Scattering Methods and their

Application in Colloid and Interface

Science - eBook PDF
Visit to download the full and correct content document:
https://ebooksecure.com/download/scattering-methods-and-their-application-in-colloid
-and-interface-science-ebook-pdf/
SCATTERING METHODS AND THEIR
APPLICATION IN COLLOID
AND INTERFACE SCIENCE
 SCATTERING
METHODS AND THEIR
APPLICATION IN
COLLOID AND
INTERFACE SCIENCE

Otto Glatter
Department of Inorganic Chemistry,
Graz University of Technology,
Graz, Austria
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
Copyright r 2018 Elsevier Inc. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any means, electronic or
mechanical, including photocopying, recording, or any information storage and retrieval system, without
permission in writing from the publisher. Details on how to seek permission, further information about the
Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance
Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.
This book and the individual contributions contained in it are protected under copyright by the Publisher (other
than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden our
understanding, changes in research methods, professional practices, or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using
any information, methods, compounds, or experiments described herein. In using such information or methods
they should be mindful of their own safety and the safety of others, including parties for whom they have a
professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability
for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or
from any use or operation of any methods, products, instructions, or ideas contained in the material herein.
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library
Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress
ISBN: 978-0-12-813580-8

For Information on all Elsevier publications

visit our website at https://www.elsevier.com/books-and-journals

Publisher: John Fedor

Acquisition Editor: Anita Koch
Editorial Project Manager: Emily Thomson
Production Project Manager: Vijayaraj Purushothaman
Cover Designer: Matthew Limbert
Typeset by MPS Limited, Chennai, India
 Preface

Scattering methods like small-angle X-ray and neutron scattering (SAXS and SANS), as
well as static and dynamic light scattering (SLS and DLS), have become leading techniques
for the characterization of structure and dynamics in soft matter. Scattering methods are
integral techniques; this means that the investigated area, the scattering volume, is several
orders of magnitude larger than the structures of interest. In most cases, the scattering vol-
ume has dimensions in the regime of millimeters, while the structures of interest can range
from nanometers to several micrometers. This means that typically one measures the con-
tribution of a larger number of scattering centers or particles, even in the case of dilute
systems. This method has the advantage of a relatively strong signal, quick acquisition of
statistically relevant data, and the experiments give a representative overview of the exist-
ing structure. The disadvantage is that no information about individual particles is avail-
able, and that the systems are in most cases not oriented. Complementary techniques with
a high spatial resolution like electron microscopy or atomic force microscopy are, there-
fore, of great importance to get a complete picture of the systems under investigation, but
will not be discussed here.
Soft matter, also called soft condensed matter, includes a wide range of systems and
materials. It is maybe easiest to define what is not included in soft matter: solids, gases,
simple fluids, and crystals. However, liquid crystalline systems are also soft matter, as
well as many complex fluids, colloidal dispersions, and gels. Soft matter science includes
colloids, polymers, and surfactant systems. Surfactants and other amphiphilic systems are
of increasing importance, due to their ability to form self-assembled systems, a key point
in the formation of nanostructured materials and nanotechnology. Molecular self-assembly
leads automatically to nanostructured systems. However, the length scales of interest
range from nanometers up to several micrometers, and to macroscopic dimensions in hier-
archically organized systems. This also leads to a wide range of interesting time-scales of
dynamic behavior, ranging from nanoseconds to several hours when fluid systems show
arrested dynamics. Soft matter science has a strong overlap with biosciences, physics, and
chemistry, especially with polymer research and more generally, with materials sciences.
One or the other aspect of these fields is taught in most universities, but scattering meth-
ods are hardly part of the curriculum.
It is impossible to cover all aspects of scattering methods and their application to soft
matter in one book. Here, I want to give a somewhat detailed introduction into SAXS,
SANS, SLS, and DLS based on my personal experience in these fields over more than 40
years, including typical examples manifesting the possibilities and limitations of these
methods. This contribution is not meant as a review of the existing literature, and is cer-
tainly biased by my personal view. Therefore, some related research fields are completely
missing, like grazing-incidence small-angle scattering (GISAXS and GISANS), inelastic

ix
x PREFACE

neutron scattering, reflectivity measurements, Fraunhofer scattering, and diffusive wave

spectroscopy. This is not because I consider these fields less important, but because of my
missing knowhow.
The limitation to my personal experience is maybe also the main difference to multiau-
thor books in this area, in which recognized experts in the different subsections give an
overview from different viewing angles. A typical example of this is the book edited by P.
Lindner and Th. Zemb (Lindner, P.; Zemb, T. Neutrons, X-rays and Light: Scattering Methods
Applied to Soft Condensed Matter. Elsevier Science: Amsterdam, 2002.).
This book is based on my experience in teaching in this field. I have to thank genera-
tions of students for their interest and challenging questions. This is not restricted to my
students in Graz, Austria, but also in many places all over the world. In the first place I
would like to mention all the participants of the, until now, 13 “Bombannes Schools” on
“Scattering Methods Applied to Soft Condensed Matter” but I should mention also my
students in Leuven, Belgium; Roskilde, Denmark; Turku, Finland; Ystad, Sweden;
Yokohama, Japan; Singapore; and Berlin, Germany.
Of course I also have to thank my undergraduate, graduate students, and postdocs over
the many years. Either they have contributed to one or another methodical detail of the
scattering and evaluation techniques, or they have helped to gain a deeper understanding
of these methods in various applications. So my thanks go to Heribert Fuchs, Michael
Hofer, Elisabeth Maurer- Spurej, Heimo Schnablegger, Norbert Maurer, Karl Gruber,
Judith Brunner-Popela, Dieter Lehner, Sabina Haber-Pohlmeier, Bertram Weyerich, Gerd
Kroner, Gerhard Popovski-Fritz, Alexander Bergmann, Doris Orthaber, Anna Stradner,
Rainer Mittelbach, Helmut Lindner, Josef Innerlohinger, Andrej Jamnik, Thomas Röder,
Thomas Frühwirt, Liliana de Campo, Anan Yaghmur, Christian Moitzi, Norbert
Freiberger, Martin Medebach, Samuel Guillot, Stefan Salentinig, François Muller, Anniina
Salonen, Matija Tomšič, Sandra Engelskirchen, Martin Dulle, Angela Chemelli, Patrizia
Foditsch, Roman Geier, Manuela Maurer, Chandrashekhar Kulkarni, Silvia Ahualli,
Guillermo Iglesias Salto, and Franz Pirolt.
In Chapter 1, Interference, Rayleigh Debye Gans Theory, the principles of scattering
are discussed. Similarities and differences to spectroscopic experiments will be summa-
rized briefly, and then the interference of the scattering wavelets, resulting in the scattered
field, will be discussed. This section includes two important steps: as we cannot measure
electric fields at these high frequencies, we have to proceed to the measurable scattering
intensities, including the averaging process necessary for isotropic, nonoriented samples,
followed by a section on the Rayleigh Debye Gans Theory. Here, we start off from the
simplest case: dilute and monodisperse systems. The important concept of the pair 2 dis-
tance distribution function, PDDF, the Fourier transform of the scattering intensities, is
introduced. The correlation length and chord distribution are of less practical importance,
but are added for the sake of completeness.
In Chapter 2, General Theorems and Special Cases, several general theorems are pre-
sented and special cases are discussed. The theorems include the concept of the Guinier
approximation, which results in the radius of gyration—or Guinier radius, and the Porod
law, which gives access to the surface of the particles. The special cases of spherical sym-
metry, elongated, rod-like particles, and flat lamellar particles are discussed in this section,
followed by the cases of aggregates and polydisperse systems.
 PREFACE xi
In Chapter 3, The Inverse Scattering Problem, the inverse scattering problem for dilute,
noninteracting systems is discussed in some detail. The scattering problem is concerned
with the calculation of the scattering function (scattering curve and the PDDF) for particles
of known size, shape, and internal structure. The inverse scattering problem deals with the
recognition of structural details of unknown particles from their scattering pattern. There
is no unambiguous way to calculate the three-dimensional structure of a scatterer from the
one-dimensional scattering function. In this chapter, a series of examples of different
shapes of homogeneous scatterers will be given in real (PDDF) and reciprocal space (scat-
tering function), in order to introduce the possibilities of extracting simple structural
details. This concept is also extended to hollow and inhomogeneous structures. For spheri-
cal, cylindrical, and lamellar symmetry, there is no loss of information and the PDDF can
be deconvoluted into the radial scattering length density profile, i.e., a direct structure
analysis is possible. A short overview describes the special situation for polymer chains.
Several parameters can be extracted directly from the scattering data.
In Chapter 4, Concentration Effects, Interactions, the condition of dilute systems is abol-
ished, i.e., particle interactions are no longer negligible. In such systems, we have to con-
sider intra- and interparticle contributions to the scattering process. This situation can be
described by the so-called form and structure factors. This concept can be applied to
spherical or globular particles, to lamellar stacks or hexagonally ordered rods.
In Chapter 5, Absolute Intensity, SAXS, and SANS, we discuss how experimental SAXS
and SANS data can be put on an absolute scale to make the results independent of the
actual experimental situation. The special case of light scattering will be discussed later in
Chapter 9, Static Light Scattering From Small Particles.
Chapter 6, Contrast Variation, is dedicated to contrast variation, and discusses the pos-
sibility of varying the contrast between the scatterers and the surrounding medium. This
can help to optimize the absolute scattering intensity, to highlight the contrast of special
regions in the sample or to avoid multiple scattering. This topic is of special importance
for SANS.
In Chapter 7, Instrumentation for SAXS and SANS, the possible instrumentation for
SAXS and SANS experiments is discussed in some detail, together with the instrumental
broadening effects. The instrumental broadening functions are important for necessary
corrections in the evaluation procedures. Again, instrumentation for light scattering
experiments will be discussed later in the specialized Chapters 9 2 11.
Chapter 8, Numerical Methods, gives an overview of the different evaluation schemes
necessary for data treatment. After some primary data handling, data can be approxi-
mated (smoothing of statistical fluctuations), corrected for instrumental broadening, and
Fourier transformed into real space (PDDF) in one process by using the indirect Fourier
transformation (IFT) method. This technique can be extended to a concentrated interactive
system as the so-called generalized indirect Fourier transformation (GIFT) technique. In
the case of special symmetry, the PDDF can be deconvoluted into the radial density distri-
bution by using a convolution square root (or simply speaking, deconvolution) technique.
Finally, simple methods for model calculations are presented.
Static light scattering (SLS) from small particles—small compared to the wavelength—is
discussed in Chapter 9, Static Light Scattering From Small Particles. This chapter includes
sections on absolute scale and contrast, as well as parameter determination.
xii PREFACE

Chapter 10, Light Scattering From Large Particles: Lorenz 2 Mie Theory, discusses SLS
from large particles. Large means their size is in the order of the wavelength of light.
Interaction of light is much more complicated in this case, as there exist possibilities of
surface resonances. The corresponding theory—known as Lorenz Mie theory—is dis-
cussed in some detail. Such large particles have a very high scattering power, and there-
fore multiple scattering is an important issue here. Finally, design principles of SLS
instruments are discussed.
The last scattering technique, DLS, is discussed extensively in Chapter 11, Dynamic
Light Scattering (DLS), including basic principles, experimental details, and evaluation
techniques. DLS is mostly used as a fast technique for particle sizing in dilute systems,
using translational diffusion measured in a homodyne experiment. However, it is also pos-
sible to learn about particle interactions from concentration series, and finally one can
study solidifying systems with a so-called ergodic-to-nonergodic transition (also some-
times called glass transition, jamming, or gelation). Rotational diffusion can be measured
for nonisotropic scatterers like rod-like particles by depolarized DLS (DDLS), measuring
only the depolarized component of the scattered light. The electrophoretic mobility is
accessible from electrophoretic DLS (EDLS) measurements performed in a so-called het-
erodyne mode. Moving or flowing samples, like soot particles in a flame, can be measured
in specialized DLS setups.
Even though some examples have been given throughout the previous chapters, the
subsequent two chapters will give more examples to demonstrate the applicability of the
scattering techniques. Chapter 12, Dilute Systems: Practical Aspects—Applications, is
restricted to dilute systems, while in Chapter 13, Concentrated, Interacting Systems:
Practical Aspects, Applications, examples of applications to interacting dense systems are
given.
Glasses, liquid crystals, and gels are typical examples of dense and highly viscous sys-
tems. Some applications in this direction are discussed in Chapter 14, Glasses, Liquid
Crystals, and Gels.
In the Appendix the basic principles of statistical thermodynamics and their relation-
ship to particle correlation functions are summarized to assist the theoretical description
of the structure factor in Chapter 4, Concentration Effects, Interactions.
As already mentioned, this presentation is far from complete, but it should give a good
entry into and overview of the scientific field of scattering techniques, and their applica-
tion to soft matter. Finally, the reference list should help the reader to find the relevant
original literature for further in-depth studies.
 C H A P T E R

1
Interference,
Rayleigh
Debye
Gans Theory

INTERFERENCE OF SCATTERED WAVES

When an electromagnetic wave is sent through a thin slab of material, the electric field
will introduce a polarization of the atoms, leading to the formation of little dipoles. The elec-
tric field oscillates with a frequency that is defined by the wavelength of the radiation sent
into the material, so the dipoles will oscillate in a forced motion with the same frequency.
Around the turn of the last century, H.A. Lorentz1 developed a classical theory of the
optical properties of matter. He treated electrons and ions as simple harmonic oscillators
(springs), which are moved by the driving force of the electromagnetic field. The results of
this procedure are qualitatively identical to those resulting from a quantum mechanical
treatment of these problems, even though quantities are interpreted differently in the clas-
sical and in quantum mechanical theory.2 The principles of the Lorentz model are essential
to understand the connections between spectroscopy and scattering, but we want to focus
here on the scattering process only. The interested reader will find an excellent overview
of the Lorentz model in Marshall (1978).2
It can be shown that a wave is not only partially absorbed by matter when passing
through a thin slab of material (exponential decrease), but also gives rise to a scattering
field, as every accelerated electric charge emits an electric field with an amplitude propor-
tional to the acceleration.3 In spectroscopic experiments we are interested in absorption
phenomena, i.e., we check the frequency-dependent absorption of radiation to find the
resonances of the systems. This frequency range close to the resonance is called the
Lorentz limit. In scattering methods we try to stay far away from these resonance frequen-
cies, ω0. For low frequencies, i.e., ω{ω0, we are dealing with the Rayleigh limit, which
holds for visible light, and for high frequencies, i.e., ωcω0, we are dealing with the
Thomson limit, which holds for X-rays. In both regimes we are interested in the scattering
wavelets that are emitted from these oscillating dipoles.
At the moment, it is only important to notice that the energy of X-rays is high enough
to be above the resonance regime ω0 for most soft matter materials and to polarize all

Scattering Methods and their Application in Colloid and Interface Science

DOI: http://dx.doi.org/10.1016/B978-0-12-813580-8.00001-8 1 © 2018 Elsevier Inc. All rights reserved.
2 1. INTERFERENCE, RAYLEIGH
DEBYE
GANS THEORY

electrons, also those in the innermost shells of the atoms, and therefore every electron in
the illuminated volume will give rise to a scattered wave. In the case of visible light the
situation is very different. The energy is lower than that of X-rays by a factor of about
4.000 (defined by the ratio of the wavelengths). This lower energy corresponds to lower
frequencies (ω , ω0), and can only polarize the electrons in the outer shell, typically the
valence electrons. Fortunately we have easy access to this polarizability as it is propor-
tional to the refractive index of the material. This fact will be discussed in more detail in
Chapter 9, Static Light Scattering From Small Particles. Here, we focus on X-ray scattering
and we ignore all prefactors relating the amplitude of the scattered wave to the amplitude
of the incoming plane wave. We set the scattered field amplitude as equal to one, because
we are not interested in the amplitude of the single scattering waves, but we want to dis-
cuss how they sum up (interfere) to the total scattering field. We discuss a virtual particle
in a vacuum with a volume V and a distribution of electrons that results in an electron den-
sity ρ(r) (number of electrons per volume element dV) at position r.
We now let a plane wave hit this particle. All scattering waves are coherent, i.e., there is
a fixed phase relation between the incident radiation and the scattered waves, and both
fields have the same frequency. Incoherent (Compton) scattering can be neglected for our
scattering process with X-rays, but is important in the case of neutrons.
The different waves will differ only in their relative phases ϕ, which will depend on the
position of the scattering centers relative to each other. The phase difference relative to an
arbitrary reference beam is given by the difference of the path lengths multiplied by the
wave number k 5 2π/λ, where λ is the wavelength of the radiation in the material. For a
traveling wave, the wave number gives the change in phase per length. This phase change
is, of course, equal to 2π if the wave has traveled one wavelength.
We choose an arbitrary reference point O in the body, and consider a beam through
this point as a reference beam. The direction of the incident beam is defined by the unit
- -
vector s0  s0 ; the direction of the scattered beam is given by s  s (see Fig. 1.1). The
path-length difference of the reference beam and a beam through the point P is:
a 2 b 5 rs0 2 rs 5 2 r ðs 2 s0 Þ; (1.1)
so we get the phase difference ϕ by multiplication with the wave number:
ϕ 5 2 ð2π=λÞ r ðs 2 s0 Þ (1.2)
We now introduce the scattering vector q with:
q 5 ð2π=λÞ ðs 2 s0 Þ: (1.3)

FIGURE 1.1 Path-length difference of two rays.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

 INTERFERENCE OF SCATTERED WAVES 3
FIGURE 1.2 The scattering vector q.

and so we get:
ϕ 5 2qr (1.4)
The difference vector (s 2 s0) lies symmetrically with the incident and the scattered
beam, or orthogonal to the “mirror plane” (dashed line in Fig. 1.2) and its magnitude is
2sin(θ/2), where θ is the scattering angle. Contrary to what older textbooks on small-angle
scattering tell us, we do not use 2θ as the scattering angle; such a definition would contra-
dict the usual definition in light scattering!
The scattering vector q has the same direction as (s
s0), and its magnitude is given by
the magnitude of (s 2 s0), 2sin(θ/2) (see Fig. 1.2) multiplied by the wave number 2π/λ:


4π θ
q 
q
5 sin (1.5)
λ 2
For small angles sinθ/2 may be replaced by θ/2, i.e., q, the magnitude of q is propor-
tional to the scattering angle θ (to be given in radians). The dimension is [length]21,
depending on the choice of λ. We use nanometers for the wavelength, so q has the dimen-
sion nm21. It should be noted that many other symbols are used in literature for the scat-
tering vector, like h, k, s, Q, etc., sometimes with a slightly different definition (missing
factor 2π). For all theoretical considerations, we shall use the scattering vector instead of
the scattering angle. This makes all our results independent of the wavelength used. It
should be kept in mind, however, that a certain q value will lead to different scattering
angles for different wavelengths! To summarize: the scattering vector has a magnitude
proportional to the scattering angle θ, has the dimension nm21, and its direction is not the
direction of the detector but points into the bisecting line between the incoming beam and
the detector direction.
Now let us come back to the phase difference ϕ. The scalar vector product qr in
Eq. (1.4) means that only the component of r that is in the direction of q is relevant for the
phase. This implies that all points in a plane perpendicular to q will have the same phase.
Scattering might, therefore, be regarded as a “reflection” by a set of planes (dashed line in
Fig. 1.2). This concept, though of great importance in crystallography, will not be used in
the following.
The product ks 5 k is often used as wave vector and the wave vector change q 5 k 2 k0 is
also called momentum transfer. According to de Broglie the relationship between the wave

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

4 1. INTERFERENCE, RAYLEIGH
DEBYE
GANS THEORY

properties and the particulate properties can be expressed by the wavelength λ that is
associated with a particle of mass m and velocity v:
h
λ5 (1.6)
mv
where h is Plank’s constant. So we see that the momentum, mv, can be written as:

mv 5
h
5
λ 2π
h
 2πλ 5 h̄  k (1.7)

where h̄ 5 h/2π. This equation holds for neutrons as well as for photons and for any elec-
tromagnetic radiation. We see that the momentum of the field or of the neutron is a vector
pointing in the direction of propagation and its magnitude is h̄ω=c 5 h̄k. The elastically
scattered wave has the same energy or wavelength as before and so the same wave num-
ber k, but the direction of the wave vector has changed from s0 to s. The corresponding
momentum transfer is h̄q (see Fig. 1.3). We may even think of a completely classical anal-
ogy of a billiard ball moving in s0 direction with a momentum of h̄k0 5 h̄ks0 (whatever h̄k
might be). In order to change its direction into s with the same speed, i.e., momentum, as
h̄k 5 h̄ks we have to knock it with another ball with momentum h̄q, i.e., we have to trans-
fer the momentum h̄q to our ball.
We can now calculate the total scattered field from our particle by summing up all sec-
ondary waves considering their relative phases. This can easily be done by using complex
notation. A complex number with magnitude 1 and phase ϕ is represented by eiϕ or
e2iqr. The number of electrons (and the number of wavelets) per unit volume is given
by the electron density ρ(r). A small volume element dr (or dV) at position r will contain
ρ(r)dr electrons. So the summation can be replaced by integration over the whole vol-
ume V of the particle:
ð
Es ðqÞ 5 ρðrÞe2iqr dr (1.8)
V

In mathematical terms, the scattered field is the Fourier transformation of the electron-
density distribution of the object.
We call the space containing all position vectors r the real space, and the space contain-
ing the vectors q the reciprocal space. This is a direct consequence of the similarity theorem
of Fourier transformation.4 The reciprocity between real and reciprocal space can also be
explained by using Eq. (1.8). The two spaces are connected by the phase qr only; the result
would be the same if r were enlarged and q diminished by the same factor. So large

FIGURE 1.3 Momentum transfer.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

 RAYLEIGH
DEBYE
GANS THEORY 5
particles (large compared to the wavelength λ) will give a scattering pattern concentrated
at small angles.
In the field of X-ray and neutron scattering the wavelength is in the order of 1021 nm,
while the structures under investigation have a dimension of at least several nanometers.
This results in small scattering angles, and therefore in the names small-angle X-ray and
small-angle neutron scattering (SAXS and SANS).
As the connection between the spatial structure and the angular dependence of the scat-
tering amplitude is given by a Fourier transformation, the most important definitions and
theorems of Fourier transformations can be found in Bracewell (1986).4

RAYLEIGH
DEBYE
GANS THEORY

The so-called Rayleigh
Debye
Gans (RDG) theory of scattering is nothing other than the
rigorous application of the idea of coherent interference to scattering, assuming that the
electromagnetic wave propagates into and through the particle regularly and homo-
geneously, i.e., the magnitude of the electric field is the same in all parts of the particle.
The RDG theory describes well SAXS and SANS, as well as static light scattering of small
particles (size much smaller than the wavelength) and low contrast. The name small angle
comes from the fact that the wavelength of X-rays and neutrons is usually much smaller
than the size of the particles under investigation.
In the following we are no longer interested in the scattering of a particle in vacuum,
as we are dealing with soft matter, but in scattering from scattering centers embedded
in a homogeneous medium such as surfactants or macromolecules and their aggregates
in solution, and also defects in glasses, and pores in noncrystalline amorphous solids,
i.e., soft condensed matter where the scattering centers exist in a surrounding medium
of (nearly) constant electron density ρ. The incident field is a plane wave in the direc-
tion s0:
E1 ðr; tÞ 5 E0 eiðks0 r2ωtÞ (1.9)
The scattered waves have a spherical wave form:
eiðkR2ωtÞ  
Es ðR; tÞ 5 Es0
R

sinϑ Φ q; t (1.10)

where R is the vector from the scattering center O to the point-like detector; and sinϑ is
the polarization term for polarized light, where ϑ is the angle between the direction of
polarization and the direction to the detector. This polarization factor is mostly relevant
for light-scattering experiments such as those that are usually performed with a polar-
ized laser source. In order to detect the scattered light intensity in a horizontal plane
the laser must be vertically polarized, i.e., ϑ 5 90 degrees, and therefore sinϑ 5 1.0. For
unpolarized light this factor has to be replaced by (1 1 cos2θ)/2, with θ being the scat-
tering angle. Most X-ray sources emit unpolarized light. However, in SAXS experiments
the scattering angle is small enough so this factor can be neglected, but it must be
considered for SWAXS (combined small- and wide-angle X-ray scattering) experiments.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

6 1. INTERFERENCE, RAYLEIGH
DEBYE
GANS THEORY

A graphical representation of the polarizing factors can be seen in Figs. 15.1
15.3 in

Marshall (1978).2 Phi (Φ) is a phase factor describing the interference of all scattered
wavelets. This will be the most interesting part of Eq. (1.10). Before we can focus on Φ
we have to discuss the amplitude factor Es0 which defines the strength of the scattered
radiation.
For this part of our discussion we start from:
1 d2 ðexÞ sinϑ
Es 5 (1.11)
c2 dt2 R
This equation tells us that the scattered field is proportional to the second derivative of
the induced dipole moment ex. If we consider scattering of X-rays (Thomson limit, ωcω0)
we get:
 2 
e
Es0 51E0 51 E0 r0 (1.12)
mc2

where the factor r0 5 e2/mc2 5 2.82 10213 cm is the classical electron radius (in cgs units, or
 
r0 5 (1/4πε0) e2/mc2 5 2.82 10215 m in SI units).5 In the case of light scattering it is conve-
nient to express the magnitude of the electric dipole moment, ex, which results from the
application of the electric field E0 in terms of the molecular polarizability, α, as:
ex 5 αE (1.13)
This polarizability α is proportional to the refractive index of the particles, as we shall
discuss in detail in Chapter 9, Static Light Scattering From Small Particles. In general we
get6,7:
k2
Es0 51E0 δεr (1.14)
4π
where δεr 5 ε/ε0 2 1 and ε is the dielectric constant of the particle. In the Thomson limit
(ωcω0), which holds for X-rays, we obtain the field dEs(R, t) at the detector in a
distance R due to scattering by the infinitesimal volume element dV 5 dr with electron
density ρ(r, t):
eiðkR2ωtÞ e2
dEs ðR; tÞ 5 E0
R mc2
 ρðr; tÞe2iqr dr (1.15)

where we have omitted the polarization term since (1 1 cos2θ)/2 is close enough to 1 for
the usual range of scattering angles in SAXS. In order to find the total scattered field we
have to integrate over the whole illuminated volume V:
ð
e2 eiðkR2ωtÞ
Es ðR; tÞ 5 E0 2
mc

R V
ρðr; tÞe2iqr dr: (1.16)

We can now express the density ρ(r, t) by its mean ρ and its fluctuations Δρ(r, t):
ρðr; tÞ 5 ρ 1 Δρðr; tÞ (1.17)

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

 RAYLEIGH
DEBYE
GANS THEORY 7
The Fourier integral in Eq. (1.16) is a linear operation (an integral over a series of terms
can be replaced by the series of the integrals over these terms), so we can rewrite
Eq. (1.16) using Eq. (1.17):
ð ð 
e2 eiðkR2ωtÞ
Es ðR; tÞ 5 E0 2
mc
 R V

ρ e2iqr
dr 1 Δρðr; tÞe
V
2iqr
dr (1.18)

The contribution of the first term, caused by the mean ρ integrated over the whole scat-
tering volume V, peaks strongly at q 5 0, as the typical size of the scattering volume is in
the order of millimeters; this is huge compared to the wavelength λ. Therefore, this term
is hidden in the primary beam which has to be blocked in the experiment by a beam stop.
So we are left with the second term only, and for the scattering at q 6¼ 0 we get only the
contributions of the fluctuations Δρ(r, t) around the mean ρ:
ð
e2 eiðkR2ωtÞ
Es ðR; tÞ 5 E0 2 Δρðr; tÞe2iqr dr (1.19)
mc R V

So we see that the scattered field Es is the Fourier transformation of the density fluctua-
tions Δρ. This result leads to the fact that the contrast can also be negative (whenever the
density of a particle is lower than that of the solvent).
Inhomogeneities of the solvent are usually very small, and their contributions are taken
into account experimentally by subtracting the scattering of the pure solvent from the scat-
tering of the solution (see Chapter 8: Numerical Methods).
In addition, we should keep in mind that ρ is the electron density of X-rays, but repre-
sents the scattering-length density of neutrons (see Chapter 5: Absolute Intensity, SAXS,
and SANS) and the refractive index for light scattering (see Chapter 9: Static Light
Scattering From Small Particles) (Fig. 1.4).

FIGURE 1.4 Assembly of discrete particles, Rk(t) is the posi-

tion relative to an arbitrary origin O of the center of mass of
particle k at time t; rk is the vector from the center to a volume
element drk inside this particle.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

8 1. INTERFERENCE, RAYLEIGH
DEBYE
GANS THEORY

Assembly of Discrete Scatterers

We can describe the density distribution Δρ(r,t) by:
X
N
Δρðr; tÞdr 5 δ½r 2 Rk ðtÞ 2 rk Δρðrk ; tÞdrk (1.20)
k51

Now we omit for simplicity all prefactors (including the fixed value of R) from
Eq. (1.19), replace the vector R pointing to the detector by the corresponding scattering
vactor q, and get:
  N ð
X
Es q; t ~ Δρðrk ; tÞe2iq½Rk ðtÞ1rk  drk
k51 Vk
XN ð 
5 Δρðrk ; tÞe2iqrk drk e2iqRk ðtÞ (1.21)
k51 Vk
XN  
5 Fk q; t e2iqRk ðtÞ
k51

where we have introduced the field Fk scattered by the particle k with volume Vk as:
ð
Fk ðq; tÞ 5 Δρðrk ; tÞe2iqrk drk (1.22)
Vk

In static scattering experiments we measure the scattered intensity as:

Is ðq; tÞ 5 jEs ðq; tÞj2
averaged over time or, for a nonergodic medium, ensemble averaged:
 2 2 X
  D

2 E e N XN D   2iqðR 2R Þ E



Is q 5 Es ðqÞ 5 I0 Fk ðqÞF 
q e k l
(1.23)
I
mc2 k51 I51

At this step one might wonder what happened to the time-dependent phase factor
ei(kR
ωt). The time average over any periodic function with arbitrary frequency is
/2 (hcos2 (ωt 1 ϕ)it 5 1/2), so the intensity of the incident field I0 is simply equal to E02/2;
1

this holds for any electric field.

The double sum in Eq. (1.23) is the general result for an assembly of discrete scatterers;
the factor Fk(q) represents the scattering amplitudes of the kth particle, the phase factor exp
[ 2 iq(Rk 2 Rl)] depends on the vector between the centers of mass of particles k and l. This
equation is, as most basic equations, difficult to analyze in general. So we will start off
from this equation and discuss several special cases.

DILUTE SYSTEMS
We start with the simplest possible case; a very dilute system of scatterers. This
assumption not only guarantees that the condition of single scattering is fulfilled automati-
cally, but also leads to a situation in which all scatterers are uncorrelated, i.e., every particle

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

 DILUTE SYSTEMS 9
of the system can be regarded as independent in respect to translation and orientation,
and no long-range order exists. So we assume that no interparticle interaction exists at all.
This condition can often be met by colloidal systems of globular particles with a low vol-
ume fraction (typically below 1%), but we have to keep in mind that high particle charges
or long thin cylinders and large vesicles may necessitate much higher dilutions. The condi-
tion of a very dilute system also leads to the situation in which ρ is equal to the density of
the solvent and Δρ is just the difference between the density of the particle and the den-
sity of the solvent (or surrounding medium).
We rewrite Eq. (1.23) and omit the constant prefactor:
  XN
 
2 XX    
Is q 5
Fk q
1 Fk q e2iqRk Fl q e2iqRl (1.24)
k51 k6¼l

If the system is very dilute and the scatterers are uncorrelated, the phase factors in the
double sum go through many multiples of 2π, and so these contributions cancel each other
and we get:
  XN  
Is q 5 jFk q j2 ; (1.25)
k51

i.e., the scattered intensity is simply the sum over the average intensities scattered by all N
individual particles, and contains information about structure and shape of these particles
averaged over orientations and particle sizes and shapes.

Monodisperse, Dilute Systems: Form Factor

If all particles are identical (monodisperse) we get:
     
Is q 5 N jFðqÞj2 5 N F20 P0 q 5 NP q (1.26)
where we have introduced the normalized averaged form factor P0(q) with the normaliza-
tion factor F20 :
 
  jFðqÞj2 jFðqÞj2

P q
P0 q 5 5 5 2 or PðqÞ 5 F20 P0 ðqÞ (1.27)
jFð0Þj2 F20 F0
with P0(0) 5 1. For simplicity in the following, we use the symbol I(q) for the form factor
P(q) for dilute systems. We shall come back to the notation P(q) when were are dealing
with concentrated systems (see Chapter 4:
Concentration

2 Effects, Interactions). Now we
have a closer look at the averaging process
FðqÞ
:

From Fields to Intensities and Spatial Averaging

Due to the high frequency of our radiation (1015
1018 Hz) it is impossible to measure
the field, i.e., the amplitude and the phase. We can only measure the intensity. In the next
step we have to take into account that our scattering centers in soft matter are not oriented
within the scattering volume. So we have to calculate the spatially averaged intensity.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

10 1. INTERFERENCE, RAYLEIGH
DEBYE
GANS THEORY

First we recall Eq. (1.22), neglecting any time dependence:

ð
FðqÞ 5 ΔρðrÞe2iqr dr (1.28)
V
ð ð
 
2

jFðqÞj 5 F q F ðqÞ 5
V
Δρðr1 ÞΔρðr2 Þ e2iqðr1 2r2 Þ dr1 dr2 (1.29)

with V as the particle volume. We put r1 2 r2 5 r and use r2 5 r1 2 r:

ð ð
jFðqÞj 5
2
Δρ ðr1 Þ Δρ ðr1 2 rÞ e2iqr dr1 dr (1.30)
V

Now we introduce the convolution square Δ~ρ2 ðrÞ of the density fluctuations:
ð
γðrÞ  Δρ~2 ðrÞ 5 Δρ ðr1 Þ Δρ ðr1 2 rÞ dr1 (1.31)
V

(Please note the difference in notation

 when comparing to existing literature. Porod
(1982)8 uses the notation γ ðrÞ 5 V1 Δρ~2 ðrÞ!)
This function is, when normalized to γ(0) 5 1, also called the spatial autocorrelation func-
tion (ACF). For more details, see the excellent textbook on Fourier transformation and
related topics by Bracewell (1986).4 Introducing Eq. (1.31) into (1.30) gives:
ð
jFðqÞj2 5 Δρ~2 ðrÞ e2iqr dr (1.32)
V

So we see that the scattered intensity is essentially the Fourier transformation of the
spatial ACF of the density fluctuations ΔρðrÞ of the particle.
Now we have to perform the spatial averaging process. This means that the autocorrela-
tion function depends only on the magnitude of the distance r 5 |r|, and the scattering
intensity is a function of the magnitude q of the scattering vector q only. It is obvious that
information about the system is lost by this averaging process; a point that is important
for the evaluation and interpretation of scattering experiments. Also, the three-
dimensional Fourier transformation (Eq. 1.32) reduces to the one-dimensional, centro-
symmetric form. The phase factor must be replaced by its average taken over all directions
of r and so we get:
ð
γðrÞ 5 ρ~2 ðrÞ 2 VðρÞ2 5 Δρ~2 ðrÞ 5 Δρ ðr1 Þ Δρ ðr1 2 rÞ dr1 (1.33)
V

The convolution square Δρ~ ðrÞ is calculated as the overlap between a particle fixed in
2

space and its identical ghost shifted by r. If Δρ(r) is constant inside the particle, Δρ~2 ðrÞ is
given by the square of this contrast, (Δρ)2 times the overlap volume between the particle
and its shifted ghost, see Porod (1948).9
The spatially averaged convolution square γ ðrÞ 5 Δρ~2 ðrÞ results from the same process;
the ghost is shifted by a distance r 5 |r|, but we have to average over all possible direc-
tions in space. This correlation function γ(r) was introduced in the field of small-angle
scattering by Debye and Bueche (1949),10 and in its normalized form as the characteristic
function γ 0(r) by Porod (1951)11 (Fig. 1.5).

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

 DILUTE SYSTEMS 11
FIGURE 1.5 The convolution square. If the electron density
Δρ(r) is constant inside the particle thenΔ~ρ2 ðrÞ describes the over-
lapping volume between the particle and its ghost, shifted by r.

For homogeneous particles we find immediately that:

ð
γ ð0Þ 5 ðΔρÞ 2
dr5 ðΔρÞ2 V
V
 (1.34)

After normalization we have:

γ ð rÞ γ ðrÞ
γ 0 ð rÞ 5 5 (1.35)
γ ð0Þ ðΔρÞ2 V 
The spatial average of the phase factor in Eq. (1.32) can be expressed by the fundamen-
tal formula also given by Debye (1915)12:
sin qr
e2iqr 5 (1.36)
qr
found by averaging over all possible directions of r (see also Guinier and Fournet (1955)13,
p. 8) (Fig. 1.6).

FIGURE 1.6 Spatially averaged convolution square γðrÞ 5 Δρ~2 ðrÞ: here we
shift the ghost again over the distance r 5 |r|, but take the average over all
directions in space.

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

12 1. INTERFERENCE, RAYLEIGH
DEBYE
GANS THEORY

Let us take a vector r with magnitude r that takes all orientations with equal probability. We
define the angle between q and r with ϕ. This angle varies between 0 and π radians. Any rota-
tion of r around q with fixed ϕ is described by the angle ψ. For any possible direction r we shall
find a direction
r so that hsinqri 5 0, and we can deal with hcosqri instead of he2iqri (remember
Euler’s identity: e2iqr 5 cosqr 2 i sinqr). The product qr can therefore be described as qr cos ϕ,
and the probability of finding the endpoint of r between ϕ and ϕ 1 dϕ is sinϕdϕ.
So we have:
ð ð
1 2π π  
hcosqri 5 cos qr cos ϕ sin ϕ dϕ dψ
4π Ψ50 ϕ50
ð
1 π  
5 cos qr cos ϕ sin ϕ dϕ
2 ϕ50

Substitution of u 5 qr cos ϕ leads to:

ð0
21 sin ðqrÞ
cosqr 5 cosudu 5
qr qr qr

The Pair 2 Distance Distribution Function

By inserting Eqs. (1.33) and (1.36) into (1.27) and (1.32) we get:
ð
IðqÞ 5 jFðqÞj2 5 Δρ~2 ðrÞ e2iqr dr
V
ðN
sinqr 2
5 4π Δ~ρ2 ðrÞ r dr (1.37)
0 qr
ðN
sinqr
5 4π γ ðrÞ r2 dr
0 qr

and by introducing the pair 2 distance distribution function (PDDF) p(r) as:
ð
2
 2 2

pðrÞ 5 r γ ðrÞ 5 r Δρ~ ðrÞ 5 r 2

Δρ ðr1 Þ Δρ ðr1 2 rÞ dr1
V
(1.38)

we obtain:
ðN
sin ðqrÞ
IðqÞ 5 4π pðrÞ dr: (1.39)
0 qr
The correlation function and the PDDF p(r) can, in principle, be calculated from I(q) by
the inverse transformation:
ð
1 N sinqr
γ ðrÞ 5 IðqÞq2 dq (1.40)
2π 0 qr

SCATTERING METHODS AND THEIR APPLICATION IN COLLOID AND INTERFACE SCIENCE

Another random document with
no related content on Scribd:
 Nouna, who was playing at packing, having been busy for twenty
minutes with a delicate Sèvres tea-pot and some yards of tissue
paper, let the china fall from her hands at these words, in a torrent of
indignation. She scarcely glanced at the broken fragments on the
floor, as she burst forth with great haughtiness in the high-flown
language she habitually used when her passions were roused:
“Indeed! Does then the wife of this miserable little wooden soldier
think the granddaughter of a Maharajah unworthy to bear the light of
her eyes? We will see, we will see. Perhaps she is a little too
imperious; there may be powers in the earth greater than hers! I will
write to my mother, who has never yet failed to fulfil my wishes, and I
will tell her to search if she can find means to humble this proud lady
of the fens, so that she may sue to me to receive me in her house,
heathen, foreigner, though I am!”
And with a superb gesture Nouna signified her contempt for the
ironical laughter her husband could not restrain.
“Oh, little empress,” he said, good-humouredly, “you will have to
learn that all magicians have limits, and that even a mother so
devoted as yours can’t carry out all the freaks that enter into one little
feminine head. The very king of the black art could not move Lady
Florencecourt!”
“The king! Perhaps not, because he is a foolish male thing,”
retorted Nouna coldly, “but what my mother wills to do she does, and
I trust her.”
And she would not suffer any further word on the subject.
George was in the depths of his heart not without a little anxiety
about this Norfolk visit. Unconventionality is so much more
unconventional in the country, where every trifling detail in which a
man differs from his neighbours is nodded over far and wide as a
sign of mental aberration, while in the case of a woman it is held to
warrant even graver doubts. Nouna herself was in the highest spirits
at the prospect; delightful as life in London was, a change after five
weeks of her new home was more delightful still. She had had made
for the occasion a varied assortment of dainty white frocks, of the
kind that charm men by their simplicity, and women by their
costliness, and a white costume with fine lines of red and gold, for
yachting on the broads, which might have carried off the palm at
Cowes. Nouna had the instinct of dress, a regal instinct which
revelled in combinations and contrasts, in forms and folds, which
everyday English women might admire or marvel at, but copied at
their peril. She travelled down, the day being cool, in a Spanish cloak
of mouse-grey velvet, lined with ivory silk, and fastened with clasps
of smoked pearl and silver. On her head she wore a cap of the same
colours. The milliner, an artist spoiled by ministering to a long course
of puppets, was aghast at the order, and suggested that it would
make Mrs. Lauriston look, well—er—brown. Nouna replied, with a
great sweep of the eyelashes, that she was brown, and she should
be sorry to look anything else. And indeed her beauty was seen to
great advantage in this original setting, and its tints might pleasantly
have suggested to the fanciful brown woods in the haze of a grey
October day.
They reached Gorleth, the nearest railway-station to Maple Lodge,
at half-past four. Sir Henry and his daughter Cicely were on the
platform, Cicely in a short grey riding habit, looking in this practical
garment a thousand times handsomer and more captivating than she
had done in her most brilliant ball-dress, according to the wont of her
countrywomen, who, from the royal ladies downwards, never look
worse than when dressed solely with the view to charm.
Let it be acknowledged once for all: the Englishwoman, to her
credit be it said, is a riding animal, a walking animal, a boating
animal, a cooking animal, a creature fond of hard work and hard
play, full of energy and capabilities for better things than the piano-
strumming and Oxford local cramming which are now drummed into
her so diligently. But her social qualities are so poor as to be scarce
worth cultivation unless some better methods be discovered than
those now in vogue. Her dancing is more vigorous than graceful, her
conversation is inane, her deportment in full dress uneasy and
deplorable, and her manner at social gatherings where no active
muscular exertion is required of her, dull and constrained. Ten girls
are handsome and attractive in a boat or on the tennis-ground to one
who at an “at-home” or a dance is passable enough to make a man
want an introduction. The metropolis has the pick of the market, if
the term may be allowed, in marriageable maidens as in flowers and
fruit. But all alike lose their freshest, greatest charm when they are
plucked from their natural setting of country green.
George had an inkling of this truth as he helped his tiny wife out of
the railway carriage, amidst the stares of a crowd of country market-
folk, who gaped as they would have done if a regulation fairy, gauze
wings, wand and all, had suddenly descended down the wide
chimney on to their cottage hearth. He should love and admire her
whatever she did, but he wanted her to sway the sceptre of conquest
over all these friends at Willingham and Maple Lodge, and his heart
ached with fear lest a breath of disapproval should touch her, lest
she should appear to any disadvantage under such new conditions.
She herself, happily, was tormented by no such fear. She ran up to
Sir Henry, who was dressed in a vile suit of coarse mustard-coloured
stuff, a common little hat on his head, and a broad smile of
recovered bliss on his face, looking as no self-respecting farmer
among his tenants would have dared to look, and rejoicing in his
escape from town and tight clothes.
“Why, you little town-mouse,” he said, laughing good-humouredly
as he looked down on the tiny lady, “I don’t know how you will live
down here. We shall have to feed you on butterflies’ wings and dew-
drops; I should think a mouthful of plain roast beef would kill you.”
“Oh no, it wouldn’t, Sir Henry,” cried Nouna, distressed and
offended by these doubts cast on her accomplishments. “I eat a
great deal, don’t I, George?”
“Well, more than one would expect, to look at you,” admitted her
husband, remembering the fiasco of the wedding breakfast.
“Besides,” said Nouna astutely, “everything that one eats comes
from the country. The town produces nothing but soot; perhaps you
think I live upon that, and that’s what made me half a black woman.”
The genuine black woman, Sundran, was meanwhile creating a
great sensation; so that, to save her from the rustic wit, which made
up in blunt obtrusiveness what it lacked in point, she was packed
with her mistress inside the Millards’ one-horse brougham, which,
like all their surroundings in their country retreat, was almost
ostentatiously modest and even shabby. George was content
enough to share the coachman’s seat.
 “I thought the maid would sit outside; I hadn’t reckoned upon your
bringing a lady of so striking a complexion, George,” said Sir Henry
apologetically. “The old carriage is such a lumbering concern that I
thought the brougham would be quicker, and there’s a cart for the
luggage.”
George laughed. “If I had my choice I’d go on the cart,” said he. “I
am yet unspoiled by my promotion to matrimony.”
It was a pleasant drive over the flat country, too marshy to be dry
and burnt up even in summer. Sir Henry and his pretty daughter kept
pace with the carriage, and flung breezy commonplaces at their
guests with smiling, healthy faces that made their conversational
efforts more than brilliant. Nouna peeped out like a little bird at the
flat green fields and the pollard willows with an expression which
seemed to say that she had quite fathomed the hidden humour of
the whole thing.
“I like the country,” she called to Cicely with an exhaustive nod, as
if she had lived in and loved the fields for years.
And at sight of the Lodge itself she grew rapturous.
Sir Henry Millard’s modest country residence was nothing more
than a fair-sized one-storied white cottage, close to the road, from
which it was separated only by a little garden just big enough to
contain a semicircular drive, a small half-moon lawn, and two side-
beds full of roses. A stone-paved verandah ran the whole length of
the house, and a hammock swung between two of the supports of
the green roof, in what would have been glaring publicity if there had
ever been any public to speak of on the quiet road in front. It would
have been rather a pretty little place if Sir Henry, to meet the
requirements of his family, had not preferred enlarging it by adding at
the back various hideous red brick wings and outbuildings of his own
designing, to the more reasonable course of taking a larger house.
The pleasure of conceiving and superintending these original
“improvements” had indeed, while it lasted, been the most unalloyed
joy of Sir Henry’s simple life; to worry the architect, who had had to
be called in at the last to put a restraining check on Sir Henry’s
inspirations, which threatened to dispense with the vulgar adjuncts of
passages and staircases; to test the building materials, samples of
which lay about the sitting-rooms for days; above all, to do a little
amateur bricklaying during the workmen’s dinner hour—were joys
the mere memory of which thrilled him more than any recollection of
his honeymoon.
Whatever the architectural defects of the house might be, Nouna
had nothing but admiration for it. The tiny little hall; the box-like
drawing-room to the right, with high glass cupboards on each side of
the fireplace containing apostle spoons, old china bowls, fragments
of quartz and the like; the bare-looking dining-room to the left,
furnished as plainly as a school-room, and even the bake-house
which led out from it, all enchanted her by their novelty; while the
bedroom up stairs, ten feet square, into which she was shown, put
the climax to this deliciously new experience, and made her feel, as
she expressed herself to her husband, “that she wished she had
married a farmer.”
To George’s delight she ran down stairs within twenty minutes of
her arrival in the simplest of white muslin frocks, with a wonderful
scarlet and gold sash. But he had no time to congratulate her on her
good sense in dressing so appropriately before she was off, in a
huge garden-hat taken with instinctive knowledge of what was most
becoming from a collection in the hall, to see the farmyard—Sir
Henry’s pride. They made an odd pair—the broad-shouldered, solid-
looking country gentleman, in his rough suit, and the small airily-clad
person who varied her progress by occasional ecstatic bounds in the
air, which made the ends of her sash swirl in the breeze like the
wings of some gorgeous butterfly. George and the girls, with Lady
Millard, followed much more sedately. When, after due admiration of
cows and horses, pigs and poultry, they all returned to the verandah,
fresh objects of interest presented themselves in a pretty group of
riders at that moment climbing the hill upon which the lodge stood.
“Uncle Horace!” cried the girls, as Nouna recognised in the eldest
of the party Lord Florencecourt. He was accompanied by two pretty
boys of about eight and ten on ponies which they already managed
as if boy and pony had been one creature.
“How Horace worships those boys!” muttered Sir Henry enviously.
Charlotte had run down to open the gate, and there was much
clatter of lively greeting. Lord Florencecourt, though he seemed
happier down here with his children than he had been in town,
showed his old constraint with Nouna. It was therefore with great
surprise not only to the young husband and wife, but to their host
and his family that they learnt the object of his visit.
“You see I haven’t lost much time in paying my respects, Mrs.
Lauriston,” he said, speaking in a lively tone, but with an ill-
concealed reluctance to meet her eyes. “Those girls would like to
flatter themselves that my visit is for them, but they are all wrong.”
“Never mind, uncle, Regie and Bertie come to see us,” cried Ella,
giving a kiss to the youngest boy.
Lord Florencecourt continued: “The fact is, Mrs. Lauriston, we
know that you will be so run after down here, that when you have
been seen a little there will be no getting hold of you. So my wife
sent me to ask you and George to stay with us from Friday to
Monday the week after next. Mr. Birch, our member, will be there,
and we thought as he has come to the front so much lately you might
like to meet him.” Nouna stole a triumphant glance at her husband,
and the girls, who were near enough to hear, could not forbear little
unseen eyebrow-raisings of astonishment. He went on: “Lady
Florencecourt will call upon you on Monday, but she thought it best
to send her invitation at once to make sure of you.”
“It is very kind of Lady Florencecourt; I shall like to come very
much,” said Nouna, who was brimming over with delight and
triumph. “Only I don’t think I could do much to entertain a rising
member of Parliament. I can’t talk politics; but perhaps he’d like to
learn to make cocked hats out of newspaper, and then he can
amuse himself when the other members are making dull speeches.”
“I’m sure he’d like it immensely if you will teach him,” said Lord
Florencecourt, with cold civility, which would have damped frivolity
less aerial than Nouna’s.
The girls thought Lady Florencecourt must have been bewitched
thus to transgress her own well-known rule of ignoring any stranger
whose pedigree was not at her fingers’ ends. She had, besides,
gone so far as to gibe at her brother for admitting “a loose-mannered
young woman of unknown and questionable antecedents”—as she
styled young Mrs. Lauriston—into the society of his daughters. And
now she was sending a pressing invitation by the mouth of her
husband, whose prejudice against the interloper was hardly
concealed! Decidedly Nouna had a dash of Eastern magic about her.
Meanwhile the young lady herself was troubling her head very little
with the problem. She was much struck with the blue eyes and curly
dark hair of the younger of the two boys, and bending down to him
with her little head perched on one side in the coquettish manner she
used alike to man, woman, child or animal, she asked with a smile
what his name was.
“Allow me to present him with proper ceremony,” said Ella
playfully. “Permit me to introduce you,” gravely to her small cousin,
“to Mrs. George Lauriston. Mrs. Lauriston,” turning to the lady, “the
Honourable Bertram Kilmorna!”
She had scarcely uttered the last word when Nouna shot up from
her bending attitude as if at an electric shock, and fixed her great
eyes, wide with bewilderment and surprise, on Lord Florencecourt,
who was standing behind Ella and his son, near enough to hear
these words and to see their effect.
“Kilmorna!” she repeated in a whisper, still looking full at the
Colonel, whose rugged face had grown suddenly rigid and grey.
Then, without further ceremony, she ran away to her husband, who
was talking to Lady Millard at a little distance.
“George, George!” she said in a tumultuous whisper, her face
quivering with excitement, “I don’t want to go to Lady
Florencecourt’s; tell him I don’t want to go!”
“Why, what’s this? How has the Colonel offended you?” asked
George laughing.
“He hasn’t offended me at all. Only I’ve changed my mind. I know I
—I shouldn’t like Lady Florencecourt. I’d rather not go.”
 But as George insisted that it was impossible to break an
engagement just made, without any reason, she broke from him with
an impatient push, and disappeared into the house just before Lord
Florencecourt, who had abruptly discovered that he was in a hurry to
be off, took his leave. Ella prevented George from fetching his wife
out.
“It is only some little caprice of hers,” she said persuasively, not
guessing that there was any mystery in the matter, and considering
the young bride’s conduct as the result of some girlish freak. “I think
she was offended because uncle didn’t introduce the boys to her.
She will be all right if you leave her alone a few minutes.”
But George was not unnaturally annoyed at his wife’s rudeness,
and he followed her into the little drawing-room, where he found her
with her nose flattened against the window, staring at Lord
Florencecourt’s retreating figure. She had no explanation to give of
her conduct, but persisted in begging him not to take her to
Willingham. As he remained firm on this point, and continued to
press her for her reasons, she grew mutinous, and at last peace was
only made between them on the conditions that she would go to
Willingham if he would not tease her with any more questions.
And George had to be content with this arrangement, being above
all things anxious to learn the meaning of the miraculous change of
front on the part of Lady Florencecourt and her husband.
 CHAPTER XIX.
At dinner at Maple Lodge on the evening of their arrival, George
Lauriston and his wife met the gentle Dicky Wood, who had come
down the day before, and spent the afternoon riding with the son of
Sir Henry’s steward. Nouna was much pleased by this compliance
with her wishes, and showed her appreciation of it by flirting very
prettily at dinner with the young guardsman. Later in the evening she
held in the verandah a little court, and chanted them some half-wild,
half-monotonous Indian songs in a tiny thread of sweet voice, with
some plaintive low notes that lived in the memory. And George, who
was standing with Ella some yards away from the rest of the group,
felt thrilled through and through by the weird melodies, and liked to
fancy that in these native songs of hers the soul-voice, that, in the
tumultuous life of emotions and sensations in which she found her
happiness, had small opportunity to be heard, forced up its little note
and promised a richer fulness of melody by and by.
It was not by the man’s choice, but the girl’s, that he and Ella
found themselves together. At the present time there was only one
woman in Lauriston’s world, and in his absorption in his wife the
ungrateful fellow was incapable even of feeling his old friendly
pleasure in Ella’s society. Her interest in him, on the other hand, as is
the way with that splendid institution for the comfort and consolation
of man—plain women, had grown tenfold stronger since he had
lowered himself to the usual dead level of his foolish sex, by
marrying through his eyes. To Ella this downfall was quite tragic; she
had thought and hoped so much for him; he had feeling, sense,
ambition, was, in fact, not the mere beautifully turned out figure-head
of a man who, under various disguises of light or dark complexion,
slim or heavy build, was continually saying to her the same
commonplaces, betraying to her the same idea-less vacuity, at
dinner, ball, and garden-party. Yet here he was, bound for life, and by
his own choice, to a beautiful pet animal, with all the fascinating
ways of a kitten, who could gambol and scratch, and bask in warmth
and shiver in cold, and whom nevertheless he undoubtedly
worshipped. Ella, whose mind was of an intellectual cast, and in
whom the passions had as yet only developed in an ardent but hazy
adoration of dead-and-gone heroes, very naturally underrated the
strength of one side of a man’s nature, and was cast down when the
creature whose sympathetic comprehension of her highest
aspirations had made her raise him to a demi-god proved to be in
truth only a very man. She fancied, poor child, that he showed
deterioration already; when she reminded him at dinner that she had
not yet returned a book of Emerson’s he had lent her, George
laughed carelessly, and said he had forgotten all about it.
“Don’t you remember you particularly advised me to read the
articles on ‘Goethe’ and ‘Napoleon’?” she asked rather acidly.
“Oh, yes, they’re very good,” said he, with a man’s irritating
frivolity, smiling at his wife, who was shutting one eye and holding
her glass of claret up to the light, in imitation of an elderly
connoisseur, for the amusement of Dicky. Then, perceiving in a
pause that he had offended Ella, he hastened to say penitently: “I
haven’t done much reading lately; but you have, I suppose; you are
always so good.”
“I don’t read because I am good, but because I like it,” she
answered coldly.
And George, reflecting on the oddity of Ella’s trying to improve him
as he had tried to improve Nouna, had taken the snub meekly as a
bolt of retributive providence.
But when she got an opportunity of speech with him alone in the
verandah, in a rather melancholy and remorseful frame of mind, she
“had her say” after her sex’s fashion.
“One mustn’t expect you to be the same person that you were
three months ago, George,” she began, with a very humble,
deprecating manner. “Otherwise I would ask you why we don’t hear
of your coming to the front as a writer, as we heard then there was a
probability of your doing.”
George laughed with the same maddening indifference to his
deterioration, and asked if he might smoke. With a cigarette between
his lips, flourishing before her eyes the privilege of a man, he felt
more of a man’s commanding position.
 “I haven’t come to the front,” said he, “because I haven’t made any
steps at all, either forward, backward, or in any direction. I’ve been
lazy, Ella, miserably, culpably lazy, and if my great thoughts have not
yet stirred the world, it is no doubt only because they have not been
committed to paper.”
“Oh, if you are satisfied, of course that is everything. Ambition, I
see, is not the great, never pausing, never ceasing motive-power
that we poor foolish women are taught to believe; it is a pretty whim,
to be taken up alternately with a fit of smoking, or mountain-climbing,
as we girls change about between tennis and tatting.”
“Not quite, Ella,” said George, doing her the justice to grow serious
when he saw how deeply and unselfishly she was in earnest.
“Ambition does not die for lying a short time hidden by other feelings;
and surely even if it loses a little of its bitter keenness, it gains by
being no longer wholly selfish.”
“A beautiful answer, at least. And no doubt contentment is better
than ambition.”
“I don’t know what contentment is, except by seeing it in the faces
of cows and pigs. No passion could be stifled by such a tepid feeling
as that. I am not contented, I am happy. So will you be some day,
and you will let your bright wits rest a little while, and you will
understand.”
Understand? No, she felt that was impossible, as she looked down
at the big, handsome man sitting on the hammock below her, his
eyes bright, not with serene, but with ardent happiness, content to
bend all his faculties to the will of a creature whom he must know to
be his inferior in every way. She did not wish to understand such a
decadence as that.
“Then you will give up all idea of writing?”
“No. I am more anxious to distinguish myself than ever, as things
have turned out. A man who suddenly finds himself to be married to
a rich wife feels as if he had got off at a false start, and is put at a
disadvantage. But so far I own my wife has taken up all my time. You
see, she didn’t know she was going to be rich any more than I did,
and being hardly more than a child, she wants as much looking after
at first as a baby at the edge of a pond.”
 “And this is the sort of woman who gets a man’s best love!”
thought Ella half bitterly, half disdainfully.
“And of course you choose her friends for her,” suggested Ella, not
quite hiding her feeling.
“I can’t quite do that, yet at least,” said George. “Nobody but all of
you has got further than acquaintance yet.”
“But of course you are very particular about those acquaintances?”
Decidedly Ella was in her most disagreeable mood to-night.
“I do my best,” said he briefly.
“And of course it’s all nonsense about the smoking-parties, and
Captain Pascoe being there nearly every night.”
George felt a shock. Mentioned in that manner, the evening calls
of his friends, the admittance among the callers of a man whom he
cordially disliked but whom he had no grounds strong enough for
insulting, were heavy accusations.
“I see my own friends as freely as I did when I was a bachelor,
certainly,” said he, cold in his turn. “Nouna is too sensible to prevent
that. As for Captain Pascoe, he has not been in our house more than
three times at the outside.”
Ella dared not say more on this subject, even if she had had more
to say. She looked out at the swallows, flying low over the young
trees of the plantation on the other side of the road, and asked
musingly:
“Do you like being rich?”
“It’s not bad for a change,” answered George philosophically.
“I hate it. I always feel with papa, so glad to shake off the big
house and the footmen and the feeling that the great human world is
surging round without touching you, and to get back to my tiny room
where I can almost water the plants in my window without coming in
at the door, and to the farm and my pensioners that I take tracts to.
They never read them, but it is quite as much a matter of etiquette to
leave them as it is to make calls in town, and they are dreadfully
insulted if I forget.”
“But you’ve always been well off?”
“Yes, but that doesn’t make any difference. Money rolls together in
such ugly fashions. Look at mamma’s. When her father made his
millions, thousands of people were ruined. Well, you know, that’s
horrible!”
“They chose to speculate, remember. They must have known no
lottery has all prizes.”
“It’s hideous to think of, all the same. On the other hand, if your
property descends to you by a long line of greedy land-scrapers, you
know it has grown in value because other people’s has decreased,
and that your tenants have to pinch themselves to make up your
handsome rent-roll. And you haven’t even done the wretched work
for it that the speculator has done to get his!”
“It’s lucky all capitalists are not so soft-hearted, or there’d be an
end to enterprise, which by the by is brother to your god Ambition.”
“Oh, I’m not making preparations for re-organising the universe,
only lifting up a little weak mew of discontent with my corner of it.
And your wife’s money: is it the result of a robbery of recent date,
like ours, or plunder that has been rolling down for generations, like
Lord Florencecourt’s?”
“Well, really, I’ve never put it to her trustees in that way, and, now I
think of it, why I really don’t know. But as Nouna’s father was a
soldier, and there’s very little loot to be got in our days, I expect it
has rolled down.”
“And you don’t really care how it was got together?”
“Yes, I do, now I think of it. But to tell you the truth, the lawyers
have managed things so easily for us that all we’ve been called upon
to do is to spend the money, a very elementary process.”
“What a strange thing!”
“Why? By the by, so it is, when one comes to think about it. It’s
altogether contrary to one’s personal and traditional experience of
lawyers.”
“When mamma married,” said Ella, pursuing her own train of
thought, “her money was tied up and fenced round with as many
precautions as if poor dear old papa had been a brigand. He often
laughs about it, and says she couldn’t buy a pair of gloves without a
power of attorney. So that it really does seem very astonishing.”
“It does,” assented George, who, never before having had
experience of money in any but infinitesimal quantities, had been
much readier to take things for granted than was this granddaughter
of a Chicago millionaire.
“What would you do, George, if you found out it had been made by
supplying bad bayonets to the English army, or anything like that?”
she asked, half-laughing, but not without a secret wonder whether
this easy-got gold would turn out to have unimpeachable
antecedents.
The question gave George a great shock. He jumped up from the
hammock across which he had been sitting, with a white face.
“Good heavens, Ella! What makes you say that?” he asked in a
low voice, each word sounding as if it were being ground out of him.
“Don’t take it like that,” said she nervously, almost as much moved
as he, and impelled by his strong feeling to be more impressed than
she had been at first with her own surmise. “I only suggested—it
came into my head—I don’t know anything about it.”
“Oh, well, you shouldn’t say things like that, you know, Ella, even
in fun. The mere suggestion gives one such an awful shock. It’s like
cold water down one’s back,” said he, trying to laugh.
“I didn’t mean it, indeed,” said she, quite unable to take a jesting
tone. “As if one would say a thing like that in earnest! I never
guessed you would think twice about a foolish speech like that!”
But they both felt uncomfortable; and both were glad when
George, noticing that Dicky Wood was standing near anxious to get
a word with the jolly nice girl Ella, but much too diffident to come
forward at the risk of intruding unwelcomely upon a tête-à-tête, drew
him into their group by asking if he had been in Norfolk before.
And so both George and Ella were able to shuffle off the burden of
a conversation which had grown decidedly difficult to keep up, and
the memory of which made a slight constraint between them, on the
man’s side especially, for two or three days.
Nouna, to her husband’s great comfort and gladness, was
behaving beautifully, and putting new life by her gaiety into the whole
household, the younger members of which, in spite of Ella’s
intelligence and her sisters’ beauty, were a little wanting in those
electric high spirits which, in the routine of a quiet country-house, are
as sunshine to the crops. The day after their arrival was Sunday, and
the morning church-going had been a fiery ordeal for George, not
from religious indifference, but from the misgiving that if Nouna could
not keep from smiling in the course of a well-conducted service in a
West End church, she would certainly be carried out in convulsions
from the Willingham place of worship, where the school children,
summer and winter, sniffed through the service in a distressing
chorus, while the loud-voiced clerk’s eccentric English rang through
the building, drowning the old vicar’s feeble voice; and where the
vicar’s wife, a strong-minded lady, whose district-visiting was a sort
of assize, had been known to “pull up” her reverend husband publicly
from her pew immediately below the pulpit when, as not infrequently
happened, he turned over two leaves of his sermon instead of one,
and went quietly on as if nothing had happened. “Turned over two
leaves? Bless me, so I have!” he would murmur, and rectify his
mistake with a tranquil nod.
So George had put his wife through a very severe drill before
starting, and had strictly forbidden her so much as to sneeze without
his permission. She had a narrow escape at the offertory, when one
of the churchwardens, with a lively remembrance of the artifices of
his own youth, shovelled a penny into the fingers of each of his
offspring with one hand, while he presented the plate menacingly
with the other. But glancing up at her husband and perceiving a
frown of acute terror on his face, she contrived to choke in silence;
and the day was gained.
On the following Monday too, when the dreaded Lady
Florencecourt fulfilled her threat of calling and proved equal to her
reputation for unamiability, the young wife was, as she triumphantly
averred afterwards, “very good.” The county censor proved to be a
fair, florid woman of middle height, rather stout, and with features so
commonplace that, without the saving shield of her title, they would
have been called common. She had arrogant and capricious
manners, an oily self-satisfied voice, and an ill word for everybody.
Whenever her husband, who accompanied her on this occasion,
ventured to make a remark, she turned to look at him with a resigned
air, as if she were used to being made a martyr at the stake of his
imbecility. She examined Nouna from head to foot through a gold
double eyeglass, as if the young wife had been a charity-girl
convicted of misconduct, and made no remark to her except to ask
her if she was interested in the Zenana Missions, to which Nouna
replied rather haughtily that Indian ladies were no more in need of
missionaries than English ones: after which thrust and counter-thrust
it may be imagined that the conversation languished, and that later in
the day George had great difficulty in persuading his wife not to
break off their engagement to go to Willingham. She said it would
just spoil the end of their visit to the Millards, for one of whom she
had begun to feel a real affection. This was the sharp-tongued Ella,
whose intelligence she had the wit to recognise, and whose smart
sayings amused her.
It was on the evening of a day in the course of which this oddly-
assorted pair of friends had been a good deal together that George,
on going up stairs to his room after a last cigar with his host, found
his wife, not as usual fast asleep like a child, but perched upon the
bed in the attitude of a Hindoo idol, with a big book open on her
crossed knees, and her eyes fixed upon the nearest candle.
“Hallo!” said he, “what’s the matter?”
She turned her eyes upon him slowly, with an air of suspicion and
curiosity.
“Nothing is the matter,” she said gravely, and turning down a whole
half-leaf of the book before her to keep the place, she closed it
carefully, and handed it to him with an affectation of solemn
indifference. “I have been reading,” she added with decision.
George looked at the title of the ponderous volume, and observed
that it was The Complete Works of Xenophon. He opened it without
a smile at the page she had turned down, and remarking that it was
about half-way through the volume, said she had got on very well if
she had read so much in one evening.
“I skipped a little—the dry parts,” she observed modestly, but in
such a tone that it was impossible for George to tell whether she
meant to be taken seriously or not.
“Dry!” he exclaimed, raising his eyebrows, “why, he is the very
lightest of light reading. Xenophon was the most frivolous man I ever
knew; he was at school with me.”
She crawled to the foot of the bed, and stretching over the rail to
the dressing-table, on which George had placed the volume, she
recovered it with a violent muscular effort, and turned back the
leaves to the title-page.
“This book was published in 1823; so you are much older than you
told me you were, I see,” she said simply, while George, unable to
contain himself longer, burst out into a long laugh, and made a dive
at her, which she evaded like a squirrel, still staring at him with
unmoved gravity, so that his mirth died away in wonderment and in a
rush of tenderness as he perceived the pathos of this futile plunge
into the mazes of learning.
As he recovered his gravity the expression of her mobile face also
changed; after a moment’s shy silence their eyes met, and each saw
the other through a luminous mist.
“What are you crying for?” she asked tremulously; and in a
moment flung herself impulsively into his ready arms. “Why didn’t
you marry Ella?” was her next question, shot suddenly into his ear in
the midst of an incoherent outburst of the passionate tenderness that
glowed ever in his heart for her.
“Marry Ella!” said he, feeling a shock of surprise at the
remembrance that he had indeed once offered to make the good
little blue-stocking his wife. “Why, what makes you ask such a
question as that? Are you jealous?”
“Oh, no. But I see that she would have had you, and therefore you
were foolish not to have her.”
“Well, I’m afraid it’s too late now, and I shall have to put up with the
consequences of my folly,” said he, pressing her tenderly to him.
“That’s just what I thought,” she agreed quite plaintively. “Miss
Glass says a good wife must cook, Ella says a good wife must read,
but nobody says a good wife must just sing and laugh and amuse
herself as I do. And so when you’re tired of kissing me, you will feel
you had better not have married me, but only have amused yourself
like Dicky Wood—” She paused significantly.
“Dicky Wood!” echoed he sharply.
“—With Chloris White.”
George moved uneasily; he was angry and disturbed.
“You must not say such things—you must not think them. The
name of such a woman as that is not fit to pass your lips.”
 “But, George,” she argued, looking straight into his eyes with
penetrating shrewdness, “if you had not been you, say, if you had
been Rahas or Captain Pascoe, I might—”
He stopped the words upon her lips with a great gravity which
awed her and kept her very still, very attentive, while he spoke.
“When God throws an innocent girl into the arms of an honest
man, Nouna, as you came into mine, she is a sacred gift, received
with such reverent love that she must always hold herself holy and
pure, and never even let any thought of evil come into her heart, so
that she may be the blessing God intended. I was born into the world
to protect you and shield you from harm, my darling; and so my love
was ready for you at the moment when your innocence might have
put you in danger, just as it will be to the end of your life.”
“Supposing you were to die first?” suggested she, not flippantly,
but with an awestruck consideration of possibilities.
“A soldier can always last out till his duty’s done,” said George,
with quiet conviction.
After this Nouna remained silent a little while, but that her ideas
had not been working in quite the desired direction was evident
when she next spoke.
“If, as you say, your love will keep me safe and good whatever I
do, I needn’t be so particular,” she argued, “and it won’t do me any
harm to go and see this Mrs. Chloris White, and ask her to leave
poor Dicky alone, and let him meet some one who will be a blessing
to him. I want him to marry Ella.”
George was thunderstruck.
“Go and see Chloris White! I’d as soon let you go to the Morgue!”
“But I know I could persuade her to give him up; I know just what I
would say, just how I would look. I’ve thought it all over; and surely
anything’s better than that he should rush back to her as soon as he
gets to town, and undo all the good we’ve done him in the country.”
She spoke with a pretty little matronly air of perfectly sincere
benevolence.
“My dear child,” said her husband decisively, laying his hand on
her head with his gravest air of authority, “you cannot go; it is out of
the question. You must not even mention such a wild idea to any
one; they would be horribly shocked. But we’ll keep poor Dicky safe
among us by much better means than that, I promise you. So now
go to sleep, and don’t ever let such an idea come into your head
again.”
She let herself be kissed quite brightly and submissively, and
rubbed her cheek against his with affection which might have been
taken to argue docility. But her own fantastic notion of helping her
friend remained in her mind quite unmoved by her husband’s
prohibition.
 CHAPTER XX.
When the time came for them to finish their stay in Norfolk by the
dreaded three days at Willingham, neither George nor Nouna made
any secret of the fact that they felt the coming visit to be a severe
ordeal. Undoubtedly it would be a cruelly abrupt change from the
cheerful homeliness of the Lodge, to the penitential atmosphere in
which the household of Lady Florencecourt passed their days. So
notorious was the character of the gracious châtelaine that
Willingham Hall was commonly known in the neighbourhood as the
House of Correction, a title to which the severely simple style of its
architecture gave no very flat denial. Willingham Church stood in the
grounds belonging to the Hall, so that Nouna had had an opportunity
of shuddering at the sombre dreariness of the mansion even before
the return call she had made with Lady Millard and Cicely, on which
occasion she had sat almost mute on a high-backed chair, looking as
insignificant and unhappy as a starved mouse, thinking that Lady
Florencecourt’s light eyes looked like the glass marbles with which
she played at solitaire, and what a good model her face would be for
one of those indiarubber heads that children squeeze up into
grotesque grimaces.
She cried at parting with the Millards, like a little girl sent to school
for the first time. Sir Henry, with his simple good humour; Lady
Millard, with her quiet manners, and the quick black eyes whose
flashing keenness and sympathy showed the burning soul of the
New World flickering in uneasy brightness among the glowing
embers of the Old; Cicely and Charlotte, fair, kind creatures, who
filled up the pauses gracefully, the one by merely smiling, the other
by a gentle rain of chatter which she had been taught to think a
fascinating social accomplishment; and, above all, Ella, of the sallow
face, the sharp tongue, and the warm heart, were a group to live
pleasantly in the memory, and to make the approaching encounter
with the unamiable hosts of Willingham more disagreeable by
contrast. It added to poor Nouna’s forlornness in these