applied

sciences
Article
Engineering Properties of New-Age (Nano) Modified Emulsion
(NME) Stabilised Naturally Available Granular Road Pavement
Materials Explained Using Basic Chemistry
Gerrit J. Jordaan 1,2, * and Wynand J. vdM. Steyn 3

1 Department of Civil Engineering, University of Pretoria, Pretoria 0002, South Africa

2 Jordaan Professional Services (Pty) Ltd., Pretoria 0062, South Africa
3 School of Engineering, Department of Civil Engineering, University of Pretoria, Pretoria 0002, South Africa;
[email protected]
* Correspondence: [email protected]; Tel.: +27-(0)-82-416-4945

Featured Application: The engineering properties obtainable during the construction of road
pavement layers using reactive stabilising agents are traditionally determined using a trail-and-
error approach based on material indicator tests, some developed more than a century ago. These
tests inhibit the limitations associated with an empirically derived test or method, often lead-
ing to costly failures. The introduction of proven and applicable nanotechnologies to treat or
stabilise granular material for use in pavement layers could result in the rejection of these tech-
nologies if not based on the understanding of the basic chemistry of both the stabilising agent



and the mineralogy of the granular materials. This article gives a basic explanation of elemen-


tary chemistry that will affect the physical engineering properties (stresses and strains) that can
Citation: Jordaan, G.J.; Steyn, W.J.v. be expected using available, proven and cost-effective nanotechnologies to improve granular ma-
Engineering Properties of New-Age terials for use in a pavement structure.
(Nano) Modified Emulsion (NME)
Stabilised Naturally Available
Abstract: Nanoscale organofunctional silanes have been developed, tested and successfully applied to
Granular Road Pavement Materials
protect stone buildings in Europe against climatic effects since the 1860s. The same nanotechnologies
Explained Using Basic Chemistry.
can also be used in pavement engineering to create strong chemical bonds between a stabilising agent
Appl. Sci. 2021, 11, 9699. https://
doi.org/10.3390/app11209699
and granular material. The attachment of the organofunctional silane to a material also changes
the surface of the material to become hydrophobic, thereby considerably reducing future chemical
Academic Editors: Luís Picado Santos weathering. These properties allow naturally available materials to be used in any pavement layer
and João Crucho at a low risk. In the built environment, scientists soon determined that the successful use of an
organo-silane depends on the type and condition of the stone to be treated. The same principles apply
Received: 24 July 2021 to the implementation of applicable nanotechnologies in pavement engineering. Understanding
Accepted: 8 October 2021 the basic chemistry, determining the properties of the stabilising agent and the organofunctional
Published: 18 October 2021 modifying agent and the chemical interaction with the primary and secondary minerals of the
material are essential for the successful application of these technologies in pavement engineering.
Publisher’s Note: MDPI stays neutral
This paper explains some basic chemistry, which fundamentally influences engineering outputs that
with regard to jurisdictional claims in
can be achieved using New-age (Nano) Modified Emulsions (NME) stabilising agents with naturally
published maps and institutional affil-
available granular materials in all road pavement layers below the surfacing.
iations.

Keywords: nanotechnology in pavement engineering; influence of emulsifying agents (surfactants);

chemistry of surfactants in emulsions; stabilisations of naturally available granular materials; miner-
alogy compatible nano-modified emulsions; organofunctional silanes; anionic emulsions; cationic
Copyright: © 2021 by the authors.
emulsions; new-age (nano) modified emulsions (NME)
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
1. Introduction
creativecommons.org/licenses/by/ With the new millennium, the world also entered the fourth Industrial Revolution
4.0/). (4RI) [1] that will “broaden and deepen the connections between the biological, physical

Appl. Sci. 2021, 11, 9699. https://doi.org/10.3390/app11209699 https://www.mdpi.com/journal/applsci

Appl. Sci. 2021, 11, 9699 2 of 25

and digital worlds in unprecedented ways” [2]. This phase of development will have an
impact on all spheres of life, affecting all industries, bringing together multiple technologies
in creating a new modern environment. Relatively new industries such as the Information
Technology (IT) industry will experience the 4RI as a natural extension of ongoing develop-
ments. However, many “traditional” industries will experience the 4RI as disruptive [3],
requiring an extensive change in “set in stone practices,” together with a considerable
change in the mindset of practitioners accustomed to traditionally operating procedures.
The pavement engineering fraternity, with specific reference to the classification and use
of naturally available granular materials, may well fit into the latter category. An under-
standing of the basic scientific principles will greatly assist in the general acceptance and
implementation of these technologies in traditional industries.
Road pavement granular materials are traditionally classified using empirically de-
rived indicator tests (some developed more than a hundred years ago). In contrast, pave-
ment engineering design has evolved over the last few decades from empirically derived
methods to a more fundamental scientific approach with the development and introduction
into practice of Mechanistic–Empirical (ME) design methods. These methods use funda-
mental failure theories based on the computer modulation of road pavement structures to
analyse and predict expected pavement behaviour trends based on calculated basic physics,
i.e., stresses and strains within the different pavement layers. Unfortunately, the testing
and characterisation of granular materials for use in pavement structures have not shown
the same advances.
The successful introduction and general acceptance of cost-effective proven and avail-
able nanotechnologies to improve granular materials for use in road pavement structures
will not succeed using empirical tests and methods, relying on a trial-and-error approach.
A scientific understanding of the mineralogy of the granular materials as well as the basic
chemistry and chemical reaction caused by the use of proven/available technologies in
a traditionally conservative industry is required in line with the expected developments
during the 4RI—the use and combination of available information and technologies to
understand the basic science behind technologies and predict, with improved confidence,
results. Such an understanding obviously also applies to traditionally used reactive sta-
bilising agents (e.g., cement, lime, modified bitumen emulsions, etc.), the general use of
which often results in “unexplained” costly failures. These traditionally used stabilising
agents are each not a single product but contain various combinations of different chemical
components, which could react differently with different materials. This article is limited
to the basic understanding of the chemical interaction of organofunctional nano-silane
modified emulsions in combination with granular material for use in pavement layers
below the surfacing.
Nanotechnology products (nano-silanes) have been used in the built environment to
improve, strengthen and protect stone buildings in Europe for almost 200 years [4]. The
same technology could find immediate application in the field of pavement engineering to
improve the cost-effective use of granular materials in road pavement structures. Scientists
responsible for the development of the first nano-silane products in the built environment
in the early 1800s [4–6] soon established that the type of stone (primary minerals) and the
condition of the stone (presence and quantity of secondary minerals) considerably affected
results achievable through any specific nano-silane treatment. These lessons learned from
the built environment must form the basis for the successful introduction of these available,
proven nanotechnologies in pavement engineering.
It follows that engineers need to have at least a basic understanding of the chemistry
involved in the use of these materials. The informed selection of applicable material com-
patible nanotechnologies that are stable for practical application under often challenging
practical field conditions will prove to be the difference between success and failure. It is
not the intention to make pavement engineers chemists, but only to provide them with
the necessary tools (basic knowledge) to make informed decisions in practice. The key is
Appl. Sci. 2021, 11, 9699 3 of 25

not to confuse with fundamental, detailed chemistry but to provide practical clarifications,
explaining results and showing the consequences of insufficient specifications.
Knowledge about these basic chemical concepts controlling material behaviour in the
field will assist greatly in the informed application of materials and the use of material-
compatible technologies by engineers specialising in road pavement engineering. The
successful introduction of new-age nanotechnologies is disruptive to traditional pavement
engineering practices, enabling the use of granular materials generally perceived as unsuit-
able in quality. Hence, the understanding of the basic chemistry controlling nanotechnology
characteristics in an emulsion, in combination with the mineralogy of naturally available
materials, can facilitate the acceptance of the engineering benefits in road construction,
leading to a substantial reduction in transportation infrastructure costs [7–9]. This article
will also demonstrate the importance of more specific specifications with regard to the
chemical properties of the emulsifying agent (surfactant) as a nano-particle used in the man-
ufacturing of a specific stabilising agent (bitumen emulsion), which forms the foundation
for the production of a material compatible New-age (Nano) Modified Emulsion (NME).
The chemical characteristics of both nano-particles, i.e., the surfactant and the nano-silane
modifier, are important factors in determining the engineering properties to be achieved
when applied in practice for the treatment/stabilisation of available granular materials.

2. Background
The use of nano-scale products for the stabilisation of granular materials in the con-
struction of the pavement layers is nothing new. Per definition, products such as cement,
lime as well as bitumen emulsion all incorporate nano-scale particles and can be considered
as nanotechnology products, i.e., containing particles of which at least one dimension is
between 1 and 100 nm in size [10]. The use of nanotechnology as a science only became
of interest after the development of equipment enabling scientists (including chemists,
physicians and engineers) to see and manipulate nano-scale particles at a molecular level
in the 1980s/90s [11,12]. This ability to manipulate nano-scale products has had an impact
on all industries, including the built environment where silicon-based nanotechnology
products are being used to improve building materials across basically all spheres of ac-
tivity. However, nano-silane products have been developed, tested and used in the built
environment to protect stone buildings in Europe since the 18600 s [4]. The more than
150 years of “lessons learnt” from the built environment can assist pavement engineers to
fast-track the implementation of these proven technologies to also protect and improve
naturally available granular materials for use in the design and construction of roads. Ex-
perience in southern Africa [13] has shown that considerable savings are a reality through
the implementation of nano-silane technologies used for the treatment and stabilisation of
granular materials for all layers below the surfacing.
Materials used in road pavements are traditionally classified using empirically derived
criteria based on material indicator tests dating back more than a century [14]. These mate-
rial classification systems often classify naturally available granular materials in climatic
regions of the world associated with a high potential for chemical decomposition (high
temperatures in combination with seasonal rainfall [15]) as “non-standard,” “marginal” or
even “sub-standard” [16]). Available and applicable nanotechnologies that could enable
the use of these materials at a low-risk in pavement structures could substantially reduce
the unit costs of road infrastructure, specifically in these regions.
Bitumen emulsion technology dates back to the early 1900s [17] when a nano-scale
particle was discovered that enables an oil substance (e.g., bitumen) to be mixed with an
aqueous substance (i.e., a water-based substance). This nano-scale particle is commonly
referred to as an emulsifying agent (known in chemistry as a surfactant and in engineering
practice commonly referred to as a “soap”). Bitumen emulsion technology enables a rela-
tively low bitumen content to be mixed with granular materials at ambient temperatures to
construct road pavement layers. Emulsion technology incorporates several advantages, in-
cluding the ability to accommodate considerably higher tensile strains in comparison to the
Appl. Sci. 2021, 11, 9699 4 of 25

unstabilised granular material as well as cement-bound materials [14,18]. However, simi-

larly to the manufacturing of asphalt, it is still a requirement to use aggregate/stone/gravel
granular materials of a relatively high quality together with the bitumen emulsion for the
construction of a pavement layer meeting the required engineering specifications [19].
Similar to the manufacturing of asphalt for surfacings, the unmodified bitumen forms
no chemical bonds with the granular aggregate/stone materials in the mix. Strength is
only achieved through covalent bonds (relatively weak) and mechanical forces created
through granular interlock and absorption of the bitumen into a porous surface of the
aggregate [15]. For this reason, some aggregates containing a high silicon content, which
usually result in relatively “clean breaks” during crushing, are notoriously difficult to
use for the manufacturing of asphalt or bitumen emulsion stabilised layers meeting the
engineering specifications. In asphalt and bitumen emulsion mixes, the use of materials
conforming to specific grading envelopes are of major importance to create a firm granular
matrix, which results in high interlocking mechanical forces being formed.
The ability to create strong chemical bonds between the stabilising agent (e.g., bitumen
or equivalent polymer) and the granular material to be stabilised (aggregate/stone/soil) can
be achieved through the introduction and use of proven material compatible organofunc-
tional nano-silanes. These nano-silane products attach to the granular materials, creating
relatively strong ionic-chemical bonds. The organofunctional part of the nano-silane parti-
cle is hydrophilic, rendering the surface of each granular particle of the material to become
hydrophobic during consolidation, preventing water access to primary and secondarily
minerals comprising each of the granular particles within the mix. The high chemical bond
strengths and the enacted hydrophobicity enable materials classified as “non-standard,”
“marginal” or “sub-standard” to be utilised successfully within any pavement layer be-
low the surfacing, at low risk. The introduction of material-compatible organofunctional
nano-silanes in the field of pavement engineering is a typical example of a disruptive
technology [3], requiring traditional approaches to the use of materials in pavement engi-
neering to become irrelevant. This combination of existing technologies in combination
with an improved scientific understanding and knowledge forms the cornerstone of the
4RI in traditional industries, especially with regard to the cost-effective provision of macro
infrastructure projects using “smart” materials in a cost-effective manner. The general
acceptance of such disruptive technologies will require the necessary improved knowledge
of the basic supportive science to become everyday practice. The key is not to overwhelm
the practicing pavement engineer with complex fundamental chemistry but to simplify
facts to be easily understandable in support of practical implementation.
Many products have been introduced throughout the last few decades claiming to
be able to provide the ability to improve granular material characteristics to enable the
use thereof in road pavement structures. These so-called “snake-oils” have generally
failed to meet expectations. In the absence of a scientifically-based approach to granular
material investigations and tests indicative of engineering principles (e.g., stresses, strains
and durability), the same can happen with the introduction of applicable/proven nano-
silane technologies for the improvement/stabilisation of granular materials in pavement
engineering [20].
The work performed by scientists in the built environment dating back almost
200 years established the basic requirements for the successful application of any spe-
cific organofunctional silane technology to improve granular/stone material characteristics.
These requirements are fundamentally based on the compatibility with the type of stone
(primary minerals) and condition of the stone (presence and amount of secondary min-
erals in the granular/stone that developed as a result of weathering due to chemical
decomposition) [21,22]. It follows that material classification should, at least, include the
scientific testing of the primary and secondary minerals present in the available granular
materials [20]. Knowledge about the mineralogy of the materials and the environmental
conditions favouring weathering through chemical decomposition [22] and the formation
of secondary minerals in granular materials will enable engineers to select with confidence
Appl. Sci. 2021, 11, 9699 5 of 25

a material compatible technology to enhance/stabilise marginal granular materials for use

in all of the pavement layers below the surfacing.
The same principles apply to the characteristics of the nano-particles (surfactant)
used to produce the emulsion stabilising agent (e.g., bitumen emulsion) and the effect
thereof on the engineering properties when used in combination with an organofunctional
silane modifying agent. In effect, the introduction of a material compatible nano-silane
creates a modified emulsifying agent combining two different nano-particles. Each of these
nano-particles could have a considerable influence on the engineering properties when
used in the production of a modified emulsion stabilising agent and applied to specific
granular material as a stabilising agent.

3. Traditional Use of Nanotechnology Products in Road Pavement Engineering

The use of nano-scale material in the road industry (over and above the use of lime
and cement) as stabilisation agents dates back more than a century, with the development
of bitumen emulsions in the early 1900s [8]. As per definition [17,23–25], bitumen emulsion
consists of bitumen, water and an emulsifying agent. The emulsifying agent is, in fact,
a nano-scale particle commonly referred to as a “Janus” particle [26] (from the Greek
mythology meaning “two-faced”) due to the dual nature of the emulsifying agent nano-
particle, attracting oil on the one side and water on the other side.
It is not the intention to discuss in detail the technology involved in the production
of bitumen emulsions [17,23,24,26,27]. It is generally known that numerous production
factors, bitumen rheology, etc., could influence the characteristics of bitumen emulsion,
which are discussed in detail in numerous publications. The objective of this paper is to
concentrate on the effects of the chemistry involved in the additives and modifications
used in the manufacturing of bitumen emulsion as a stabilising agent. Understanding
the role of the emulsifying agent nano-particle is comparable to that of organofunctional
nano-silane products used in the built environment. Hence, the discussion in this paper is
limited to the role of the emulsifying agent that enables water to be mixed with oil (organic
substance, in this case, bitumen) substances, which, under normal conditions, do not mix.
Not only does the emulsifying agent enable the oil (e.g., bitumen) to be mixed with water,
but crucially, when modified with the addition of a material compatible nano-silane, the
characteristics could also dramatically influence the engineering properties achievable
when the nano-modified emulsion is used with a specific granular material. It follows that
a basic understanding of the role of the nano-emulsifying agent also needs to be addressed.
The mixing of oil (e.g., bitumen) and water is achieved through the addition of a
chemical nano-particle (the emulsifying agent, soap or surfactant) at high shear (e.g., high
mix revolutions), which forces the oil and water together with the emulsifying agent
through small openings or between plates, which enables the bitumen (oil) particles to be
separated and mixed and attached to the emulsifying agent already mixed and attached
to the water molecules. The emulsifying agent typically has a hydrophilic (water-loving)
head and a lipophilic (oil-loving) (hydrophobic) tail consisting of between 12 and 18 (or
even more) carbon atoms [17]. The chemical composition of typical emulsifying agents is
shown in Figure 1 (anionic) and Figure 2 (cationic). The hydrocarbon tail of the emulsifying
agents is often replaced in chemical formulas by the letter “R”.
The higher the number of carbon atoms in the hydrocarbon tail, the more firmly the
emulsifying agent will attach to the organic stabilising agent (e.g., bitumen molecule). The
hydrocarbon tail embeds itself into the bitumen molecule. In comparison, if the earth
resembles the size of a bitumen particle, the hydrocarbon tail of a good emulsifying agent
(high number of carbon atoms) will typically penetrate the crust of the earth to a depth of
approximately 8 km (equivalent to approximately 5 nm in a bitumen molecule) and covers
an area of approximately 10 km2 [25].
Appl. Sci. 2021, 11, 9699 6 of 25
Appl. Sci. 2021, 11, x FOR PEER REVIEW 6 of 28
Appl. Sci. 2021, 11, x FOR PEER REVIEW 6 of 28

Figure 1. Typical
Figure 1. Typical composition of ancomposition of an anionic
anionic emulsifying emulsifying agent.
agent.
Figure 1. Typical composition of an anionic emulsifying agent.

.
.

Figure 2. Typical Figure 2. Typical

composition of acomposition of a cationicagent.
cationic emulsifying emulsifying agent.
Figure 2. Typical composition of a cationic emulsifying agent.

The visual representation of the anionic emulsifying agent shown in Figure 2 is

expressed in chemical formulation as follows [24,25]:
 an area
(high of approximately
number of carbon 10 kmwill
atoms) [25].
typically penetrate thetail
crust
sembles
semblesthe size
the of aof
size bitumen
a bitumenparticle, the hydrocarbon
particle, the hydrocarbon of aofof
tail the
good earth to a depth
emulsifying
a good emulsifying ofagent
agent
(highThe
approximatelyvisual
number
(high number8 representation
km (equivalent
of carbon atoms)
of carbon of
to the
willwill
atoms) anionic
approximately
typically emulsifying
5 nm
penetrate
typically in a agent
bitumen
the crust
penetrate shown
the crust in
molecule)
of the
of earth Figure
and 2 is
covers
to a to
the earth depth ex-
a depth of of
pressed
an area ofinapproximately
approximatelychemical
approximately 8 km8formulation
km (equivalent as approximately
10 km2 [25].
(equivalent to follows [24,25]:5 nm5 in
to approximately nma in
bitumen
a bitumenmolecule) andand
molecule) covers covers
an area
The of
an area approximately
of approximately
visual representation 10 km
10 [25].
of2km
the 2 [25].
anionic emulsifying agent shown in Figure 2 is ex-
CH3(CH2)nCOO− + Na+ (where n is normally a multiplier between 12 and 18 [17]:
Appl. Sci. 2021, 11, 9699 pressedTheinThe
chemical
visualvisual formulation
representation
representation as the
of follows
of anionic[24,25]:
emulsifying
the anionic emulsifyingagent shown
agent shownin Figure 2 7isof2ex-
in Figure 25
is ex-
pressed in chemical
pressed in chemical formulation
formulationas follows [24,25]:
as follows [24,25]:
CH3(CH2)nCOO− + Na+ (where n is normally a multiplier between 12 0and 18 [17]:
⫽
CH3CH(CH3(CH
2)nCOO2)nCOO− + Na (where
− ++ Na n is nnormally
+ (where is normallya multiplier between
a multiplier between 12 and 18 [17]:
12 and 18 [17]:
(CH2 )n COO− + Na+ (where n is normally a multiplier
CH3CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂ C between 12 and 18 [17]:
\ 0
⫽ 0 0 (1)
O¯Na⁺
CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂ C ⫽ ⫽
CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂
CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂ C\ C (1)
non-polar hydrocarbon group Ionic group \O¯Na⁺
\ (1) (1)
(water-insoluble) (water-soluble)O¯Na⁺ O¯Na⁺
Equationnon-polar
(1) is simplified to:
hydrocarbon group Ionic group
non-polar(water-insoluble)
non-polar hydrocarbon
hydrocarbon group (water-soluble)
group Ionic group
Ionic group
Equation (1) is simplified to:
(water-insoluble)
(water-insoluble) 0 (water-soluble)
(water-soluble)
⫽ (1)
Equation (1) is(1)simplified
Equation to: to:
is simplified
CH₃(CH )ₙ C (2)
Equation (1) is simplified to: \ 0
⫽ 0 0
O¯Na⁺
CH₃(CH )ₙ C ⫽ ⫽ (2)
CH₃(CH )ₙ C\)ₙ C
CH₃(CH (2) (2)
with the value of “n” typically varying between 12 and 18 [17].
\O¯Na⁺
\
Formula (2) is further simplified to:
O¯Na⁺
O¯Na⁺ (2)
with the value of “n” typically varying between 12 and 18 [17].
withFormula
with the(2)
the with
value ofis“n”
value
the further
value of simplified
oftypically
“n” typically
“n” to: between
varying
typically
varying between
varying O and1218
between
12 and 18 [17].
12[17].
and 18 [17].
⫽
Formula (2) is(2)further
Formula is further simplified
simplified to: to:
"R" − C
O (3)
\
⫽ O O
O¯Na⁺
"R" − C ⫽ ⫽ (3)
"R" "R"− \− C C (3) (3)
O¯Na⁺
\ \
Similarly, a typical cationic emulsifying agent shown in Figure 3, is depicted as: (3)
O¯Na⁺
O¯Na⁺
Similarly, a typical cationic emulsifying agent shown in Figure 3, is depicted as:
Similarly, a typical cationic emulsifying agent shown in Figure 3, is depicted as:
H
Similarly, a typical
Similarly, cationic
a typical emulsifying
cationic emulsifying agent shown
agent in Figure
shown 3, is3,depicted
in Figure as: as:
is depicted
|
"R" − N − Cl (4)
H| \
|
HH HH
"R" − N | −| Cl (4)
(4)
"R" − | \
"R"N− N− Cl− Cl (4) (4)
The properties and stability of the emulsion H | \H |is\a function of numerous factors, includ-
ing the chemical properties of the emulsifying H H Hagent
H (e.g., the length of the carbon-tail
shown as “n”), the percentage of the emulsifying agent added during the emulsifying
process, the manufacturing process and the properties of the bitumen. In terms of chemical
stability, it is worth noting that the bond strengths between the various atoms in the emul-
sifying agent differ substantially. These bond strengths could also play a major role in the
stability of the emulsion, especially in combination with a second nano-particle and/or
when a modification to the emulsification agent is introduced. The bond strengths between
some of the major atoms comprising the emulsifying agent are summarised in Figure 3
(compiled from published information [28]).
From Figure 3, it is seen that the bond strengths between the elements comprising an
anionic emulsifying agent (pink arrow combinations) are considerably stronger than the
bond strengths comprising the typical cationic emulsifying agent (green arrow combina-
tions). This simplified chemistry explains the general trends found in the stability normally
associated with anionic versus cationic bitumen emulsions in practice, assuming all manu-
facturing processes are optimised in line with good practices. The implication in practice
is that an anionic nano-modified emulsion will normally have a longer shelf life (due to
higher stability) than a nano-modified cationic emulsion, an important practical factor,
especially considering remote areas of implementation, uncertain climatic conditions and a
construction industry often faced with unplanned delays due to political and managerial
Appl. Sci. 2021, 11, 9699 8 of 25

factors, not within the control of the contractor. The importance of the characteristics of the
emulsifying agent nano-particle combined with a material compatible organofunctional
nano-silane in the performance of the nano-modified emulsions as a stabilising agent for
the treatment/stabilisation of granular materials is demonstrated in Section 7 of this article.
The results show the variation in the engineering measured properties possible in practice
with all input parameters carefully controlled. In this experiment, the only variable is the
Appl. Sci. 2021, 11, x FOR PEER REVIEW
characteristics of the various emulsifying agents used by the various manufactures in8 the of 28
production of the nano-modified emulsions.

Figure3.3.Comparison
Figure Comparisonofofthe
thebond
bondstrengths
strengthsbetween
betweenthethevarious
variouselements
elementscomprising
comprisingthe
thedifferent
different
emulsifying agents (anionic in pink and cationic in green) (compiled from published information
emulsifying agents (anionic in pink and cationic in green) (compiled from published information [28]).
[28]).
4. Basic Chemistry Applicable to the Understanding of the Successful Introduction of
TheCompatible
Material properties and stability of the emulsion
Nanotechnology Solutionsisfor
a function of numerous
the Treatment, factors, includ-
Improvement
and/or
ing the chemical properties of the emulsifying agent (e.g., the length of the below
Stabilisation of Granular Materials for Use in Road Pavement Layers carbon-tail
the Surfacing
shown as “n”), the percentage of the emulsifying agent added during the emulsifying
4.1. Silicon Characteristics in the Material Sub-Strata and Applications within the
process, the manufacturing process and the properties of the bitumen. In terms of chemi-
Built Environment
cal stability, it is worth noting that the bond strengths between the various atoms in the
Silicon (Si)
emulsifying is the
agent second
differ most abundant
substantially. element
These (after oxygen),
bond strengths couldcomprising
also play amore
majorthan
role
26 per cent of the crust of the earth (by weight). In comparison, oxygen makes up more
in the stability of the emulsion, especially in combination with a second nano-particle
than 49 per cent by weight of the crust of the earth. The rest of the elements contained in the
and/or when a modification to the emulsification agent is introduced. The bond strengths
crust of the earth in combination makes approximately 25 per cent by weight of the crust
between some of the major atoms comprising the emulsifying agent are summarised in
of the earth. Silicon is found in nature as oxides (SiO2 ) or silicates (SiO4 ), forming the basis
Figure 3 (compiled from published information [28]).
of most rock-forming minerals [15]. Commonly known naturally available materials such
From Figure 3, it is seen that the bond strengths between the elements comprising an
as granite, feldspar, hornblende, asbestos, clay and mica are a few examples of materials
anionic emulsifying agent (pink arrow combinations) are considerably stronger than the
normally containing high percentages of silicon [22].
bond strengths comprising the typical cationic emulsifying agent (green arrow combina-
Silicon is also one of the most useful elements to mankind. In the form of sand and
tions). This simplified chemistry explains the general trends found in the stability nor-
clay, it is commercially used as a cost-effective product to produce building components
mally associated with anionic versus cationic bitumen emulsions in practice, assuming all
such as pottery, bricks, cement, glass, etc. Silicon also plays an important role in plant
manufacturing processes are optimised in line with good practices. The implication in
as well as animal life, forming part of cell structures and found in plant remains as well
practice
as skeleton is that an anionic
structures. It is nano-modified emulsion
considerably versatile in will normallyinherent
application, have a longer
to mostshelf life
of the
(due to higher stability) than a nano-modified cationic emulsion, an important practical
factor, especially considering remote areas of implementation, uncertain climatic condi-
tions and a construction industry often faced with unplanned delays due to political and
managerial factors, not within the control of the contractor. The importance of the charac-
teristics of the emulsifying agent nano-particle combined with a material compatible or-
ganofunctional nano-silane in the performance of the nano-modified emulsions as a sta-
Appl. Sci. 2021, 11, 9699 9 of 25

nanotechnology-based products currently in common use in the built environment, with

“excellent mechanical, optical, thermal and electrical properties” [28].
The silicon present in nature as silicates can form 4 bonds with oxygen atoms, which
may be orientated in various geometric structures, forming a three-dimensional infinite
structure [29,30] to form minerals and the surface of the sub-strata or rock surface as
commonly referred to. Figure 4 shows a very simplified illustration of the composition
of naturally available materials (rocks), as numerous elements are found in nature that
combines with the basic silicon lattice to form a large variety of minerals commonly found in
all rock
Appl. Sci. 2021, formations.
11, x FOR PEER REVIEWOf importance is the illustrated attraction of exposed siliceous materials
10 of 28
on the surface of granular materials to water molecules freely available in the atmosphere.

Figure 4. Simplified demonstration of the most common sub-strata or rock formations in nature.
Figure 4. Simplified demonstration of the most common sub-strata or rock formations in nature.
Rock surfacings contain “broken chains” of chemical bonds that form a layer of free
Rock surfacings contain
energy “broken
[15] on the surface chains”
of granularofmaterials
chemical bonds that
(rock/gravel form
or soil). Theasurfaces
layer of
ofthese
free
energy [15] on the surface of granular materials (rock/gravel or soil). The surfaces of
Appl. Sci. 2021, 11, 9699 10 of 25

these naturally available materials (with a few exceptions, e.g., talk) are hydrophilic (water-
loving) and attract water molecules freely available in the atmosphere. Hence, freshly
crushed stone is instantaneously covered by numerous layers of water molecules that
(a water molecule is approximately 0.1 nm in size or 1 Angstrom (Å)). These layers of
water molecules covering the area of the stone are invisible to the eye and other senses
(touch/smell). Water molecules (H2 O) are always accompanied by their natural derivatives
of negatively charged oxygen (O−2 ) and positively charged hydrogen (H+1 ) in the atmo-
sphere that surrounds the surface of granular materials (rock/gravel/soil) and is attached
to the surface as shown in Figure 4.
The freely available hydrogen (H+1 ) combines with the negatively broken oxygen
chains of the Si elements to form (OH)−1 bonds on the surface. The siliceous surfacings
containing O−2 and (OH)−1 bonds are hydrophilic in nature and hence, attract water. The
simplified lattice shown in Figure 4 forms the basic understanding of the application of
various silane-nanotechnologies developed using the properties of the silicon element,
which have been used in the built environment for more than 150 years to protect buildings,
monuments and statues [4]. These same basic technologies are also directly applicable to
the field of pavement engineering to enable generally available natural resources (granular
materials) to be used more cost-efficiently within road pavement structures.

4.2. Chemistry of Organofunctional Nano-Silanes for Application in Pavement Engineering

Most of the nanotechnology products currently used in the built environment to
protect, preserve and/or strengthen building materials are based on the silane (SiH4 )
derivative of silicon (the same derivative, which has found application as the basis for the
development of stone consolidants for more than a 150 years [4]). Each hydrogen (H) atom
in the silane (SiH4 ) can be replaced by any other element or group(s) to form a large variety
of nano-products with numerous fields of application.
The most common reactive groups are hydrogen (H), chloride (Cl), fluorine (F) and
a RO group, where R is the general symbol for the alkyl group, also known as the
organo-functional group in silane-chemistry (also referred to as the hydrocarbon group
discussed and explained in the composition of the emulsifying agents demonstrated in
Figures 2 and 3), which may, inter alia, include chemical compounds such as CH3 (methyl)
or CH3 CH2 (ethyl).
The CH3 -Si bond is a very stable (non-reactive) bond (known as organo-silane), with
low surface energy with hydrophobic (water-repellent) or oleophilic (oil-loving) character-
istics. The reactive group RO is referred to as an alkoxy (alkyl + oxygen) group [4]. Silicon
(Si) forms the centre of the RO group together with the second functional group(s) (X) (e.g.,
methoxy, ethoxy, etc.) to form the chemical molecule RO-Si-X. These secondary functional
(pendant) groups may be highly reactive (in cases where the element of carbon (C) is
excluded from the formulation) and define the functionality of a specific nano-silane [4].
The functional group (R) will attach to organic material (such as bitumen or an alternative
material compatible polymer with an oil basis), while the functional group(s) (X) will attach
to inorganic material (granular material such as rock/gravel/soil). Hence, an organo-
functional nano-silane combines the functionality of a reactive group with a non-reactive
group in a single molecule.
It should be noted that the organofunctional nano-silane is not replacing the stabilising
agent in the stabilisation of granular road building materials. The molecule is too small to
effectively bridge the gaps between the material fractions. However, in practice, the nano-
silane can very effectively fulfil the role of a bonding agent (adhesive agent, a well-known
concept in the asphalt industry), which is designed to permanently bind the stabilising
agent (the bitumen or equivalent organic substitute with similar characteristics) to the
granular materials (stone/aggregate/soil). Si–O chemical bonds are some of the strongest
found in nature (refer to Figure 3). The relatively small size of the nano-silane particle
(depending on the type of nano-silane and the quality of the product, the size of nano-
silanes may vary from about 5 nm to less than 1 nm) results in a considerably high surface
Appl. Sci. 2021, 11, 9699 11 of 25

area per volume ratio [7]. In other words, a relatively small amount of the nano-silane is
required to totally encapsulate all particles of the granular material (stone/gravel/soil)
that is being treated/stabilised (for example, 1 litre of nano-silane could easily have the
same coverage area of about a 1000 litres of bitumen, with a bitumen particle being in the
order of 1000 to 5000 nm in size) [7,17]).
As mentioned, the organofunctional nano-silane particle will, in effect, have the prop-
erties of a “coupling agent” commonly referred to in the asphalt industry as an aggregate
adhesive. Aggregate adhesives or aggregate promoters are well-known terminologies
in pavement engineering, and such nanotechnologies have been used for at least three
decades [31] as modifiers to bitumen emulsions. However, the use of silicon-based nan-
otechnology products in pavement engineering is relatively new and has been developed
mainly over the last 15 years.
The functionality of the silane R-Si-X molecule in terms of an aggregate adhesive
mainly refers to the ability of the (X) reactive group to be removed from the molecule when
in contact with water (to effectively be chemically detached by water) and replaced by a
hydroxyl (OH) group, during a process referred to as hydrolysis [4].
where:
Hydrolysis: Si-X + H2 O = Si-OH + XH (5)
The one product of hydrolysis is the Si-OH binding referred to as silanol [4]. Silanols are
now able to react with each other to form siloxane bonds in a condensation reaction when
in contact with an inorganic material (e.g., granular material such as rock/gravel/soil) [4],
covering the total area of each particle in the granular material. It should be noted that the
by-product during condensation should preferably be water (H2 O), as shown in the example
(not all available nano-silane products produce water as a by-product, at worst a non-toxic
alcohol should be allowed to form as a by-product during condensation—refer toxicology
requirements [7]).
where:
Condensation: Si-OH + OH-Si = Si-O-Si + H2 O (6)
Of importance to the field of pavement engineering is that the organic (R) (organofunc-
tional) group attached to the silicon by means of a direct Si-C bond is not affected by
hydrolysis and will remain stable (non-reactive) also during condensation. It follows that
in the case of CH3 -Si-(OCH3 )3 (methyl-trimethoxy-silane), the methyl group (CH3 ) directly
attached to the silicon atom will remain stable throughout the process of hydrolysis and
condensation, while the hydrogens in the methoxy ((OCH3 )3 ) groups will react with water.
These effects of hydrolysis and condensation are demonstrated as follows [4]:
where:
Hydrolysis: CH3 -Si-(OCH3 )3 + 3H2 O = CH3 -Si-(OH)3 + 3CH3 -OH (7)
Condensation:
OH− OH−
| |
CH3 − Si − (OH)3 + (OH)3 − Si − CH3 = CH3 − Si −O− Si −CH3 + H2 O (8)
| |
OH− OH−
In order to be effective as a consolidant, the silane-compounds must be able to form
three-dimensional networks and hence, must have at least three reactive groups. The
pavement engineering implications (macro-effect) of the above nano-silane formulations
are demonstrated in Figure 5, which should be considered together with Figure 4 and the
similarities with the emulsifying agent shown in Figures 1 and 2.
Appl. Sci. 2021, 11, 9699 12 of 25
Appl. Sci. 2021, 11, x FOR PEER REVIEW 13 of 28

A 3-Dimentional matrix
forms during consolidation of
the nano-silane onto the
material substrata to cover
and surround all material
particles fully and create a
hydrophobic (water-repellent)
surfacing with the
organofunctional “R” part of
the consolidated nano-silane
facing outwards

Figure 5. Simplified demonstration of the chemical interaction between a stabilising agent, organofunctional nano-silane
Figureand
modification Simplified
5. the mineralogydemonstration of the
of the rock/stone/soil chemical
granular interaction
material sub-strata.between a stabilising agent,
organofunctional nano-silane modification and the mineralogy of the rock/stone/soil granular
material sub-strata.

The effective result shown in Figure 5 is that the surface of each particle comprising
the granular material (rock/aggregate /soil) will chemically be changed from a hydrophilic
(water-loving) to a hydrophobic (water-repellent) state that attracts an organic material
(such as oil/bitumen or an equivalent material compatible polymer). Consequently, the
Appl. Sci. 2021, 11, 9699 13 of 25

water molecules that are naturally attracted to exposed surfaces of granular materials
(stone/aggregate/soil) due to the presence of broken chemical bonds as discussed and
demonstrated in Figure 4, will now actively be repelled together with the water that is the
by-product formed during the condensation phase (as per the example shown in Figure 5).
Figure 5 represents a most basic schematic explanation of the practical use of nano-
silane science in pavement engineering. The changing and matching of reactive and
non-reactive bonds to the silicon element can result in literary numerous different nano-
products with different characteristics, which could match the numerous minerals available
in naturally available materials such as stone, gravel or soils.
At the same time, through creating the appropriate bonds, the surface of these ma-
terials will become water repellent, negating the negative impact that water has on the
durability of materials through the prevention of (or at least limiting) weathering due to
chemical decomposition (a pre-requisite of the process of weathering of materials through
chemical decomposition (chemical change) and the formation of resultant secondary min-
erals in the presence of and access to water [15]). In pavement engineering design analyses,
it is usually assumed that material mineral properties will stay unchanged during the
design period. This basic assumption is incorrect, and even over a design period of 20 to
40 years, dramatic changes can occur (even in freshly crushed stone—given conducive
environmental conditions [15]), which will influence the design assumptions considerably.
This aspect alone shows the potential benefit of the use of organofunctional nano-
silane products in pavement engineering as a protective agent for high-value, freshly
crushed stone against chemical decomposition and deterioration over its design life (e.g., a
20-year normal design period). Rehabilitation investigations conducted on major freeways
in the Gauteng province of South Africa have shown that high-quality newly constructed
stone G1 (Figure 6) [32] base-course material can deteriorate over a period of 22 years
to an equivalent G4 to G6 quality material. Similarly, secondary roads in the Gauteng
region of South Africa have shown that a cement-treated base-course layer can deteriorate
from a cement-treated layer (Unconfined Compressive Strength (UCS) between 750 to
1500 kPa) quality layer to an equivalent G7/8 quality material [32], over a period of
20 years (rehabilitation investigations undertaken in the Gauteng Province of South Africa
Appl. Sci. 2021, 11, x FOR PEER REVIEW 15 of 28
by the main author).

Figure 6. Classification of granular materials (comparative summarisation of some characteristics of

Figure 6. Classification
the material of (refer
classification [32]) granular materials [33,34]).
CBR compaction (comparative summarisation of some characteristics of
the material classification [32]) (refer CBR compaction [33,34]).
4.3. Modification of Nano-Silanes through Hydroxy Conversion Treatments (HCT) Based on the
Mineralogy of the Granular Material Sub-Strata
Although approximately 60 percent of the crust of the earth contains Si-O bonds, not
all naturally available granular materials are silicon-rich. Non-silicate materials include
carbonate materials such as calcretes and dolerites that are predominant in certain areas
of the world and laterites (abundant in warm/humid conditions conducive to chemical
weathering and the leaching-out of silicate materials). In such cases (e.g., with calcretes,
Appl. Sci. 2021, 11, 9699 14 of 25

4.3. Modification of Nano-Silanes through Hydroxy Conversion Treatments (HCT) Based on the
Mineralogy of the Granular Material Sub-Strata
Although approximately 60 percent of the crust of the earth contains Si-O bonds, not
all naturally available granular materials are silicon-rich. Non-silicate materials include
carbonate materials such as calcretes and dolerites that are predominant in certain areas
of the world and laterites (abundant in warm/humid conditions conducive to chemical
weathering and the leaching-out of silicate materials). In such cases (e.g., with calcretes,
dolomites, etc.), very little or even no silicon may be available in the material to create the
Si-O-Si bonds, as explained in the example.
The part of the earth conducive to weathering due to chemical decomposition is
situated in areas associated with the presentence of moisture (humid conditions) and
high variations in seasonal temperature variations. These environmental conditions are
especially pronounced between the Tropics of Capricorn and Cancer. The mineralogy of
the naturally available materials (especially in areas close to the Equator), may be deprived
of readily available silicon and may not be able to form Si-O bonds with the nano-silanes, as
shown in Figure 5. In these areas, the nano-silanes need to be complemented with a material
compatible nano-particle conversion to created strong chemical bonds with the minerals
in the available granular materials. This conversion of a nano-silane is generally referred
to as a Hydroxy Conversion Treatment (HCT), which is best characterised by its ability
to form bonds with the available minerals in the granular materials (stone/gravel/soil).
For example, in the case of carbonate-rich materials (e.g., dolomites and calcretes), the
nano-particle added to the nano-silane in the form of an HCT must be able to form strong
chemical bonds with the Calcium-carbonates (Ca(CO3 )) in the material. The example of an
HCT treatment of a nano-silane for use with carbonate-rich material is demonstrated in
Figure 7, where the added HTC is designed to form strong chemical bonds with the carbon
elements in the material sub-strata.
From the above example, it should be clear that the different nano-products applicable
to various mineral compositions must accurately be identified through scientific testing [20]
to obtain the required information to identify a material compatible nano-silane product,
with or without the addition of an applicable HTC, in order to achieve the required results
to eliminate the risk of failure. Similar conversions will be required for other materials
that may contain minerals with a relatively low free silicon content. For example, laterite
may contain anything from 90 percent to 10 percent silicon-based minerals [15], which may,
inter alia, depend on the parent material (primary minerals), the climatic conditions, and
the extent of chemical weathering that has taken place [22].
Appl. Sci. 2021, 11, 9699 15 of 25
Appl. Sci. 2021, 11, x FOR PEER REVIEW 16 of 28

Figure 7. Hydroxy Conversion Treatment (HCT) of a nano-silane modification to a stabilising agent to enable a strong
Figure
bond 7. Hydroxy
with carbonate Conversion Treatment (HCT) of a nano-silane modification to a stabilising agent
materials.
to enable a strong bond with carbonate materials.
From the above example, it should be clear that the different nano-products applica-
ble to various mineral compositions must accurately be identified through scientific test-
5. The Clay Problem
ing [20] to obtain the required information to identify a material compatible nano-silane
The identification of a material compatible HCT treatment in the case of highly chemi-
cally weathered materials may be more complex due to the high percentages of secondary
minerals with little silicon present in the naturally available granular materials. The pre-
dominant minerals present in these materials are usually closely associated with a high
percentage of clay within the materials. Such materials may present additional challenges
in terms of practical constraints associated with workability. Due to the sub-nano size of
some clay particles (Figure 8 [35]) and the formation of nano-sheets by high percentages
of clays, the nano-silane particle size to be added needs to be able to penetrate the clay
matrix in order to achieve a hydrophobic stable state within the material. In the absence
of such internal hydrophobicity, the clay sheets will shear under loading, breaking any
protective stabilising agent and allow water to access the clay crystals within the clay
Appl. Sci. 2021, 11, 9699 16 of 25

matrix, rendering the hydrophobicity of the stabilised material to become ineffective. The
Appl. Sci.stabilising
2021, 11, x FOR agent also
needs to be of nano-size in order to effectively bind the material
PEER REVIEW 18 of 28
together in combination with the applicable nano-silane.

Figure 8. Typical
Figure dimensions
8. Typical in Angstrom
dimensions of commonly
in Angstrom ofavailable
commonly clay crystals
availablethatclay
formcrystals
during chemical decomposition
that form during
within naturally available materials [35].
chemical decomposition within naturally available materials [35].

A micro-size molecule in the stabilising agent will prove problematic with the nano-
size granular material particles (clay particles) effectively “swimming” within the relatively
large particles of the stabilising agent with no bonding between the material particles pos-
sible. This aspect is practically demonstrated by the material test results shown in Figure 9.
The material stabilised with a material compatible New-age (Nano) Modified Emulsion
(NME) stabilising agent, as shown in Figure 9, contained between 20 and 25 percent of
fines passing through the 0.075 mm sieve of which more than 60 percent was identified
as mica, clay and talk minerals. The NME stabilising agent is an anionic NME manufac-
Appl. Sci. 2021, 11, 9699 17 of 25

tured using a bitumen emulsion. It is seen that an increase in the stabilising agent from
1 percent to 1.5 percent led to a decrease in the Unconfined Compressive Strength (UCS)
in a dry condition just after rapid curing [18] (UCSdry ) from about 4800 kPa to 2600 kPa
(highlighted in pink), while the Indirect Tensile Strength (ITS) in a dry condition after rapid
curing [18] (ITSdry ) decreased from 420 kPa to 230 kPa (highlighted in pink). Although
these results are still very good considering the quality of the material that was stabilised
(G8—refer comparison in Figure 6) (demonstrating the considerable advantages of the use
of a material compatible anionic NME stabilising agent), the decrease in the measured
engineering properties are considerable. This decrease can directly be attributed to the
relatively large particle size of the stabilising agent (1000 to 5000 nm) together with the
relatively high percentage of the material passing through the 0.075 mm sieve19size
Appl. Sci. 2021, 11, x FOR PEER REVIEW of 28
of which
a large percentage can be considered as problematic materials (i.e., clay, mica and talk).

Base and Sub-base material for Accelerated Pavement Testing (APT) (MMLS3) of thin (chip seal) surfacings
Material Test results
Fraction %
Material grading Coarse Sand (CS) 29 - 33
100 Fine Sand (FS) 28 - 35
BSM Not Good Coarse Fine Sand (CFS) 10 - 11
90
Grading envelopes)
80 Medium Fine Sand (MFS) 11 - 17
Fine Fine Sand (FFS) 6- 8
Percentage Passing

70
60 Silt and Clay (S & C) 35 - 39
50
40 OMC (%) 11.4
30 MDD (kg/cub m) 2030
BSM Good
20 GM 1.85
(Grading envelopes)
10
0 Atterberg Limits
0.075

0.15

19.2
0.3

0.6

1.2

2.4

4.8

9.6

Liquid Limit (LL) 28 - 30

Sieve Size (mm)
Plasticity Index (PI) 8 - 14
PI (0.075)
Mineral Percentages present in Material Sample Linear Shrinkage (LS) 4- 7
Minerology Total sample % 0.075 mm Fraction % CBR (mod AASHTO)
Mineral Groups Individual Combined Individual Combined 95% 10 - 17
Quartz 43.2 43.2 23.0 23.0 93% 9 - 14
Plagioclase 14.8 6.6 Classification
Augite 2.4 1.3 H.R.B. A-2-6
Enstratite 0.0 0.5 COLTO G8
Actinolite 3.8 1.4 TRH14 G8
Microcline 6.5 4.2
Mineral Groups:
27.5 14.0 (Weathering = chemical decomposition)
Mica: Muscovite 12.2 12.2 36.2 36.2 Primary (Not subject to Weatering)
Clay: Kaolinite 6.1 15.0 Primary (Subject to Weathering)
Clay: Smectite 7.5 3.0 Mica
Secondary minerals
Calcite 0.5 14.1 6.5 24.5 (Nano-scale crystals/molecules)
Talc 3.1 3.1 2.3 2.3

Results: Stabilisation
Agent New-age Modified Emulsion (NME) Conventional Emulsion stabilisation Unit
% 0.7 1.0 1.2 1.5 1.5% SS60 Emulsion + 1.0 % Cement

UCS(dry) 3395 4807 4859 2620 3277 kPa

UCS(wet) 1745 1830 1671 1865 656 kPa
UCSw/d % 51 38 34 71 20 %

ITS(dry) 254 420 268 232 167 kPa

ITS(wet) 61 321 221 184 61 kPa
ITSw/d % 24 76 82 79 37 %

Figure 9. Results from the anionic NME stabilisation (using a bitumen emulsion) of a material containing between 22 and
25 per cent of9.
Figure fines passing through
Results from the
the0.075 mm sieve
anionic size of stabilisation
NME which more than 60 percentaconsists
(using bitumen
a material of mica, clay and talk of
emulsion)
particles.
containing between 22 and 25 per cent of fines passing through the 0.075 mm sieve size of which
more than 60 percent consists of mica, clay and talk particles.
Appl. Sci. 2021, 11, 9699 18 of 25

6. Material Compatible Anionic NME Nanotechnology Stabilising Agents Enabling

the Use of Unsuitable Granular Materials to Become a Valuable Asset in
Road Construction
The example shown in Figure 9 is a good indicator of the disruptive nature of the
introduction of proven available nanotechnologies into the field of pavement engineering.
Using traditional material classification systems, the indicator material test results shown
in Figure 9 would have identified the material to be unsuitable for use in any load-bearing
layers of a pavement structure, even for low-volume roads. However, the stabilisation
results gave confidence to the use of the material in the sub-base with 1 percent anionic
NME stabilising agent (highest results in terms of tensile strength) and with 1.5 percent in
the base layer (highest Retained Compressive Strength (RCS) of 71 percent).
A high RCS can be related to high resistance to possible damage due to water-ingress
from the top in the case of a compromised surfacing layer. This pavement structure con-
structed with the anionic NME stabilisation as indicated was evaluated using Accelerated
Pavement Tests (APT) [8,9]. The design traffic loading of 3 Million Standard 80 kN dual-
wheel single axle loads (E80s) was surpassed with ease with an estimated load-bearing
capacity of at least three times that of the design traffic loading in terms of applicable
pavement deformation performance criteria [36]. The stabilised materials have also shown
remarkable resilience against overloading with a damage co-efficient of n < 2 (normally
assumed to be 4.2 [37]). It follows that road pavement structures containing anionic NME
stabilised base and sub-base layers will be ideally suited for the construction of roads
where law enforcement in terms of vehicle over-loading is limited or even totally absent.
Available nanotechnologies have been used under laboratory conditions to achieve
acceptable engineering results on materials of considerably poorer quality than shown in
Figure 9. Figure 10 shows the exposed surface of a material sample crushed during an
ITSwet test of relatively poor laterite. This material contained almost 50 percent of fines
passing through the 0.075 mm sieve size, of which almost 70 percent was identified through
XRD scans as kaolinite clay particles. In this case, a material compatible HCT modified
high-quality sub-nano size silane was used with a nano-polymer to stabilise the material.
The crushed sample shown in Figure 10 was tested to have an ITSwet of 80 kN with good
hydrophobicity achieved throughout the sample as shown by the beading [7] effect of the
water sprayed onto the exposed surface of the broken sample after testing. These anionic
NME treated materials will be suitable for use in the upper load-bearing layers of some
low-volume roads (refer criteria [38]). The sub-nano size silane and nano-polymer needed
to be carried into the material using water as a carrier and thoroughly mixed. As well
known, high percentages of clay in a wet condition present considerable challenges in
terms of workability in the field. In practice, workability may need to be addressed by
mixing a percentage of material such as sand or naturally available gravel into the material
to practically enable the material to be workable when adding the modified stabilising
agent into the material using water as a carrier.
The material shown in Figure 10 may be considered to be an extreme example of
a granular material not to be considered for use in traditionally accepted pavement en-
gineering. However, such materials are all too common in areas close to the equator,
associated with high humidity and high-temperature conditions. Granular materials of
similar characteristics (shown in Figure 10) may be the only material available over con-
siderable distances. Hence, any improved use of granular materials of very poor quality,
similar to that demonstrated in Figure 10, may be of considerable cost benefit to any road
project [39].
The use of materials of such a poor quality may be unthinkable in traditional pavement
engineering. However, this extreme example demonstrates that with scientific knowledge
about the mineralogy [20], in combination with applicable basic knowledge of the basic
chemistry, material compatible nano-silane technologies, modified with a material compat-
ible HCT, can be selected and utilised to change the material characteristics to an extent
where even poor quality laterites can effectively be treated to become hydrophobic and
Appl. Sci. 2021, 11, 9699 19 of 25

stabilised
Appl. Sci. 2021, to anREVIEW
11, x FOR PEER extent
where it can meet the engineering specifications of load-bearing21 of 28
layers in a pavement structure [35].

Figure 10. Water

Figure beading
10. Water of water of
beading spayed
water onspayed
an exposed laterite
on an material
exposed samplematerial
laterite stabilisedsample
with a material compatible
stabilised with
HCT modified sub-nano size anionic silane and graded nano-polymer after crushing while performing an ITSwet test—
a material
almost 50 percentcompatible HCT
of the material modified
passed throughsub-nano
the 0.075 mmsizesieve
anionic
size ofsilane
which and graded
almost nano-polymer
70 percent was measuredafter
to be
Kaolinite clay particles.
crushing while performing an ITSwet test—almost 50 percent of the material passed through the
0.075 mm sieve size of which almost 70 percent was measured to be Kaolinite clay particles.
The material shown in Figure 10 may be considered to be an extreme example of a
7. Influence of thegranular
Chemicalmaterial not to be considered
Characteristics for use in traditionally
of the Emulsifying Agent on accepted pavement engi-
the Potential
neering.Achievable
Engineering Properties However, such materials are all too common in areas close to the equator, asso-
ciated with high humidity and high-temperature conditions. Granular materials of similar
A good emulsifying agent (i.e., an emulsifying agent with a relatively long carbon tail)
characteristics (shown in Figure 10) may be the only material available over considerable
also contributes significantly towards
distances. Hence, the engineering
any improved properties
use of granular to beofachieved
materials very poorwhen used
quality, similar to
for the stabilisation of granular materials for use in roads. These characteristics
that demonstrated in Figure 10, may be of considerable cost benefit to any road are nor-project
mally not addressed [39].in specifications (e.g., [23,40–42]). It follows that bitumen emulsions
manufactured according Thetouse of materials
such of suchcould
specifications a poorresult
qualityinmay be unthinkable
substantial in traditional
differences in the pave-
ment engineering.
engineering properties when used However,
to stabilisethis extreme
the example demonstrates
same materials [43]. Underthat with scientific
conditions
where procurementknowledge
procedures about the mineralogy [20], in combination with applicable basic knowledge of
are based on the award of tenders based mainly on the low-
the basic chemistry, material compatible nano-silane technologies, modified with a mate-
est tender, modified bitumen emulsion manufacturers would need to produce the modified
rial compatible HCT, can be selected and utilised to change the material characteristics to
bitumen emulsions anwithin specification
extent where even poor using thelaterites
quality lowestcanpossible input
effectively costs. The
be treated lowesthydro-
to become
phobic are
cost emulsifying agents andnormally
stabilised toalso
an extent where it
associated can meet
with carbonthe engineering specifications
tails (Figures 1 and 2) ofof load-
limited length. bearing layers in a pavement structure [35].
The considerable influence of the chemical characteristics of the emulsifying nano-
particle (surfactant) as part of an anionic NME stabilising agent is demonstrated through
the use of eight different anionic NME stabilising agents for the stabilisation of the same
material. These eight different anionic bitumen emulsions were sourced from five different
suppliers (some using more than one different emulsifying agent). Variations in bitumen
characteristics were limited by ensuring that all suppliers use bitumen produced by the
same refinery within the same time frame. External factors other than the type of emulsify-
ing agent are further reduced by modifying the different emulsions using the exact same
Appl. Sci. 2021, 11, 9699 20 of 25

type and volume of material compatible nano-silane from the same flow-bin. The resultant
anionic NME stabilising agents were used on the same material sourced at the same time
in the same quarry, thoroughly mixed to ensure that material variations will have a limited
impact on results. The granular material used was a relatively good G5/6 (refer to Figure 6)
granite containing about 10 percent Muscovite. The material was stabilised using 1 percent
per mass (containing about 0.5 percent residual bitumen) of the anionic NME (about 21
litres/m3 of granular material) to stabilise the granular material. All samples were mixed,
cured and tested in the same laboratory using the same technicians in a blind testing
regime. The UCS tests (dry and wet [18]) and the ITS tests (dry and wet [18]) of three
samples each were measured and compared using the eight different bitumen emulsions,
all manufactured meeting the applicable National Standards [23].
The results using the eight different nano-modified bitumen emulsions manufactured
using different emulsifying agents are shown in Figure 11 (UCS dry and wet), Figure 12
(ITS dry and wet) and Figure 13 (Retained Compressive Strength (RCS) (UCSwet /UCSdry
as a percentage) and Retained Tensile Strength (RTS) (ITSwet /ITSdry as a percentage). The
different suppliers are identified by the letters A to E. The number of emulsions prepared
using different emulsifying agents received from each supplier is shown by the number
following the alphabet letter, e.g., A1, A2. Where the emulsifying agent is known and to
compare the same emulsifying agents from different suppliers, these emulsifying agents
are identified by a further number, e. g, A1-1 and D1-1.
Although all the bitumen emulsions used conformed to the National standard [23]
currently used in practice in South Africa, some alarming variations in the measured
engineering properties of UCS, ITS, RCS and RTS were measured. Depending on the
property tested, a variation of 30 to more than 50 percent in the average measurements
between the eight different anionic NME products were recorded. Given the relatively
good material (CBR > 45 @ 95% mod AASHTO [32,33]) used to compare the engineering
properties, these results are alarming. Of particular concern is the comparison of the
retained strengths. It is seen that the effect of the nano-silane modification (specifically
added to improve granular materials against the effect of water) could be affected to a
concerning degree by the chemical characteristics of the emulsifying agent (surfactant). It
follows that both the nano-particles (emulsifying agent) used to manufacture the emulsion
and the material compatible nano-silane are of importance to achieve optimum results. The
use of a relatively inferior emulsifying agent in the manufacturing of the bitumen emulsion
could result in the manufacturing of an anionic NME stabilising agent not meeting the
engineering specifications, especially when used in combination with naturally available
granular materials of relatively poor quality.
It follows that the manufacturing of bitumen emulsion not specifying the character-
istics of the emulsifying agent can be problematic in practice and can lead to unforeseen
construction problems. In an open procurement process, the achieving of the engineer-
ing properties is the prime objective. Hence, the use of inferior products can be limited
through the implementation of an end-product specification. In such cases, the contractor
and supplier must guarantee that the product to be used will be of a quality suitable to
meet the minimum engineering properties as specified. Such an approach will ensure
that the end-product will meet the engineering requirements of the design and limit any
risk associated with chemical variations. During the design process, the design engineer
must do sufficient tests to ensure that an available NME stabilising agent can meet the
specifications with confidence. As a result of these findings, it is recommended that a high-
quality modified emulsifying agent (modification of a high-quality emulsifying agent with
a material compatible nano-silane) be used for the manufacturing of the NME stabilising
agent to confidently meet the engineering specifications and limiting any risks associated
with the possible use of an inferior component.
Appl. Sci. 2021, 11, 9699 21 of 25
Appl. Sci. 2021, 11, x FOR PEER REVIEW 23 of 2

Appl. Sci. 2021, 11, x FOR PEER REVIEW 23 of

Figure 11. Comparison of the UCS results (dry and wet) using eight different bitumen emulsions from five different sup-
Figure 11. Comparison of the UCS results (dry and wet) using eight different bitumen emulsions
pliers, with variations in the emulsifying agent (surfactant) used in the manufacturing of the anionic NME as the only
variable–from five different
all anionic suppliers,used
bitumen emulsions withwere
variations
producedinmeeting
the emulsifying
the Nationalagent (surfactant)
Standard [23]. used in the
Figure manufacturing
11. Comparison of ofthe
theUCS results
anionic NME(dryas
and
thewet)
onlyusing eight different
variable– bitumen
all anionic emulsions
bitumen from five
emulsions useddifferent
were sup-
pliers, with variations in the emulsifying agent (surfactant) used in the manufacturing of the anionic NME as the only
produced meeting the National Standard [23].
variable– all anionic bitumen emulsions used were produced meeting the National Standard [23].

Figure 12. Comparison of the ITS results (dry and wet) using eight different bitumen emulsions from five different sup-
pliers, with variations in the emulsifying agent (surfactant) used in the manufacturing of the anionic NME as the only
variable—all anionic bitumen emulsions used were produced meeting the National Standard [23].
Figure Figure
12. Comparison of the ITS of
12. Comparison results (dryresults
the ITS and wet) using
(dry andeight
wet)different bitumen
using eight emulsions
different from five
bitumen different sup-
emulsions
pliers, with variations in the emulsifying agent (surfactant) used in the manufacturing of the anionic NME as the only
from five different suppliers, with variations in the emulsifying agent (surfactant) used in the
variable—all anionic bitumen emulsions used were produced meeting the National Standard [23].
manufacturing of the anionic NME as the only variable—all anionic bitumen emulsions used were
produced meeting the National Standard [23].
Appl. Sci. 2021, 11, 9699 22 of 25
Appl. Sci. 2021, 11, x FOR PEER REVIEW 24 of 28

Figure 13. Comparison of the relative retained UCS strengths (RCT) (UCSwet/UCSdry as a percentage) and relatively re-
Figure 13. Comparison of the relative retained UCS strengths (RCT) (UCSwet /UCSdry as a percentage)
tained ITS strengths (RTS) (ITSwet/ITSdry as a percentage) using eight different bitumen emulsions from five different sup-
pliers,and
withrelatively
variationsretained ITS strengths
in the emulsifying agent (RTS) (ITSwet
(surfactant) /ITS
used the as
in dry a percentage)
manufacturing using
of the eightNME
anionic different
as the only
variable—all
bitumenanionic bitumen
emulsions emulsions
from used were
five different produced
suppliers, withmeeting the National
variations Standard [23].
in the emulsifying agent (surfactant)
used in the manufacturing of the anionic NME as the only variable—all anionic bitumen emulsions
used were produced meeting Although all the bitumen
the National Standardemulsions
[23]. used conformed to the National standard [23
currently used in practice in South Africa, some alarming variations in the measured en
8. Conclusions gineering properties of UCS, ITS, RCS and RTS were measured. Depending on the prop
Nano-silane erty
based tested, a variation
products haveofbeen
30 to more
usedthan 50 percent
in Europe forinalmost
the average
two measurements
centuries to between
protect stone buildings against the impact of climate and pollution. Early in therelatively
the eight different anionic NME products were recorded. Given the 1800s, the good mate
rial (CBR > 45 @ 95% mod AASHTO [32,33]) used to compare the engineering properties
development of these products was performed on a trial-and-error basis, with scientists
these results are alarming. Of particular concern is the comparison of the retained
often encountering conflicting results. These conflicting results soon led to the realisation
strengths. It is seen that the effect of the nano-silane modification (specifically added to
that the “type of stone”
improve(primary
granular minerals) and the
materials against the“condition of the
effect of water) stone”
could (secondary
be affected to a concerning
minerals) are important aspects that determine the successful outcome of the application
degree by the chemical characteristics of the emulsifying agent (surfactant). It follows tha
both the
of a specific nano-scale nano-particles
silicon-based (emulsifying
product developed agent)
forused to manufacture the emulsion
the protection/stabilisation of and the
granular materialsmaterial compatible nano-silane are of importance to achieve optimum results. The use o
(stone/gravel/soil).
Over the lastafewrelatively
decades, inferior emulsifying
numerous agent in the
silicon-based manufacturing products
nanotechnology of the bitumen
have emulsion
could result in the manufacturing of an anionic
been developed for use in the built environment, utilising the “excellent mechanical,NME stabilising agent not meeting the
optical, thermal and electrical properties” inherent in the silicon element. The same available
engineering specifications, especially when used in combination with naturally
nanotechnologies,granular materials
incorporating theof“lessons
relativelylearnt”
poor quality.
from the built environment, can find
It follows that the manufacturing
direct application in road pavement engineering to enhance, of bitumen emulsion
protect not specifying
and stabilise the character
naturally
istics of the emulsifying agent can be problematic in practice and can lead to unforeseen
available granular materials that are traditionally considered marginal or inadequate for
construction problems. In an open procurement process, the achieving of the engineering
use in the upper pavement layers below the surfacing.
properties is the prime objective. Hence, the use of inferior products can be limited
In order to limit risksthe
through and eliminate theofpossibility
implementation an end-productof failure, engineers
specification. need
In such to take
cases, the contractor
cognisance of theand lessons
supplier learned in the built
must guarantee thatenvironment.
the product to It beisused
essential
will beto of know thesuitable to
a quality
scientifically determined
meet themineralogy of the material
minimum engineering that is
properties as available for use.
specified. Such In addition,
an approach will it
ensure tha
the to
is also of importance end-product
understand willthe
meet thechemistry
basic engineering requirements
involved in theofuse
theofdesign andnan-
various limit any risk
associated
otechnology products. Thiswith chemical variations.
understanding During the
is instrumental todesign process,the
recognising theadvantages
design engineer mus
and limitations ofdo anysufficient tests to material
one available ensure that an available
compatible NME stabilising
product agent can
in combination meet
with thethe specifi
naturally available granular materials for use in a pavement structure. Basic knowledge
of elementary chemistry is considered essential to ensure that applicable technologies are
used and that the impact on engineering results is understood and any potential risk is
identified and timeously addressed.
Unmodified bitumen emulsions do not create chemical bonds with the material sub-
strata that when used as a stabilising agent. Bond strengths are achieved through electrical
Appl. Sci. 2021, 11, 9699 23 of 25

and mechanical forces and absorption into the material surfacing cervices. However,
strong chemical bonds can be achieved through the introduction of material compatible
nanotechnology organofunctional nano-silane modifications to the bitumen emulsion (or
any equivalent polymer stabilising agent). The chemical interaction of the nano-silane
modifier can be compared to the use of an emulsifying agent (nanoparticle) to create
bitumen emulsions, which enables water to be mixed with oil (bitumen). The characteristics
and the bond-strengths of the elements comprising a specific emulsifying agent will also
affect the stability of the emulsion and the properties of the end-product. Changes in
chemical composition of the emulsifying agent (also known as a surfactant or “soap”) can
meaningfully influence the engineering properties that can be achieved using a modified
bitumen emulsion with the addition of a material compatible nano-silane.
The influence of the chemical characteristics of the emulsifying agent as the only
variable in an anionic NME mix is demonstrated using eight different products from
five different suppliers. Differences of up to 50% in the measured UCS (dry and wet)
and ITS (dry and wet)) were measured using different emulsifying agents as the only
component variable. It is recommended that this aspect be addressed in practice by
engineers through the introduction of end-product specifications. The introduction of
end-product specifications will put the onus (and risk) on the contractor and his supplier
to ensure that quality products are used meeting the minimum engineering specifications.
The understanding of the basic elementary chemistry of the applicable, proven nan-
otechnology used will ensure that risks are minimised. The testing of the basic bitumen
stabilising agent and the influence of the nano-particle (the emulsifying agent or surfactant)
on the engineering properties was performed with the specific objective to demonstrate the
need for engineers to realise the importance of quality control during the manufacturing,
ensuring that material compatible materials are utilised, with chemical properties that
will guarantee that macro projects can successfully be implemented using new disruptive
nanotechnologies by adhering to basic scientific principles.
The main objectives of the modification of an emulsifying stabilising agent are to:
• Ensure that a high strength chemical bond is established between the stabilising agent
and the naturally available granular materials;
• Achieve a high level of hydrophobicity of each particle within the granular materials
layer through a 3-dimensional consolidation of the nano-silane, covering the total of
surface area of each particle, and
• Protect each particle within the granular material against the effect of water and
neutralise the presence of any secondary minerals (e.g., clay) within the granular
material by ensuring that a material compatible nano-silane (modified where necessary
with a HCT nano-particle), is utilised based on the scientifically measured mineralogy
of the granular material.
A material-compatible organofunctional nano-silane with an applicable HCT (when
needed), is introduced into the stabilising agent that will ensure that the required chemical
bonds are activated during the stabilising process. The quantity of the modifier to be
added is a function of the surface area to be covered. It follows that the fine fractions (the
percentage passing the 0.075 mm sieve size and the percentage of clay (less than 0.002 mm
fraction) is of importance in the adjustment of the nano-silane percentages to be added
to achieve the objectives successfully. It follows that the modification of the stabilising
agent to optimally achieve the required engineering properties is not conducive to a “one
solution fits all” product approach.
It is shown that materials of a very poor quality (unthinkable using traditional pave-
ment engineering approaches to material utilisation) can be treated and stabilised to obtain
the required engineering properties meeting engineering specifications in terms of com-
pressive strengths, tensile strengths and durability in pavement layers, depending on the
design traffic loading. This is possible with the application of scientific knowledge and
applying high-quality nano-scale products, i.e., emulsifying agents (surfactants), material-
compatible nano-silane products with the required chemical compositions together with
Appl. Sci. 2021, 11, 9699 24 of 25

material-compatible HCT modifications when applicable. These disruptive nanotechnolo-

gies have been proven in laboratories, through Accelerated Pavement Tests (APT) [8,9] and
in practice on several roads in southern Africa [13].

Author Contributions: G.J.J., under the directive of the Head of Department of Civil Engineering,
W.J.v.S., has been leading the research into the provision of affordable road infrastructure at the
faculty of Engineering, University of Pretoria. W.J.v.S. recognized the potential of nanotechnology
solutions in the field of pavement engineering more than a decade ago. G.J.J., through involvement
in the private sector and the support of road authorities, has been instrumental in the development
of scientific principles, ensuring that implementation can be achieved and tested at a minimum risk.
All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The support of GeoNANO Technologies (Pty) Ltd., 18 Davies road, Wychwood,
Germiston 1401, South Africa, Tel.: +27844078489, Available online: www.geonano.co.za, accessed
on 7 October 2021, [email protected], in support of students in the Department of Civil Engi-
neering, University of Pretoria, Pretoria, South Africa to test a wide variety of materials as part of
final year projects and post-graduate theses, testing the various principles identified in this article,
is acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Man, G.-M.; Man, M. Challenges in the Fourth Industrial Revolution. Sciendo Land Forces Acad. Rev. 2019, 24, 303–307. [CrossRef]
2. Republic of South Africa. Report Recommendations & Way Forward; Presidential Commission on the Fourth Industrial Revolution:
Pretoria, South Africa, 2020.
3. Steyn, W.J.v.M. The Upside of Disruptive 4IR Technology and Innovation; University World News—Africa Edition: London, UK, 2021.
4. Wheeler, G. Alkoxysilanes and the Consolidation of Stone; The Getty Conservation Institute: Los Angeles, CA, USA, 2005.
5. Von Ebelman, J.J. Untersuchungen über die Verbinddungender Borsäure mit Aetther. Ann. Chem. Pharm. 1846, 57, 319–353.
[CrossRef]
6. Van Hoffman, A.W. Stone-preserving processes: Royal Institute of British Architects. Builder 1861, 1, 103–105.
7. Jordaan, G.J.; Steyn, W.J.vdM. Fundamental Principles Ensuring Successful Implementation of New-Age (Nano) Modified
Emulsions (NME) for the Stabilisation of Naturally Available Materials in Pavement Engineering. Appl. Sci. 2021, 11, 1745.
[CrossRef]
8. Rust, F.C.; Akhalwaya, I.; Jordaan, G.J.; Du Plessis, L. Evaluation of a nano-silane-modified emulsion stabilised base and subbase
under HVS traffic. In Proceedings of the 12th Conference on Asphalt Pavements for Southern Africa (CAPSA 2019), Sun City,
South Africa, 13–16 October 2019.
9. Rust, F.C.; Smit, M.A.; Akhalwaya, I.; Jordaan, G.J.; Du Plessis, L. Evaluation of two nano-silane-modified emulsion stabilised
pavements using accelerated pavement testing. Int. J. Pavement Eng. 2020, 1–14. [CrossRef]
10. Kelsall, R.W.; Himley, I.W.; Geoghegan, M. Nanoscale Science and Technology; Wiley: Chisester, UK, 2004.
11. Zhang, S. Material Characterisation Techniques; CRC Press: Boca Raton, FL, USA, 2008; ISBN 1420042947.
12. Steyn, W.J.v.d.M. Potential Applications of Nanotechnology in Pavement Engineering. J. Transp. Eng. 2009, 135, 764–772.
[CrossRef]
13. Jordaan, G.J.; Kilian, A.; Muthivelli, N.; Dlamini, D. Practical Application of Nano-Technology in Roads in southern Africa. In
Proceedings of the 8th Transportation Technology Transfer (T2) Conference, Lusaka, Zambia, 8–10 May 2017.
14. Jordaan, G.J.; Kilian, A. The cost-effective upgrading, preservation and rehabilitation of roads—Optimising the use of available
technologies. In Proceedings of the 2016 Southern Africa Transportation Conference (SATC 2016), Pretoria, South Africa, 4–7 July
2016.
15. Weinert, H.H. The Natural Road Construction Materials of Southern Africa; National Book Printers: Cape Town, South Africa, 1980.
16. Southern Africa Transport and Communications Commission (SATCC). Guideline: Low-Volume Sealed Roads; Southern Africa
Development Community (SADC), SADC House: Gaborone, Botswana, 2003; ISBN 99912-0-456-5.
17. James, A. Overview of Asphalt Emulsion; Transportation Research Circular, Number E-C102; Transportation Research Board:
Washington, DC, USA, 2006.
Appl. Sci. 2021, 11, 9699 25 of 25

18. Jordaan, G.J.; Kilian, A.; Du Plessis, L.; Murphy, M. The development of cost-effective pavement design approaches using
mineralogy tests with new nano-technology modifications of materials. In Proceedings of the 2017 Southern Africa Transportation
Conference (SATC 2017), Pretoria, South Africa, 6–9 July 2017.
19. Asphalt Academy. Technical Guideline (TG2): Bitumen Stabilised Materials—A Guideline for the Design and Construction of Bitumen
Emulsion and Foamed Bitumen Stabilised Materials; Asphalt Academy c/o CSIR Built Environment: Pretoria, South Africa, 2009.
20. Jordaan, G.J.; Steyn, W.J.vdM. Testing of granular/soil characteristics for the optimisation of pavement designs using reactive
stabilising agents including “new-age” nano-technologies. In Proceedings of the 12th Conference of Asphalt Pavements for
Southern Africa (CAPSA 2019), Sun City, South Africa, 13–16 October 2019.
21. Mshali, M.R.S.; Visser, A. Influence of Mica on Unconfined Compressive Strength of a cement-treated weathered granite gravel.
In Proceedings of the 2013 Southern African Transportation Conference (SATC), Pretoria, South Africa, 8–11 July 2013.
22. Netterberg, F. Pedocretes; RR430; NITRR; CSIR: Pretoria, South Africa, 1985.
23. South African National Standards. SANS 4001-BT3, (2014). Civil Engineering Specifications Part BT3: Anionic Bitumen Road Emulsion;
South African Bureau of Standards (SABS): Pretoria, South Africa, 2014.
24. Simpson, P.L. Overview of Asphalt Emulsion Applications in North America; Transportation Research Circular, Number E-C102;
Transportation Research Board: Washington, DC, USA, 2006.
25. Baumgardner, G.L. Asphalt Emulsion Manufacturing Today and Tomorrow; Transportation Research Circular, Number E-C102;
Transportation Research Board: Washington, DC, USA, 2006.
26. Casagrande, C.; Veyssié, M. “Janus Beads”: Realization and Behaviour at Water/Oil Interfaces. C. R. Acad. Sci. 1988, 306, 1423.
[CrossRef]
27. Solá, N.Q. Highly Concentrated Bitumen Emulsions—A State of the Art, Review of Experimental Results. Màster en Ciències
Aplicades a l’ Enginyeria, Universitat de Lleida, Catalonia, Spain, 2013.
28. The Chemical Rubber Company. Handbook of Chemistry and Physics; A Division of the Chemical Rubber Company; CRC Press:
Cleveland, OH, USA, 1973.
29. Grim, R.E. Clay Minerology, 2nd ed.; McGraw-Hill Book Company: New York, NY, USA, 1968.
30. Pearch, C.A. Silicon Chemistry and Applications; The Chemistry Society: London, UK, 1972; pp. 28–47.
31. AkzoNobel Surface Chemistry. Adhesion Promoters; Technical Bulletin; AkzoNobel: Stockholm, Sweden, 2003.
32. Committee of Land Transport Officials (COLTO). Draft TRH14: Guidelines for Road Construction Materials; National Institute for
Transport and Road Research (NITRR); CSIR: Pretoria, South Africa, 1985.
33. American Association of State and Highway Transportation Officials (AASHTO). M145-91: Standard Specification for Classification
of Soils and Soil-Aggregate Mixtures for Highway Construction Purposes; American Association of State Highway and Transportation
Officials (AASHTO): Washington, DC, USA, 1995.
34. American Society for Testing Materials (ASTM). D3282-09: Standard Practice for Classification of Soils and Soil-Aggregate Mixtures for
Highway Construction Purposes; The American Society for Testing and Materials: Pennsylvania, PA, USA, 2009.
35. Moore, J.E. Clay mineralogy problems in oil recovery. Pet. Eng. 1960, 32, 78–101.
36. Jordaan, G.J. Optimisation of Flexible Road Pavement Rehabilitation Investigations and Design; Department of Civil Engineering,
University of Pretoria: Pretoria, South Africa, 2013; ISBN 978-1-77592-036-6.
37. Highway Research Board (HRB). The AASHO Road Test; National Academy of Science—National Research Council: Washington,
DC, USA, 1962.
38. Jordaan, G.J.; Steyn, W.J.vdM. Cost-Effective Upgrading of Gravel Roads Using Naturally Available Materials with New-Age Modified
Emulsion (NME) Stabilisation; Department of Civil Engineering, University of Pretoria: Pretoria, South Africa, 2020; ISBN
978-0-620-91415-4.
39. Jordaan, G.J. Life-cycle cost analysis—An integral part of pavement rehabilitation design. In Proceedings of the 10th Conference
on Asphalt Pavements for Southern Africa (CAPSA 2011), Drakensberg, South Africa, 11–14 September 2011.
40. Queensland Government. Technical Specification: Transport and Main Road Specifications-MRTS21 Bitumen Emulsion; Department of
Transport and Main Roads, The State of Queensland: Brisbane, Australia, 2020.
41. Bureau of Indian Standards. Bitumen Emulsion for Roads—Specification (Second Revision); Bureau of Indian Standards: New Delhi,
India, 2004.
42. Transportation Research Board. Asphalt Emulsion Technology; Transportation Research Board: Washington, DC, USA, 2006.
43. Murphy, M.R.; Jordaan, G.J.; Modise, T.; Dryburgh, R.C. The influence of the characteristics of emulsifying agents on the
stabilisation of granular materials using nano-silane modified bitumen emulsions. In Proceedings of the 12th Conference of
Asphalt Pavements for Southern Africa (CAPSA 2019), Sun City, South Africa, 13–16 October 2019.