Characterization of Liquids, Nano- and Microparticulates, and Porous Bodies using Ultrasound by Andrei S. Dukhin and Philip J. Goetz by Andrei S. Dukhin and Philip J. Goetz - Read Online

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Characterization of Liquids, Nano- and Microparticulates, and Porous Bodies using Ultrasound - Andrei S. Dukhin

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Preface to the Second Edition

Ultrasound for Characterizing Colloids was first published in 2002. We decided to work on the second edition after two print runs were sold out and the book became unavailable. By the beginning of 2008, we gathered substantial justifications to prepare a new edition of the book instead of running an extra print of the first edition.

First of all, about 40 papers had been published in various scientific journals by users of our instruments. There were, in addition, about a dozen of our own papers and several papers published by other scientists in the field. These papers demonstrated the wide spectrum of applications for characterization methods by ultrasound.

Second, we discovered promising ways of using ultrasound that were known in specific scientific areas but not to us. These had not been mentioned in the first edition and we wanted to rectify the situation. One of the most striking examples was seismoelectric current. This electroacoustic and electrokinetic phenomenon had been known in geology for 70 years. However, there is practically no information about it in the major books on colloid and interface science despite the fact that it can be defined as streaming current that is nonisochoric at ultrasound frequencies. Frenkel’s theory of this effect is the first electroacoustic theory (1944) known to us, whereas Ivanov’s experiment is dated about the same time (1940) along with the first electroacoustic experiments by Hermans (1938). We present detailed descriptions, both theoretical and experimental, of this little known electrokinetic effect in Chapters 5 and 13.

Seismoelectric current may become important in characterizing porous bodies. It clearly offers a simple way to measure ζ-potential in pores. In addition, it has the potential to characterize porosity and pore sizes.

Another important example of discoveries in old works is longitudinal rheology and a host of related applications. Interpretation of acoustic data in rheological terms opens many new ways for applying ultrasound for characterizing complex systems. Mason predicted this 50 years ago for polymer solutions. There were other enthusiasts, but the lack of instruments and systematic reviews brought this field to a complete stop. We present here a review of the many works in longitudinal viscosity and provide some applications of our acoustic spectrometer as a longitudinal rheometer. One of the most important applications is the measurement of the bulk viscosity, an obscure second-viscosity coefficient of regular Newtonian liquids.

Another example is Passynski’s theory (1938) that relates the speed of sound with the size and solvation number of ions. This theory was used by Bockris and others 40 years ago but had since been neglected. There is much discussion about measuring nanoparticles with sizes down to 1 nm using dynamic light scattering. This was done many decades ago using sound speed measurements with appropriate theoretical treatments. We discuss this in Chapter 12.

There are several other new sections in the second edition. Most of them are on applications described in Chapters 8–13 but there are some new theoretical developments discussed in Chapters 3–5 as well.

This field has become so wide-ranging in methods and applications that we have started talking more about the versatility of ultrasound for characterization purposes. This is explored in Chapter 1.

This second edition is almost double the size of the first and has 50% more references. In preparing the first edition, we made the statement that it marked the end of ultrasound’s ‘childhood’ in the field of colloids. This second edition marks the beginning of adulthood. The number of groups working with our instruments has increased from 100 to 350. Geography has become much more diverse. In addition to groups in the United States, Germany, Japan, Taiwan, China, United Kingdom, Belgium, Finland, Singapore, South Korea, Mexico, and Canada, we have now users of our instruments in the Netherlands, Brazil, Thailand, Malaysia, India, Russia, Lithuania, Austria, Switzerland, Italy, Spain, France, Czech Republic, Columbia, Kuwait, Australia, and South Africa.

We would also like to express our gratitude to our international agents: Quantachrome GmbH (Europe), Nihon Rufuto (Japan), Horiba USA, Acil Weber (Brazil), Advantage Scientific (China), and LMS (SE Asia). Without their dedication, we would not have been able to achieve so much in such a short time. They learned these new methods and now actively promote and teach them to others.

We would like also to mention the contributions from our colleagues at Dispersion Technology: Betty Rausa, Lazlo Kovacs, Ross Parrish, Kenneth Schwartz, and Arthur Sigel. By taking proper care of everyday problems and the company’s needs, they gave us time to write this second edition.

Andrei Dukhin

President, Dispersion Technology, Inc.

Preface to the First Edition

The roots of this book go back 20 years. In the early 1980s Philip Goetz, then President of Pen Kem, Inc., was looking for new ways to characterize ζ-potential, especially in concentrated suspensions. His scientific consultants, Bruce Marlow, Hemant Pendse, and David Fairhurst, pointed towards utilizing electroacoustic phenomena. Several years of effort resulted in the first commercial electroacoustic instrument for colloids, the PenKem-7000. In the course of their work, they learned much about the potential value of ultrasound and collected a large number of papers published over the last two centuries on the use of ultrasound as a technique to characterize a diverse variety of colloids. From this it became clear that electroacoustics was only a small part of an enormous new field. Unfortunately, by that time Pen Kem’s scientific group broke apart: Bruce Marlow died, David Fairhurst turned back to design his own electrophoretic instruments, and Hemant Pendse concentrated his efforts on the industrial online application of ultrasound. In order to fill the vacuum of scientific support, Philip Goetz invited me to the United States, motivated by my experience and links to the well-established group of my father, Professor Stanislav Dukhin, then Head of the Theoretical Department in the Institute of Colloid Science of the Ukrainian Academy of Sciences.

Whatever the reasons, I was fortunate to become involved in this exciting project of developing new techniques based on ultrasound. I was even luckier to inherit the vast experience and scientific base created by my predecessors at Pen Kem. Their hidden contribution to this book is very substantial, and I want to express here my gratitude to them for their pioneering efforts.

It took 10 years for Phil and me to reach the point when, overwhelmed with the enormous volume of collected results, we concluded that the best way to summarize them for potential users was in the form of a book. There were many people who helped us during these years of development and later in writing this book. I would like to mention here several of them personally.

First of all, Vladimir Shilov helped us tremendously with the electroacoustic theory. I believe that he is the strongest theoretician alive in the field of electrokinetics and related colloidal phenomena. Although he is very well known in Europe, he is less recognized in the United States.

More recently, David Fairhurst joined us again. He brought his extensive expertise in the field of particulates, various colloids-related applications, and techniques; his comments were very valuable.

In our company, Dispersion Technology, Inc., Ross Parrish, Manufacturing and Service Manager, and Betty Rausa, Office Manager, extended their responsibilities last year, thereby allowing Phil and me the time to write this book. We are very grateful for their patience, reliability, and understanding.

We trust that publishing this book will truly mark the end of ultrasound’s childhood in the field of colloids; it is no longer a new technique for colloids. Currently, there are more than 100 groups in the United States, Germany, Japan, Taiwan, China, United Kingdom, Belgium, Finland, Singapore, South Korea, Mexico, and Canada using Dispersion Technology’s ultrasound-based instruments. We do not know the total number of competing instruments from Malvern, Matec, Colloidal Dynamics, and Sympatec which are also being used in the field, but we estimate that there are over 200 groups working with them worldwide. We strongly believe that this is only the beginning. Ultrasonics has come of age and we hope that you will also share this view after reading this book and learning of the many advantages ultrasound can bring to the characterization of colloid systems.

Andrei Dukhin

President, Dispersion Technology, Inc.

List of Symbols

Andrei S. Dukhin and Philip J. Goetz

Indexes

Chapter 1

Introduction

Andrei S. Dukhin and Philip J. Goetz

Publisher Summary

The roots of our current understanding of sound go back to more than 300 years when Newton suggested the first theory for calculating the speed of sound. Newton’s work is still interesting today because it demonstrates the importance of thermodynamic considerations when describing ultrasound phenomena. Newton assumed that sound propagated while maintaining a constant temperature—that is, an isothermal case. Laplace later corrected this misunderstanding by showing that it was actually adiabatic in nature. The history of light and sound in colloid science is very different. Light has been an important tool since the first microscopic observations of Brownian motion and the first electrophoretic measurements. It became more important in middle of the twentieth century because of the use of light scattering to determine particle size. There are two distinctively different ultrasound-based measuring methods. One is called acoustics and the other one is known as electroacoustics. They measure completely different parameters. Acoustics is simpler because a single field is involved—field of the mechanical stress. The versatility of ultrasound-based methods makes them comparable with several traditional techniques, such as particle sizing by light scattering, electrophoretic light scattering, microelectrophoresis, and shear rheology. The propagation of ultrasound through a porous body generates a host of different effects that can be used for characterization purposes.

Several key words define the scope of this book’s second edition. All the words are mentioned in the title: ultrasound, liquids, nano- and microparticulates, and porous bodies. The key word, ultrasound, refers to characterization techniques described in this book, while all the others indicate the types of objects (such as dispersions and emulsions) that are studied by methods based on ultrasound. Each word is a key to a major scientific discipline. Ultrasound establishes acoustics as the main scientific basis for the measuring techniques presented here. The other key words define hydrodynamics, rheology, porosimetry, and colloidal and interfacial science as disciplines that deal with particulates and porous bodies.

Historically, there has been curiously little real communication between acoustics and the scientific disciplines mentioned above. There is a large body of literature devoted to ultrasound phenomena in liquids, particulates, and porous bodies, but it has been mostly written from the perspective of scientists in the field of acoustics. There is limited recognition of ultrasound phenomena as of real importance for learning the properties of liquids, particulates, and porous bodies, and, in turn, developing applications. Scientists in these fields have not embraced acoustics as an important tool for characterizing their objects of interest. The lack of serious dialogue between these scientific fields is perhaps best demonstrated by the fact that there are no references to ultrasound or acoustics in the major handbooks on colloid and interface science [1, 2], rheology [3, 4], hydrodynamics [5–8], and porosimetry [9].

One may ask, Perhaps this link does not exist because it is not important? To answer this question, let us consider the potential place of ultrasound-related effects within an overall framework of nonequilibrium phenomena. It will be helpful to first classify nonequilibrium phenomena in two dimensions, as outlined in Table 1.1: the first is determined by whether the relevant disturbances are electrical, mechanical, or electromechanical in nature; the second is based on whether the time domain of that disturbance can be described as stationary, low frequency, or high frequency. The low- and high-frequency ranges are separated on the basis of the relationship between either the electrical or mechanical wavelength, λ, and some system dimension, L.

Table 1.1

Colloidal Phenomena

Light scattering clearly represents electrical phenomena in colloids at high frequency (the wavelength of light is certainly smaller than the system’s dimensions). However, until very recently, there was no mention in textbooks of mechanical or electromechanical phenomena in the region where λ is shorter than the system’s dimensions. This would appear to leave two empty spaces in Table 1.1. Such mechanical wavelengths are produced by sound or, when the frequency exceeds our hearing limit of 20 kHz, ultrasound. Ultrasound wavelengths lie in the range from 10 µm to 1 mm, whereas the system’s dimensions are usually in the range of centimeters. For this reason, we consider ultrasound-related effects to lie within the high-frequency range. One of the empty spaces in Table 1.1 can be filled by acoustic measurements at ultrasound frequencies that characterize nonequilibrium phenomena of a mechanical nature at high frequency. The second empty space can be filled by electroacoustic measurements that permit characterization of electromechanical phenomena at high frequency. This book helps fill these gaps and demonstrates that acoustics (and electroacoustics) can provide useful knowledge to various scientific disciplines. As an aside, we do not consider the use of high-power ultrasound for modifying systems here. We only undertake the use of low-power sound as a noninvasive investigation tool that has unique capabilities.

Several questions may come up when starting to read this book. We think it is important to deal with these questions right away, with some preliminary answers, which will be later clarified and expanded upon in the main text. Here are these questions and the short answers.

Why should one care about acoustics if generations of scientists have successfully worked on a particular field without it?

While it may be true that the usefulness of acoustics is currently not widely understood, it seems that earlier generations of scientists had a somewhat better appreciation. Many well-known scientists applied acoustics for characterization purposes, as will be described in a detailed historical overview in the next section. Briefly, we mention the names of Stokes, Rayleigh, Maxwell, Henry, Tyndall, Reynolds, and Debye. An interesting but not well-known fact is that Lord Rayleigh, the first author of a scattering theory, titled his major book as Theory of Sound. He developed the mathematics of scattering theory for both sound and light, but apparently considered sound to be more deserving of a book title than light.

If acoustics is so important, why has it remained almost unknown as a characterization tool for such a long time?

We think that the failure to exploit acoustic methods might be explained by a combination of factors: the advent of the laser as a convenient source of monochromatic light; technical problems with generating monochromatic sound beams over a wide frequency range; the mathematical complexity of the theory; and complex statistical analysis of the raw data. In addition, acoustics is more dependent on mathematical calculations than other traditional instrumental techniques. Many of these problems have now been solved mostly by the advent of fast computers and the development of new theoretical approaches. As a result, there are a number of commercially available instruments—developed by Matec, Malvern, Sympatec, Colloidal Dynamics, and Dispersion Technology—that utilize ultrasound for characterization of colloids.

What information do ultrasound-based instruments yield?

The versatility of ultrasound-based characterization methods deserves a special section in this chapter, as seen below.

Over the last decade, we have personally thought on several occasions that we have exhausted new ideas and have finished developing a family of ultrasound-based characterization instruments. Reality has proved us wrong every time. New possibilities suddenly appear that we had not thought about earlier. One of the most astounding examples is the application of electroacoustics in studying porous bodies. We recently discovered a paper published 60 years ago that presents a theory of the electroacoustic effect in a porous body. This was the first electroacoustic theory that was published by Frenkel in 1944 [10]. What was even more surprising is that this old theory was initiated by an even older experiment of seismoelectric current, observed by Ivanov in 1940 [11]. These works create the basis for applying electroacoustics for studying properties of porous bodies.

Where can one apply ultrasound?

It can be applied for any liquid-state system that is Newtonian or non-Newtonian and as diverse as pure water to pastes. The following list gives some idea of the existing applications for which the ultrasound-based characterization technique is appropriate:

aggregative stability, cement slurries, ceramics, chemical-mechanical polishing, coal slurries, coatings, cosmetic emulsions, environmental protection, flotation, ore enrichment, food products, latex, emulsions and micro emulsions, mixed dispersions, nanosized dispersions, nonaqueous dispersions, paints, photo materials.

This list is not complete. A table in Chapter 8 summarizes all experimental studies currently known to us.

What are the advantages of ultrasound over traditional characterization techniques?

There are so many advantages of ultrasound that we will discuss for a particular application in following sections of this chapter. Here is a striking example: ultrasound eliminates the need for sample dilution and special preparation for particle-sizing and ζ-potential measurements.

Finally, we would like to stress that this book primarily targets scientists who consider ultrasound for characterization purposes. We will emphasize those aspects of acoustics that are important for these goals and neglect many others.

1.1. Historical Overview

When preparing the first edition of this book almost 10 years ago, we did an extensive search of the relevant literature. Since that time, we found only a single old article of great importance that was missing from our original review. It turns out that the first electroacoustic theory was developed 7 years earlier than thought by a completely different person in a completely different place. There are also recent developments that deserve to be mentioned. These changes are incorporated in the text below.

The roots of our current understanding of sound go back to more than 300 years when Newton suggested the first theory for calculating the speed of sound [12]. Newton’s work is still interesting today because it demonstrates the importance of thermodynamic considerations when trying to adequately describe ultrasound phenomena. Newton assumed that sound propagated while maintaining a constant temperature, that is, an isothermal case. Laplace later corrected this misunderstanding by showing that it was actually adiabatic in nature [12].

This thermodynamic aspect of sound is a good example of the importance of keeping a historical perspective. In at least two incidences in the past 200 years, the thermodynamic contribution to various sound-related phenomena was initially neglected and only later found to be important. The first neglect of thermodynamics happened in the nineteenth century when Stokes’s purely hydrodynamic theory for sound attenuation [13, 14] was later corrected by Kirchhoff [15, 16]. The second neglect occurred in the twentieth century when Sewell’s hydrodynamic theory for sound absorption in heterogeneous media [17] was later extended by Isakovich [18] with the introduction of a mechanism for thermal losses.

Table 1.2 lists the important steps in the development of our understanding of sound. From the beginning, sound was considered to be a rather simple example of a wave on which a general theory of wave phenomena was developed. Later, the new body of understanding for sound was extended to other wave phenomena, such as light. Tyndall, for example, used references to sound to explain the wave nature of the light [23, 24]. Newton’s corpuscular theory of light was first opposed both by the celebrated astronomer, Huygens, and the equally celebrated mathematician, Euler. They both believed that light, like sound, was a product of wave motion. In the case of sound, the velocity depended upon the relation between elasticity and density in the body that transmitted the sound. The greater the elasticity of the body, the greater is the velocity; the lower the density of the body, the greater is the velocity of the sound. To account for the enormous velocity of propagation in the case of light, the substance that transmitted it was assumed to have both extreme elasticity and extreme density.

Table 1.2

Milestones in Understanding Sound in Relation to Colloids

The dominance of sound over light as examples of the wave phenomena continued even with Lord Rayleigh. He developed his theory of scattering mostly for sound and paid much less attention to light [12, 27–30]. At the end of the nineteenth century, sound and light parted ways because further investigation was directed more on the physical roots of each phenomenon instead of on their common wave nature.

The history of light and sound in colloid science is very different. Light has been an important tool since the first microscopic observations of Brownian motion and the first electrophoretic measurements. It became more important in middle of the twentieth century because of the use of light scattering to determine particle size.

In contrast, sound remained unknown in colloid science, despite a considerable amount of work in the field of acoustics where fluids that were essentially colloidal in nature were used. The goal of these studies was to learn more about acoustics than about colloids. This was the spirit in which the ECAH theory (Epstein-Carhart-Allegra-Hawley [46, 55]) for ultrasound propagation through dilute colloids was developed.

Although acoustics was not specifically used for colloids, it was a powerful tool for other purposes [89, 90]. For instance, it was used to learn more about the structure of pure liquids and the nature of chemical reactions in liquids. These studies, associated with the name of Prof. Eigen who received a Nobel Prize in Chemistry in 1967 [52, 53, 78], are described in more detail in the chapter, Fundamentals of Acoustics.

Curiously, the penetration of ultrasound into colloid science began with electroacoustics, which is more complex than traditional acoustics. An electroacoustic effect was predicted for ions by Debye in 1933 [31], and later extended to colloids by Hermans and, independently, Rutgers in 1938 [33].

Recently, we have learned that at about the same time, electroacoustic phenomena were observed in geology by Ivanov in 1940 [35]. Theory of this effect, called seismoelectric current, became the first ever electroacoustic theory by Frenkel in 1944 [9]. Early experimental electroacoustic work is associated with Yeager and Zana who conducted many experiments in the 1950s and 1960s with various coauthors [39–42]. This work was later continued by Marlow, O’Brien, Ohshima, Shilov, and the authors of this book [58, 64, 65, 67, 68, 79, 80, 91]. As already mentioned, there are now several commercially available electroacoustic instruments for characterizing the ζ-potential.

Acoustics has only very recently attained some recognition in the field of colloid science. It was first suggested as a particle-sizing tool by Cushman and others in 1973 [56], and later refined by Uusitalo and others [50]. Acoustics for sizing was suggested for large particles by Riebel [63]. Development of a commercial instrument that could measure a wide range of particle sizes was begun by Goetz, Dukhin, and Pendse in the 1990s [72, 81–83]. At the same time, a group of British scientists including McClements, Povey, and others [66, 69–71, 84, 85] actively promoted acoustics, especially for the study of emulsions. As mentioned earlier, there are now several commercially available acoustic spectrometers, manufactured by Sympatec, Matec, and Dispersion Technology.

In conclusion of this short historical review, we would like to mention a development that we consider of great importance for the future—the combination of both acoustic and electroacoustic spectroscopies. The synergism of this combination is described in the papers and patents by Dukhin and Goetz [68, 73, 74, 80–83, 86, 87].

1.2. Versatility of Ultrasound-Based Characterization Techniques

There are two distinctively different ultrasound-based measuring methods. One is called acoustics and the other one is known as electroacoustics. They measure completely different parameters. Acoustics is simpler because a single field is involved—field of the mechanical stress. The measured parameters are usually sound speed and attenuation coefficient. The electroacoustic method is more complicated because it is based on the coupling of two fields—electrical and mechanical. The measured parameters are the magnitude and phase of the electroacoustic signal.

Four raw parameters can be used as a fingerprint of a particular liquid system.

• Sound speed

• Attenuation coefficient (usually at multiple frequencies)

• Magnitude of the electroacoustic signal

• Phase of the electroacoustic signal

Alternatively, the raw data could be theoretically treated so that a multitude of other properties can be characterized. The theoretical treatment is the main reason for ultrasound’s versatility for characterization purposes. It turns out that there are two very different sets of calculated parameters that can be extracted from the raw data, depending on degree of our a priori knowledge about the system.

If our prior knowledge is limited and we are forced to model a system as a homogeneous medium with unknown viscoelastic properties, then the ultrasound-based method allows us to calculate following parameters:

• Viscosity longitudinal within the 1–100 MHz frequency range

• Viscous longitudinal modulus G″

• Bulk viscosity for Newtonian liquids

• Elastic longitudinal modulus G′

• Compressibility

• Newtonian liquid test in the megahertz range

• Isoelectric point—range of aggregative instability

• Optimum dose of surfactant

• Volume fraction of the dispersed phase from sound speed

• Kinetics of dissolution, crystallization

• Kinetics of sedimentation

• Verification of large particle presence in opaque systems

We would like to stress here that the system might be very complex and intuitively heterogeneous, but it should not prevent the application of the homogeneous mode to its description. For instance, milk can be treated as a homogeneous liquid when we ignore the fact that it is actually a collection of fat droplets, proteins, and sugars in water. Basically, any liquid system can be modeled as homogeneous or heterogeneous. These models are creations in our minds for adequate characterization of various physical and chemical properties.

In the case of ultrasound-based techniques, we can first model a system as homogeneous and calculate the set of parameters presented above. Then, as the next step, we can apply the heterogeneous model and theoretically treat the same set of experimental raw data for extracting another set of parameters, given below:

• Particle size distribution of solid particles with known density

• Particle size distribution of soft particles (droplets) when thermal expansion coefficient is known

• Volume fraction of solids at the submicrometer range

• Hook’s parameter for particle bonds in structured systems

• Microviscosity

• ξ-Potential in particulates

• Surface conductivity

• Debye length when conductivity is known

• Ion size from compressibility in aqueous solution

• Ion size from electroacoustics in aqueous and nonaqueous solutions

• Electric charge of macromolecules

• Porosity, pore size, and ξ-potential in porous bodies

• Properties of deposits and sediments

Application of the heterogeneous model usually requires a priori information about the volume fraction of the dispersed phase. This parameter may be extracted from the raw data in some special cases, for instance when particles are rigid and their sizes range from 0.1 to 1 µm. Sometimes, it can be calculated from the sound’s speed as well. However, for the most reliable results, volume (weight) fraction of the dispersed phase must be treated as an independently known input parameter.

In terms of traditional measuring techniques, ultrasound can combine the descriptions of rheology, particle size distribution, and ζ-potential into one unit instead of three independent instruments. This has substantial advantages over traditional methods. We discuss some of them below.

1.3. Comparison of Ultrasound-Based Methods with Traditional Techniques

The versatility of ultrasound-based methods makes them comparable with several traditional techniques, such as particle sizing by light scattering, electrophoretic light scattering, microelectrophoresis, and shear rheology.

1.3.1. General Features

A major distinction of ultrasound-based techniques, in contrast to traditional light-based characterization methods, is that sound can propagate through concentrated, opaque liquid systems and even porous bodies. This peculiar feature opens up the opportunity for tremendous simplification in sample preparation. In particular, ultrasound-based methods applied to concentrated dispersions and emulsions eliminate the need for dilution. Systems can be characterized as they are. Dilution required by traditional techniques can destroy aggregates or flocs. The corresponding measured particle size distribution for the diluted system would not be correct for the original concentrated sample.

Eliminating dilution is especially critical for ζ-potential characterization because the parameter is a property of both the particle and the surrounding liquid; dilution changes the suspension medium and the ζ-potential. This feature of eliminating dilution is applicable to both the measurements of particle size and ζ-potential. Sample handling for characterizing these parameters becomes as simple as in traditional rheological methods.

Acoustic methods are very robust and precise [73, 74]. They are much less sensitive to contamination in comparison to traditional light-based techniques because the high concentration of particles in a fresh sample dominates any small residue left from the previous sample.

Ultrasound-based methods are relatively fast. A single measurement can normally be completed within a few minutes. This feature, together with the ability to measure flowing systems, makes acoustic attenuation very attractive for on-line characterization.

1.3.2. Particle Sizing

The numerous advantages of using ultrasound for characterizing particle size are summarized in Table 1.3. Detailed analysis of ultrasound-based techniques is given later in this book. The following is a short summary.

Table 1.3

Features and Benefits of Acoustics over Traditional Particle-Sizing Techniques

There are several advantages of ultrasound-based over light-based instruments because of the longer wavelength used. The wavelength of ultrasound in water, at the highest frequency typically used (100 MHz), is about 15 µm. It increases even further to 1.5 mm at the lowest frequency (1 MHz). In contrast, light-based instruments typically use wavelengths on the order of 0.5 µm. If the particles are small compared to the wavelength, the Rayleigh long-wavelength requirement is said to be satisfied. Particle sizing in this long-wavelength range is more desirable than in the intermediate- or short-wavelength ranges because of the lower sensitivity to shape factors and a simpler theoretical interpretation. So, applying the longer wavelengths available by acoustics allows us to characterize a greater range of particle sizes while still meeting the long-wavelength requirement.

Nature has provided one more significant advantage of ultrasound over light which relates to the wavelength dependence. As the wave travels through the colloid, the combined effects of both scattering and absorption cause the extinction of both ultrasound and light [32, 88]. As most light scattering experiments are performed at a single wavelength, it is not possible to experimentally separate the two contributions of scattering and absorption to the total extinction. More often than not, the absorption of light is simply neglected in most light scattering experiments, which can lead to errors.

In the case of ultrasound, the absorption and scattering are distinctively separated on the wavelength scale. Figure 1.1 illustrates the dependence of ultrasound attenuation as a function of relative wavelength, ka, as defined by:

(1.1)

where a is the particle radius and λ is the wavelength of ultrasound.

Figure 1.1 Scattering attenuation and viscous absorption of ultrasound.

The attenuation curve has two prominent ranges. The lower frequency region corresponds to absorption; the higher frequency region corresponds to scattering. It is obvious from Figure 1.1 that both contributions can be easily separated because there is very little—indeed almost negligible—overlap.

This peculiar aspect of ultrasound frequency dependence tremendously simplifies the theory. In the majority of cases, absorption and scattering can be considered separately. Except for the cases with very high volume fractions and some special nonaqueous systems with soft particles [49], this simplification is valid.

1.3.3. Measurements of ζ-Potential

In contrast to acoustics, electroacoustics is a relatively new technique. In principle, it provides information for both particle-sizing and ζ-potential characterization. However, we believe that acoustics is better suited to particle sizing than electroacoustics. For this reason, as justified later in Chapters 4, 5, and 7, we consider electroacoustics to be primarily a technique for characterizing only the electric surface properties, such as the ζ-potential. In this sense, electroacoustics competes with microelectrophoresis and other traditional electrokinetic methods. However, electroacoustics has many advantages over traditional electrokinetic methods, which can be summarized as follows:

• No dilution required, volume fraction up to 50% vol

• Less sensitive to contamination, easier to clean

• Higher precision (± 0.1 mV)

• Low surface charges (down to 0.1 mV)

• Electrosmotic flow not important

• Convection not important

• Measurement at high ionic strength exceeding 1 M level

• Measurement at very low ionic strength in nonpolar liquids

• Small sample volume, as little as 1 ml

• Faster

In addition, as explained later in Chapter 8, electroacoustic probes can be used for various titration experiments.

1.3.4. Longitudinal and Shear Rheology

Ultrasound-based methods are similar to rheology in that they rely on applying stress to the system to learn about some of its properties. The difference is the type of stress applied. Traditional rheology uses shear stress, whereas ultrasound is a wave of longitudinal stress. Thus, there are two different rheological methods—shear rheology and longitudinal rheology. Chapter 3 presents detailed definitions and comparison of these two measurement techniques. Here we will only mention the main differences.

First of all, the two different rheological methods work at very different frequency ranges. Shear rheology is applicable at a low frequency range up to roughly 100 kHz. Longitudinal rheology functions only at the megahertz frequency scale. This makes both methods complimentary, not competitive.

Second, longitudinal rheology is nondestructive. Longitudinal stress does not break bonds between particles. It only causes the bonds to expand and collapse.

Third, longitudinal rheology provides information about the bulk viscosity of Newtonian liquids. Bulk viscosity is a more sensitive probe of any structural feature in a Newtonian liquid but it is impossible to measure using shear-based techniques.

Finally, measurement of the ultrasound attenuation at multiple frequencies helps in assessing whether a particular liquid can be described as Newtonian at the megahertz frequency range.

1.3.5. Characterization of Porous Bodies

This is a relatively new field for ultrasound-based methods and still is under development. However, there is sufficient amount of data to be optimistic about the method’s future.

Characterization of porous bodies usually includes measurements of the porosity, pore size, and the electric charging of the walls of the pores. The measurement of porosity and pore size can be achieved using gas adsorption and mercury porosimetry. The characterization of electric charging usually relies on streaming current/potential measurement.

The propagation of ultrasound through a porous body generates a host of different effects that can be used for characterization purposes. Detailed analysis of the seismoelectric current may be the most promising: it simply is a streaming current at high ultrasound frequency in the nonisochoric mode. If this development can be confirmed, this method could compete with mercury porosimetry and minimize usage of this environmentally dangerous material. The seismoelectric current method would allow characterization of the electric surface properties of materials with very low hydrodynamic permeability because of small pore size. Many materials of this kind are impossible to be measured with classical electrokinetic methods.

References

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