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Tharwat F. Tadros
Formulation Science and Technology
Also of Interest
Handbook of Colloid and Interface Science.
Volumes 1–4
Tadros, 2018
ISBN 978-3-11-054050-5

Suspension Concentrates.
Preparation, Stability and Industrial Applications
Tadros, 2017
ISBN 978-3-11-048678-0, e-ISBN 978-3-11-048687-2

Polymeric Surfactants.
Dispersion Stability and Industrial Applications
Tadros, 2017
ISBN 978-3-11-048722-0, e-ISBN 978-3-11-048728-2

Formulations.
In Cosmetic and Personal Care
Tadros, 2016
ISBN 978-3-11-045236-5, e-ISBN 978-3-11-045238-9

Emulsions.
Formation, Stability, Industrial Applications
Tadros, 2016
ISBN 978-3-11-045217-4, e-ISBN 978-3-11-045224-2
Tharwat F. Tadros

Formulation
Science and
Technology
|
Volume 4:
Agrochemicals, Paints and Coatings
and Food Colloids
Author
Prof. Tharwat F. Tadros
89 Nash Grove Lane
Workingham RG40 4HE
Berkshire, UK
[email protected]

ISBN 978-3-11-058755-5
e-ISBN (PDF) 978-3-11-058800-2
e-ISBN (EPUB) 978-3-11-058756-2

Library of Congress Control Number: 2018935454

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2018 Walter de Gruyter GmbH, Berlin/Boston

Cover image: Nik_Merkulov / iStock / Getty Images
Typesetting: PTP-Berlin, Protago-TEX-Production GmbH, Berlin
Printing and binding: CPI books GmbH, Leck

www.degruyter.com
Preface
This volume describes industrial applications in agrochemicals (Part I), paints and
coatings (Part II) and food colloids (Part III). The discussion of agrochemical formula-
tions begins with a general introduction (Chapter 1) describing the requirements of the
various types of systems. This is followed by Chapter 2, which focuses on emulsifiable
concentrates (ECs), in which the active ingredient is mixed (or dissolved) in an oil and
two surfactants. When this oil is added to an aqueous solution in the spray tank, it
spontaneously emulsifies forming an oil/water (O/W) emulsion. The mechanism of
self-emulsification is described. These ECs are now mostly replaced with a concen-
trated O/W emulsion (Chapter 3), which provides a number of advantages, such as
using less oil and surfactant and the possibility of incorporating an adjuvant (which
enhances the biological efficacy) in the continuous phase. Chapter 4 deals with the
formulation of suspension concentrates (SCs), which are commonly used to replace
wettable powders (which can be dusty and hazardous to the operator). The main fac-
tors involved in SC formulation and its long-term physical stability are described with
particular reference to the rheological methods that can be applied for their assess-
ment. Chapter 5 describes the formulation of oil-based suspensions, whereby the oil
can be polar or nonpolar. The requirements for both types to achieve colloid stability
are described and this is followed by a description of the use of anti-settling systems
in nonaqueous suspensions. Finally, the emulsification of the oil-based suspension in
aqueous and electrolyte solution media is described. Chapter 6 describes the formu-
lation of suspoemulsions (mixtures of suspensions and emulsions) highlighting the
possible interactions between the suspension particles and the emulsion droplets.
This can lead to various instability problems such as homoflocculation, heterofloc-
culation, coalescence of emulsion droplets and recrystallization. The methods that
can be used to reduce or eliminate such instabilities are described with particular
reference to polymeric surfactants. Chapter 7 deals with the formulation of controlled-
release systems with particular reference to the microencapsulation of liquid and solid
AIs, controlled release from matrix-based microparticles and granules. Chapter 8 de-
scribes the formulation of adjuvants that are required to enhance the bioefficacy of the
AI Several factors must be considered when selecting an adjuvant for a given AI These
include interactions at the air/water interface and their effect on spray droplet for-
mation, spray impaction and adhesion, wetting and spreading, evaporation of spray
droplets and formation of deposits, solubilisation of the AI by surfactant micelles and
its effect on transport and interaction between agrochemical, surfactants and target
species.
Part II deals with the formulation of paints and coatings. Chapter 9 describes the
nature of the dispersed particle, the dispersion medium and film formers, the depo-
sition of particles and their adhesion on substrates and the flow characteristics (rhe-
ology) of the paint formulation. Chapter 10 describes the formulation of film formers

https://doi.org/10.1515/9783110588002-001
vi | Preface

using emulsion and dispersion polymerization. Chapter 11 deals with the formulation
of pigments for paint application. Topics such as the wetting of powders, breaking of
aggregates and agglomerates, wet milling and colloid stabilization of the paint dis-
persion must be considered. Chapter 12 describes the process of enhancing particle
deposition and its final adhesion. This is governed by long-range forces such as double
layer repulsion (or attraction) and short-range (surface forces). Chapter 13 illustrates
the rheological techniques that can be applied during paint formulation, whereas
Chapter 14 shows how these rheological methods can be applied during paint formu-
lation. Chapter 15 gives examples of the flow properties of some commercial paints.
Part III describes the formulation of food colloids. It starts with a general introduc-
tion (Chapter 16) highlighting the complexity of food systems. Chapter 17 starts with
a description of the interaction between food grade surfactants and the structure of
the liquid crystalline phases. This is followed by a description of binary and tertiary
phase diagrams, monolayer formation and the relationship between the liquid crys-
talline structure and emulsion stability. Chapter 18 deals with the formulation of food
emulsions using proteins, protein/polysaccharide and surfactant/polysaccharide in-
teractions. The structure of portents and their interaction and conformation at the
liquid/liquid interface are described. Chapter 19 describes the process of surfactant
association structures, microemulsions and emulsions in food. Chapter 20 deals with
the rheology of food emulsions with particular reference to interfacial and bulk rheol-
ogy. The correlation between interfacial rheology and emulsion stability is highlighted
using two examples, namely mixed surfactant and protein films. The bulk rheology of
emulsions is described with particular reference to microgel dispersions and the frac-
tal nature of the aggregated network. Chapter 21 deals with foam formulations in food
of which whipping cream and bread dough are the most common. In the first case, the
air bubbles are stabilized by fat crystals that adhere to air bubbles during the whipping
process forming a protective layer and preventing bubble coalescence. In the latter
case, the bread quality is determined by a high bread volume and a fine crumb struc-
ture. Several theories have been proposed to explain foam stability, namely: surface
viscosity and elasticity theory, where the adsorbed surfactant film is assumed to con-
trol the mechanical-dynamical properties of the surface layers by virtue of its surface
viscosity and elasticity; the Gibbs–Marangoni effect theory; surface forces theory (dis-
joining pressure π), which operates under static (equilibrium) conditions in relatively
dilute surfactant solutions (h < 100 nm); stabilisation by micelles (high surfactant
concentrations > cmc); stabilization by lamellar liquid crystalline phases, which is
particularly the case with nonionic surfactants that produce lamellar liquid crystalline
structure in the film between the bubbles; stabilisation of foam films by mixed surfac-
tants whereby a combination of surfactants give slower drainage and improved foam
stability; and stabilization by solid particles, which involves particles adsorbing at the
air/liquid interface. Chapter 22 looks at the relationship between rheology and mouth
feel. After describing the main rheological measurements that need to be applied to
obtain such a correlation, some emphasis is given to the break-up of Newtonian and
 Preface | vii

non-Newtonian liquids. The complexity of flow in the oral cavity is described and
subsequently a description is given of the relationship between texture and rheology.
Finally, some examples of practical food colloids are given.
This book (Volume 4) gives a number of formulation examples in the areas of agro-
chemicals, paints and coating and food colloids. It is a valuable text for formulation
scientists involved in the formulation of these systems. It may also be useful for aca-
demics involved in a research area related to any of these formulations.

Tharwat Tadros
May 2018
Contents
Preface | v

Part I: The formulation of agrochemicals

1 Introduction to the formulation of agrochemicals | 3

2 Formulation of emulsifiable concentrates | 9

3 Formulation of emulsion concentrates | 15

3.1 Formation of emulsions | 15
3.2 Mechanisms and methods of emulsification | 16
3.3 Role of surfactants in emulsion formation | 18
3.4 Selection of emulsifiers | 20
3.4.1 Hydrophilic–lipophilic balance concept | 20
3.4.2 Phase inversion temperature concept | 23
3.5 Emulsion stability | 25

4 Formulation of suspension concentrates | 35

4.1 Introduction | 35
4.2 Preparation of suspension concentrates
and the role of surfactants/dispersing agents | 36
4.3 Control of the physical stability of suspension concentrates | 40
4.4 Characterizing suspension concentrates and assessing
of their long-term physical stability | 50

5 Oil-based suspension concentrates | 59

5.1 Introduction | 59
5.2 Stability of nonaqueous suspensions | 59
5.3 Emulsification of oil-based suspensions | 66
5.4 Polymeric surfactants for oil-based suspensions and the choice
of emulsifiers | 68
5.5 Emulsification into aqueous electrolyte solutions | 69
5.6 Proper choice of anti-settling system | 69
5.7 Rheological characteristics of oil-based suspensions | 70

6 Formulation of suspoemulsions | 71
6.1 Introduction | 71
6.2 Suspoemulsions investigated | 72
x | Contents

7 Formulation of controlled-release systems | 79

7.1 Introduction | 79
7.2 Microencapsulation | 79
7.3 Encapsulation by phase separation from aqueous solution | 81
7.4 Microencapsulation of solid particles | 82
7.5 Controlled release of agrochemicals
from matrix-based microparticles | 83
7.6 Controlled release from granules | 86

8 Formulation of adjuvants | 89
8.1 Introduction | 89
8.2 Interactions at the air/solution interface and their effect
on droplet formation | 92
8.3 Spray impaction and adhesion | 96
8.4 Droplet sliding and spray retention | 99
8.5 Wetting and spreading | 101
8.6 Evaporation of spray drops and depsoit formation | 105
8.7 Solubilization and its effect on transport | 107
8.8 Interaction between surfactants, agrochemicals
and target species | 110

References | 113

Part II: The formulation of paints and coatings

9 Formulation of paints and coatings | 117

9.1 Introduction | 117
9.2 Dispersion particles | 118
9.3 Dispersion medium and film formers | 120
9.4 Deposition of particles and their adhesion to the substrate | 124
9.5 Flow characteristics (rheology) of paints | 124

10 Formulation of film formers | 125

10.1 Emulsion polymerization | 125
10.2 Dispersion polymerization | 135

11 Formulation of pigment dispersions for paint application | 141

11.1 Wetting of the bulk powder | 141
11.2 Breaking of aggregates and agglomerates (deagglomeration) | 148
11.3 Wet milling (cominution) | 153
 Contents | xi

11.4 Colloid stabilization of paint dispersions | 156

11.4.1 Electrostatic double layer repulsion | 157
11.4.2 Steric repulsion | 160

12 Enhancement of particle deposition and adhesion in paints

and coatings | 167
12.1 Particle deposition | 167
12.2 Particle–surface adhesion | 172

13 Control of the rheology of paint formulations | 177

14 Application of rheological techniques to paint formulations | 193

15 Examples of the flow properties of some commercial paints | 203

References | 207

Part III: The formulation of food colloids

16 Introduction to the formulation of food colloids | 211

17 Interaction between food-grade agent surfactants and water and structure

of the liquid crystalline phases | 215
17.1 Binary phase diagrams | 216
17.2 Ternary phase diagrams | 222
17.3 Monolayer formation | 222
17.4 Liquid crystalline phases and emulsion stability | 226

18 Formulation of food emulsions using proteins and protein/polysaccharides

and polysaccharide/surfactants | 229
18.1 Protein structure | 229
18.2 Interfacial properties of proteins at the liquid/liquid interface | 231
18.3 Proteins as emulsifiers | 232
18.4 Protein–polysaccharide interactions in food colloids | 233
18.5 Polysaccharide–surfactant interactions | 236

19 Surfactant association structures, microemulsions

and emulsions in food | 239

20 Rheology of food emulsions | 245

20.1 Interfacial rheology | 245
xii | Contents

20.2 Correlation between emulsion stability and interfacial rheology | 247

20.2.1 Mixed surfactant films | 247
20.2.2 Protein films | 248
20.3 Bulk rheology of emulsions | 249
20.4 Formation of networks | 251
20.5 Rheology of microgel dispersions | 253
20.6 Fractal nature of the aggregated network | 253

21 Foam formulations in food | 255

21.1 Foam stability | 255
21.2 Foam destabilization | 261

22 Food rheology and mouthfeel | 267

22.1 Introduction | 267
22.2 Rheological measurements | 267
22.3 Mouthfeel of foods: the role of rheology | 270
22.3.1 Break-up of newtonaian liquids | 272
22.3.2 Break-up of non-Newtonian liquids | 273
22.4 Complexity of flow in the oral cavity | 274
22.5 Relationship between rheology and texture | 274

23 Practical applications of food colloids | 279

References | 283

Index | 285
|
Part I: The formulation of agrochemicals
1 Introduction to the formulation of agrochemicals
Agrochemical formulations include a wide range of systems suited to specific appli-
cations [1, 2]. Agrochemicals are usually effective at several grams to hundreds of
grams of active ingredient per 1,000 m2 . It is, however, difficult to apply such a small
amount uniformly to the crop. The active ingredient is always first formulated in a
suitable diluent such as water or an organic solvent and when the formulation is ap-
plied it is further diluted in the spray tank to ensure uniform deposition upon spray-
ing. In some cases, an agrochemical is a water-soluble compound of which paraquat
and glyphosate (both are herbicides) are probably the most familiar. Paraquat is a
2,2 bypyridium salt and the counter ions are normally chloride. It is formulated as a
20 % aqueous solution which is simply diluted into water at various ratios (1 : 50 up
to 1 : 200 depending on the application) upon application. To such an aqueous so-
lution, surface active agents (sometimes referred to as wetters) are added which are
essential for a number of reasons. The most obvious reason for adding surfactants is
to enable the spray solution to adhere to the target surface and spread over it to cover
a large area. However, this picture is an oversimplification since the surface-active
agent plays a more subtle role in the optimization of the biological efficacy. Thus, the
choice of the surfactant system in an agrochemical formulation is crucial since it must
perform a number of functions. To date, this choice is made by a trial and error proce-
dure, due to the complex nature of application and the lack of understanding of the
mode of action of the chemical. It is the objective of this book to apply the basic prin-
ciple of colloid and interface science to agrochemical formulations, their subsequent
application, and the optimization of their biological efficacy.
The main purpose of any agrochemical formulation is to make handling and ap-
plication of the active ingredient as easy as possible. An important function of the
formulation is to optimize its biological efficacy. In most cases, this is achieved by
controlling the physical characteristics of the formulation and use of adjuvants. An
important criterion for any agrochemical is its safety both to the crop and the agro-
chemical worker. This requires adequate control of the spray droplet spectrum, reduc-
tion of any drift and removal of any toxic effect on contact with the individual. These
stringent requirements can be achieved through careful analysis of all the interfacial
phenomena that are involved in application. The concept of “Pesticide Delivery Sys-
tem” (PDS) must be applied, whereby the active ingredients are made available to a
specified target at a concentration and duration designed to accomplish an intended
effect, i.e., obtain the fullest biological efficacy while minimizing various harmful ef-
fects.
Most agrochemicals are water-insoluble compounds with various physical prop-
erties, which have first to be determined in order to decide on the type of formulation.
One of the earliest types of formulations are wettable powders (WP), which are suit-
able for formulating solid water-insoluble compounds that can be produced in a pow-

https://doi.org/10.1515/9783110588002-002
4 | 1 Introduction to the formulation of agrochemicals

der form. The chemical (which may be micronized) is mixed with a filler such as china
clay and a solid surfactant such as sodium alkyl or alkyl aryl sulphate or sulphonate
is added. When the powder is added to water, the particles are spontaneously wetted
by the medium and, upon agitation, dispersion of the particles takes place. It is clear
that the particles should remain suspended in the continuous medium for a period
of time depending on the application. Some physical testing methods are available to
evaluate the suspensibility of the WP. Clearly, the surfactant system plays a crucial role
in wettable powders. In the first place, it enables spontaneous wetting and dispersion
of the particles. Second, by adsorption on the particle surface, it provides a repulsive
force that prevents aggregation of the particles. This process of aggregation increases
the settling of the particles and may also cause problems upon application, such as
nozzle blockage.
The second and most familiar type of agrochemical formulation is emulsifiable
concentrates (ECs), as described in Chapter 2. This is produced by mixing one agro-
chemical oil with another one, such as xylene or trimethylbenzene, or a mixture of
various hydrocarbon solvents [1]. Alternatively, a solid pesticide could be dissolved
in a specific oil to produce a concentrated solution. In some cases, pesticide oil may
be used without the addition of any extra oils. A surfactant system (usually a mix-
ture of two or three components) is always added for a number of purposes. First, the
surfactant enables self emulsification of the oil on addition to water. This occurs by
a complex mechanism that involves a number of physical changes, such as lowering
interfacial tension at the oil/water interface, enhancement of turbulence at that in-
terface with the result of spontaneous production of droplets. Second, the surfactant
film that adsorbs at the oil/water interface, stabilizes the produced emulsion against
flocculation and/or coalescence. As we will see in later sections, emulsion breakdown
must be prevented, otherwise excessive creaming or sedimentation or oil separation
may take place during application. This results in an inhomogeneous application of
the agrochemical on the one hand, and possible losses on the other. The third role of
the surfactant system in agrochemicals is to enhance biological efficacy. As we will
look at later, it is essential to arrive at optimum conditions for effective use of agro-
chemicals. In this case, the surfactant system will help spreading the pesticide at the
target surface and may enhance its penetration.
In recent years, there has been great demand to replace ECs with concentrated
aqueous oil-in-water (O/W) emulsions [1–3] as will be described in Chapter 3. This
replacement provides several potential advantages. In the first place, the added oil
can be replaced with water, which is of course much cheaper and environmentally
acceptable. Secondly, removing the oil could help to reduce undesirable effects such
as phytotoxicity, skin irritation, etc. Third, by formulating the pesticide as an O/W
emulsion, it is possible to control the droplet size to an optimum value, which may
be crucial for biological efficacy. Fourth, water-soluble surfactants, which may be de-
sirable for biological optimization, can be added to the aqueous continuous phase.
As we will see in the subsequent chapters, the choice of a surfactant, or a mixed sur-
 1 Introduction to the formulation of agrochemicals | 5

factant system is crucial for preparation of a stable O/W emulsion. In recent years,
macromolecular surfactants have been designed to produce very stable O/W emul-
sions which could be easily diluted into water and applied without any detrimental
effects to the emulsion droplets.
More recently, microemulsions are being considered as potential systems for
formulating agrochemicals. Microemulsions are isotropic, thermodynamically stable
systems consisting of oil, water and surfactant(s) where the free energy of formation
of the system is zero or negative [4]. It is obvious why such systems, when they can
be formulated, are very attractive, since they have an indefinite shelf life (within a
certain temperature range). Since the droplet size of microemulsions is very small
(usually less than 50 nm), they appear transparent. The microemulsion droplets may
be considered as swollen micelles and hence they will solubilize the agrochemical.
This may result in considerable enhancement of the biological efficacy. Thus, micro-
emulsions may offer several advantages over the commonly used macroemulsions.
Unfortunately, formulating the agrochemical as microemulsion is not straightforward
since one usually uses two or more surfactants, an oil and the agrochemical. These
tertiary systems produce various complex phases and it is essential to investigate
the phase diagram before arriving at the optimum composition of microemulsion
formation. A high concentration of surfactant (10–20 %) is needed to produce such
a formulation. This makes such systems relatively more expensive to produce when
compared to macroemulsions. However, the extra cost incurred could be offset by an
enhancement of biological efficacy which means that a lower agrochemical applica-
tion rate could be achieved.
A similar concept has been applied to replace wettable powders, namely with
aqueous suspension concentrates (SCs) that will be described in Chapter 4. These sys-
tems are more familiar than ECs and they were introduced several decades ago [2, 5].
Indeed, SCs are probably the most widely used systems in agrochemical formulations.
Again, SCs are much more convenient to apply than WPs. Dust hazards are absent,
and the formulation can be simply diluted in the spray tanks, without any vigorous
agitation. As we will see in Chapter 20, SCs are produced by a two or three stage pro-
cess. The pesticide powder is first dispersed in an aqueous solution of a surfactant
or a macromolecule (usually referred to as the dispersing agent) using a high-speed
mixer. The resulting suspension is then subjected to a wet milling process (usually
bead milling) to break any remaining aggregates or agglomerates and reduce the par-
ticle size to smaller values. One usually aims at a particle size distribution ranging
from 0.1 to 5 µm., with an average of 1–2 µm. The surface or polymer added adsorbs on
the particle surfaces, resulting in their colloidal stability. The particles must be sta-
bly maintained over a long period of time, since any strong aggregation in the system
may cause various problems. First, as the aggregates are larger than the primary par-
ticles, they tend to settle faster. Second, any gross aggregation may result in lack of
dispersion on dilution. The large aggregates can block the spray nozzles and may re-
duce biological efficacy as a result of the inhomogeneous distribution of the particles
6 | 1 Introduction to the formulation of agrochemicals

on the target surface. Apart from their role in ensuring the colloidal stability of the
suspension, surfactants are added to many SCs to enhance their biological efficacy.
This is usually produced by solubilization of the insoluble compared in the surfactant
micelles. This will be discussed in later sections. Another role a surfactant may play
in SCs is to reduce crystal growth (Ostwald ripening). The latter process may occur
when the solubility of the agrochemical is appreciable (say greater than 100 ppm) and
when the SC is polydisperse. The smaller particles will have a higher solubility than
the larger ones. With time, the small particles dissolve and become deposited on the
larger ones. Surfactants may reduce this Ostwald ripening by adsorption on the crys-
tal surfaces, thus preventing deposition of the molecules at the surface. This will be
described in detail in Chapter 5.
Chapter 6 describes the formulation of oil-based suspensions, which are currently
used for the formulation of many agrochemicals, in particular those which are chem-
ically unstable in aqueous media [2]. These suspensions permit the use of oils (such
as methyl oleate) which may enhance the biological efficacy of the active ingredient.
In addition, one may incorporate water-insoluble adjuvants into the formulation. The
most important criterion for the oil used is to have the minimum solubility of the ac-
tive ingredient otherwise Ostwald ripening or crystal growth will occur upon storage.
The oil-based suspension has to be diluted in water to produce an oil-in-water emul-
sion. A self-emulsifiable system must be produced and this requires the presence of
the appropriate surfactants for self emulsification. The surfactants used for self emul-
sification should not interfere with the dispersing agent that is used to stabilize the
suspension particles in the nonaqueous media. Displacement of the dispersing agent
with the emulsifiers can lead to flocculation of the suspension. To prevent sedimenta-
tion of the particles (sine the density of the active ingredient is higher than that of the
oil in which it is dispersed), an appropriate rheology modifier (anti-settling agent) that
is effective in the nonaqueous medium must be incorporated into the suspension. This
rheology modifier should not interfere with the self emulsification process of the oil
based suspension. Two main types of nonaqueous suspensions may be distinguished:
(i) Suspensions in polar media such as alcohol, glycols, glycerol, esters. These media
have a relative permittivity εr > 10; in this case, double layer repulsion plays an
important role, in particular when using ionic dispersing agents.
(ii) Suspensions in nonpolar media, εr < 10, such as hydrocarbons (paraffinic or aro-
matic oils), which can have a relative permittivity as low as 2. In this case, charge
separation and double layer repulsion are not effective and hence one has to de-
pend on the use of dispersants that produce steric stabilization.

Chapter 7 describes the formulation of suspoemulsions [2], which are mixtures of sus-
pensions and emulsions where two active ingredients are formulated with one as an
aqueous suspension and the other as an oil/water emulsion. This offers convenience
to the farmer and may also result in synergism in biological efficacy. A wider spec-
trum of disease control may be achieved, particularly with many fungicides and her-
 1 Introduction to the formulation of agrochemicals | 7

bicides. With many suspoemulsions, an adjuvant that enhances the biological efficacy
is added. The formulation of suspoemulsions is not an easy task; one may produce a
stable suspension and emulsion separately but when these mix they become unstable
due to the following interactions:
(i) Homoflocculation of the suspension particles. This can happen if the dispersing
agent used for preparation of the suspension is not strongly adsorbed and hence
it becomes displaced by the emulsifier, which is more strongly adsorbed but not
a good stabilizer for the suspension particles.
(ii) Emulsion coalescence. This can happen if the emulsifier is not strongly adsorbed
at the O/W or W/O interface, resulting in its partial or complete displacement
by the suspension dispersant, which is not a good emulsion stabilizer, and this
results in coalescence of the emulsion droplets with ultimate separation of oil
(for O/W) or water (for W/O).
(iii) Heteroflocculation between the oil droplets and suspension particles. The latter
may be partially wetted by the oil and reside at the O/W interface (this is partic-
ularly the case if the oil droplets are much larger than the suspension particles).
Heteroflocculation can also occur with suspension particles dispersed in a W/O
emulsion.
(iv) Phase transfer and crystallization. This happens when the suspension particles
have some solubility in the oil phase. The small suspension particles which have
higher solubility than the larger ones (due to curvature effects) may become dis-
solved in the oil phase and they become recrystallized onto the larger suspension
particles (a form of an Ostwald ripening process). Large and sometimes needle
shaped crystals may be produced as a result of crystal habit modification (that
sometimes occurs with Ostwald ripening).

An important application in agrochemicals is that of controlled release formulations,

as described in Chapter 8. Several methods are used for controlled release, of which
microcapsules (CS) are probably the most widely used [2]. These are small particles
with size range 1–1,000 µm consisting of a core material and an outer wall. The latter
isolates the core material from the environment and protects it from degradation and
interaction with other materials. The core active ingredient is designed to be released
in a controlled manner as required. Microencapsulation of agrochemicals is usually
carried out by interfacial condensation, in situ polymerization or coacervation. Inter-
facial condensation, whereby two monomers, one oil-soluble (placed say in an emul-
sion droplet) and one water-soluble, placed in the continuous medium undergo inter-
facial polycondensation producing a capsule wall of polyurea or polyurethane. The
polymer wall must have appropriate molecular weight, glass transition temperature,
and thickness to achieve the desirable controlled release. The polymer wall should not
interact with the agrochemical. This polymer wall must not cause any environmental
damage on degradation after application and hence a biodegradable polymer is pre-
ferred. The polymer wall must be easily manufactured and should also be stable on
8 | 1 Introduction to the formulation of agrochemicals

storage and usage. The main advantages of micrcapsule formulatios are: controlled or
slow release of the core active ingredients thus improving residual activity; reduction
of application dosage; stabilization of the core active ingredient against environmen-
tal degradation; reduction of mammalian and fish toxicity; reduction of phytotxicity;
reduction of environmental pollution.
It can be seen from the above short discussion that agrochemical formulations
are complex multi-phase systems and their preparation, stabilization and subsequent
application require the application of the basic principles of colloid and interface sci-
ence, as is described in several textbooks [6–8].
2 Formulation of emulsifiable concentrates
Many agrochemicals are formulated as emulsifiable concentrates (ECs), which, when
added to water, produce oil-in-water (O/W) emulsions either spontaneously or by gen-
tle agitation [1]. Such formulations are produced by the addition of surfactants to the
agrochemical if the latter is an oil with reasonably low viscosity or to an oil solution
of the agrochemical if the latter is a solid or an oil with high viscosity. As discussed
below, spontaneous emulsification requires a number of criteria that must be met to
control the properties of the interfacial region, in particular producing a low interfa-
cial tension. The latter is generally produced by using a mixed emulsifier system, e.g. a
mixture of calcium dodecyl benzene sulphonate and an ethoxylated nonionic surfac-
tant, as will be described below. With such an emulsifier mixture, 5 % concentration
may be sufficient to produce spontaneous emulsification. In some agrochemicals, spe-
cific emulsifier systems have to be used to ensure the spontaneity of emulsification.
One of the main problems with ECs is the batch-to-batch variation of the agrochemi-
cal and emulsifier systems which may result in lack of spontaneity of emulsification.
Thus, to successfully formulate an EC, one must have rigorous quality assurance and
use several tests such as effect of water hardness, temperature, agitation in the spray
tank, etc. Quantitative evaluation of the formulation is required using interfacial ten-
sion measurements, droplet size analysis of the resulting O/W emulsion, subjecting
the EC to stress tests, e.g. temperature variation, etc.
In most cases, ECs are formulated by a simple trial and error approach, by screen-
ing a number of emulsifier systems for a specific agrochemical formulation. Unfortu-
nately, the hydrophilic–lipophilic balance (HLB) method that is commonly used for
selection of emulsifiers (Chapter 3) is inadequate for selecting emulsifiers for ECs [9].
Other indices such as the cohesive energy ratio concept (CER), described by Beerbower
and Hill [10], may provide a better option. Essentially, the method involves selecting
suitable emulsifiers by balancing the interactions of their hydrophobic parts with the
oil phase and the hydrophilic parts with the aqueous phase. This requires knowledge
of the solubility, polar and hydrogen bonding parameters of the various components.
Unfortunately, these interaction parameters are only available for a small number of
emulsifiers and hence their application to the wide variety of emulsifiers used in ECs is
limited. This discussion clearly shows that selecting emulsifiers for ECs still requires a
large number of experimental screening to produce a product that satisfies the spon-
taneity of emulsification and stability under practical conditions. In addition, with
many ECs, other components such as crystal growth inhibitors (for solution of solids
in oil), defoamers and other stabilizers are added and this requires investigation of
their presence on the final formulation properties.
The most common procedure for testing ECs is based on the recommendation of
the World Health Organization (WHO), which states that “any creaming of the emul-
sion at the top, or separation of the emulsion at the bottom, in a 100 ml cylinder shall

https://doi.org/10.1515/9783110588002-003
10 | 2 Formulation of emulsifiable concentrates

not exceed 2 ml when the emulsion is tested as follows”. Into a 250 ml beaker having an
internal diameter of 6–6.5 cm and 100 ml calibration mark and containing 75–80 ml of
standard hard water (containing 342 ppm, calculated as calcium carbonate, prepared
using 0.304 of anhydrous CaCl2 and 0.39 g MgCl2 ·6H2 O to make 1 l using distilled wa-
ter), 5 ml of EC is added, using a Mohr-type pipette, during stirring with a glass rod
(4–6 mm in diameter), at about 4 revolutions per second (rps). The EC should be added
at a rate of 25–30 ml/min, with the point of the pipette 2 cm inside the beaker; the flow
of the concentrate should be directed toward the centre, and not against the side,
of the beaker. The final emulsion is made to 100 ml with standard hard water, stir-
ring continuously, and then immediately poured into a clean, dry 100 ml graduated
cylinder. The emulsion is kept at 29–30 °C for 1 h and examined for any creaming or
separation. Both temperature and water hardness have a major effect on the perfor-
mance of the EC. This is illustrated in Fig. 2.1 and Fig. 2.2, which show the effect of
water hardness on the amount of cream that separates from a typical formulation.

14
1000 ppm 600 ppm
12
0 ppm
Cream by volume (%)

pm
10 150 p
pm
8 300 p

0 Fig. 2.1: Effect of water hardness

0 1 2 3 4 5 on the amount of cream separated
Hours as a function of time for a typical EC.

9
8
7
6
Cream (ml)

5
4
3
2
1
0
0 200 400 600 800
Fig. 2.2: Amount of cream separated
Water hardness (ppm) as a function of water hardness.
 2 Formulation of emulsifiable concentrates | 11

Fig. 2.1 shows that the rate at which the amount of cream reaches equilibrium is fairly
independent from the water hardness. This means that measuring the separated
cream at an arbitrary time of 1 h is adequate for relative comparison of the various
formulations. The best performance for this particular EC appears to be observed at
a water hardness of 300 ppm, but this may not be generalizable for all other ECs.
Fig. 2.2 shows that the stability of the produced emulsion improves as water hard-
ness increases, reaching a maximum at ≈ 500 ppm, above which the stability of the
emulsion decreases with further increase in water hardness.
Fig. 2.3 shows the effect of temperature on the stability of the emulsion produced
from an EC.

High 77 °F
Relative emulsion stability

85 °F

100 °F

Low

1000 500 0 500 1000 1500

(Na as ppm CaCo3) (ppm CaCo3) Fig. 2.3: Effect of temperature on the stability
Water hardness of an emulsion produced from an EC.

It can be seen from Fig. 2.3 that temperature variations encountered in practice have
a significant effect on emulsion stability. Generally speaking, increasing temperature
shifts the optimum performance to softer water and lowering it has the opposite effect.
This reflects the effect of temperature on the solution properties of the emulsifiers, in
particular those of the nonionic ethoxylate type. The latter becomes less water soluble
as the temperature or electrolyte concentration increases, as a result of the dehydra-
tion of the ethoxylate chain (breaking of hydrogen bonds between ethylene oxide and
water). This amounts to a decrease of the HLB number of the emulsifier with increase
of temperature and electrolyte concentration resulting in reduction of the emulsion
stability.
Several mechanisms have been proposed to explain the spontaneity of emulsifi-
cation of ECs. The first mechanism is due to interfacial turbulence that may occur as
a result of mass transfer, schematically represented [1, 2] in Fig. 2.4
12 | 2 Formulation of emulsifiable concentrates

(a) (b)

Fig. 2.4: Schematic representation of sponta-

neous emulsification: (a) interfacial turbulence;
(b) diffusion and stranding; (c) ultralow interfa-
(c) cial tension.

In many cases, the interface exhibits unsteady movement; streams of one phase are
ejected and penetrate into the second phase as is illustrated in Fig. 2.4 (a), which
shows localized reduction in interfacial tension caused by the non-uniform adsorp-
tion of the surfactant molecules at the O/W interface [11] or by the mass transfer of
the surfactant molecules at the O/W interface [12, 13]. With two phases that are not in
chemical equilibrium, convection currents may be formed, conveying liquid rich in
surfactants towards areas of liquid deficient of surfactant [14, 15]. These convection
currents may give rise to local fluctuations in interfacial tension, causing oscillations
of the interface. Such disturbances may amplify themselves leading to violent inter-
facial perturbations or eventual disintegration of the interface; when liquid droplets
are “thrown” into the other [16].
The second mechanism that may account for spontaneous emulsification is based
on diffusion and stranding as illustrated in Fig. 2.4 (b). This is best illustrated by care-
fully placing an ethanol-toluene mixture (containing say 10 % alcohol) onto water.
The aqueous layer eventually become turbid as a result of the presence of toluene
droplets [17]. In this case, interfacial turbulence does not occur, although spontaneous
emulsification apparently takes place. It has been suggested [18, 19] that the alco-
hol molecules diffuse into the aqueous phase, carrying some toluene in a saturated
three-component subphase. At some distance from the interface, the alcohol becomes
sufficiently diluted in water to cause the toluene to precipitate in the aqueous phase.
This phase transition might be expected to occur when the third component increases
the mutual solubility of the two previously immiscible phases.
 2 Formulation of emulsifiable concentrates | 13

The third mechanism of spontaneous emulsification may be due to the produc-

tion of an ultralow (or transiently negative) interfacial tension [20], as illustrated in
Fig. 2.4 (c). This mechanism is thought to be the cause of formation of microemulsions.
3 Formulation of emulsion concentrates
Many agrochemicals have been formulated as oil-in-water (O/W) emulsion concen-
trates (EWs). These systems offer many advantages over the more traditionally used
emulsifiable concentrates (ECs). By using an O/W system, one can reduce the amount
of oil in the formulation since in most cases a small proportion of oil is added to the
agrochemical oil (if this has a high viscosity) before emulsification. In some cases, if
the agrochemical oil has a low to medium viscosity one can emulsify the active ingre-
dient directly into water. With many agrochemicals with low melting points, which
are not suitable for the preparation of a suspension concentrate, one can dissolve the
active ingredient in a suitable oil and the oil solution is then emulsified into water. EWs
which are aqueous-based produce less hazard to the operator, reducing skin irritation.
In addition, in most cases EWs are less phytotoxic to plants when compared to ECs. The
O/W emulsion is convenient for the incorporation of water-soluble adjuvants (mostly
surfactants). EWs can also be less expensive compared to ECs since a lower surfactant
concentration is used to produce the emulsion and also one replaces a great propor-
tion of oil by water. The only drawback of EWs compared to ECs is the need to use
high speed stirrers and/or homogenizers to obtain the required droplet size distribu-
tion. In addition, EWs require control and maintenance of its physical stability. As will
be discussed later, EWs are only kinetically stable and one has to control the break-
down process that occur on storage such as creaming or sedimentation, flocculation,
Ostwald ripening, coalescence, and phase inversion.
In this section, we will start with the principles of formation of emulsions and the
role of the surfactants [3]. This is followed by a section on the procedures that can
be applied to select the emulsifiers. The third section will deal with the breakdown
processes that may occur on storage and methods of their prevention. The last section
will deal with the assessment and prediction of the long-term physical stability of EWs.

3.1 Formation of emulsions

Consider a system in which an oil is represented by a large drop 2 of area A1 immersed

in a liquid 2, which is now subdivided into a large number of smaller droplets (1) with
total area A2 (A2 ≫ A1 ) as shown in Fig. 3.1 The interfacial tension γ12 is the same
for the larger and smaller droplets since the latter are generally in the region of 0.1 to
few µm.
The change in free energy from state I to state II is made from two contributions
[3]: A surface energy term (that is positive) that is equal to ∆Aγ12 (where ∆A = A2 − A1 ).
An entropy of dispersions term which is also positive (since producing a large number
of droplets is accompanied by an increase in configurational entropy) which is equal
to T∆Sconf .

https://doi.org/10.1515/9783110588002-004
16 | 3 Formulation of emulsion concentrates

2
Formation
1 1
2
Breakdown Fig. 3.1: Schematic representation of emulsion
I (flocc. + coal.) II formation and breakdown.

From the second law of thermodynamics,

∆Gform = ∆Aγ12 − T∆Sconf . (3.1)

In most cases, ∆Aγ12 ≫ T∆Sconf , which means that ∆Gform is positive, i.e. the forma-
tion of emulsions is non-spontaneous and the system is thermodynamically unstable.
In the absence of any stabilization mechanism, the emulsion will break by floccula-
tion, coalescence, Ostwald ripening, or a combination of all these processes. In the
presence of a stabilizer (surfactant and/or polymer), an energy barrier is created be-
tween the droplets and therefore the reversal from state II to state I becomes non-
continuous as a result of the presence of these energy barriers. This is illustrated in
Fig. 3.2. In the presence of the above energy barriers, the system becomes kinetically
stable [3]. As discussed in Chapters 7 and 8 of Vol. 1, the energy barrier can be created
by electrostatic and/or steric repulsion which overcomes the everlasting van der Waals
attraction.

Gflocca
GII

Gcoala Gflocc
Gbreak
GV
Gcoal

GI

II V I

Fig. 3.2: Schematic representation of free energy path for breakdown (flocculation and coalescence)
for systems containing an energy barrier.

3.2 Mechanisms and methods of emulsification

To prepare an emulsions oil, water, surfactant and energy are needed [3]. This can be
considered by looking at the energy required to expand the interface, ∆Aγ (where ∆A is
the increase in interfacial area when the bulk oil with area A1 produces a large number
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