/2 lifetime of a foam film or foam
θ equilibrium contact angle
Φl volume fraction of liquid or wetness of foam
Φg volume fraction of gas fraction
Φg,critical critical gas fraction
φs volume fraction of dispersed solid
χ bubble shape deformation factor
ω angular frequency
Ψo surface potential

Constants

AH Hamaker constant
AR retarded Hamaker constant
F Faraday constant
g gravitational constant
kB Boltzmann constant
Kn dissociation constant
xxii List of symbols

NA Avogadro number
Rg ideal gas constant
Re Reynolds number
T absolute temperature

Abbreviations

BCP block copolymer

CBF common black film
CMC critical micelle concentration
CPP critical packing parameter
DLVO Derjaguin, Landau, Verwey, Overbeek theory
FTT film trapping technique
HLB hydrophilic/lyphophile balance
MTR Manev–Tsekov–Radoev theory
NBF Newton black film
POE polyethylene oxide
RH relative humidity
WP Weaire-Phelan (foam cell structure)
Preface

The aim of this book is to provide a comprehensive, well-structured insight into the
physical chemistry of liquid foams which can be used by both academics and
industrialists. Liquid foams may occur naturally or by design and may be desirable
or undesirable. Generally, there is a multitude of complex causes of foaming and
antifoaming and the text is structured to give clarity to the field by providing an up-to-
date, state-of-the-art guide explaining the chemistry of real foam systems. It is hoped
that the reader will achieve a reasonably clear understanding of why foaming occurs,
how it can be measured and how it can be prevented. As the use of foams spans
different disciplines, some introductory aspects of physics, chemical engineering and
material science of foams are included but this is relatively easy to follow. This book
is orientated toward the descriptive rather than the theoretical and contains many
diagrams. It is also a rich source of information and references, arranged in a way
which the reader should find useful and also provides an historical prospect to the area
of foams and foaming.
The most popular academic books dealing solely with foams include the classics
Foams by J. J. Bikerman (1973), published by Springer-Verlag, Berlin and The
Physics of Foams by D. Weaire and S. Hutzler (1999), published by Clarendon
Press, Oxford. Both of these books ran into several updated editions but considerable
advancements in the field have been made since their publication. Other early texts
are Foams and Biliquid Foams-Aphrons by F. Sebba (1987), published by Wiley and
the two books – Antifoaming (edited by P. Garrett, 1993) and Foams (edited by R. K.
Prud’homme and S. A. Kahn, 1996) – published in the Surfactant Science Series
(Marcel Dekker). These are fairly well-read books but are essentially a collection of
viewpoints which describe many varied aspects of foaming and antifoaming science.
Foam and Foam Films by D. Exerowa and P. M. Kriglyako (1997), published by
Elsevier in the Studies in Interfacial Science Series, has been well received but
presents a strongly fundamental text with the main emphasis on thin films. More
recently is the book Foam Engineering, edited by P. Stevenson (2012) and published
by Wiley, covers rheology, flow and foam processing and is aimed toward the
chemical engineering community. Another recent book, Foams Structure and
Dynamics (2013) edited by a group of French scientists and published by Oxford
University Press, was directed toward the Physics community.
There are many other books available but they are multi-authored, specialist texts
edited by engineers, chemists, chemical engineers or physicists. They usually include an
xiv Preface

ad hoc assortment of specialist research or review papers focused on foams or foaming

within specific areas. For example, an early book by Schraum (1994) covered the oil
industry and E. Dickenson and coworkers edited several books on the food industry
which included chapters on food foams. Another multi-authored book, Foamspex, came
out as a European Union project and covers the large-scale applications and modeling of
foam spreads and extinguishment aspects of firefighting foams. This was published by
SP Sweden (the Swedish National Testing and Research and Fire Technology Institutes)
in 2001. Other texts on polymer foam systems are more specialized, for example,
Polymer Foam Handbook, edited by N. J. Mills and published by Elsevier (2007) and
Handbook of Polymeric Foams and Foam Technology, edited by D. Klemper and
coworkers and published by Hanser (2004).
This book is a single-authored, comprehensive text which gives a current and
coherent picture of foam chemistry. The book will probably be of most interest to
senior undergraduate and graduate students of physical chemistry, chemical engineer-
ing, surface and colloid chemistry, life sciences and applied physics. It is also aimed at
scientists and engineers in industry who frequently encounter foams under practical
conditions. In these cases, the presence, absence and nature of foam can determine the
economic and technical success of the process. Although some prerequisite scientific
knowledge is expected from the reader, only the bachelor’s level in sciences is needed
to adequately understand the principles presented. In fact, the book could prove to be
of interest to less academic amateur scientists, for example, with interests in the
brewing of beer.
The book contains twelve chapters. Chapter 1 outlines the most important proper-
ties of foams and their uses in everyday situations. The physical and chemical aspects
of foams and foaming are reviewed and the main features of wet and dry foams are
described. Surface active agents and the relevant basic thermodynamics are also
introduced. Chapter 2 describes the nature and properties of chemical foaming
surfactants together with their role in stabilizing bubbles. Chapter 3 is an important
chapter from a fundamental viewpoint since it covers soap films, which are the basic
structural elements in foams, and it reviews the role of the intermolecular forces
which define the stability of thin films. Techniques for measurement of the stability
and draining of foam films are also discussed. In Chapter 4, an overview of the
different types of processes in foaming is presented. These include the ascent of
bubbles in liquids, the drainage of liquids through foams and the diffusion of gas
through the foam, humidity and evaporation. Chapter 5 covers the generation of
foams and includes a range of methods used both in laboratory and in industry. In
Chapter 6, the coalescence of bubbles and techniques for measuring the coalescence
process are described. Coalescence of bubbles in solutions of different types of
inorganic electrolytes is reviewed in light of recent experiments in which the bubble
approach speed is taken into consideration. Chapter 7 discusses the classification of
bubble and foam stability and the different types of stabilization mechanisms which
can operate. In addition, the various types of additives which can be used in stabiliza-
tion of foam systems are summarized.
 Preface xv

In Chapter 8, the historic background of particle stabilized foams is presented

together with their use in established processes such as deinking and flotation. The
role of contact angle, particle shape, charge, detachment forces, capillary pressure
and the influence of the formation of different types of particle networks is discussed.
Chapter 9 covers foaming in non-aqueous liquids, which is less commonly encoun-
tered in non-aqueous fluids than in water-based media, but it is an important topic to
consider. It occurs in a wide range of industrial processes – for example, during the
processing of crude oils, drilling fluids, lubricants, solvent (base cleaners), etc.
Chapter 10 covers defoaming and antifoaming. Problems are caused by foaming
throughout a range of industrial processes – for example, in the production and
processing of paper, pharmaceuticals, materials, textiles, coatings, crude oils, wash-
ing, leather, paints, adhesives, lubrication, fuels, heat transfer fluids, etc. and in the
processing of food and beverages such as sugar beet, orange and tomato juice, beer,
wine and mashed potatoes. The different types of antifoaming additives used to
prevent formation and destruction of foams are classified and also the physical
chemical mechanisms involved. Foam test methods are described in Chapter 11,
including both laboratory and industrially developed techniques. Finally, in Chapter
12, several new developments in the area of foam research are reviewed. This
includes the growth and stability of foams in microgravity and mechanisms involved
in the production of metal foams at high temperature, which have the potential to be
used in the automobile and aircraft industries. In addition, foaming in the environ-
ment is documented (natural waters, sea waters and polluted waters). Insects, mam-
mals and reptiles produce stable foams from bio-surfactants or surface active proteins
which have complex structures.
1 Basic principles and concepts

Thoughts without content are empty, intuitions without concepts are blind.
Immanual Kant, Critique of Pure Reason, B25, 1781.

1.1 Introduction

Foams can exist in the wet, dry or solid state and can be seen almost everywhere, in the
home, in the surrounding natural environment and in numerous technological applica-
tions. In fact they are prevalent, and it is almost impossible to pass through an entire
day without having contact with some type of liquid or solid foam. They have several
interesting properties which enable them to fill an extremely wide range of uses; for
example, they possess important mechanical, rheological and frictional characteristics
which enable them to behave similar to solids, liquids or gases. Under low shear, wet
(bubbly) foams exhibit elastic properties similar to solid bodies, but at high shear, they
flow and deform in a similar manner to liquids. On the application of pressure or
temperature to wet foams, the volume changes proportionately, and this behavior
resembles that of gases. Interestingly, it is the elastic and frictional properties of wet
foams which lead to their application in personal hygiene products such as body lotions,
foaming creams and shaving foams. While shaving, foam is applied to the skin and the
layer on the blade travels smoothly over the surface, reducing the possibilities of nicking
and scratching. Another example is their use as firefighting foams, where properties
such as low density, reasonably good mechanical resistance and heat stability are
required in order to be effective in extinguishing gasoline fires. Essentially, they act
by covering the flames with a thick semi-rigid foam blanket. The low density allows the
water in the foam to float even though it is generally denser than the burning oils. The
chemical composition and mechanical properties of these types of foams can be varied to
optimize the firefighting utility.
Foams are also found in many food items, either in finished products or incorporated
during some stage in food processing. They primarily provide texture to cappuccino,
bread, whipped cream, ice-cream topping, bread, cakes, aerated desserts, etc.
Surprisingly, several novel types of food foams have been recently produced from
cod, mushroom and potatoes, using specially designed whipping siphons powered by
pressurized gas with lecithin or gelatin as alternative foaming agents to replace egg and
2 Basic principles and concepts

creams (1). Several modern architectural designs and works of art have also been
manufactured from bubbles and foams, and they are also used for entertainment pur-
poses. Foam and bubble exhibitions frequently take place at the Science Museum,
London, where young children are enclosed within soap bubbles and foams. In fact, it
has been reported that 50 children were packed inside a soap bubble which became a
world record (2). Foams play an important role in evolution, particularly in the insect and
animal world. For example, while female frogs lay eggs they also secrete a fluid which is
whipped up into foam by the male frogs, and this robust foam protects the eggs by
becoming a shield against the physical and biological environment.
Foaming also occurs in cleaning and detergency which is utilized in cleaning
factories, shops, offices, machines, factories, cars, workshops, garages, floors, etc.
In many of these applications, it is important to optimize the extent of foaming. This
has been achieved by manufacturers synthesizing new types of low-foaming non-
ionic chemical detergents. However, in some applications where customers prefer to
see some foam, small amounts of special foam-producing substances were included in
their product as foam improvers, boosters or foam stabilizers. During the 1950s and
1960s, wet detergent-based foams were well known to cause major problems when
discharged into streams and rivers. They were often odorous, and when rivers flowed
over weirs, the foams frequently increased in height and were frequently blown into
neighboring environment. However, over the past 50 years, more effective biode-
gradable (green) surfactants (soft detergents) have been developed which consider-
ably reduced foaming.
Often wet (bubbly) foams have been formulated to perform specific functions such
as decontamination control (e.g. for cleaning materials inside nuclear reactors) and in
oil-recovery, agriculture and beverages such as Guinness stout, where the foam head
must remain stable during pouring and consumption. In addition, the method of gen-
erating foam is dependent on the application and requirements of the foam. In Fig. 1.1,
four different everyday foams are shown. While firefighting and shaving cream foams
are produced by release of gas under pressure, the bubbles in Guinness foams are
produced by fermentation, and detergent foams are produced by entrapment of air during
agitation.
In most cleaning operations, the foaming performance is not necessarily related to
the volume of the foam or stability, although different applications may require
different amounts of foam with an abundance of foam usually preferred in body-
cleaning products. However, this is not the situation for washing machines where
vigorous agitation occurs and foam volume needs to be minimized. Foams can often
cause problems in commercial processes such as in paper-making and distillation
where over-production of wet foams leads to loss of efficiency and downtime in plant
production. Under these circumstances, it is often necessary to add antifoamer,
defoamer or foam breakers (3).
Foams are also capable of immobilizing large volumes of air and combining lightness
in weight with strength and elasticity, and these properties are critical in their use in
many well-established industrial processes such as froth or foam flotation. This is one of
the largest and most important industrial uses of bubbles and wet foams which have been
 1.1 Introduction 3

(a) (b)

(c) (d)

Fig. 1.1 Applications of wet foams. (a) Firefighting foams act to cover or blanket out the flames (prevent
air reaching the fire) and must remain stable at high temperatures. (b) Shaving foams are designed
to give rheological flow properties (similar to an elastic solid). (c) Beer foams such as Guinness are
stabilized by a protective film of proteins which define the texture and enhance the flavor and
retain their stability until the beer is consumed. (d) Detergent foams (in dishwashing) are stabilized
by low molecular weight synthetic surfactants.

used for more than 100 years. During the extraction of mineral ore, it is necessary to
separate the particles by flotation so that the more valuable hydrophobic ore particles
(sulfides of copper, zinc, gold, etc.) adsorb at the foam interface and remain suspended by
capillary forces while the less valuable hydrophilic particles (usually silicates) sink in the
liquid (4). The amount of ore that can be separated for a given amount of liquid is directly
proportionate to the surface area of the foam (bubbles), and huge masses of ore can be
easily processed using relatively small volumes of water. Figure 1.2(a) shows a schematic
drawing of a foam or froth flotation cell, and Fig. 1.2(b) shows a typical foam of froth.
The terms “foams” and “froths” which can be considered as weakly stabilized foams
are often used interchangeably, but in industry a three-phase system (a gas–water
macrocluster with dispersed particles) is considered a froth, and a structure
containing only the gas and liquid phases is considered a foam. The link between the
stability of a flotation froth and flotation performance has been investigated both in
the plant and in the laboratory by using a modified a froth stability test column (5).
In this test, a gas is continuously sparged into a foaming solution, and simultaneously
froth collapses at its free surface occurs. When the rate of froth collapse equals
4 Basic principles and concepts

(a) Air Air

Hydrophobic particles
stick to the air bubbles Floating particles
removed from the top
of the cell

Water

Hydrophilic particles
sediment to the bottom

(b)

Fig. 1.2 (a) Schematic representation of a flotation cell and (b) the froth of foam with particles attached to
the bubbles. Flotation of mineral particles is the largest industrial application of bubbles and
foams. The process involves the separation of the more valuable minerals such as copper, zinc and
lead from the less valuable silicates. Billions of tons of ore are treated annually using this
technology.

the rate of generation of fresh froth, an equilibrium height is attained. The equilibrium
foam height, divided by the superficial gas velocity, is used as a measure of froth
stability. From these studies, it was found that the variations in flotation performance
are directly related to changes in froth stability. In addition to mineral processing, froth
flotation has also been successfully used in other separation processes such as the
treatment and recycling of effluent, proteins, plastic wastes, etc. The flotation process
is also extremely important in the deinking of waste paper (6) and enabling recycling of
about 30% of paper. Foams also play an important role in the extraction of residual oil
from porous rocks (7).
Although this text is mostly limited to wet foams, it is also important to note that solid
polymeric foams (which are usually oil based and are usually manufactured from
wet foams) are generally considered as a specific group of material foams. They can
be classified as rigid, semi-rigid, semi-flexible or flexible depending on cellular
morphology, composition and other physical characteristics. They are manufactured
with a specific range of properties, achieved by controlling the degree of crystallinity
 1.1 Introduction 5

(a) (b)

Fig. 1.3 Running shoe showing some of the important foam polymers which are used as components.

and the extent of cross-linking of the polymeric framework. Close-cell material foams
contain cells that are permanently trapped (isolated). In other cases where the cells are
open or connected to neighboring bubbles by gas channels, both gas and solid may be
considered to exist as continuous phases. However, only closed-packed structures are
regarded as true polymer foams, and these products are more expensive to manufacture
therefore, the cells are filled with special gases to improve insulation. Self-skin foams
are frequently found, for example, in shoe soles and mattresses and are often manu-
factured with high-density skins and low-density cores. Open cells have networks or
channels which allow air to flow (e.g. polyurethane seat cushion).
Their properties are extremely dependent on the method of preparation and manu-
facturing particularly during the solidification. Most close-cell foams have fairly rigid
structures, but open-cell foams have been developed which are generally more flexible.
Originally, foamed rubber and phenol-formaldehyde and urea-formaldehyde resin
foams were developed in the early 20th century followed by more specific foam
polymers such as polyurethane (PU), polystyrene (PS), ethylene-vinyl acetate (EVA)
and polyvinyl chloride (PVC). Many specialized polymer foams have been developed
for the consumer market, and these have been utilized in numerous applications in recent
years. For example, a considerable amount of research and development has been
invested in foams for lightweight running shoes where low mass is needed to reduce
the energy consumption of the athlete. Figure 1.3 shows the cross-section of a pair of
trainers, indicating the different sections and major foam components.
Several foam component parts such as the rubber innersole and the foam midsole
compression which is molded from EVA copolymer are used to provide cushioning or
control torsion of the foot. The foams have been developed to withstand compression
and bending loads caused by feet. PU foams have been used as an alternative to EVA for
midsoles, but the density of PU is higher although the compression is lower. The shoe
components are bonded together so that adhesive action of the foam is important.
Different gases are often used in these types of foams. For example, Nike’s large bubbles
contain SF6 gas as an insert in the main foam. Another recent development is the
memory foam footbed. Most major shoe manufacturers show their design innovations
on websites. A background on the polymer/structural properties relationships is given
6 Basic principles and concepts

Fig. 1.4 In the figure, along the lower right side, Cellulose fibre Important traditional and novel
applications of wet and dry foams.

by Mills 2005 (8), while information on the application of foams has been published on
several websites (see, e.g., www.foamstudies.bham.ac.uk).
Polymer foams are also widely used in boats, aircraft furnishing, cycle helmets, etc. and
are manufactured from a variety of plastics and polymers. They are also used as light-
weight cellular engineering materials which require a high strength to weight ratio, for
space applications and have been used as core material in sandwich-structured composites.
The combination of low weight and unique elastic properties are ideal for packing and
cushioning, and polyurethane is used in the manufacture of seat covers and chairs whereas
foamed polystyrene is used as take-out boxes, trays in restaurants, coffee cups in cafes, seat
cushions, car seats, car bumpers and thermal or sound insulations. In addition to polymers,
rigid dry foams may be produced from metal, glass, concrete and ceramics, and these have
found widespread application in, for example, domestic insulators, air conditioners and
reinforcements. They are used for thermal insulating, vibration damping and for acoustic
absorption. Following the introduction of material foams, the principles governing the more
advanced technology has become fairly well established, and it has become possible to
match the effective properties such as stiffness or rigidity, strength, compression to the
cellular architecture. Overall, both wet and dry foams cover a wide range of both traditional
and novel applications, and many of these have been summarized in Fig. 1.4.
Novel and potential application of foams are frequently reported in the daily press. For
example, an expanding foam has recently been developed that could be pumped into
bodies of wounded soldiers to reduce internal bleeding (9). The technique involves
injecting two chemicals into the badly injured soldier’s abdomen which react to generate
a rapidly expanding foam which solidifies and seals the injuries in the body organs,
 1.2 The physics and chemistry of foams and foaming 7

preventing the loss of blood. This gives sufficient time for the soldier to be taken to a
field hospital where the foam can be easily removed by surgeons. It is also shown as a
potential bone substitute. Bone has a compact surface with a cellular core and is
composed of both mineral substances and tissues. The bone tissues are made up from
cells, fat and natural polymers (such as polysaccharides, collagen, polyphosphates, etc.).
Recent developments in synthetic foam technology have led to the production of cellular
materials from starch-based (biodegradable) polymers and polyethylene (bio-inert)
polymers as possible replacements for bones (10). Syntactic dry foams have also been
developed containing hollow particles such as glass ceramic and polymer spheres
embedded in a matrix material. In the literature, numerous separate texts have been
published covering specific types of polymer foams – for example, polyurethane or
polystyrene foams.

1.2 The physics and chemistry of foams and foaming

Although foams have been shown to be extremely useful from the industrial viewpoint,
they have, in addition, unique academic appeal within the physical chemistry, physics
and biophysics communities from a scientific viewpoint and have served as useful
models for numerous investigations over several centuries. Foams have been studied
extensively within both universities and industrial laboratories. Foams are extremely
complex systems, and early fundamental studies by Thomas (11) showed a basic
relationship between soap foams and the cellular structures of plants and animals.
This approach has led to a deeper understanding of natural processes through which
many biological systems emerge. Also similar structural features have been revealed
during grain growth in metallurgical systems (12). Within the physics community, a
strong emphasis has been placed on the mechanics, film permeability, rheological
properties (such as the variation in elasticity with gas fraction) and the structural
rearrangements occurring as the bubbles become less spherical and more highly
packed during the transition from wet to dry foam. In fact, it is the liquid content and
geometry (surface area, bubble size and size distribution, shape (compaction) and order/
disorder which are considered to be important parameters to consider, since these can
lead to a fundamental understanding into the relationship between the scaling and
structure. Most of the pre-1999 studies dealing with basic static and quasi-static proper-
ties of dry foams have been well described in the classic book by Weaire and Hutzler,
entitled The Physics of Foams (13). More recently, Drenckhan and Saint-Jalmes
presented a historical perspective entitled The Science of Foaming from a physicist
viewpoint (14).
Physicists and mathematicians have been contemplating the structure of foams over a
considerable period of time, often focusing on idealized ordered foams. However,
ordered foams are not very diverse and collectively contain only a few kinds of cells,
whereas real foams are disordered and contain a variety of shapes. Many theoretical
computer simulations have been carried out over the past 20 years, using the Surface
Evolver (15) to compute the evolution and equilibrium structures of foams, and this has
8 Basic principles and concepts

been found to enhance the understanding of real foams physics. The Surface Evolver is
an interaction program which can be used to derive a minimal energy surface or to model
the process of evolution of a surface which is shaped by surface tension and other
energies such as gravitational energy, squared mean curvature, etc. The program evolves
the surface toward minimal energy by a gradient descent method. It is also necessary to
introduce user-defined surface integrals or knot energies. For example, computations on
the equilibrium microstructure of soap films with random structure and with a wide
range of cell-sized distributions have been reported (16).
For many experimental foam studies, physicists need a convenient highly repro-
ducible sample which was assumed to be stable for extended time periods. Plateau
(17) used a soap solution to produce thin films and foams but had difficulties in
achieving sufficient stability. Later, formulations were improved by the addition of
glycerin which raised the viscosity and retarded the evaporation of water, and
since then many different types of chemical recipes have been described which
produce highly stable foams. Strong (18) has published a long list of formulations
for preparing foams with extremely long lifetimes. Over the past 50 years, numerous
experimental studies have been carried out by physicists based on a stable foam
system: a commercial shaving cream (Gillette foam regular) is produced by an aerosol
method. This is a complex mixture, comprised of an aqueous solution of mixed ionic
surfactants (triethanolamine and stearic acid) which is supersaturated with hydro-
carbon gases. On release of the contents, the bubbles are generated from solution with
the surfactants adsorbing at the bubble interface which stabilizes the foam. This
system produces nearly spherical bubbles (with 20–30-micron diameter and a gas
fraction of about 0.92) which are highly stable for more than 24 hours with negligible
drainage within this period due to the high viscosity. More recently, the physics
community has shifted toward the dynamic rather than the static nature of wet
foams, and many studies have been documented which involve the creation and
manipulation of relatively small, discrete and equal volume-sized bubbles which
have a tendency to self-order under confinement while producing crystalline and
microfluidic foam structures (19). Such monodispersed foam systems have been
shown to have many useful applications in areas such as templating, colloids and
granular systems.
However, for the physical chemist most of the attention has been focused on the
mechanisms involved in stabilization and destabilization and the surface-active materi-
als (which may be chemicals, polymers, particles or mixtures) in wet foams and their
role in their assembly in the interfacial layers. Numerous papers and several books have
been published on foam generation, stabilization, antifoaming/defoaming and foam
films (20). It has been shown that the both dynamic and equilibrium surface tension
and interfacial rheology play important roles in defining the foaming characteristics and
overall structure of the foam. Wet foams are, in reality, stabilized by a huge range of
different types of surface-active agents that adsorb at the interface and reduce the free
energy or tension. Hence, from the chemical aspects, it is the adsorption kinetics and
type and amount of surface-active agent at the gas and liquid interfacial which play an
intricate role in the generation of foam. Collapse and instability usually involves film
 1.3 The wetness and dryness of foams 9

rupture and frequently depends on the sensitivity of the chemical composition and
structure of the adsorbed film. Stability is more dependent on the viscoelasticity proper-
ties and the repulsive interaction between the film lamellae. In fact, changing the
concentration of the surfactant or the introduction of alternative surfactants (antifoamers
or foam boosters) or mixtures enhances or reduces the generation and stability of
the foam.

1.3 The wetness and dryness of foams

Foam properties depend on the gas fraction in cases where they contain low volumes of
gas, and the bubbles that are spherical are usually referred to as bubbly liquids or bubbly
foams. At high gas content, they are no longer spherical and thus behave as solids with a
high shear modulus. Under these circumstances, elastic energy is required to shear the
network. In his classic text in 1973, Bikermann (21) defined wet foams as systems where
the volume of gas is much lower so that they can be called an agglomeration of gas
bubbles, and this state occurs where the bubbles are separated from each other by thin
liquid films. Each bubble is so closed that it has no gas-filled channels which can connect
between neighboring bubbles. However, more generally, the system could be wet or dry,
and in cases where a connection exists and there is a continuous gas phase, it is
considered as an open foam structure. Cork, wood, coral and sponges are dry natural
foams, whereas with bread (a man-made foam) the yeast produces small bubbles which
grow into a close-cell structure (Fig. 1.5). However, if the bread is allowed to rise
excessively, it develops into a dry open-cell structure with the spaces interconnected by
threads of paste. Generally, a rigid dry foam system is usually regarded as a special class
of dry foam produced by an irreversible chemical process.
The evolution toward dry foam proceeds by the reduction of water from the
system, and it is usually caused by liquid drainage under gravity and by the suction
produced by the pressure gradients that exist between regions of different curvature
(capillary suction). Overall, wet foams may essentially be regarded as naturally
evolving non-equilibrium systems, consisting of a collection of coarse polydispersed
gas bubbles, packed into a smaller volume of liquid. In the case of pure water, the
bubbles usually burst but in the presence of a sufficiently high enough concentration
of surfactant, the liquid drains away gradually and the curved bubble surfaces are
gradually transformed into characteristic irregular polyhedral foam cells bounded by
thin soap films with almost plain surfaces of contact. The transitions in structure
which occur from wet to dry foam systems are illustrated by the two-dimensional
(2D) scheme in Fig. 1.6.
Generally, the liquid fraction of a foam is defined by the ratio of the volume of liquid
to the total volume of the foam. Aqueous foams typically contain as much as 95% gas
and 5% liquid, with the aqueous phase consisting of 99% liquid while the remaining 1%
is the vital surface-active ingredients (typically a chemical surfactant). In general, the
structure and dynamics of foams are determined by the amount of gas in the system, and
the ratio of gas to liquid is defined as the foam number or wetness. However, the liquid
 (a) (b)

(c) (d)

Fig. 1.5 Common types of dry foams. Bread exhibits a close-cell structure, but coral, cork and synthetic
sponges show open-cell structures.

(a) (b)

(c) (d)

Fig. 1.6 Schematic 2D representation of a wet and dry foam with different volume fractions. (a) Very wet
non-drained foam consisting of non-interacting bubbles; (b) wet foam partially drained with
interacting bubbles causing deformation; and (c) further drainage causes lamellae to further thin
and swell in the Plateau borders. (d) Finally, a well-drained foam. Dry foam consisting mostly of
gas phase entrapped in polyhedral cells separated by thin films with thickness <100 nm.
Note curvature of some bubbles walls owing to unequal internal pressures. The nature of the thin
film has been subject to intense study. From ref (22).
 1.4 Capillary pressure and the Laplace–Young equation 11

fraction may vary from about 1% (which is considered a dry foam by the physics
community) to about 35% (a wet foam). During the transformation from spherical
(polyederschaum) to polyhedral structure, the water content or degree of wetness of
the foam changes (as expressed by its liquid volume fraction Φl or gas volume fraction
Φg). These two values are interrelated, as seen from the equation

Φl ¼ 1  Φg ð1:1Þ

The critical gas fraction Φg,critical is defined as the value of Φg in which the individual
bubbles are spherical, and this state is most commonly considered as a bubbly liquid.
Higher values of Φg cause deformation of the bubbles. In order to obtain a gas fraction of
Φg > Φg,critical a force is required to drive out the liquid from the foam. For a typical
foam with polydispersed gas bubbles, the value of Φg,critical is about 0.72. As Φg
approaches unity then the foam takes on a polyhedral structure, and calculations give
pffiffiffi
a value Φg;critical ¼ πð2 3Þ1 ffi 0:907 for a 2D model of a mondispersed (hexagonal)
foam. For a polydispersed (disordered) foam, Φg,critical has a value of 0.84 from a
computer simulation (13); Φ is sometimes called the wetness and the ratio of foam
volume to the volume of liquid in the foam; and (1/Φ) is the expansion factor or
expansion ratio. The relative density is the ratio of the density of wet and dry
foams, and defined as ρR = ρf/ρl and for polymer foams ρRP = ρf/ρe, provided there is
no filler or solid additives.

1.4 Capillary pressure and the Laplace–Young equation

One of the most important relationships which define the transitional states in wet
and dry foam structures is the balance between the capillary pressure within the thin
foam films and the drainage of liquid from the structure by gravitational forces. For
a gas bubbles (with radius r) submerged in a liquid (in an equilibrium state and in
the absence of gravitation forces), the shape must be spherical in order to balance
the minimum surface area requirements, and there must be a pressure difference
across it. The equation which defines the capillary pressure (or the value of the
pressure difference) to the curvature of the surface was deduced independently in
the 18th century by Young (23) and Laplace (24). This situation for a bubble is
illustrated in Fig. 1.7.
The derivation is as follows: if we take γ is the surface tension of the interface then the
total surface free energy of the bubble is 4πr2γ, and if the radius was to decrease by dr
then the change in surface free energy would be 8πrγ/dr. Since the shrinking in size
causes a decrease in the surface energy, then the tendency to do so must be balanced by a
pressure difference across the film ΔP (between the inside relative to outside). The work
done to achieve this against this pressure difference is ΔP4πr2dr which is equal to the
decrease in surface free energy. The relationship between the pressure and surface
tension is, therefore,
12 Basic principles and concepts

Fig. 1.7 Under equilibrium conditions, the pressure difference (ΔP) between the external pressure Pl
exerted from the liquid phase on a gas bubble and the internal gas pressure Pg are related to the
radius of the bubble (r) and the surface tension of the liquid (γ) by the Laplace–Young equation.

2γ
ΔP4πr2 dr ¼ 8πr2 dr or ΔP ¼ ð1:2Þ
r

where ΔP represents the pressure difference between the inside and outside of the
bubble or the pressure over a curved surface. This pressure is defined as the capillary
pressure Pc and is inversely proportional to the radius of curvature and directly
proportional to the surface tension. It may be also concluded from Equation 1.2
that for small bubbles, the pressure inside the bubble is greater than that outside. For
the general case of soap films, it is necessary to invoke two principal radii of
curvature to describe a curved surface so that for bubbles with surfaces of curvature
r1 and r2 the pressure difference will be
 
1 1
ΔP ¼ γ þ ð1:3Þ
r1 r2

It may be noted that r1 is positive if the center of curvature of r2 lies in the gas phase
and also for r2. However, soap film may be a saddle shape, and in this case the radii must
have an opposite sign. Also, in the specific case of r1 = –r2, the pressure difference ΔP is
zero, and this is the situation for a soap film with two plane surfaces. In foam thin film
structures, the pressure is lower and the film is thicker in the Plateau border due to the
interfacial curvature, so that a capillary suction effect occurs on the liquid from the
center of the film to its periphery.

1.5 Plateau rules and pentagonal dodecahedral structures

Foams or froth consist of a random agglomerate of roughly spherical bubbles, and a

series of pronounced structural changes occur during draining which eventually
leads to the formation of cells. The mean curvature and cell size are important
since they affect the gas diffusivity in close-cell foams and the gas flow resistance in
open-cell foams. Structural transformation process was originally studied by Joseph
 1.5 Plateau rules and pentagonal dodecahedral structures 13

Plateau (Plateau rules) in the 18th century in a series of experiments using soap
films constructed on wire frames from which a series of classical geometric rules
were formulated. These rules are based on the balance between the interfacial
surface tension forces and the surface area of the system which are required to be
minimized to ensure the lowering of the Gibbs free energy and stability. The first
rule states that when three smooth liquid lamellae are joined by intersecting at every
edge, the intersection – formed by any three bubbles (faces) – must come into
contact at a point. Once they are stabilized, each pair of intersections form borders
with an angle of inclination of exactly 120°. These borders are defined as the
Plateau–Gibbs borders and constitute the structural skeleton of the foam
(Fig. 1.8). The Plateau borders or edges always number exactly 4, and they meet
at a common vertex where the angle is always that of a tetrahedral with the value of
109° and 28 min.
As a bubbly foam drains and the liquid content is reduced, the bubbles gradually
transform into an almost regular ideal polyhedrals and from purely theoretical geo-
metric considerations, the regular pentagonal dodecahedron is the ideal lattice shape
which almost satisfies the geometric rules. Such a crystal has 12 identical faces, each
of a regular pentagon. However, the precise shape of the polyhedral is an unsolved
mathematical problem since this structure does not exactly fit or represent an agglom-
eration of dodecahedrons because the cells cannot completely fill the space without
allowing for voids or pores. This situation was initially investigated by Kelvin (25) in
1887 who found that the closest polyhedral structural element which nearly satisfies
all the mechanical constraints was a space structure (a filling arrangement) closely
resembling the tetrakaidecahedron but with curved edges and non-planar hexagonal
faces). From modeling and simulations, a modified version of Kelvin’s arrangement of
the tetrakaidecahedron, was derived (26). This non-regular polyhedron is known as
the β-tetrakaidecahedron and represents an idealized foam structure consisting of a
collection of regular tetrakaidecahedron bubbles, with thin films defining the walls
and the network unit composed of one node and four liquid-filled half-channels. As the
amount of liquid in the channels and modes increases, the mean curvature decreases,
and the edges and corners of the polygonal bubbles become more curved. Figure 1.8
shows the structural arrangements of the foam.
Almost 100 years after Kelvin, Weaire and Phelan (27) of Trinity College, Dublin,
proposed an improved or counter-solution of Lord Kelvin’s conjecture which was
derived from a clathrate structure (Na8 Si46) and was based on two polyhedrons, one
with 14 sides and one with 12 sides that nest together in a group of eight, as shown
in Fig. 1.9. Their computations show that it has about 0.3% less surface area than
Kelvin’s solution, and the Weaire–Phelan (WP) structure is at present the lowest
energy structure known for an ideal monodispersed foam in dry limit. A giant
version of this monodispersed foam structure (consisting of 4500 bubbles) was
developed in the architecture design of the Aquatic Centre of the 2008 Beijing
Olympics (28).
Interestingly, the WP structure has been recently produced in the laboratory using a
container designed so that the walls acted as a template, which was used to capture the
14 Basic principles and concepts

Fig. 1.8 For low liquid fractions almost all the liquid is in the network of Plateau borders. In an
idealized foam, four borders join in a tetrahedral arrangement with angles approximately 109°.
The liquid network unit is composed of a node and four half-channels. The edge length of the node
in each cell is L.

(a) (b)

Fig. 1.9 (a) The β-tetrakaidecahedron or modified Kelvin cell. According to Plateau rules, an ideal
polyhedral aqueous foam requires the packing of 3D space with repetitions of a polyhedron. A
pentagonal dodecahedron is the nearest among regular polyhedrons, but this is not ideal and thus
cannot fill space without voids (the packing leaves interstices, and the individual films in a real
polyhedral foam are not five sided). A better choice is an irregular polyhedron – the β-
tetrakaidecahedron with eight hexagonal and four quadrilateral, with slightly curved surfaces. (b)
The Weaire Phelan structure built from a unit cell of six 14-hedra and two 12-hedra.

geometry of the structure. The template was positioned in a surfactant solution and
monodispersed bubbles were released from below the template, with the diameter of the
bubbles chosen to match the scale of the template (29). The structure was realized on the
inner surface of the template walls and corresponded to the 100 faceted planes of the WP
structure. In Fig. 1.10, the computer-generated WP structure and the template realization
are illustrated. Layers of six bubbles could be formed and the container sealed so that the
confined sample contains defect-free monocrystals of the WP structure.
 1.5 Plateau rules and pentagonal dodecahedral structures 15

Fig. 1.10 (a) Computer-generated exploded views of two layers of bubbles in the WP structure. Bubble
centers in each layer lie on two parallel 100-faceted planes. (b) Frontal view, with the A3B periodic
unit shown. (c) Realization of the WP structure in a pattern mold. From ref (29).

Williams (30) also proposed a modified version of the tetrakaidecahedron struc-

ture which consist of two square faces, eight pentagonal faces and four hexagonal
faces. This structure had a statistical distribution of face shapes which closely
approximates the range of film shapes found in nature, but this has been less
used. However, generally, none of these models realistically describes or matches
geometric properties of practical foam systems. In the real world, no foam consists
of exactly identically sized bubbles, and not all the films between bubbles are
planar. There have been various explanations for this non-ideal behavior; for
example, Adamson and Guest (31) suggested a simple idea that it may be due to
local variations in pressure in the liquid inside the laminas. Such pressure variations
would affect the structure and nature of foam drainage.
To summarize, there is no simple model structure that can serve as a convenient
mathematic idealization of a polyhedral foam, and real foams are polydispersed
and rarely in the shape of Kelvin tetrakaidecahedron. This has been well recog-
nized for a considerable period of time, and early experimental studies by Matzke
(32) showed that films consisting of individual bubbles tended to be irregular. From
observations of several hundred carefully prepared internal bubbles, it was found
that only slightly more than half of the faces were five-sided, and about 10% of the
polyhedral structures were pentagonal dodecahedrons. Clearly, pentagons alone
cannot completely fill space, but they can be frequently seen within a 3D froth of
bubbles such as in detergent solutions. Pentagons are also found in nature – for
example, in sea urchin skeletons, turtle shells, insect wings, honeycombs, human
fat cells, vegetable cells or metal crystallites. For many years, soap froths were
intensively studied since their structures are the archetype for numerous other
cellular and biological systems. In fact, it has often been suggested that pentagon
symmetry may be related to the five-fold structures often seen in life; for example,
five fingers and five toes. All these systems comply with the balance of local forces
which constrain to a minimum surface area, resulting in an abundance of pentago-
nal faces.
Modeling and computer simulations have been used to describe growth and the
interaction of soap bubbles in such closely packed formulations. These have proved
16 Basic principles and concepts

useful in solving many difficult geometric problems which frequently involve some form
of optimization. Essentially, the topology of the interconnecting of polygons is based on
the minimizing of the energy (surface area). This has proved directly applicable to many
complex problems such as finding the surface of minimal area between fixed boundaries.
For example, calculating the shortest road network between several different cities often
needs to be resolved. This also has direct applications to construction and architecture
where, again, optimization of resources and materials plays an important role. Within the
physics/bubble/foam community, modeling has proved to be extremely useful, and it
enables the relationships between liquid content, bubble size and film thickness of foams
to be determined. In addition, with dry polymer foams, modeling is frequently applied to
predict physical properties such as elasticity and strength.

1.6 Foam structures produced from bubbles with narrow size distributions

The simplest method of generating foams is by shaking together a gas and liquid
containing a foaming agent such as a fatty acid soap. Adsorption of the foaming agent
occurs rapidly at the gas/liquid interface, causing encapsulation of the bubble and
producing some degree of elasticity, which stabilizes the protecting thin film. Due to
differences in density between gas and liquid phases, the bubbles (which usually range in
size from about 10 microns to 1 cm) float on the surface, generating foam. However, to
achieve a 2D bubble or foam raft, it is important to produce bubbles with a narrow size
distribution, and this can be achieved in the laboratory by releasing compressed gas at
constant gas pressure down a narrow capillary or nozzle (usually about 0.2 to 1 mm
diameter) that is immersed in aqueous solution containing foaming surfactant. As the
bubble grows, the air/liquid interface expands and floats to the surface, giving an
arrangement of different configurations depending on the number of bubbles and their
packing configuration at the interface, as shown in Fig. 1.11.
During the 1930s and 1940s, experiments with bubble rafts were carried out to
illustrate the concept of packing of atoms and ions in a minimal energy configuration.
It is interesting to see the hexagonal pattern formed from uniform-sized bubbles
caused by the short-range order, which results in each bubble surrounding itself by
neighboring bubbles. This remarkable order arises spontaneously and can be simply
explained in terms of surface tension and capillary forces. The short-range structural
arrangements are repeated throughout the raft, leading to long-range ordering. At
Cambridge University in 1947, Bragg and Nye (34) generated monodispersed bubbles
using a nozzle; this led to the preparation of a 2D bubble raft in which defects could be
detected. From these studies the basics concepts of crystallization could be illustrated
and it could also be demonstrated how grain boundaries, dislocations, lattice defects
and recrystallization arise. Later, Smith (35) developed the method further and found
these systems to be useful as models applicable to grain growth and the kinetics of
phase separation. More recently, deformation experiments were carried out on
2D bubble rafts by Arciniaga and coworkers (36) in which two distinct transition or
failure modes were detected; this corresponded to a brittle fracture at high
 1.6 Foam structures produced from bubbles with narrow size distributions 17

Thin pipette attched to pump

Air

Soap solution

(a) (b)

(c) (d)

Fig. 1.11 The experimental set-up for the construction of a bubble raft and below typical bubble rafts
with different configurations of monodispersed bubbles on the surface of the liquid: (a) three
separate bubbles; (b) one possible packing of three bubbles – capillary forces will attract the
bubbles together; (c) a lower energy packing of three bubbles; (d) hexagonal bubble packing.
From ref (33).

deformations and plastic pinch-off under small deformations. This work was parti-
cularly relevant to the field of fundamental metallurgy. A typical bubble raft with
dislocations and defects is shown in Fig. 1.12.
In order to carry out experiments with smaller bubbles, smaller nozzles and higher
pressures were required, but it was found that the bubbles became less monodispersed
due to hydrodynamic effects. This problem was solved by introducing a background
circulation of the liquid which caused the rapid detachment of monodispersed
bubbles. This approach eventually led to the development of flow focusing bubble
generators and microflow bubble generators. More recently, the Physics Foam
Research Group at Trinity College, Dublin (37, 38), prepared wet foam rafts from
small (diameter 200 µm) bubbles using a solution of conventional commercial
surfactant (a liquid detergent) and confirmed the observations made by Bragg and
18 Basic principles and concepts

Fig. 1.12 A typical 2D bubble raft. Grain boundaries, dislocations, lattice defects and recrystallization can
be detected. The short-range ordering is repeated throughout the raft, leading to a long-range
structure packing which resembles the arrangement of closely packed crystals.

(a)

(b)

Fig. 1.13 (a) The ordered arrangement of a foam surface consisting of at least three layers of bubbles
(mono-dispersed of size 200 micron) and (b) a simulation of a (111) face center cubic packing
corresponding to the packing scheme ABC which shows detailed agreement with the experiment.
From ref (37).

Nye in 1947 for 2D bubble rafts. These workers observed two different surface patterns
of the top bubble layer which were described as triangular and square surface arrange-
ments. In addition, they successfully developed techniques for preparing stable 3D wet
assemblages which they could use to describe a rich variety of 3D crystal and defect
structures. Also, computer simulations of these structures were made. These workers
suggested that the stability and ordering of these structures (constructed from relatively
large bubbles of about 200 microns) could not be explained by current thermodynamic
and kinetic theories. In Fig. 1.13, a foam raft is shown consisting of bubbles giving an
 1.6 Foam structures produced from bubbles with narrow size distributions 19

Fig. 1.14 Photograph showing at least five layers of bubbles arranged in a packing direction (100).
Bubble diameter 0.5 mm. From ref (37).

ordered arrangement of at least three layers of bubbles which could be modeled as a

(111) face center cubic packing arrangement.
In Fig. 1.14, a five-layer arrangement is shown, and sequences of up to seven-layer face
center cubic planes were observed. In these structures, imperfections and stacking faults
caused by point defects and vacancies of two bubbles (di-vacancies) were reported. In
addition stacking faults similar to those found in opals were detected. In more recent
studies, a flat-sided pyramid container that enabled ordered face center cubic single crystal
foams of up to 500 bubbles to be produced was used. Also it was found feasible to produce
strained and deliberately defective crystalline foam structures (38).
It has also been shown from recent experiments that bubbles of equal volume
readily crystallize into ordered polyhedral structures when introduced into tubes
where the width of the tubes has the same order of dimension as the diameter of the
bubbles. Several characteristic structures have been identified experimentally and it
was found that these structures tend to become generated in specific regions where
the structure characteristics and dimensions are defined by the lower surface energy
situation. Tobin and coworkers (39) carried out experiments with tubes with
circular, square and triangular cross-sections and produced a variety of new ordered
foam structures. The simple bubble generation apparatus is shown in Fig. 1.15.
In addition, computer simulations were carried out in which the surface energy per
bubble was computed using the Brakke’s Surface Evolver software (15). From these
simulations the relationship between the energy per bubble and the characteristic tube
width to bubble radius (defined as λ) was determined, where λ was varied by changing
the tube diameter or bubble diameter. In Fig. 1.16, the dependence of surface energy on λ
and the range of different ordered structures which could be generated are illustrated.
The structures of the foams were labeled S-N, where S stands for square and N is the
number of bubbles in the unit cell. Seven square structures were identified which could
be simulated using the Surface Evolver. However, it was found that some of these
simulated structures were hard to achieve experimentally.
20 Basic principles and concepts

Fig. 1.15 Schematic representation of the apparatus used to produce ordered foam structures in tubes.
Equal bubble volume achieved by having constant air flow is very important. From ref (39).

S-1
Energy per bubble

7
/(γ VB2/3)

S-2

0.8 1.2 1.6 2.0 2.4 2.8

l = C*/r
Fig. 1.16 The relationship between the energy per bubble and λ (defined by the characteristic tube width to
bubble radius and calculated from λ = c*/r) obtained from computation carried out using the
Brakke’s Surface Evolver software (15). Several different types of structure are shown, such as the
bamboo structure at λ values less 1.9 and the staircase structures at higher λ values. However, the
transition does not occur where the energy curves intersect but instead at λ = 2.2. From ref (39).

In addition, a series of experiments were carried out by Szekrenyesy and

coworkers (33) in which 3D foams were produced by raft preparation techniques,
with the aim of studying the stability of complex foam systems. The bubble rafts were
constructed by releasing bubbles from an orifice which rose to the air/water interface
in a temperature-controlled sealed cell which was designed to eliminate external
disturbances (Fig. 1.17). These rafts could be classified as (a) a single bubble on the
 1.7 Foam structures produced from bubbles with wide size distributions 21

Plan parallel
(a) glass plates
Seal

(b)

Teflon
ring
(c)

From
thermostate Capillary Gas From levelling
(d)
inlet vessel

(e)

Fig. 1.17 Model foam systems (left) consisted of (a) single bubbles, (b) 2D foam in steady state, (c) 2D foam
during decay, (d) three-bubble thick film, and (e) real foam and the apparatus for investigation
of foam models. From ref (33).

surface of a liquid; (b) a 2D foam consisting of a one-bubble thick foam film on the
surface of a liquid in the steady state; (c) the same system as (b) but in the state of
spontaneous decay; (d) a three-bubble thick foam in its steady state; and finally (e) a
thicker foam with similar features to a real practical foam, but not too far from its
original state and structure.
For each of the models, the stability of the bubble rafts was investigated from a
chemical approach by changing the surfactant and salt concentrations, the bubble
size and the foam complexity. These experimental models clearly demonstrated the
difficulties in simulating real foam systems. It was concluded that the dynamic processes
involved the thinning of lamellae, elasticity of the surface layer, hydrodynamics
and flow through the Plateau borders of different structure, gas diffusion, etc., were
inter-related and could not be modeled as separate entities.

1.7 Foam structures produced from bubbles with wide size distributions

A simple approach to foaming can be demonstrated by bubbling air through a glass frit
set in the base of a cylindrical glass column which contains an aqueous solution of soap.
Bubbles with sizes larger than several microns rise to the surface fairly rapidly due to
gravity, and the liquid is collected at the bottom of the column. The situation which
develops is shown in Fig. 1.18.
22 Basic principles and concepts

Fig. 1.18 The structures of foam occurring during formation and drainage of foam in a column. From ref (40)

In the foam column, several different transitional structures may occur with structures
having high gas fractions near the top of the column, graduating to low gas content
structures near the base of the column. The drainage of excess liquid from the foam
column into the underlying solution is initially driven by hydrostatics, which causes the
bubbles to become distorted. The pressure difference between neighboring cells (ΔP) is
related to the radius of curvature (r) of the Plateau border by ΔP = 2γ/r, as discussed in
Section 1.4. The generalized model for drainage involves the Plateau borders subsequently
forming a network, through which the liquid flows due to gravity. Foam collapse usually
occurs from the top to the bottom of the column, and thin films in the kugelschaum
(spherical) foam region are susceptible to rupture by shock, temperature gradients or
vibration. Within the column, the two fairly well-known, easily recognizable, more or
less extreme structures can be observed which have different degrees of wetness.
Overall, the foam may be considered as a temporary dilute dispersion of bubbles in the
liquid, but when the volume fraction falls below about 30%, they transform from their
spherical shape and distort into polyhedral gas cells with thin flat walls. The polyhedra
are almost regular dodecahedra, and the junction points of the interconnecting channels
are the Plateau borders. At any height in the foam column, the negative Laplace pressure
in the Plateau borders is γ/r, and this pressure is balanced by gravity (ρgHf), so that the
bubble size is related to the foam height by the equation

2γ
r¼ ð1:4Þ
ρgHf

where Hf is the height of the foam above the bulk liquid.

 1.8 Surface-active agents are needed to stabilize bubbles and wet foams 23

1.8 Surface-active agents are needed to stabilize bubbles

and wet foams

Since dry foams usually originate from bubbles which produce initially wet bubbly
foams, it is important to begin this introduction by briefly surveying the history and basic
physical chemistry of bubbles and wet foam systems. First of all, it is important to
stress that bubble formation and foaming are not trivial processes. Essentially, foaming
may be defined as a synergistic process where it is necessary to add a surface-active
material (a third component to the air/water mixture). The presence of a surfactant
entering the gas/liquid interface reduces the surface tension (lowers the interfacial
energy) relative to that of the pure liquid. For example, water has a surface tension of
72.8 mN m−1 at room temperature and lowers to about 35 mN m−1 upon addition of a
good surfactant.
Pure liquids of low viscosity, such as water, cannot produce wet foams unless a
surface-active material is present. In fact, when a gas bubble is introduced below the
surface of a pure liquid, it bursts almost immediately as soon as the liquid has drained
away, and although bubbles can be generated or produced by ultra clean water, they last
only a few milliseconds. A simple test for the purity of water can be made by vigorously
shaking the sample in a closed glass container. The purity of the water is usually
estimated from the bubble persistence time, and a bubble persistence of just one second
on water is an indication of the presence of a surface-active impurity, such as dust.
Hence, this bubble persistence can be used as a clear signal of impurities. However,
some degree of stability can be achieved by slightly impure, highly viscous fluids (such
as melted organic polymers) which sustain the thin film, and hence the foam structure,
due to low drainage. Generally, the cleanliness of the system and the vessel can have an
important influence on foaming.

1.8.1 The adsorption of chemical surfactants at the air/water interface

Since a surface-active foaming agent must be present in the aqueous environment to
produce bubbles and foam, it is important to consider them in detail. The most common
surface-active foaming agents are chemical surfactants, which can be considered to be
partially soluble molecules, have some affinity for the air/water interface and are
amphiphilic chemical molecules. They consist of a lipophilic tail which has a similar
form (usually a long chain hydrocarbon) and a hydrophilic head group which consists
of a range of different types of polar groups. These are two entities which are classified
as hydrophobic (water-avoiding or hating group) and hydrophilic (water-preferring
or loving groups) and they vastly differ in their solubility in water, which causes
them to rapidly adsorb at the air/water interface. The hydrophilic head groups have a
strong tendency to interact and solubilize in the water. The main types of surfactants are
distinguished and characterized by the head groups: ionic (anionic or cationic of
ampholyte) and nonionic. Several different types of surfactants structures are shown
in Fig. 1.19.
24 Basic principles and concepts

O
(a)
O–
Na+
O– O
O
S
O O
O
O

CH3
(b)
NH2+

CH3

(c) CONH(H2)3 N+ CH2COO–

CH3

(d)

O O H
n
O O n H

Hydrophobic Hydrophilic
fragment fragment

Fig. 1.19 Representative head-group structures of different surfactant classes; (a) anionic, fatty
acid and sodium di(2-ethylhexyl) sulfosuccinate; (b) cationics; (c) a group of
zwitterionic surfactants; (d) nonionic surfactants – alcohol ethoxylated branched and
straight-chained.

The most common type of surfactants are the anionic surfactants, which may be
expressed in the case of fatty acid by the formula RCOO− Na+, indicating its negative
charged functional head groups. Cationic surfactants often have quaternary amine
structures with the positive charge on the nitrogen atom and tend to adsorb on
negative-charged surfaces (e.g., glass and silica and are considered to be poor
foaming agents). Amphoteric surfactants exhibit both positive and negative charged
groups, thus exhibiting zwitterionic properties, so that the charge changes with
pH. Nonionic surfactants consist of hydrophilic head groups, and an important
 1.8 Surface-active agents are needed to stabilize bubbles and wet foams 25

Table 1.1 Commonly encountered hydrophilic groups in surfactants.

General class name General solubilizing structure

Sulfonate R—SO 3M
þ

Sulfate R—OSO 3 M þ
−
Carboxylate R—COO M+
Phosphate R—OPO 3 M
þ
0
Ammonium R—Nþ Rx Hy X ðx ¼ 1  3; y ¼ 3  1Þ
0
Quaternary ammonium R—Nþ R3 X
Betaines R—N (CH3)2CH2COO−
+

Sulfobetaines R—N+(CH3)2CH2CH2SO3−
Polyoxyethylene R—OCH2CH2(OCH2CH2)nOH
Polyoxyethylene sulfates R—OCH2 CH2 ðOCH2 CH2 Þn OSO 3 M
þ

Polyols R—OCH2 —CH(OH) — CH2OH

Sucrose esters R — O — C6H7(OH)3 — O —C6H7(OH)4
Polyglycidyl esters R — (OCH2CH[CH2OH]CH2)n –··– OCH2CH[CH2OH]CH2OH

class are the alcohol ethoxylated branched and straight-chained surfactants. In

Table 1.1 the most commonly encountered hydrophilic groups in chemical surfac-
tants are listed.
Block copolymers of type AnBm, where A chains are hydrophilic and B are
hydrophobic, are also surface active. There are many other common hydrophilic
groups found in commercial chemical surfactants such as phosphates, betaines,
polyethylene sulfates, and many different types of natural surfactants such as sucrose
and glucose types which are manufactured from plant oils. Various modifications
have been explored in the search for surfactants with improved functional foaming
performance. Recent developments in synthetic surfactants include Gemini surfac-
tants which consist of two lipophilic and two hydrophilic segments in the same
molecule, with the two surfactant portions separated by a spacer which can vary in
length. They give superior surface activity to conventional surfactants and, by
adjusting the spacer length, they can be designed to give low or high foaming
characteristics (41). A typical Gemini surfactant is shown in Fig. 1.20. Unusual
heterogemini surfactants with two different chains and two different head groups
have also been prepared.
Water is an unusual liquid in that it has a high surface tension (excess surface energy).
This results from its characteristic tetrahedral hydrogen-bonded structure. Although the
structure is not fully understood, it is generally accepted that weak fleeting hydrogen
bonds link the individual water molecules in bulk solution, but the links are weak and do
not completely break such that they experience symmetrical interactions in the
surrounding environment and are attracted iso-tropically (equally in all directions).
(42, 43). However, water molecules at the interface adopt a less balanced structural
arrangement leaving some with unequal attractive hydrogen bonding arrangements, as
shown schematically in Fig. 1.21(a). Although the standard model of water which was
Another Random Scribd Document
with Unrelated Content
as well nourish resentment against the rock on which it ineffectually
dashed itself. For the first time in her life Dora Fletcher had met a
man who was as indifferent to her feelings as he was to her sex,
and, curiously enough, she was not altogether displeased by this.
Calamity, meanwhile, was playing his own game in his own way.
Withdrawing into the shadows, he awaited the return of Skelt from
his murderous errand. He had not long to wait. A moment or two
after Dora Fletcher had been so curtly ordered back to her cabin, the
head of the ex-boatswain appeared over the taffrail. He cast a
hurried glance right and left, then cautiously clambered over the rail
and lowered himself on to the deck. As he did so a hand shot out
from the darkness and clutched his throat with a grip of steel. Not
until he was on the verge of being suffocated did the choking grip
relax, and then a hand fastened upon his shoulder.
"Silence. Come with me," said a voice which sent a thrill of terror
through him.
Skelt had no alternative but to obey, and so, with the Captain's
heavy hand still upon his shoulder, accompanied him into the cabin.
"Now," said Calamity as he seated himself and surveyed his prisoner,
"be good enough to explain this disobedience to orders."
The fellow looked at him in astonishment. It was disconcerting
enough to find himself a prisoner in the hands of the man he had
intended to murder, but it was amazing to be accused by him of
what sounded like a minor offence.
"I don't understand," he answered sullenly.
"Is that how you have been in the habit of addressing your
Captain?"
"Sir," growled the man.
"Remember that the next time you speak. Now then, what is your
excuse for being on the after-deck when, as you know, no men are
allowed there after sunset unless by express command?"
Something akin to hope arose in the ex-bos'n's breast. Could it be
possible, he thought, that the Captain was unaware of his real
intention and thought that he had merely disobeyed one of the
ship's regulations? And, being wholly ignorant of the extraordinary
methods of the terrible skipper of the Hawk, Jasper Skelt permitted
himself the luxury of a little secret contempt.
"I didn't know anything about the orders, sir," he answered.
"Indeed? Do you know the penalty for disobedience on board a
privateer?"
"No, sir."
"Death."
The man started nervously and turned a shade paler. Things were
not going quite so well as he had thought, after all.
"I've never been aboard a privateer before, sir," he replied humbly.
"So I presume. What's more, I don't think you're likely ever to be
aboard another."
Again the ex-boatswain glanced nervously at the skipper. The last
remark struck him as being unpleasantly ominous. The question
which followed confirmed his worst fears.
"Did the men know why you came aft to-night?"
"I—I can't say, sir," faltered Skelt.
"You mean to say that you told none of them what you intended to
do?"
The man's knees were trembling. He made an attempt to speak, but
seemed to choke before he could get the words out.
"Answer me!" rapped out the Captain, and Skelt started as if at the
sound of a pistol-shot.
"N—no, sir," he faltered, hardly realising what he said.
"Then I am to understand that they didn't know you intended to
murder me?"
Skelt's last hope deserted him. His face turned an ashen grey. He
tried to speak, but only a dry sob of abject terror escaped him.
"If you don't answer my question, you die inside two minutes," said
Calamity quietly.
"Not all of them, sir," replied the wretched man.
"You admit that you meant to kill me, then?"
"God forgive me, sir, I——"
"Never mind about God," interrupted the Captain grimly. "It's me
you're up against at the moment. Answer me, did all the men know
of this?"
"Yes, sir."
"And they were all quite willing you should do it."
"Only two objected, sir."
"Who were they?"
"Li Chang and Brunton, sir."
"But they made no effort to warn me."
"The others said they'd kill them if they did."
"I see."
Calamity leant back in his chair and surveyed his prisoner with the
calm, questioning scrutiny of a scientist surveying some new and
interesting specimen.
"So," he remarked at length, "it never occurred to any of you that I
might be acquainted with everything that went on in the foc'sle; you
even felt sure that I knew nothing of the little indignation meeting
you held last Sunday. You were actually such fools as to suppose
that, having shipped the worst gang of port vermin that ever soiled a
ship's decks, I should remain quietly in my cabin in the hope that
they were behaving themselves like decent men. I never thought
that rascality and faith went hand in hand."
Skelt made no answer, and the Captain rang a little hand-bell on the
table. Next moment the steward, a huge Chinaman called Sing-hi,
entered the cabin.
"You lingee?" he inquired.
"Yes." Calamity turned to the prisoner. "Have you anything to say?"
he asked.
"For God's sake don't be hard on me," implored the would-be
murderer with abject piteousness. "Give me a chance, sir, and I'll do
anything for you. Only one chance, sir, only one, and, before Christ,
I'll be your slave."
A queer smile came over Calamity's face as he regarded the cringing
servility of the ruffian.
"You would, would you?" he observed. "If I asked you to kill a
certain man fora'd while he was asleep, would you do it?"
"Yes, sir, if you'll spare my life. I'll do anything, sir!" cried the man,
with grovelling eagerness.
"You'd swear to do it?"
"I'll take my oath on the Bible, sir."
"I thought you would," answered the Captain grimly. "Steward, lock
the man up in your room and don't hesitate to kill him if he tries to
escape. Savee?"
"Savee plenty muchee," answered the huge Chinaman with a grin,
whereupon he caught hold of the ex-boatswain's collar, swung him
round, and hustled him out of the cabin. When they had gone,
Calamity arose and made his way to the bridge, where Mr. Dykes
was on watch.
"Anything to report?" asked the Captain.
"No, sir."
"How are you managing with the crew?"
"Well, sir, they ain't quite as peaceful as they might be; not since we
met the Ann."
"Indeed? why?"
"They seem to think we might have made her a prize and taken her
into port. In fact," added the mate, warming up, "I may as well tell
you there's going to be trouble, sir."
"Mutiny, you mean?"
"Yep, and when they start there'll be blue murder. It's that swine we
picked up that's been workin' the mischief."
"Then we must deal with him, Mr. Dykes."
"I guess it'll be a stiff proposition, Cap'n; he's gotten all the crew
behind him. D'rectly you lay hands on him, it'll be like a spark in a
powder-barrel."
"Then you regard him, virtually, as Captain of the ship?"
The mate made no answer, but shrugged his shoulders significantly.
He believed that, in utterly disregarding the wishes of the crew, and,
at the same time, maintaining an iron discipline, Calamity had bitten
off "a bigger chunk than he could chew." However, he considered it
prudent to keep this opinion to himself, and therein he was
undoubtedly right.
"By to-morrow morning," went on the Captain after a pause, "all
signs of mutiny will, I think, have disappeared."
"I hope to God they will, sir."
"I feel sure that an appeal to the men's reason, such as I shall make
to-morrow, will not fail in its effect."
"An appeal to their reason, sir!" gasped the mate.
"Yes. A mild demonstration of the absurdity of attempting to
mutiny."
"I don't get you, sir."
"No? Well, muster all hands on deck at eight bells. Good-night, Mr.
Dykes."
"Good-night, sir," answered the mate, and, walking to the bridge-rail,
expectorated over the side. "Well," he muttered, "if it ain't enough to
make a feller spit blood. An appeal to their reason! Gee, he'll be
holdin' family prayers in the cabin next."
At six bells, which was an hour before his watch was up, the mate
perceived a man mounting the bridge-ladder.
"Hello!" he exclaimed, "who are you?"
"Brunton, sir," answered the man.
"Well, what d'you want? It's not your watch."
"Have you seen Skelt, sir?"
"Seen Skelt!" roared the mate. "What the hell do you take me for?
D'you think I know where every perishin' son of a cock-eyed monkey
aboard this packet is?"
"He was going to murder the Captain, sir. I couldn't get away before,
as all the others were watching me. I only got out now because they
think he's funked it."
"Goin' to murder—here, fetch the second-mate up, quick!"
The man hurried to Smith's cabin and roused out the sleeping
occupant, who stumbled up to the bridge vomiting profanity of
varied hues.
"Get aft!" shouted the mate, "they're murderin' the old man."
Smith turned and dashed off to the Captain's cabin, which he
entered without even the ceremony of knocking. It was empty, but
from a small room adjoining came the sound of stentorian snores.
"Blimey!" muttered Smith, glancing round him. "He don't sound as if
he were dead."
His eye fell on the ship's log which lay open on the table.
Instinctively he glanced at it and, under the entry for the day, read
the following:
"Jasper Skelt, boatswain of the barque Esmeralda. Died at sea.
Cause, misadventure."
He slowly returned to the bridge and told the mate what he had
seen.
"You're sure he was alive?" asked the latter.
"Well, he was makin' a noise like a motor-'bus climbin' a hill,"
answered Smith.
At eight bells that morning Mr. Dykes, in quite a different frame of
mind to that of a couple of hours ago, sent the bos'n to muster all
hands on deck. The men tumbled out sullenly, muttering among
themselves in a manner which seemed to justify the mate's recent
warning to the Captain.
Suddenly one of them gave a cry.
In the clear, grey morning light, they beheld, hanging from one of
the derricks, the lifeless body of Jasper Skelt. His hands and feet
were tightly bound with cords, and he was suspended from the
boom by a rope round his neck.
Judging from the men's faces as they stared at the ghastly
spectacle, Calamity's "appeal" was not likely to prove a vain one.
 CHAPTER XI
THE FIGHT
The German gunboat, that the Hawk had been following so
assiduously, had disappeared in the fog of the Sunday on which the
Ann was stopped. Nevertheless, Calamity set the course each day
with an unhesitating decisiveness which seemed to suggest that he
had some definite plan in view. A day or two after that encounter a
large steam-yacht painted war-grey, and flying no ensign, was
sighted steaming in a northerly direction. Calamity, who was on the
bridge at the time, examined her through his glasses and then
handed them to Smith, the mate being below.
"What do you make of her?" he asked.
The second-mate, after a long and careful scrutiny, handed the
glasses back.
"Looks like a commerce-destroyer," he said, "but blowed if I can tell
what nationality she is."
"H'm, we'll soon find out," answered the Captain. "Go for'ad and
send a shot after her as soon as I've altered the course."
Smith left the bridge, and, mounting the foc'sle, took the tarpaulin
cover off the quick-firer which was mounted there. Meanwhile
Calamity had brought the Hawk's nose round so that he was now in
the wake of the strange ship.
"All ready, sir!" shouted Smith.
"Then let her have it."
The second-mate carefully laid the gun and next minute a shell went
hurtling over the yacht's stern; too high to do any damage, yet near
enough to make any nervous persons on board feel more nervous
still. The noise brought the privateer's crew tumbling on deck, eager
to see what was happening. Then, before the sound of the shot had
died away, the yacht was observed to be changing her course—
steaming round in the arc of a circle to starboard of the Hawk.
Obviously she was not running away, and the inference was that she
intended to fight.
"Pipe to quarters!" cried Calamity from the bridge; but before the
bos'n had time to obey the order the men were rushing to their
places. It seemed as if there was going to be a fight at last.
The yacht, a steamer of about 3,000 tons, came round with her
bows pointing towards the Hawk's starboard quarter, and, as she
reached that position, there came the sullen boom of a gun. A shell
whistled above the privateer's upper works, smashing to splinters
one of the boats which the carpenter had been repairing on the
davits. A second shot followed hard upon the first, and then a third,
which smashed one of the raised skylights above the engine-room,
sending a shower of broken glass upon the men below.
"Blimey!" ejaculated Smith as he stood by his gun, lanyard in hand,
"this looks like the real thing—not half it don't."
The damage done by the last two shots would have been greater
still had not Calamity thrust the quartermaster away from the wheel
and taken it himself. Under his control, the Hawk slewed round so
that she presented only her bows as a target for her opponent. As
the sound of the latter's guns died away, she was seen to hoist the
German naval ensign at her stern, while a signal hoist was run up to
the mast-head signifying "Surrender or I sink you."
There was a lull, the two vessels facing each other bows-on like a
couple of fierce dogs about to fight. Then a little bundle trundled up
to the Hawk's triatic stay, broke, and two burgees, one blue and
white, the other red, fluttered out in the breeze. It was Calamity's
answer: "Stand by to abandon ship." As his men looked up and read
the signal there was a burst of hoarse laughter, followed by a ringing
cheer. They realised the grim humour of the message, and
thoroughly appreciated it.
During the next half-hour the engagement consisted only of the
exchange of a few shots, one or two of which did damage on both
sides. The belligerents were manoeuvring for position, each trying to
force the other to fight facing the sun, which would, of course, place
him at a serious disadvantage. While these tactical evolutions were
in progress, a couple of the Hawk's men received wounds and Miss
Fletcher, who had been watching the spectacle through her cabin
porthole, rushed on deck, in spite of the risk she ran of being hit
herself. She was helping to remove one of the injured men, when
Calamity caught sight of her.
"Send that fool-woman to her cabin!" he roared to Mr. Dykes.
The mate hesitated. He was extraordinarily impressed by the girl's
plucky act, but the Captain's order, though a wise one, struck him as
being unduly harsh. Besides, he was loth to miss such a unique
opportunity of, perhaps, doing daring deeds under her very eyes.
"D'you hear what I say?" shouted the Captain.
"Excuse me, sir," he answered; "but who's to look after the wounded
if Miss Fletcher doesn't?"
"If the girl wants to make herself useful she can dress the men's
wounds in the hold. But I won't have a woman on deck during a
fight."
It was an ungracious order, but Mr. Dykes had nothing for it but to
leave the bridge and acquaint Miss Fletcher with the Captain's
instructions.
"The skipper's compliments," he said, "and would you attend to the
wounded when they're taken down to the hold?"
The girl glanced at him sharply; probably the hesitating manner in
which he spoke roused her suspicions.
"That's not what he said?" she challenged.
"Well, I guess it's as near as no matter."
"You mean he has ordered me off the deck?"
The mate made a deprecatory gesture and turned away. For a
moment the girl hesitated, half inclined to defy the Captain's orders
and remain on deck. Then the futility of any such act of defiance
occurred to her, and she returned to her cabin, locking the door
behind her.
"Oh!" she exclaimed, stamping her foot with rage, "I hate him!"
She continued to hate him ardently for a while, and then, as this
gave little real satisfaction, she opened her cabin door and peered
out just as Smith was passing.
"Are you going on to the bridge?" she asked.
"Yes," he answered, pausing.
"Then be good enough to tell the Captain that he can tend the
wounded himself," she burst out, and slammed the door before the
astonished second-mate could recover from his surprise.
He duly delivered her message, but it was doubtful if Calamity heard
it; certainly he made no comment, and Smith thought it wise to let
the matter go at that.
The two vessels were still fencing and manoeuvring, getting a shot
in when and wherever they could. But at last both the commanders
tired of these fruitless tactics, and then the engagement began in
real earnest. The yacht was armed with lighter guns than those of
her opponent, but she had more of them, and, in addition,
possessed the advantage of speed, being capable of answering her
helm twice as quickly as the privateer. This enabled her to swing
round at all angles, catch the Hawk broadside-on and sweep her
decks fore and aft. Notwithstanding this, she by no means had it all
her own way, for the privateer kept up a steady, well-trained fire that
made things aboard her adversary more than lively.
As only those men who served the guns were allowed on deck, the
casualties were relatively small on the Hawk. Whenever a man fell,
his place was taken by another from the reserve men in the foc'sle
and thus unnecessary losses were avoided. A hospital of sorts had
been rigged up in the for'ad hold and here the wounded men were
carried and placed on mattresses until such time as they could be
attended to.
Calamity had thrown off his jacket, and, with arms bared to the
elbows, was working the quick-firer on the bridge, three of the gun's
crew having been killed or wounded.
"Hit her amidships, in the engine-room!" he shouted to Mr. Dykes,
who had charge of the gun on the poop.
A minute or two later there was a loud explosion on the yacht,
owing to one of her guns being hit while loaded, by a shell from the
Hawk. A wild cheer went up from the privateers' men, and Calamity,
thinking he might board his adversary in the confusion, bellowed an
order to the quartermaster.
"Hard a starboard! Quick, damn your eyes!"
"Hard a——" the quartermaster started to echo, but before he could
finish a fragment of shell struck him, and Calamity, swinging round
to see what had happened, was bespattered with blood and brains.
He sprang to the wheel, and, pushing aside the dead body with his
foot, altered the helm. But it was too late, the other had divined his
purpose and was drawing off. Instantly the Hawk started in pursuit,
but, as she came round in the yacht's wake, a ricocheting shell
dropped through the engine-room skylight and there was an
explosion below which shook the vessel from stem to stern. Volumes
of hissing steam ascended through the gratings and ventilators,
while, above the roar, came the agonised shrieks of some wretched
firemen who were being scalded to death in the stokehold.
A man, his face a wet, shapeless, raw mass of flesh, stumbled out of
the fiddley, staggered a few paces, and fell sprawling on the deck.
Another followed whose hair, still attached to the skin, was falling off
in lumps, and he, too, collapsed on the deck. At the same moment
the steady throb of the engines ceased and the Hawk began to lose
way. Meanwhile the German had drawn off, and, for the time being,
firing ceased on both sides. The enemy, it would seem, was in little
better condition than the privateer, for she was steaming at a rate of
certainly not more than five knots. Calamity, watching her from the
bridge, cursed aloud as he saw his hoped-for prize slowly but surely
getting away while he was unable to prevent her or to go in pursuit.
"Send for McPhulach!" he cried; but, before anyone could obey, the
chief-engineer mounted to the bridge.
"I'm sair dootin' we'll hae to bide where we are," he remarked
placidly.
"Do you mean to say the engines are wrecked?" demanded Calamity.
"I wouldna go sae far as tae say that," answered the engineer. "Ye
micht speak o' them as assorted scrap-iron."
The Captain laid a firm hand on McPhulach's arm.
"You've got to repair those engines," he said quietly.
"Eh!"
"You heard me."
"Losh presarve us, mon, the A'michty Himsel' couldna do it!"
"The Almighty's not chief engineer of the Hawk, so you needn't
worry about that. Get those engines going or I'll string you up at the
end of a derrick."
"Guid God, are ye mad, mon!" gasped the engineer.
"Mad or sane, I'll do what I say."
"I tell ye the engine-room's like a steam-laundry," wailed McPhulach.
"There isna a pipe that isna squairting steam out of some crack or
itha, and it'll take all the cotton-waste in the ship to bind up the
leaks. It's a plumber's job, no' an engineer's."
"Well, if you can't do your job, I'll undertake to do mine," said the
Captain grimly.
McPhulach emitted a groan, then took from his pocket a short and
very rank briar pipe. A look of phlegmatic resignation had come over
his face.
"Maybe ye're richt, skipper," he said. "Hae ye got sic a thing as a
plug o' tobaccy on ye'r pairson?"
Calamity handed him a pouch of tobacco. McPhulach filled his pipe,
and, remarking that he might run short, also put some tobacco loose
in his pocket.
"Gin ye hae a match, I'll go below and see what can be done," he
said.
The Captain produced a box of vestas. The engineer lit his pipe, and,
absent-mindedly dropping the matches into his own pocket, left the
bridge.
The mate, meanwhile, had been superintending the removal of the
wounded and the washing down of the decks. Three men had been
killed, not including two firemen scalded to death in the stokehold,
and the wounded numbered eleven. The latter were made as
comfortable as possible in the hold and the former were carried into
the wheel-house pending burial.
Gradually the commerce-destroyer became smaller and smaller,
until, by evening, all that was visible of her was a feathery smoke-
trail on the horizon.
Soon after eight bells that night, McPhulach succeeded in performing
a miracle—the Hawk's engines began to move.
 CHAPTER XII
A DESPERATE VENTURE
Slowly, like a convalescent taking his first walk and as yet doubtful of
his strength, the Hawk began to push the seas aside and move
ahead. The engines, instead of working with rhythmic regularity,
were banging and thumping in jerky spasms—still, they were
working—the bridge shook with their ponderous vibrations, while the
wire funnel stays tautened and slacked as the smokestack quivered.
The first duty accomplished after the clearing up of the decks was
the disposal of the dead, which were placed in canvas bags weighted
with firebars to ensure their sinking. There were no prayers,
services, or ceremonies of any kind; they were simply dropped over
the side....
In the hold Calamity and the mate were at work with their coats off
and shirt-sleeves rolled up. Some of the hatch-covers had been
removed to secure better ventilation and a couple of lanterns
suspended from the girders flickered feebly in the semi-twilight.
Against the bulkheads were two rows of mattresses arranged so as
to leave a passage between them, and on some of these lay
wounded men, each with a coarse, black blanket thrown over him.
The Captain, assisted by Mr. Dykes, was attending to the more
serious cases in a manner which caused the mate considerable
secret astonishment. He had expected to see the skipper perform
the duties of surgeon in a rough and ready if not a brutal way, and
had felt a strong sympathy for his prospective victims. Instead,
Calamity handled the men with almost professional skill, performing
even serious operations with deft, quick fingers, and without either
nervousness or hesitation. A smile, a cheery word of
encouragement, a full-flavoured joke worked wonders, and a man,
even in excruciating pain, would grin feebly at some broad jest
uttered by the Captain.
Dora Fletcher, who had thought better of her first hasty decision,
was dressing some of the minor wounds. To her, Calamity's new rôle
came as a startling revelation of a hitherto unsuspected phase of his
character. She, who had seen him commit acts of unquestionable
brutality, now watched him pass from bed to bed with an air of quiet
assurance that inspired even the worst cases with new confidence
and hope. Men flinched apprehensively as he approached to
examine their injuries, but his touch, though firm, was as gentle as a
woman's, and their fears were quickly set at rest.
He scarcely even glanced at the girl, and when he did so it was to
give some curt directions as from a surgeon to a nurse. Yet she felt
strangely happy and triumphant, for at last he had been forced to
recognise and to demand her assistance. She felt herself necessary
to him, and the terse orders, involving her co-operation in the work
of succour, seemed to her a tacit admission of the fact. Henceforth
she would at least be an entity in his eyes; he would have to
acknowledge her existence, even if he resented it.
After the Captain and Mr. Dykes had gone; throughout the whole
night, indeed, the girl remained at her post. She found plenty to do;
giving cooling drinks to those whose throats were parched with
fever, readjusting dressings which had worked out of place, and
performing the hundred and one offices which fall to the lot of a
watcher of the sick. At intervals during the night the mate or Smith
would enter the dim hold, which now reeked with the pungent odour
of antiseptics, to proffer their services, and once Mr. Dykes tried to
persuade her to turn in. But she rejected the suggestion indignantly,
and ordered him out of the place, whereupon he departed
sheepishly. At about five o'clock in the morning Calamity looked in
again and seemed surprised to find her there.
"How long have you been on watch?" he asked.
"Since you left," she answered.
"Then you'd no right to. Dykes or Smith should have told off a man
to keep watch. Get off to your bunk. I don't want a sick woman
aboard."
Without a word she left the sick-bay, and then, for the first time,
realised how exhausted she really was. Without troubling to undress,
she flung herself upon the bunk and was asleep almost before her
head touched the pillow.
All that day and the next as well, the Hawk chugged her way in a
northerly direction, her speed never exceeding six knots and
sometimes falling below that. How McPhulach had contrived to patch
up her engines sufficiently to do even so much was a mystery no
one but himself could have explained. Still, they might break down
again at any moment, and it was absolutely necessary to find some
port where the repairs could be carried out more thoroughly, and
with the proper appliances. In the meantime much of the damage
sustained in the encounter with the yacht had been repaired. Paint
and canvas had done much to cover the effects of shot and shell,
and outwardly, at least, the Hawk had resumed her normal
appearance. But it was merely superficial, like the creams and
cosmetics used by a faded beauty to hide the ravages of time. In
fact she was, as Smith put it, "a whited bloomin' sepulchre."
On the second morning, as Miss Fletcher was going down to the
hold, she met Mr. Dykes.
"The skipper's orders are that you're to take four-hour watches, so
that you'll have a rest between each spell," he said.
She merely nodded and passed into the hold. The dim, yellow glow
of the lanterns was fading in the growing daylight, making the
surroundings more gloomy and depressing than even the half-light.
She moved from bed to bed with noiseless steps, performing various
little services for the sufferers. One man, who knew that he was
dying, asked her to write down and witness his last will and
testament—a curiously pathetic document—and for another she
wrote a letter that was to be posted at the first port the ship
touched. In a far corner she found a man making feeble efforts to
undo the front of his shirt. He was too weak to speak, and,
wondering what he wanted, the girl unbuttoned it to find a small
silver crucifix suspended from a piece of string round his neck.
Divining his need, she placed it in his hand, and the coarse,
misshapen fingers closed over the Symbol; thus he died.
Soon afterwards the Captain entered and passed between the beds,
stopping to ask each of the patients how he was getting on, and
giving a cheery word of encouragement to everyone. At last he
reached the bed where Dora Fletcher stood over the dead figure,
whose fingers still clasped the little silver crucifix.
"H'm," he grunted, "another loss. Anything to report?"
In a few words the girl described the condition and progress of the
various patients. At the conclusion Calamity nodded, but made no
comment.
"I should like to ask you a favour, Captain," she said quietly.
"A favour? Well, what is it?" he demanded in a tone that was the
reverse of encouraging.
"Do you think you could give this poor fellow"—she indicated the
dead man on the bed—"a Christian burial? I—I think he would have
wished it."
A look of mingled surprise and annoyance came into the Captain's
face as he glanced at the unconscious figure.
"The man's dead, isn't he?"
"Yes, of course," answered the girl, puzzled by the question.
"Then what difference can it make to him how he's buried?"
demanded Calamity, and, without waiting for an answer, walked
away.
Later on that day Mr. Dykes urged the request again at Miss
Fletcher's desire.
"I can't make distinctions," replied the Captain. "The man's got to
take his chance of paradise with the rest. I'm not going to give him
an unfair advantage over the others. Besides, this is a cheerful ship,
and I don't intend to depress the living by reading burial services
over the dead. They'll get their proper ratings without my
assistance."
So that evening the corpse, sewed up in canvas and weighted with a
piece of pig-iron, was cast over the side without ceremony.
Early on the following morning the look-out upon the foc'sle head
reported land on the starboard bow.
The news brought the men rushing on deck at once, for the sight of
land to sailors at sea is always an interesting event, savouring of
adventure, women, and wine. The news was immediately reported
to the Captain, who hurried on to the bridge and scrutinised the
seeming cloud for some time through the glasses which Smith, who
was on watch, handed to him.
"H'm," grunted Calamity, "an island."
"One of the Palau Group I should say, sir."
"Which means that it's German—eh?"
"Was German, sir," corrected the second-mate.
"There's no knowing; among so many scattered islands it's quite
possible that one or two may have been overlooked by our cruisers."
"Maybe, sir," answered Smith doubtfully.
Calamity again focussed the glasses on the dark smudge in the dim
distance. As he had just pointed out to the second-mate, it was
quite possible that some of the small islands which went to make up
what was once called the Bismarck Archipelago had escaped official
annexation. This seemed the more probable since two German
vessels, the gunboat and the commerce-destroyer, were apparently
still at large in these waters. Both ships, particularly the former,
would require a coaling station not too far away, and what more
likely, therefore, than that there should be one hidden away among
these innumerable islands?
The Hawk slowly bore down upon the land, but her speed was now
so reduced that night had set in before those on board were able to
get a really good view. By the following morning, however, they
found themselves within a mile of it, and its palm-fringed beaches
could be seen plainly from the deck. There was nothing about the
island to excite wonder or interest, save that it just happened to be
dry land amidst a boundless waste of blue waters. Numbers of such
islands, many of them far larger, were to be met with in these
latitudes.
Yet, because it was land, and suggestive of illicit pleasures, there
was an air of suppressed excitement aboard the Hawk. Throughout
the day she coasted slowly round it, but never once did a canoe or a
catamaran put off to trade; indeed, not a vestige of human life was
to be seen. At last, after they had nearly completed a circuit of the
island, a small harbour was sighted at the eastern extremity. On a
hill, overlooking the entrance, was a structure which suggested a
fort, and this at once gave Calamity the idea that the gunboat which
had hitherto eluded him was probably ensconced within this harbour.
To "dig out" the pirate and take possession of her spoils was the first
thought which occurred to him, but another and a stronger motive
made him decide to enter the harbour at all costs. This was the fact
that the Hawk's engines were next door to useless, and, unless they
could be more effectually repaired, would become entirely so. It was
quite possible, he reflected, that if the island really was a German
station, there would be appliances for dealing with engine-room
mishaps.
So, towards sundown, he steered boldly for the harbour, even
blowing the steam syren to call attention to his visit. The flagstaff on
the fort, he noticed, was bare, although as the Hawk drew nearer it
was possible to make out an inconspicuous wireless installation.
"German without a doubt," he remarked to himself. "If it were British
the Union Jack would be floating up there."
He turned to Mr. Dykes and in a few words explained what he
wanted done. The Hawk was to pose as a harmless American
merchantman which had put in for the purpose of trying to obtain
some coal. The large crew, totally out of proportion to the number
required to man a peaceful "tramp," were to remain in the foc'sle,
except one or two who were to lounge about the deck for show
purposes. Therefore in a very few minutes the decks were deserted
except for the look-out and a couple of grimy firemen who leant over
the bulwarks expectorating into the water. Half an hour later, the
Hawk reached the mouth of the harbour and the syren emitted three
ear-piercing shrieks.
The sound had scarcely died away when a boat, manned by natives
and with a white man seated in the stern-sheets, put off from a
small, wooden jetty beneath the fort. When within hailing distance,
the man in the stern stood up and put both hands to his mouth.
"Wie heisst das schiff?" he bawled.
"Don't get you," answered Calamity; "have another try."
"Vot schip vos dot?" bellowed the other, who was evidently some
sort of port official.
"This is the American steamer Hawk, Singapore for Valparaiso."
"Vy you no show your flarg?" inquired the official, his boat coming
nearer the Hawk every moment.
"Sorry; if I'd known it was your birthday, guess I'd have hoisted a bit
of bunting," replied the pseudo Yankee skipper, and gave an order
which resulted in the Stars and Stripes fluttering out astern.
The reply, however, did not appear to please the official.
"You 'eave-to!" he commanded. "I vant to see your papers."
Calamity rang down "Stop," the engines ceased thudding and a
couple of men came out on deck and threw a rope-ladder over the
side. A moment later the boat came alongside and the official, a
short, fat little man, ascended the ladder with some difficulty,
alighting on deck hot and breathless. Meanwhile his coffee-coloured
cox'n having made the boat fast to a rung of the rope-ladder, sat
down and lighted a cheroot.
"You vas der Captain?" asked the newcomer of Calamity, as soon as
he had recovered his breath.
"Yes."
"You must produce your papers."
"If you'll come with me, sir, I'll show them to you," answered
Calamity politely, and led the way towards his cabin.
Suddenly he stopped near the after-hatch, from which a couple of
the covers had previously been removed.
"Like to have a squint at the cargo?" he asked. "Guess it'll interest
you."
The fussy little man looked surprised at the question, but he stepped
up to the hatch, and, leaning over the combing, peered into the
obscure depths below. While he was still in this convenient attitude
an impelling force caught him in the small of the back, and he shot
downwards into the hold, alighting head foremost on a heap of
sand-ballast. Then, before he had recovered sufficiently to raise a
shout, the hatch-covers were promptly clapped on again and he was
left there in the dark to meditate on the ups and downs of a port
official's life.
Having satisfactorily disposed of this inquisitive person, Calamity
returned to the bridge and the Hawk began to steam slowly past the
fort into the harbour. Two or three sentinels on the hill watched her
progress, but they having seen her boarded by one of their officials
doubtless concluded that all was well. Meanwhile Mr. Dykes had
managed to convince the dusky cox'n in the waiting boat alongside
that his master would remain on board, whereupon the man saluted,
cast off the painter, and steered his boat shorewards.
When the Hawk had rounded the bend which hid the upper portion
of the harbour from view, Mr. Dykes gave vent to a sudden
exclamation of astonishment.
"Durned if that ain't our old bug-trap?"
Looking in the direction indicated by the mate, Calamity saw the
pirate gunboat beached just beyond the jetty and lying on her side,
evidently for the purpose of being repaired. His assumption, then,
had been correct: this island was a secret coaling station and place
of refuge for the very few German vessels which were still at large.
However, he made no comment aloud, and in a few more minutes
the anchor was let go and the Hawk swung peacefully at her
moorings.
The situation in which Calamity had voluntarily placed himself by
entering this harbour was, as he fully realised, fraught with infinite
peril. He knew that if he now attempted to escape he risked being
sunk by the guns on the fort, yet he could not remain where he was
much longer without being subjected to investigations which would
result in capture, if not worse. Under the circumstances, therefore,
there was only one thing to do, and that was to attack the fort and
capture it. This plan, viewed impartially, seemed hopelessly
impossible, especially if, as appeared highly probable, the fort were
strongly garrisoned. Still, Calamity did not hesitate between this and
the only alternative—surrender.
He sent for the two mates to whom, in a few curt sentences, he
outlined his plan of action. It was simple in the extreme, and, by
reason of its amazing boldness, might even be successful. The
Germans, he argued, though regarding the vessel with suspicion,
would hardly anticipate the landing of an armed party, which was
what he contemplated. The brief twilight would soon descend, and,
the Hawk being safely bottled up in the harbour, the enemy would
probably not worry much about her till the morning; therefore the
attack was to be carried out as soon as darkness fell.
When this had been explained Calamity and his officers set about
making preparations for the landing. A party consisting of as many
men as could be packed into the ship's boats was to effect a landing
under cover of the darkness, while those left on board were to open
fire on the fort with the machine-guns directly the enemy discovered
the attack. By this means it was hoped to cover the landing
operations and prevent the defenders turning their heavier guns on
the storming party. To this end Mr. Dykes was placed in temporary
command of the Hawk, Calamity himself undertaking to lead the
attack from the shore.
In a remarkably short space of time the preparations were complete,
and the only thing they waited for now was darkness—the swift,
enveloping darkness of the tropics.
 CHAPTER XIII
THE EBB TIDE
At last night came. Calamity gave the word and the men streamed
out of the foc'sle, some rushing to the falls ready to lower the boats
from the davits, others stowing arms and ammunition under the
thwarts. Every man had his own particular duty to discharge; there
was no confusion, no shouting of orders, no wild and objectless
rushing about—everything was done quietly and systematically.
"Stand by!"
The Captain's voice was low but penetrating. Everyone stood still at
his post.
"Slip!"
The boats dropped from the davits, the falls were cast off, the oars
flung out, and the bowmen stood up, ready to push off at the order.
Quickly, and with scarce a sound, the landing party swarmed down
the rope-ladders and took their places in the boats.
"Give way!"
As one man, the rowers bent to their oars, the boats shot out into
the darkness, and were lost to view by those left on board. The oars
had been muffled, so that the only sounds which could be heard
were the soft plash of the blades as they dipped into the water and
the creaking of the thwarts and stretchers. But soon these noises
died away in the distance, and then all seemed perfectly still to the
dark figures crouching beside the guns on the Hawk's decks.
About five minutes after the boats had left a tongue of flame
suddenly leapt from the fort, followed by a dull boom. Evidently the
Germans had just discovered the attack, and were attempting to
sink the boats before they reached the shore. The sound of the gun
had scarcely died away when Mr. Dykes passed the word to open fire
on the fort, and there ensued a lively duel between the latter and
the Hawk. As it was a pitch dark night, each side had to guide its fire
by the flashes of the enemy's guns, so that, at first, the shooting
was somewhat erratic. But, after a while, the Germans began to get
the range of the Hawk and to make such good practice that Mr.
Dykes had to order some of his men to fill bags with sand ballast
and stack them along the bulwarks to afford additional protection to
the gun crews. Unfortunately, the enemy's guns were of much
heavier calibre than the Hawk's, so that, when a shell struck the
vessel, it did considerable damage.
"By Gum!" ejaculated the mate, "this is getting durned hot."
He had not reckoned upon receiving such a tremendous fusillade
from the fort, and, though by no means a timorous man, began to
fear that the Hawk would be sunk at her moorings. So far as he was
able to tell at present, there had been only a few casualties on
board, the bulwarks and sandbags affording an excellent protection
for the men working the guns, although, had it been daylight, these
would probably have been of little avail. But the steamer herself had
suffered considerably; the deck-houses were mostly in splinters, all
the skylights had been smashed, and where the funnel had once
stood there was now only a jagged stump. Once the enemy
succeeded in battering down the defences, his guns would simply
annihilate every living thing on board.
"I wish some of them shells would cut our cables," he murmured to
himself, "then we could just skidoo out of the harbour, and the old
man couldn't say a word."
The notion of slipping the cables himself and creeping out of the
harbour occurred to him more than once, but each time he
dismissed it from his mind. It would certainly savour of cowardice to
leave Calamity and his men on the island without a chance to
retreat, while, if the Captain should ever succeed in getting within
reach of him afterwards, the consequences would be very far from
pleasant.
By this time one of the Hawk's machine-guns had been put out of
action, and still the fort kept up an unceasing bombardment. Mr.
Dykes was now fervently hoping that Calamity would abandon the
attack, return on board, and get out of this hornet's nest with all
possible speed—if, of course, the steamer was not already too
battered about to get under way. With this possibility in view, he
sent a man to fetch McPhulach and was exceedingly surprised to
learn that the engineer could not be found.
"Ain't he in his cabin?" he inquired.
"No, sir, nor yet in the engine-room," replied the messenger.
"But he must be, the skipper said he was to stand by the engines."
"'E's not there," repeated the man.
"See if he's in the alleyway."
The man departed but returned with the information that McPhulach
was not in the alleyway. Moreover, nobody on board had seen him
since the landing party left.
"Fetch up Mr. Sims," said the mate.
Mr. Sims was the second-engineer, a melancholy man with watery
eyes, a pallid face, and chronic dyspepsia, who never mixed with the
other officers or uttered a word if he could possibly help it. He was,
too, an indifferent engineer; but, as McPhulach had once said, the
biggest success as a nonentity he had ever met.
"How long will it take us to get under way?" inquired the mate when
Mr. Sims appeared.
"Half an hour, may be."
"What!" ejaculated Mr. Dykes.
Mr. Sims nodded in confirmation of his statement.
"Ain't there no steam, then?"
Mr. Sims shook his head.
"Then what in thunder have you been doing down there? Didn't you
have orders to keep up a full head of steam?"
Mr. Sims nodded.
"For God's sake use your tongue, man," roared the mate. "Why ain't
there no steam?"
"Because all the firemen are on deck."
Mr. Dykes almost danced with rage, yet this time he could say
nothing for the simple reason that he now recollected having
ordered all hands on deck for the purpose of serving the guns and
passing up ammunition out of the hold.
"Oh, get to hell out of it!" he spluttered and Mr. Sims vanished back
into obscurity.
Having despatched some firemen below to get up steam, the mate
again fell to considering the advisability of drawing off since the
enemy's fire showed no signs of slackening. To do him justice, it was
not from fear of being himself hit at any moment, but rather from a
vivid anticipation of the fate in store for him and the others on board
if they fell into the hands of the enemy. Still, if Mr. Sims's report was
correct, nothing could be done for at least half an hour.
In order to assure himself that the firemen were doing their utmost,
Mr. Dykes left the bos'n's-mate in charge of the deck and descended
to the stokehold—a thing he would not have dared to do had
McPhulach been on board. Having ascertained that there was
already a fair pressure of steam, he returned to the deck and
personally tested the capstans used for hauling up the anchors.
"I'm goin' to get out of this death-trap," he said to the bos'n's-mate,
"so stand by to pick up the anchor. Keep the men at the guns till I
give the word to cease firing, else them durned Germans will smell a
rat and butt in before we can quit."
"'Ow about the Cap'n, sir?" asked the man doubtfully.
"Damn your eyes, do what I tell you, and don't ask fool questions!"
snapped the mate.
The man walked away, somewhat unwillingly Mr. Dykes thought,
which made him all the more angry and determined to carry out his
plan. He wasn't going to be dictated to by a swab of a bos'n's-mate
or anyone else so long as he was in charge of the ship.
Having rung down "Stand by" to the engine-room, he went on to the
foc'sle head to superintend the weighing of the anchor. When all was
ready and he was about to pass the word to the man at the steam
capstan, Miss Fletcher suddenly appeared on the foc'sle.
"What are you going to do?" she asked.
"Get under way," he answered curtly.
"And leave the Captain and his men in the lurch?"
"There ain't any Captain, nor men either, by now, so just quit this
foc'sle," answered the mate in a voice of suppressed rage.
"That's as it may be," said the girl quietly, "but you're not going to
heave that anchor."
"Eh!" exclaimed Mr. Dykes, scarce able to believe his ears.
"I say that you shan't leave this harbour till the Captain comes on
board."
For a moment Mr. Dykes was so overcome with mingled
astonishment and indignation that he could not speak. Then,
uttering an oath, he sprang towards her, apparently with the
intention of thrusting her off the foc'sle. Suddenly, however, he
stopped dead as he caught sight of a revolver in the girl's hand.
Then, while they still stood eyeing each other, the vessel gave an
unexpected lurch which nearly threw them off their feet. The mate
sprang to the side and gazed down into the dark water below.
"Euchred!" he ejaculated. "The tide's runnin' out and we're fast
aground."
 CHAPTER XIV
THE ATTACK
Having failed in his attempt to effect a landing without discovery,
Calamity regarded the crossfire between the fort and the Hawk as
the next best thing, as it would to some extent distract the attention
of the Germans from his own operations. Nevertheless, the
defenders did not concentrate their fire wholly on the steamer, and
some of their guns were firing, more or less promiscuously, into the
harbour. Fortunately, they did not appear to have either searchlights
or illuminating shells, for it was only the darkness and consequent
inaccurate aim of the gunners that prevented the little force from
being annihilated before a single boat touched the shore. Even as it
was, the water around them was constantly sending up cascades
where shells or fragments of bursting shrapnel struck it.
"Pull like hell!" roared Calamity above the din.
The men needed no urging and the boats leapt through the water
with oars that bent under the strain. Suddenly, above the thunder of
the guns, a terrible cry was heard, and where there had been a
boatload of men a moment before, there was now only some
splintered wreckage with a few wounded men clinging to it. Yet none
dared go to their assistance for that would have meant inevitable
destruction now that one, at least, of the enemy's guns had found
the range. So, deaf to the shrieks of their comrades, the men in the
remaining boats pulled like demons, expecting every moment to be
blown out of the water by a well-placed shot. But at last the first
boat, which was under the charge of the Captain himself, grounded.
The men leapt out, waist-deep in the water, and, grabbing their rifles
and cartridge belts, waded ashore. The other boats quickly followed,
and Calamity, collecting his force, led it up the beach at the double
towards some warehouses or "go-downs" that served to screen the
enemy's fire.
Here he let them have a few minutes "stand-easy," while he
consulted with his lieutenants, Smith and the bos'n. He had already
formed a fairly accurate idea of the nature and strength of the
defences to be overcome, and had arranged his plans accordingly.
The fort, so far as he had been able to ascertain with the aid of
glasses when steaming past it, appeared to be built principally of
mud and shale with an outer defence consisting of a tall bamboo
stockade. The approach from the harbour side consisted of a very
steep incline which seemed totally devoid of any sort of cover and
without anything in the nature of a road or track. But the fact that it
was so steep placed the defenders at one disadvantage, because it
made it practically impossible for them to train their big guns on the
attacking force, although a well-directed musketry fire could not fail
to cause fearful havoc in the latter's ranks. Still, Calamity's chief
asset was the darkness, which, for one thing, prevented the
Germans from seeing what a ridiculously small force he had with
him.
Calamity gave the order to advance, the party left the shelter of the
"go-downs," and moved towards the hill in open order. It was not till
they started to climb that the enemy showed himself to be aware of
their presence on the island. Then a brisk rifle-fire was opened on
them from the fort, but the aim was too high, and the bullets flew
harmlessly above the sailors' heads. Even by the time they were
halfway up, only one man had been hit, and his wound was so slight
that he continued to advance with the others. But now with each
forward step the danger increased, and, as the attackers drew
nearer and nearer to the stockade the bullets came perilously near,
one or two men dropping out of the advance. But the long, thin line
of creeping figures never wavered, though not one of them had as
yet fired a shot. For the last fifty yards or so they simply crawled
forward on their bellies, while a hail of bullets whistled above their
heads.
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