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Green Energy and Technology

Tina Kegl
Anita Kovač Kralj
Marko Kegl
Breda Kegl

Nanomaterials
for Environmental
Application
Fuel Additives for Diesel Engines
Green Energy and Technology
Climate change, environmental impact and the limited natural resources urge
scientific research and novel technical solutions. The monograph series Green
Energy and Technology serves as a publishing platform for scientific and
technological approaches to “green”—i.e. environmentally friendly and sustain-
able—technologies. While a focus lies on energy and power supply, it also covers
“green” solutions in industrial engineering and engineering design. Green Energy
and Technology addresses researchers, advanced students, technical consultants as
well as decision makers in industries and politics. Hence, the level of presentation
spans from instructional to highly technical.
**Indexed in Scopus**.

More information about this series at http://www.springer.com/series/8059

Tina Kegl Anita Kovač Kralj
• •

Marko Kegl Breda Kegl

•

Nanomaterials
for Environmental
Application
Fuel Additives for Diesel Engines

123
Tina Kegl Anita Kovač Kralj
Faculty of Chemistry Faculty of Chemistry
and Chemical Engineering and Chemical Engineering
University of Maribor University of Maribor
Maribor, Slovenia Maribor, Slovenia

Marko Kegl Breda Kegl

Faculty of Mechanical Engineering Faculty of Mechanical Engineering
University of Maribor University of Maribor
Maribor, Slovenia Maribor, Slovenia

ISSN 1865-3529 ISSN 1865-3537 (electronic)

Green Energy and Technology
ISBN 978-3-030-54707-3 ISBN 978-3-030-54708-0 (eBook)
https://doi.org/10.1007/978-3-030-54708-0
© Springer Nature Switzerland AG 2020
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
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Preface

Nanotechnologies have been steadily delivering new nanomaterials with exciting

properties which may significantly differ from those of corresponding bulk mate-
rials. These special properties make nanomaterials potentially very attractive and
important constituents in many modern technologies and processes. In this context,
diesel engines are no exception and, as it looks, nanomaterials might help in making
the diesel engine suited better for the ever-stringent environmental requirements.
Diesel engines are excellent machines which nowadays power immense quan-
tities of vehicles, trains, ships, and various machineries. Unfortunately, they come
with some problems, mainly related to engine harmful emissions. This is one of the
reasons for intensive research related to development of alternatives which would
power our transport in the future. As it stands, however, it does not seem likely that
an economically and technically viable replacement for a diesel engine will be
available in the very near future. Effectively, this means that diesel engines prob-
ably still have a long way to go and one should waste no time in trying to make
them better and cleaner. In this context, nanomaterials came into focus as poten-
tially highly valuable fuel additives, offering opportunities in improving diesel
engine performance and reducing the engine harmful emissions.
This book is a comprehensive review of opportunities, potentials, and associated
challenges related to engagement of nanomaterials as fuel additives in diesel
engines. The goal of this book is to provide a one-point entry for quick initial
orientation or road map drafting for managers, engineers, and researchers either
already working on this field or being about to enter it. This is achieved by pro-
viding a summarized overview of the most important nanomaterial-related data
published recently in connection with:
• diesel engine fuel injection, spray, and combustion,
• diesel engine characteristics,
• synthesis and characterization of various nanomaterials,
• overview of diesel engine base fuels and preparation of nanofuels,
• nanofuel properties and their effects on diesel engine emissions and other engine
characteristics, and

v
vi Preface

• practical viability of nanofuel usage, ranging from technical issues to environ-

mental and health concerns.
Most of the literature covered and referenced was published within the last few
years, especially in the period of 2017–2019. The data published in this literature is
elaborated into a summarized form by providing useful tables and charts. So, this
book provides an excellent starting point and a source of fresh ideas for anyone
being at least partially involved into the development of either cleaner diesel
engines or nanomaterials for environmental application.

Maribor, Slovenia Tina Kegl

Anita Kovač Kralj
Marko Kegl
Breda Kegl

Acknowledgements The authors are grateful for the financial support from the Slovenia Research
Agency (Ph.D. research fellowship contract No. 1000-18-0552 and core research funding No. P2
0032, P2 0137, and P2 0196).
Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2 Diesel Engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1 Diesel Engine Process Characteristics . . . . . . . . . . . . . . . . . . . . . 7
2.2 Diesel Engine Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.1 Ecology Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.2 Economy Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.3 Engine Performance Characteristics . . . . . . . . . . . . . . . . . 12
2.3 Diesel Engine Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3.1 Fuel Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.3.2 Fuel Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3 Nanomaterials for Diesel Engine Applications . . . . . . . . . . . . . . . . . 29
3.1 Synthesis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.1.1 Sol-Gel Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.1.2 Sol-Gel Combustion Method . . . . . . . . . . . . . . . . . . . . . 31
3.1.3 Hydrothermal and Solvothermal Methods . . . . . . . . . . . . 31
3.1.4 Sonochemical Method . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.1.5 Coprecipitation Method . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.1.6 Arc Discharge Method . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.1.7 Mechanical Ball Milling Process . . . . . . . . . . . . . . . . . . . 35
3.1.8 Green Synthesis Method Using Plant Extracts . . . . . . . . . 35
3.2 Characterization Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.2.1 SEM and TEM Techniques . . . . . . . . . . . . . . . . . . . . . . 36
3.2.2 EDXS Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2.3 XRD Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

vii
viii Contents

3.2.4 TGA Technique . . . . . . . . . . . . . . . . . . . . . . ......... 39

3.2.5 FT-IR Spectroscopy . . . . . . . . . . . . . . . . . . . ......... 40
3.2.6 VSM Technique . . . . . . . . . . . . . . . . . . . . . . ......... 41
3.3 Synthesis and Characterization of Nanomaterials Used
as Fuel Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... 41
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... 57
4 Nanofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.1 Nanofuel Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4.2 Nanofuel Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.2.1 Nanofuels with NMs Based on Silver . . . . . . . . . . . . . . . 75
4.2.2 Nanofuels with NMs Based on Aluminum . . . . . . . . . . . . 77
4.2.3 Nanofuels with NMs Based on Cerium . . . . . . . . . . . . . . 77
4.2.4 Nanofuels with NMs Based on Cobalt . . . . . . . . . . . . . . . 77
4.2.5 Nanofuels with NMs Based on Copper . . . . . . . . . . . . . . 77
4.2.6 Nanofuels with NMs Based on Iron . . . . . . . . . . . . . . . . 79
4.2.7 Nanofuels with NMs Based on Magnesium . . . . . . . . . . . 81
4.2.8 Nanofuels with NMs Based on Titanium . . . . . . . . . . . . . 81
4.2.9 Nanofuels with NMs Based on Zinc . . . . . . . . . . . . . . . . 81
4.2.10 Nanofuels with NMs with C NTs . . . . . . . . . . . . . . . . . . 81
4.2.11 Nanofuels with NMs Based on Carbon, Graphite,
and Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 99
4.2.12 Nanofuels with Other NMs . . . . . . . . . . . . . . . . . ...... 99
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
5 Nanofuel Usage in Diesel Engines . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.1 Nanomaterial Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.1.1 Secondary Atomization . . . . . . . . . . . . . . . . . . . . . . . . . . 108
5.1.2 Catalytic Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5.1.3 Reactive Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
5.1.4 Thermal Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
5.2 Transformation of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . 114
5.3 Effects on Diesel Engine Parts and Systems . . . . . . . . . . . . . . . . . 116
5.4 Effects on Diesel Engine Process Characteristics . . . . . . . . . . . . . 117
5.4.1 Injection Process Characteristics . . . . . . . . . . . . . . . . . . . 117
5.4.2 Fuel Spray Characteristics . . . . . . . . . . . . . . . . . . . . . . . 118
5.4.3 Combustion Process Characteristics . . . . . . . . . . . . . . . . . 119
5.5 Effects on Diesel Engine Characteristics . . . . . . . . . . . . . . . . . . . . 120
5.5.1 NMs Based on Silver . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.5.2 NMs Based on Aluminum . . . . . . . . . . . . . . . . . . . . . . . 123
5.5.3 NMs Based on Cerium . . . . . . . . . . . . . . . . . . . . . . . . . . 129
5.5.4 NMs Based on Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.5.5 NMs Based on Copper . . . . . . . . . . . . . . . . . . . . . . . . . . 133
5.5.6 NMs Based on Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
Contents ix

5.5.7 NMs Based on Magnesium . . . . . . . . . . . . . . . . . . . . . . . 140

5.5.8 NMs Based on Titanium . . . . . . . . . . . . . . . . . . . . . . . . 140
5.5.9 NMs Based on Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.5.10 Carbon NTs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5.5.11 NMs Based on Carbon, Graphite, and Graphene . . . . . . . 142
5.5.12 Organic NMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
5.5.13 Other NMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.5.14 Overview of Nanofuel Influence on Diesel Engine
Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.6 Identification of Best Performing Nanofuels . . . . . . . . . . . . . . . . . 146
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
6 Practical Viability of Nanofuels Usage in Diesel Engines . . . . . . . . . 159
6.1 Technical Issues and Challenges . . . . . . . . . . . . . . . . . . . . . . . . . 159
6.1.1 NMs Size and Dosage . . . . . . . . . . . . . . . . . . . . . . . . . . 160
6.1.2 Nanofuels Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6.1.3 DPF Efficiency and Durability . . . . . . . . . . . . . . . . . . . . 163
6.1.4 ECU Programming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
6.2 Environmental and Human Health Risks . . . . . . . . . . . . . . . . . . . 165
6.2.1 Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
6.2.2 Human Health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
7 Conclusions and Future Perspectives . . . . . . . . . . . . . . . . . . . . . . . . 177
Chapter 1
Introduction

Despite substantial efforts on various alternatives, the world’s transport is still almost
completely powered by internal combustion engines [12]. Among these, diesel
engines play a decisive role since they are used to power vehicles, trains, ships,
and, beyond this, also a wide range of various machineries [18]. A diesel engine
is an excellent machine with extraordinary properties. However, it also comes with
various drawbacks, and perhaps the main problems are its harmful emissions, espe-
cially nitrogen oxides (NOx ), smoke, particulate matter (PM), carbon monoxide
(CO), and unburned hydrocarbons (HC).
To address the harmful emissions’ problem while keeping engine power and effi-
ciency within acceptable limits, the following fields are being investigated intensively
[14]:
• engine management,
• after-treatment technologies, and
• usage of various alternative fuels.
Engine management is mostly related to the control of the fuel injection process.
Modern electronically controlled fuel injection systems (EC-FIS) must enable high
injection pressure capability and injection pressure control, flexible injection timing
control, and injection rate control according to the current engine operating regime
[14]. In this way, it is possible to mitigate the formation of harmful emissions to a
great extent. After-treatment technologies are used to reduce the quantity of pollutants
that enter the environment. After-treatment technologies for diesel engines comprise
diesel oxidation catalyst (DOC), lean-NOx trap (LNT), selective catalytic reduction
(SCR), diesel particulate filters (DPF), and exhaust gas recirculation (EGR) [5, 9].
DOC is usually used to reduce CO and unburned HC emissions, while LNT and
SCR technologies are used mainly to reduce NOx emission. A DPF can be used
to remove PM from diesel engine exhaust gases, while EGR can be engaged to
reduce NOx emissions and improve brake thermal efficiency [5]. Finally, engagement
of alternative fuels also offers an opportunity to achieve a reduction of harmful
emissions. A wide range of various alternative fuels, either pure or blends from

© Springer Nature Switzerland AG 2020 1

T. Kegl et al., Nanomaterials for Environmental Application, Green Energy
and Technology, https://doi.org/10.1007/978-3-030-54708-0_1
2 1 Introduction

various sources, come with rather diverse fuel properties. Therefore, alternative fuel
usage typically has to be accompanied by adequately modified engine management
and properly adapted after-treatment systems [11].
Nowadays, the most frequently investigated alternative fuel candidates for diesel
engines are biodiesels from various source materials, vegetable oils, water-in-diesel
emulsion, natural gas and liquefied petroleum gas, methane and propane, dimethyl
ether (DME) and dimethyl carbonate (DMC), Fischer–Tropsch diesel, hydrogen,
methanol, bioethanol, propanol, and butanol [2, 4, 7, 13, 14, 16, 19]. Some of those
alternative fuels can be used pure, while others have to be mixed with mineral diesel
or with other alternative fuels.
Among all alternative fuels, biodiesels, alcohols, natural gas, and DME are consid-
ered to be four of the most promising and attractive alternatives, because they may
easily be acquired, handled, and stored [8]. Among these, biodiesels look to be
especially attractive since they can be easily extracted from biomass while being
biodegradable and environmentally friendly. Furthermore, they can decrease net
CO2 emissions, air pollution, and reduce acid rain. Additional benefits include
sustainability, fuel security, regional development, and a decrease in rural poverty
[1].
Unfortunately, the usage of alternative fuels in a diesel engine may result in various
undesired consequences. Among those, increased fuel consumption, decreased
engine power, higher NOx emission, piston ring sticking, and even cold start prob-
lems are some of the more frequently reported ones [1, 14, 18]. To tackle these
disadvantages, various strategies can be applied, among which the usage of fuel
additives looks to be a particularly promising one [10]. Namely, according to labora-
tory experiments, proper engagement of adequate fuel additives may actually result
in improved engine performance and reduced exhaust emissions.
In recent years, nanomaterials (NMs) came into focus as possible novel and very
promising fuel additives for diesel engines [10, 15, 17]. A diesel engine fuel with
NMs additive can be obtained by dispersing NMs (particles, …) into a suitable base
fuel and taking measures to prevent their bonding and deposition in the fuel tank or
fuel pipes; for the sake of simplicity, such a fuel will be referred to as a NMs-enriched
fuel or simply as nanofuel throughout this book. Furthermore, a nanofuel must exhibit
uniform distribution of NMs molecules within the fuel and long-term stability of the
suspension. To prepare such a stable nanofuel without NMs agglomeration, special
treatment and addition of various surfactants might be necessary [3].
Till today, a respectable amount of investigations has already been done to
study the effects of nanofuels usage on various diesel engine characteristics. Some
researchers investigated nanofuel spray characteristics by studying spray angle, pene-
tration, and atomization. Quite some work was related to the nanofuels combustion
process, mostly based on studying in-cylinder temperature and pressure, heat release
rate, and exhaust gas temperature. Most of the work, however, was related to harmful
diesel engine emissions, effective power, brake-specific fuel consumption, and brake
thermal efficiency [3, 6].
This book aims to provide a compact and structured overview of current knowl-
edge and recent investigation results related to NMs additives engaged in various
1 Introduction 3

Fig. 1.1 Topics covered in this book and their interrelations

diesel engine base fuels. To provide a proper foundation, the most important diesel
engine characteristics as well as NMs synthesis methods and characterization tech-
niques are also presented. The topics covered in this book and their interrelations are
illustrated in Fig. 1.1.
The structure of this book is as follows: Chap. 2 describes briefly the referred
diesel engine characteristics: injection, fuel spray, and combustion characteristics,
harmful diesel emissions, fuel consumption, and engine performance and presents
the underlying base fuels used to prepare the nanofuels engaged in diesel engines.
In Chap. 3, the synthesis methods and characterization techniques of NMs for diesel
engine applications are presented; actual synthesis procedures and characterization
results of NMs used as fuel additives in diesel engines are also given. Chapter 4 deals
with nanofuels preparation and their physical and chemical properties; these prop-
erties are compared by those of corresponding base fuels. The book is focused on
the influence of various nanofuels on the injection, fuel spray, and combustion char-
acteristics, emission characteristics, and on engine performance. For this purpose,
Chap. 5 deals with experimental laboratory results obtained with diesel engines run
with NMs-enriched fuels and discusses mainly the short-term benefits of NMs fuel
additives. A practical viability evaluation of nanofuels usage in a diesel engine, by
considering technical, environmental, and human health aspects, is given in Chap. 6.
Finally, Chap. 7 gives some conclusions and future perspectives.
4 1 Introduction

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stability, engine performance and emission characteristics. Energy Convers Manag 178:146–
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19. Verhelst S, Turner JWG, Sileghem L, Vancoillie J (2019) Methanol as a fuel for internal
combustion engines. Prog Energy Combust Sci 70:43–88
Chapter 2
Diesel Engines

In recent years, the diesel engine sector has been one of the most active and inno-
vative communities of technological development in the quest to improve diesel
engine characteristics including ecology, economy, and engine performance. By
using mineral diesel and alternative fuels, various modern technologies, including
engine management and after-treatment technology, have been developed in order to
improve diesel engine characteristics [68]. Most notably, precise control of the injec-
tion process, enabled by improved mechanically controlled fuel injection systems
(MC-FIS) and, especially, by electronically controlled fuel injection systems (EC-
FIS), enables better injection and combustion processes, and consequently delivers
improved engine power, reduced fuel consumption, and reduced formation of harmful
emissions.
In general, an EC-FIS comprises a high-pressure supply pump, a common rail,
injectors, an ECU, and sensors (Fig. 2.1). The common rail pressure is controlled by
varying fuel discharge of the high-pressure supply pump by a pump control valve.
It is detected by a high-pressure sensor installed on the common rail and controlled
to the predetermined value depending on engine load and speed. The common rail
pressure is applied to the nozzle side of the injector as usually and also to the back
side of the nozzle. The injection quantity and timing are varied by controlling the
back pressure of the nozzle by means of an electromagnetically controlled solenoid
valve. The injection quantity is controlled by changing the pulse width applied to
the solenoid valve; the injection timing is controlled by changing the timing of the
pulse. When using piezoinjectors instead of injectors with solenoid valves, fuel at
high pressure is constantly delivered to the tip of the injector where a needle rests and
blocks the fuel from being injected. The greatest advantage of piezoinjectors is the
rate and precision in which fuel can be delivered, since the actuator can be rapidly
activated and deactivated. Piezoinjectors are also known for their superior reliability.
The result is increased longevity, durability, efficiency, and reduced emissions .

© Springer Nature Switzerland AG 2020 5

T. Kegl et al., Nanomaterials for Environmental Application, Green Energy
and Technology, https://doi.org/10.1007/978-3-030-54708-0_2
6 2 Diesel Engines

Fig. 2.1 Electronically controlled fuel injection system

Fig. 2.2 Exhaust gas after-treatment technologies

Among various exhaust gas after-treatment technologies, the most promising are
various combinations of (Fig. 2.2):
• diesel oxidation catalyst (DOC),
• lean NOx trap (LNT),
• selective catalytic reduction (SCR),
• diesel particulate filters (DPF), and
• exhaust gas recirculation (EGR) technologies,
which may reduce the release of harmful emissions into the environment. For illus-
tration, Fig. 2.2 shows an example assembly of after-treatment units with the corre-
sponding chemical reactions [20, 54, 108, 143]. The reduction of HC and CO emis-
sions in the DOC is followed by the reduction of PM emissions in the DPF and NOx
emissions reduction in the LNT and SCR units.
A modern DOC is a monolith honeycomb substrate, coated with a platinum metal
group catalyst and packaged into a stainless steel container [20]. The conversion
efficiency of the DOC depends on exhaust gas temperature, exhaust mass flow rate,
2 Diesel Engines 7

selected catalyst, and monolith diameter and length. A DPF consists of a metallic
honeycomb structure with a ceramic compound inside. Among various types of
DPF, the wall flow filter seems to remove the PM in the most efficient way [20]. A
LNT consists of a storage component and a precious metal supported on alumina.
The LNT works under alternative cyclic conditions of lean (excess of oxygen) and
rich (excess of fuel) conditions. Under the lean conditions, NO2 is absorbed onto
the catalyst and stored as a nitrate at the surface. Under fuel-rich conditions, this
stored nitrate in the LNT unit is released as NH3 and NO and then reduced to N2 .
NH3 formation by NOx reduction within LNT causes a discontinuous NH3 supply
to the SCR. A SCR converter consists of a honeycomb monolith, coated or extruded
with various catalysts (V/W/TiO2 , V2 O5 /WO3 /TiO2 , Fe-zeolites, Cu-zeolites …) [20,
147]. The NOx conversion efficiency of the SCR depends on the used catalyst and its
configuration (coated type, extruded type), temperature, and ammonia/nitrogen ratio
[145]. In order to reduce the NOx with minimal impact on other pollutant emissions,
the EGR technology is often used, which requires the determination of optimal
EGR rate in dependence on current engine operating regime [135]. It may be worth
noting that the presented after-treatment technologies are theoretically sufficient to
completely remove CO, HC, PM, and NOx emissions. Thus, under ideal conditions
only N2 , H2 O, and CO2 emissions would exit the exhaust system and enter the
environment.
Besides of the engine management and after-treatment technologies, various alter-
native fuels offer another opportunity to reduce harmful emissions. This, however,
is perhaps the most challenging option, due to the substantial diversity of alternative
fuel properties, especially, if we take into account the wide range of possibilities
offered by fuel additives.

2.1 Diesel Engine Process Characteristics

Diesel engine process characteristics are mainly related to [68]:

• injection,
• fuel spray, and
• combustion processes.
The most important injection process characteristics are injection timing (the
moment of injection start, given in crankshaft angle (CA) before top dead center
(TDC)), injection pressure, injection duration, and injection rate (fuel quantity
injected into the combustion chamber per unit time). Fuel spray characteristics are
related to spray tip penetration, spray cone angle, and droplet size. Both, injection
process characteristics and fuel spray development, depend strongly on the fuel prop-
erties, type of engine and fuel injection system (FIS), and on engine operating regime.
Finally, all of the mentioned characteristics and parameters, including the combus-
tion chamber geometry, influence the combustion process characteristics such as the
in-cylinder pressure, in-cylinder temperature, and heat release history.
2.3 Diesel Engine Fuels 19

[69]. By engaging oxygenated additives, the calorific value of the fuel is usually
decreased; therefore, the brake power can be reduced and specific fuel consumption
can be increased essentially. Investigation results show that oxygenated additives
can either increase or decrease NOx emission. For example, these additives may
increase the amount of fuel burned in the premixed combustion phase; this leads
to higher in-cylinder temperatures and NOx emission [42, 111, 146]. On the other
hand, the addition of oxygenated additives can increase the enthalpy of vaporization
and reduce adiabatic flame temperature of fuels, which can lead to lower in-cylinder
temperature and consequently lower NOx formation [53, 85].
Antioxidant additives, like butylated hydroxyl anisole, butylated hydroxyl
toluene, ethanox, pyrogallol, diphenylamine, tert-butylhydroxyquinone, glycerol
triacetate, and propyl gallate, can enhance the fuel stability by inhibiting or slowing
the formation of free radicals [14, 15, 76, 93]. Antioxidant additives can increase the
cetane number and flash point of the fuel and reduce its calorific value. Butylated
hydroxyl anisole and butylated hydroxyl toluene can also slightly increase the brake
thermal efficiency [116].
Cold flow improver additives, like polymethyl acrylate, ethylene vinyl acetate
copolymer, and polymaleic anhydride, are used to improve the cold flow properties
by preventing crystal growth and improving the overall crystallization behavior of
the fuel [81, 141]. Cold flow improver additives can remarkably improve the low-
temperature performance of biodiesel–diesel blends.
Lubricity improver additives consist of an active polar head group, forming a
protective film on the surface of engine-moving metal parts, and a fuel-soluble hydro-
carbon tail. They might be important to achieve normal engine operation and to
prevent reduced engine lifetime. Lubricity improver additives are fatty acid esters,
unsaturated fatty acids dimers, aliphatic amines, and long-chain monocarboxylic
acids [51].
Cetane improver additives such as nitrites, peroxides nitrates, amyl nitrates, alkyl
nitrates, di-tert-butyl peroxide, aldehydes, and tetra-azoles can increase the cetane
number of a fuel and consequently result in shorter ignition delays [51]. Among the
commercially used cetane improvers, alkyl nitrates, such as hexyl-nitrates, octyl-
nitrates, and amyl-nitrate, are the most important ones [76].
Metal-based additives such as CuCl2 , FeCl3 , and CoCl2 are combustion-
improving catalyst [60, 76]. They offer some potential to reduce harmful diesel
engine emissions and fuel consumption and to improve engine thermal efficiency
[51, 70].
In recent years, various nanomaterials, acting as diesel engine fuel additives,
gained substantial attention. According to investigation results obtained so far, these
additives look to be extremely promising. This follows from the wide range of options
they offer in influencing practically all important engine characteristics by affecting
many processes from fuel combustion to exhaust treatment [28, 53, 127].
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 O. platensis, 473;
O. segmentatus, 473
Opiliones (= Phalangidea, q.v.), 440
Opisthacanthus, 307
Opisthoparia, 244
Opisthophthalmus, 307
Opisthothelae, 386
Opopaea, 394
Orchestia, 139;
hermaphroditism, 104;
O. gammarellus, 137, 139;
habitat, 211
Orchestina, 394
Oribata, 467
Oribatidae, 457, 458, 459, 460, 462, 467;
anatomy, 459
Orithyia coccinea, 524, 540
Ornithodoros, 469;
O. megnini, 469;
O. moubata, 469;
O. talaje, 469;
O. turicata, 469
Ornithoscatoides, 374
Orometopus, 226, 245;
O. elatifrons, 230
Ortmann, on Brachyura, 181 n.;
on bipolarity, 200;
on crayfishes, 213;
on Pycnogons, 513 n.
Ostracoda, 107;
pelagic, 202
Oudemans, 528 n.
Ovary, of Cladocera, 44, 45;
of Danalia, 132;
of Spiders, 332
Oxynaspis, 88
Oxyopes, 419;
O. lineata, 419
Oxyopidae, 419
Oxyptila, 412
Oxyrhyncha, 191 f.;
habits, 192;
enemies, 192;
habitat, 198
Oxystomata, 185 f.;
respiration, 186, 187

Pachycheles, 170;
P. panamensis, distribution, 202
Pachygnatha, 407;
P. clerckii, 407;
P. degeerii, 407;
P. listeri, 407
Pachygrapsus, 196;
P. marmoratus, 193, 194, 196
Pachylasma giganteum, 91
Pachylomerus, 388
Pachysoma, 69
Pagurian, 180;
eyes of deep-sea, 149, 150
Paguridea, 171
Pagurinae, 180
Palaemon, 164;
excretory glands, 13;
fresh-water, 212;
P. serratus, 158, 164;
Bopyrus parasitic on, 133
Palaemonetes, 164;
P. antrorum, habitat, 210;
P. varians, 161;
distribution, 212
Palaemonidae, 159, 164
Palaeocaris, 115, 118
Palaeophonus, 294, 298
Palamnaeus, 307;
P. swammerdami, tarsus, 304
Palinuridae, 167
Palinurus, 165, 167;
habitat, 198, 202;
P. elephas, 167;
P. quadricornis, embryo, 165
Pallene, 505, 537;
P. attenuata, 541;
P. brevirostris, 510, 524, 537, 541, 542;
P. dimorpha, 538;
P. emaciata, 541;
P. empusa, 541;
P. grubii, 538;
P. languida, 537;
P. longiceps, 538;
P. novaezealandiae, 537;
P. producta, 542;
P. pygmaea, 537, 541;
P. spectrum, 542;
P. spinosa, 537
Pallenidae, 537
Pallenopsis, 506, 511;
P. holti, 542;
P. tritonis, 542
Palp, of Pycnogons, 507
Palpal organ, 322, 378
Palpebral lobe, 227
Palpigradi, 258, 422
Palpimanidae, 323, 325, 398
Palpimanus, 398
Panamomops diceros, 405
Pandalidae, 164
Pandalus, 164;
P. annulicornis, 164
Pandinus, 307
Panoplax, 195
Pantopoda, 501 n. (= Pycnogonida, q.v.)
Panulirus, 165, 167
Parabolina, 232, 247
Parabolinella, 247
Parabuthus, 298;
P. capensis, 298, 299
Paradoxides, 222, 232, 236, 247;
P. bohemicus, 246
Paragaleodes, 429
Paralomis, 179, 181
Paranaspides, 117;
P. lacustris, 117;
distribution, 210;
habitat, 210
Paranebalia, 242
Paranephrops, 157;
distribution, 213
Paranthura, 124
Parantipathes, Synagoga parasitic on, 94
Paranymphon, 507;
P. spinosum, 542
Parapagurus, 180
Parapallene, 537
Parapeneus, 162;
P. rectacutus, 159
Parapylocheles scorpio, eyes, 149
Parasiro, 448;
P. corsicus, 448
Parasites, in Tardigrada, 484
Parasitic castration, 100, 136
Parastacidae, 157;
distribution, 213
Parastacus, 157;
distribution, 213
Paratropidinae, 387
Paratropis scrupea, 387
Parazetes auchenicus, 533
Pardosa, 417;
female carrying young, 341;
P. amentata, 417, 418;
P. lugubris, 418
Pariboea spinipalpis, 534
Parthenogenesis, in Phyllopoda, 32;
in Cladocera, 44, 46, 49;
 in Ostracoda, 108
Parthenope, 193;
P. investigatoris, 192
Parthenopidae, 193
Pasiphaea, 163
Pasiphaeidae, 163
Pasithoe, 532;
P. umbonata, 535;
P. vesiculosa, 535, 541
Pasithoidae, 532
Patten, 270, 271, 277
Patten and Redenbaugh, on Limulus, 266, 270, 272
Paturon, 319, 320
Peckham, 376, 377, 378, 381, 382
Pecten, 328
Pectines, of Scorpions, 302, 302;
function of, 299;
of Glytoscorpius, 294
Pedicle, 317
Pedipalpi, 258, 308;
habits, 309;
external structure, 309;
legs, 309;
internal structure, 310;
alimentary canal, 310;
nervous system, 311;
classification, 312
Pedipalpi (appendages), 263, 303, 309, 321, 422, 426, 433, 440, 458
Pedunculata, 84
Pelagic Crustacea, marine, 202;
lacustrine, 207
Pelops, 467
Peltiidae, 63
Peltogaster, 95;
structure, 95;
males, 99;
castration caused by, 100;
P. curvatus, castration caused by, 100;
P. sulcatus, 95
Peltura, 247
Peneidae, 162
Peneidea, 158, 162;
metamorphosis, 159
Penella sagitta, 74
Peneus, 158, 162;
metamorphosis, 159, 159, 160, 161
Pentanymphon, 504, 537
Pentaspidae, 87
Pentastoma, 488 n.;
P. denticulatum, 489, 494;
P. emarginatum, 489;
P. serratum, 489
Pentastomida, 258, 488 f.;
structure, 489;
habitat, 488;
life-history, 488, 493;
hosts of, 496, 497
Pephredo hirsuta, 535, 541
Peracantha, 43, 53;
alimentary canal, 43
Peracarida, 114, 118
Pereiopod, defined, 110;
reduced hind, in Galatheidea, 168;
 in Hippidea, 170;
in Paguridea, 172;
in Dromiacea, 184;
in Oxystomata, 185
Periegops hirsutus, 393
Peroderma cylindricum, 75
Petrarca bathyactidis, 93
Pettalus, 448
Pezomachus gracilis, parasitic in cocoons of Spiders, 367
Phacopidae, 249
Phacopini, 243
Phacops, 223, 232, 235, 249;
P. latifrons, 227;
P. sternbergi, 248
Phaeocedus braccatus, 397
Phagocytes, in Danalia, 132
Phalangidea, 258, 440 f.;
habits, 441;
external structure, 442;
internal structure, 444;
nervous system, 446;
classification, 447;
British species, 453
Phalangiidae, 449
Phalangiinae, 450
Phalangium, 444, 450, 526;
mouth-parts, 443;
P. balaenarum, 502;
P. cornutum, 450;
P. littorale, 501;
P. opilio, 445, 446, 450, 526
Phalangodes, 449;
 P. armata, 449;
P. terricola, 449
Phalangodidae, 448
Phanodemus, 535
Phidippus, 421;
P. morsitans, 365, 421
Philichthyidae, 73
Philichthys, 73;
P. xiphiae, 73 n.
Phillipsia, 251;
P. gemmulifera, 250
Philodrominae, 413
Philodromus, 413;
P. aureolus, 413;
P. margaritatus, 413
Philoscia muscorum, 129
Pholcidae, 336, 401
Pholcus, 320, 401;
P. phalangioides, 401
Phoroncidia, 404;
P. 7–aculeata, 318
Phoroncidiinae, 317, 404
Phosphorescence, of Copepoda, 59;
relation to eyes in deep-sea Crustacea, 150, 151
Phosphorescent organs, of Euphausiidae, 145;
of Stylocheiron mastigophorum, 151
Phoxichilidae, 539
Phoxichilidiidae, 538
Phoxichilidium, 506, 512, 520, 521 n., 523, 525, 538;
P. angulatum, 520;
P. exiguum, 541;
 P. femoratum, 508, 524, 538, 540;
P. globosum, 540;
P. mollissimum, 517;
P. olivaceum, 540
Phoxichilus, 505, 512, 539;
P. australis, 539, 540;
P. böhmii, 539;
P. charybdaeus, 514, 515, 539;
P. laevis, 537, 539, 541;
P. meridionalis, 539;
P. mollis, 539;
P. proboscideus, 532;
P. procerus, 539;
P. spinosus, 505, 508, 510, 537, 539, 541, 542;
P. vulgaris, 539
Phreatoicidae, 136;
distribution, 211, 217
Phreatoicidea, 136
Phreatoicopsis, 136;
distribution, 211
Phreatoicus, 136;
distribution, 210, 211, 217;
P. assimilis, habitat, 210;
P. typicus, habitat, 210
Phronima, 140;
P. sedentaria, 140
Phrynarachne, 414;
P. decipiens, 374, 414
Phrynichinae, 313
Phrynichus, 313
Phrynidae, 309, 310, 312
Phrynopsis, 313
Phrynus, 312
Phryxidae, 130
Phyllocarida, 111, 242
Phyllocoptes, 465
Phyllopoda, 19 f.;
appendages, 24 f.;
alimentary canal, 29;
vascular system, 29;
nervous system, 30;
reproductive organs, 31;
habitat, 32;
genera, 35
Phyllosoma, larva of Palinurus, 166
Phytoptidae, 464
Phytoptus, 464 n., 495 (= Eriophyes, q.v.)
Pickard-Cambridge, F., 352
Pickard-Cambridge, O., 318, 321 n., 323 n., 359 n., 372, 374, 380,
385, 401 n., 436, 438, 450, 451, 452
Pillai, 375
Pilumnus, 191
Pinnotheres pisum, 195
Pinnotheridae, 195
Pipetta, 514, 533;
P. weberi, 533
Pirata, 417
Piriform glands, 335, 349
Pisa, 193
Pisaura mirabilis, 416
Pisauridae, 416
Placoparia, 251
Plagiostethi, 443, 447, 449, 452
Plagula, 317
Planes minutus, habitat, 202
Plankton, characters of, 203;
fresh-water, 207, 216;
Cladocera in, 50
Plastron, 316
Plate, on Tardigrada, 481, 482, 484
Plator insolens, 415
Platoridae, 415
Platyarthrus hoffmannseggii, 129
Platyaspis, 121
Platybunus, 450, 451
Platycheles, 535
Plectreurys, 393
Pleopod, defined, 110
Pleura, 234 f.
Pleurocrypta microbranchiata, 133
Pleuromma, 59;
P. abdominale, 59;
P. gracile, 59
Pliobothrus symmetricus, Pycnogon larvae in, 523
Pocock, 298, 308 n., 312, 328, 329, 425 n., 534 n.
Podasconidae, 130
Podogona, 258, 439
Podon, 54
Podophthalmata, 112
Podoplea, 61
Podosomata, 501 n. (= Pycnogonida, q.v.)
Poecilotheria, 390
Poisonous hairs, of Spiders, 365
Pollicipes, 84;
fertilisation, 86;
P. cornucopia, 85;
P. mitella, 85
Pollock, 340
Poltyinae, 410
Poltys, 410;
P. ideae, 318
Polyartemia, 36;
antennae, 26, 28;
range of, 34;
P. forcipata, 36
Polyaspidae, 84
Polycopidae, 109
Polygonopus, 539
Polyphemidae, 54;
appendages, 42;
ovary, 47;
reproduction, 49
Polyphemus, 47, 54;
P. pediculus, habitat, 206, 208
Polysphincta carbonaria, parasitic on Spiders, 368
Pompeckj, on Calymenidae, 244
Pompilus, 368
Pontellidae, 60
Pontoporeia, 137;
distribution, 212;
P. affinis, 138;
P. femorata, 138;
P. loyi, 138;
 P. microphthalma, 138
Porcellana, 168, 170;
Zoaea, 168;
P. platycheles, 170
Porcellanidae, 170;
habitat, 198
Porcellio, 129
Porcupine, 540
Porhomma, 406
Porocephalus, 488 n., 495;
P. annulatus, 490, 496;
P. aonycis, 496;
P. armillatus, 496;
P. bifurcatus, 496;
P. clavatus, 496;
P. crocidura, 496;
P. crotali, 496;
P. geckonis, 496;
P. gracilis, 496;
P. heterodontis, 496;
P. indicus, 496;
P. lari, 496;
P. megacephalus, 497;
P. megastomus, 497;
P. moniliformis, 497;
P. najae sputatricis, 497;
P. oxycephalus, 497;
P. platycephalus, 497;
P. proboscideus, 493, 494;
larvae of, 493, 494;
hosts of, 496;
P. protelis, larva, 495;
P. subuliferus, 497;
P. teretiusculus, 489, 491, 492, 492, 497;
P. tortus, 497
Portunidae, 191
Portunion, 134;
P. maenadis, 134;
life-history, 135, 136
Portunus, 191
Potamobius (= Astacus), 157;
distribution, 213
Potamocarcinus, 191;
distribution, 213
Potamon, 191
Potamonidae, 191
Praniza, larva of Gnathia, 125
Prawn, 151, 153, 158, 164, 198;
fresh-water, 212, 214
Pre-epistome, 443
Prestwichia (Euproöps), 275, 278, 279
Preyer, on anabiosis in Tardigrades, 484
Prionurus, 298, 299
Prismatic eye, of Trilobites, 229
Procurved eyes, 316
Prodidomidae, 395
Prodidomus, 396
Proëtidae, 251
Proëtus, 251;
P. bohemicus, 248
Prokoenenia, 423;
P. chilensis, 423;
P. wheeleri, 423
Prolimulus, 279
Promesosternite, in Limulus, 264
Proparia, 244
Prosalpia, 450
Prosoma, of Arachnida, 260;
of Limulus, 260, 263;
of Eurypterida, 285;
of Scorpion, 301
Prosthesima, 397
Prostigmata, 471
Protaspis, 239, 239, 240
Proteolepas, 94;
P. bivincta, 94
Protocaris, 243
Protolenus, 247
Protolimulus, 279
Protolycosa anthrocophila, 383
Przibram, on regeneration in Crustacea, 156
Psalidopodidae, 164;
habitat, 204
Psalidopus, 164
Psalistops, 389
Psechridae, 399
Psechrus, 399
Pseudalibrotus, 137
Pseudidiops, 388
Pseudocuma, 121;
distribution, 215
Pseudocumidae, 121
Pseudoniscus, 279
Pseudopallene, 511, 537;
 P. circularis, 540;
P. spinipes, 537 n.
Pseudoscorpiones, 258, 430 f.;
habits, 430;
external structure, 431, 432;
internal structure, 433;
development, 434, 435;
classification, 436;
British species, 438
Pseudo-stigmatic organs, 467
Pseudozoaea, larva of Stomatopod, 143
Pterocuma, 121
Pterolichus, 466
Pteronyssus, 466
Pterygometopus, 249
Pterygotus, 283, 291, 292;
P. osiliensis, 290
Ptychoparia, 247
Pucetia viridis, 419
Pupa, of Cirripedia, 81, 82
Purcellia, 448
Pychnogonides, 501 n.
Pycnogonida, 501 f.;
body, 505;
chelophores, 505;
palpi, 507;
ovigerous legs, 507;
glands, 511;
alimentary system, 513;
circulatory system, 516;
nervous system, 516;
eyes, 517;
 integument, 518;
reproductive organs, 519;
eggs, 520;
development, 520;
habits, 524;
systematic position, 525;
classification, 528 f.;
British species, 540 f.
Pycnogonidae, 539
Pycnogonum, 503, 539;
P. australe, 540;
P. crassirostre, 540;
P. littorale, 501, 540, 541;
P. magellanicum, 540;
P. magnirostre, 540;
P. microps, 540;
P. nodulosum, 540;
P. orientale, 540;
P. philippinense, 540;
P. pusillum, 540;
P. stearnsi, 540
Pygidium, 235
Pylocheles, 180;
P. miersii, 173
Pylochelidae, 180;
habitat, 204
Pylopagurus, 180;
relation to Lithodidae, 177, 178
Pyrgoma, 92

Rachias, 388
Railliet, on classification of Pentastomids, 495
Ranina dentata, 188
Raninidae, 188
Rastellus, 320, 387
Ratania, 68;
mouth, 63
Réaumur, 360
Recurved eyes, 316
Red spider, 455, 472
Red-water, 456
Regeneration, of Crustacean limbs, 155, 156
Regillus, 414
Reichenbach, on embryology of Astacus, 12
Reighardia, 495, 497;
hosts of, 497
Remipes, 171;
R. scutellatus, 171
Remopleurides, 232, 247;
R. radians, 229, 248
Reproduction (incl. Breeding), of Cladocera, 43 f.;
of Anaspides, 116;
of Lobster, 156;
of Limulus, 274;
of Spiders, 365; of Ticks, 461;
of Pycnogons, 520
Reproductive (generative) organs, of Crustacea, 15;
of Phyllopods, 31;
of Cladocera, 43;
of Arachnids, 257;
of Limulus, 271;
of Scorpions, 305;
of Spiders, 333;
of Solifugae, 428;
of Phalangidea, 446;
 of Acarina, 461;
of Tardigrada, 482;
of Pentastomida, 492;
of Pycnogons, 519
Respiration, of Crustacea, 16;
of Anaspides, 115;
of Albunea, 170;
of Corystes, 170, 189
of Birgus, 174;
of Oxystomata, 186, 187;
of Catometopa, 194, 195;
of Arachnids, 256.
(See also Respiratory organs.)
Respiratory organs, of Arachnids, 256;
of Limulus, 269, 270;
of Eurypterids, 288;
of Scorpions, 305;
of Spiders, 336;
of Tardigrada, 482;
of Pentastomida, 491.
(See also Respiration.)
Rhagodes, 425, 429
Rhagodinae, 429
Rhax, 429
Rhipicentor, 469
Rhipicephalus, 469;
R. sanguineus, 470
Rhizocephala, 95 f.;
compared with Monstrilla, 66;
with Anelasma, 89;
castration caused by, 100;
males, 106;
association with Entoniscidae, 136
Rhomphaea, 402