Adding nano sized materials like nanofibers, nanotubes, nanowires, nanorods and nanosheets to fluids results in producing new generation of fluids having superior properties in comparison with conventional fluids. In fact, nanoscale colloidal suspensions loaded with condensed nanomaterials are named nanofluids. This system consists of two phases: liquid phase (base fluid) and solid phase (nanoparticles). Using nanoparticles, the thermoplastic properties such as thermal diffusivity, thermal conductivity, viscosity and convective heat transfer coefficient of the fluid will be significantly enhanced. Achieving such properties need making stable nanofluids which has shown serious challenge in recent years (Yu et al., 2011, Trisaksri et al., 2007, Wang et al., 2007, Wang et al., 2008). Using nanofluids, cooling systems with higher efficiency have been designed for cars. Decreasing cooling system weight and reducing its complexity are the most important advantages of using nanofluids. In this way, compact cooling system with smaller size and weight can be designed for cars' radiator. Improving thermal conductivity of ethylene glycol-based fluids using nanomaterials has attracted much attention as engine coolant. In conventional cooling systems, a ratio of 50:50 of water and ethylene glycol is used as coolant. However, there are advantages of using ethylene glycol based nanofluids such as low pressure operation compared with mixture of water and ethylene glycol. Nanofluids based coolants have boiling point higher than conventional ones helping it reject more heat through coolant system. It has been shown that using nanofluids in cars' radiator could reduce frontal area of radiator up to 10%. In this way, nanofluids could reduce aerodynamic drag and fuel saving up to 5%. Nanofluids could also reduce friction and wear in pumps and compressors, leading to fuel saving up to 6%. These all reveal that nanofluids are suitable materials which not only could improve cars cooling system performance but also can greatly influence the structure design of cars (Wang et al., 2008, Li et al., 2009, Kakac et al., 2009, Xie et al., 2009, Yu et al., 2009, Yu et al., 2007, Kole et al., 2007, Tzeng et al., 2005).

#### *3.5.2. Heat transfer improvement using nanofluids*

26 New Advances in Vehicular Technology and Automotive Engineering

2002, Sanchez et al., 2007).

2002, Sanchez et al., 2007).

**3.5. Nanofluids and nanolubricants**

*3.5.1. Nanofluids: Properties and application in automotive industry*

**3.4. Nano-coatings with good lubrication for engine application**

It is well known that mechanical friction could significantly influence the internal combustion (IC) engine fuel economy. Valve train, piston system crank and bearing system are the most important sources of frictions (Fig. 19) (Dahotre et al., 2005, Kabacoff et al.,

These friction sources could reduce engine life and increase oil consumption. Coatings could reduce frictions and result in lower oil usage. Examples of these coatings are Ni-Mo-MoS2, Ni-BN, graphite-Ni, etc. Recently, nano-structured materials have been utilized to improve friction properties of piston rings. Zirconium ceramic coatings can modify surface properties. Nano-size zirconium powder can be dispersed in a mineral oil. The nanoparticles can reach working surface of the engine when the piston moves. The nanosize zirconium help ceramic particles better bond to the metal surface. Heat generated during engine operation would be enough to cure ceramic powder attached to the engine surface. After curing, ceramic coating produces hard and smooth surface at different parts of the engine including cylinder walls, piston rings, piston top, valve tops and bearing surfaces. The nano-size zirconium particles can also improve fuel economy, power output, oil burning and reduce noise, vibration of engine and pollution discharge (Rao et al., 1997, Wuest et al., 1997, Rastegar et al., 1997, Cole et al., 1997, Ebisawa et al., 1991, Kabacoff et al.,

Adding nano sized materials like nanofibers, nanotubes, nanowires, nanorods and nanosheets to fluids results in producing new generation of fluids having superior properties in comparison with conventional fluids. In fact, nanoscale colloidal suspensions loaded with condensed nanomaterials are named nanofluids. This system consists of two phases: liquid phase (base fluid) and solid phase (nanoparticles). Using nanoparticles, the thermoplastic properties such as thermal diffusivity, thermal conductivity, viscosity and convective heat transfer coefficient of the fluid will be significantly enhanced. Achieving such properties need making stable nanofluids which has shown serious challenge in recent

**Figure 19.** New coatings used to improve (right) engine body structure and (left) cylinders.

Maxwell's model reveals that increase in volume fraction of spherical nanoparticles results in thermal conductivity improvement of a liquid. Moreover, increase in surface area-tovolume ratio of the particles leads to an increase of the conductivity of the liquid. In addition to particles size and particles loading, the particles sphericity (defined as the ratio of the surface area of a perfect spherical particle to that of non-spherical particle at the same volume) is another parameter influencing thermal conductivity of a suspension. Hamilton and Crosser's (Yu et al., 2009, Yu et al., 2007, Kole et al., 2007, Tzeng et al., 2005) revealed that decreasing particle sphericity from 1.0 to 3.0 results in significant increase in thermal conductivity more than two times. Particle with 10 nm diameters has surface-area to volume ratio of 1000 times greater than a particle with 10 μm size. Consequently, it has been expected to enhance thermal conductivity using nanometer sized particles much greater than micrometer sized particles.

Attempts have been carried out to improve heat transfer ability of water/ethylene glycol liquids (used in a car radiator) using nanoparticles. Nano CuO and Al2O3 particles are added to these liquids. Results showed significantly enhanced thermal conductivity of the liquids using these nanometric materials. It is shown that using 4 vol% nano-CuO (30 nm diameter) can increase thermal conductivity of the ethylene glychol by 20%. The same observation was seen in case of using nano-Al2O3 particles in water. It has been found that reducing nano-CuO particles' size results in further increase in thermal conductivity of the liquid. In another research, the effects of addition of nano sized ZnO, Al2O3 and TiO2 particles (at 5 vol%) to an ethylene glycol on its thermal conductivity and viscosity was studied. The highest thermal conductivity and the lowest viscosity were observed for the liquid loaded with MgO nanoparticles. Carbon nanotube is found effective nanoparticle to enhance thermal conductivity of water and ethylene glycol. Using 1 vol% carbon nanotube can improve water/ethylene glycol mixture conductivity up to 175% (Kakac et al., 2009, Xie et al., 2009, Yu et al., 2009, Yu et al., 2007, Kole et al., 2007, Tzeng et al., 2005).

The Role of Nanotechnology in Automotive Industries 29

Automobiles powered by fuel cells are believed to have considerable market in near future and it is envisioned about 80 million fuel cell vehicles will be on the road by 2020 (Serrano et al., 2003). High efficient energy conversion, safety, high energy density, nonpolluting are the advantages of employing fuel cells as energy source for driving a car (Jacobson et al., 2005). However, high cost, low volumetric power density, low durability and cell life plus high sensitivity to purity gas stream and complex operation are disadvantage of using fuel cells. Thus, hybrid configuration of fuel cells with batteries or supercapacitors is being developed in order to supply power for peak-power demands such as acceleration and start-up and also recovering braking energy (Kötz et al., 2001). In fact, despite of comparable energy density of fuel cells (100-1000 Wh.kg-1) relative to combustion engines, they have few order of magnitude lower power densities, rendering them as steady energy source. On the other hand, supercapacitors possess high power density comparable to combustion engines (Fig. 20). Therefore, hybrid systems of fuel cells and supercapacitors or batteries are an efficient configuration for replacing the combustion engines. In general there are six types of fuel cells systems including i) alkaline fuel cells ii) polymer electrolyte membrane fuel cells (PEFCs) iii) direct methanol fuel cells (DMFC) iv) phosphoric acid fuel cells v) molten

carbonate fuel cells and vi) solid oxide fuel cells (Winter & Brodd, 2004).

**Figure 20.** Ragone plot of the energy storage domains for the various electrochemical energy conversion systems compared to an internal combustion engine and turbines and conventional

Although one can drive a car powered by some classes (PEFCs) of fuel cells, there are still some challenges associated with employing them which are mostly high cost, fuel supply/storage and life time. Generally the fuel choice is hydrogen and oxygen which finally

capacitors (Winter & Brodd, 2004).

*3.7.1. Fuel cells*

### **3.6. Lubricating oils for cars using nanoparticle additives**

Lubricants like mineral oil are used to reduce friction and wear in automobile engine. The pistons movement in cylinder of an engine produces frictions as a result of metals wear. This may lead to reduced engine efficiency as well as lowered engine life. Oils are used as lubricant to reduce friction. The conventional oils need to be exchanged after a special engine working time. In fact, the oil lubricant properties will be gradually reduced. Researches to produce better oils with longer life are developed in recent years. Nanotechnology is one of the most effective ways of fulfilling this target (Wu et al., 2007, Chinas-Castillo et al., 2003). It has been shown that nanoparticles could improve lubricant behavior of conventional oils. Particles shape, size and concentration are influential parameters affecting wear and friction reduction. It has been shown that gold particles having particle size of 20 nm has the best lubricating effects. Dialkyldithiophosphate modified copper nanoparticles is shown as an effective nanoparticle with high ability of improving anti-wear ability of metal surface by producing an anti-friction film. Diamond and inorganic fullerene-like (IF) particles are other examples of anti-wear nanoparticles being used as additives for lubrication. The most important mechanisms which result in friction reduction are colloidal effects, rolling effects, protective film and third body. Diamond nanoparticles were added to oil to improve its anti-wear ability. This nanoparticle has found to improve oil lubricant behavior via various mechanisms including: (a) ball bearing effects of the spherical particles existed between rubbing surfaces, (b) the surface polishing and (c) increasing surface hardness. Adding CuO nanoparticles to oil could significantly reduce friction coefficient. Ball bearing at high temperature and viscous effect at low temperature are the reasons CuO nanoparticles can improve anti-wear behavior of oil. The nanoparticles depositions at worn surfaces would be responsible for shear stress reduction leading to tribological properties improvement of the surface (Wu et al., 2007, Chinas-Castillo et al., 2003, Zhou et al., 1999, Rapoport et al., 1999, Chen et al., 1998).

#### **3.7. Energy criterion in cars**

To replace combustion engines, different strategies and methods have been developed. Among them, electrochemical energy production/storage is the most important option owing to sustainability and being environmentally friendly (Schlapbach & Zuttel, 2001). The so-called electrochemical energy storage and conversion systems include fuel cells, batteries and supercapacitors. Although batteries have found their way in marketplace in different applications and fuel cells and supercapacitors are competing to establish promising applications, there are still many challenges to be solved to have energy conversion/storage systems which could surpass combustion engines in terms of power/energy performance and cost (Winter & Brodd, 2004). Nanomaterials are finding great contribution to overcome these challenges (Arico et al., 2005; Serrano et al., 2009).

#### *3.7.1. Fuel cells*

28 New Advances in Vehicular Technology and Automotive Engineering

thermal conductivity of water and ethylene glycol. Using 1 vol% carbon nanotube can improve water/ethylene glycol mixture conductivity up to 175% (Kakac et al., 2009, Xie et

Lubricants like mineral oil are used to reduce friction and wear in automobile engine. The pistons movement in cylinder of an engine produces frictions as a result of metals wear. This may lead to reduced engine efficiency as well as lowered engine life. Oils are used as lubricant to reduce friction. The conventional oils need to be exchanged after a special engine working time. In fact, the oil lubricant properties will be gradually reduced. Researches to produce better oils with longer life are developed in recent years. Nanotechnology is one of the most effective ways of fulfilling this target (Wu et al., 2007, Chinas-Castillo et al., 2003). It has been shown that nanoparticles could improve lubricant behavior of conventional oils. Particles shape, size and concentration are influential parameters affecting wear and friction reduction. It has been shown that gold particles having particle size of 20 nm has the best lubricating effects. Dialkyldithiophosphate modified copper nanoparticles is shown as an effective nanoparticle with high ability of improving anti-wear ability of metal surface by producing an anti-friction film. Diamond and inorganic fullerene-like (IF) particles are other examples of anti-wear nanoparticles being used as additives for lubrication. The most important mechanisms which result in friction reduction are colloidal effects, rolling effects, protective film and third body. Diamond nanoparticles were added to oil to improve its anti-wear ability. This nanoparticle has found to improve oil lubricant behavior via various mechanisms including: (a) ball bearing effects of the spherical particles existed between rubbing surfaces, (b) the surface polishing and (c) increasing surface hardness. Adding CuO nanoparticles to oil could significantly reduce friction coefficient. Ball bearing at high temperature and viscous effect at low temperature are the reasons CuO nanoparticles can improve anti-wear behavior of oil. The nanoparticles depositions at worn surfaces would be responsible for shear stress reduction leading to tribological properties improvement of the surface (Wu et al., 2007,

Chinas-Castillo et al., 2003, Zhou et al., 1999, Rapoport et al., 1999, Chen et al., 1998).

To replace combustion engines, different strategies and methods have been developed. Among them, electrochemical energy production/storage is the most important option owing to sustainability and being environmentally friendly (Schlapbach & Zuttel, 2001). The so-called electrochemical energy storage and conversion systems include fuel cells, batteries and supercapacitors. Although batteries have found their way in marketplace in different applications and fuel cells and supercapacitors are competing to establish promising applications, there are still many challenges to be solved to have energy conversion/storage systems which could surpass combustion engines in terms of power/energy performance and cost (Winter & Brodd, 2004). Nanomaterials are finding great contribution to overcome

**3.7. Energy criterion in cars**

these challenges (Arico et al., 2005; Serrano et al., 2009).

al., 2009, Yu et al., 2009, Yu et al., 2007, Kole et al., 2007, Tzeng et al., 2005).

**3.6. Lubricating oils for cars using nanoparticle additives**

Automobiles powered by fuel cells are believed to have considerable market in near future and it is envisioned about 80 million fuel cell vehicles will be on the road by 2020 (Serrano et al., 2003). High efficient energy conversion, safety, high energy density, nonpolluting are the advantages of employing fuel cells as energy source for driving a car (Jacobson et al., 2005). However, high cost, low volumetric power density, low durability and cell life plus high sensitivity to purity gas stream and complex operation are disadvantage of using fuel cells. Thus, hybrid configuration of fuel cells with batteries or supercapacitors is being developed in order to supply power for peak-power demands such as acceleration and start-up and also recovering braking energy (Kötz et al., 2001). In fact, despite of comparable energy density of fuel cells (100-1000 Wh.kg-1) relative to combustion engines, they have few order of magnitude lower power densities, rendering them as steady energy source. On the other hand, supercapacitors possess high power density comparable to combustion engines (Fig. 20). Therefore, hybrid systems of fuel cells and supercapacitors or batteries are an efficient configuration for replacing the combustion engines. In general there are six types of fuel cells systems including i) alkaline fuel cells ii) polymer electrolyte membrane fuel cells (PEFCs) iii) direct methanol fuel cells (DMFC) iv) phosphoric acid fuel cells v) molten carbonate fuel cells and vi) solid oxide fuel cells (Winter & Brodd, 2004).

**Figure 20.** Ragone plot of the energy storage domains for the various electrochemical energy conversion systems compared to an internal combustion engine and turbines and conventional capacitors (Winter & Brodd, 2004).

Although one can drive a car powered by some classes (PEFCs) of fuel cells, there are still some challenges associated with employing them which are mostly high cost, fuel supply/storage and life time. Generally the fuel choice is hydrogen and oxygen which finally

exhaust water. Hydrogen supplication, refuelling infrastructure and storage of hydrogen are still ongoing challenges (Chan, 2007). Although hydrogen has very high gravimetric energy density, its' application hindered due to low volumetric energy density. Storing hydrogen in liquid state require employing highly expensive cryogenic tanks (Fig. 21). Compressing hydrogen gas also urges using costly storage facilities. There has been considerable research to develop new materials enabling storage of hydrogen at high enough concentration at not too high pressure and too low temperature. Initial interest was focused on metal hydrides through chemisorptions of hydrogen (Fig. 22). However, efforts were quite unsuccessful to synthesis metal alloys reaching to theoretical limit (~8wt%) unless some promising results were reported for nanosized metal (oxide) composites (Arico et al., 2005). Metal alloys such as LaNi, TiFe, MgNi are generally expensive and in all cases are heavy which makes commercialization of products dealing with mobile applications problematical.

The Role of Nanotechnology in Automotive Industries 31

materials are the sole candidates for this purpose. Carbon nanomaterials (Dillon et al., 1997) and metal organic framework (MOFs) (Ce´te et al., 2005; Zhou et al., 2007) are two dominate studied classes of materials with the goal of solid-phase storage of H2. By the advent of carbon nanotubes at early 90s (Iijima, 1991; Iijima & Ichihashi, 1993), great deal of attention was attracted to this novel nanomaterial. Dillon *et. al.* (Dillon et al., 1997) for the first time reported high capability of single-walled carbon nanotubes (SWNTs) as porous media for H2 uptake, reporting 5 to 10wt% of H2 adsorbtion at ambient conditions. Chen *et. al.* (Chen et al., 1999) later reported significant enhancement of H2 uptake (20wt%) of multi-walled carbon nanotubes (MWNTs) upon doping with alkali metals at 300K and 0.1MPa. These results were beyond the requirements that have been established by Department of Energy (DOE) of US where gravimetric density of H2 must be at least 6wt%. However, subsequent studies revealed that CNTs are not promising candidates for H2 uptake. The results indicate metal doping of CNTs can enhance the H2 uptake of nanotubes, but hardly exceeds 4wt%

Novel nano-porous materials, MOFs, have been centre of attention for gas adsorbtion. These materials are product of reaction of metals ions with rigid organic molecules (Ce´te et al., 2005). Due to exceptionally high surface area and tunable chemical structure of MOFs, high potential for high enough H2 uptake is envisioned. In September 2011, Daimler introduced a concept vehicle, Mercedes-Benz F125!, which was pictured to be derived by 2025 (http://media.daimler.com). The most interesting technology of this conceptual car is its source of energy which is hybrid of Li-S battery (See below for more details) and hydrogen fuel cell. Despite current technology used in available fuel cell vehicles, liquid or compress hydrogen, storage facility of hydrogen is based on MOFs materials in this concept vehicle. The manufacturer claims one will be able to derive up to 1000km with maximum speed of

Although interest to fabricate solid-phase hydrogen reservoir using CNTs are now quenched, emergence of the carbon-based thinnest materials, *i.e.* graphene, again revived hopes to have carbon-based hydrogen storage tanks (Park et al., 2007; Dimitrakakis et al., 2008; Burress et al., 2010). In fact, as the H2 storage mechanism in carbon nanostructures relies on physisorption on graphenic surface, the hydrogen uptake is proportional to specific surface area of nanostructure which reaches ultimate value for carbon nanostructures in graphene (2630 m2.g-1) (Dimitrakakis et al., 2008). Researches on developing high surface area graphene-based materials are ongoing and more time requires confirming whether graphene-based nanoporous materials are able to solve the mystery of the hydrogen storage

Another major issue which hinder widespread application of fuel cell vehicles, is high cost associated with manufacturing them (Fig. 23). The expensive constituents of fuel cells including the catalyst and electrolyte membrane are the origin of high cost of fuel cells (Steele & Heinzel, 2001). In addition, performance and life time of these classes of fuel cells (PEFC, DMFC) can be remarkably improved by nano-engineering of the catalyst and electrolyte membrane. In fact, the commercialization of fuel cells will very much rely on the ability to reduce the cost and improve the performance of catalyst, membrane and other

(Liu et al., 1999; Béguin & Frackowiak, 2006).

220km.h-1 before it is needed to be refilled.

or not (Subrahmanyam et al., 2011).

**Figure 21.** GM ElectroVAN, the first hydrogen fuel cell powered car introduced at 1966. The hydrogen and oxygen stored in super-cooled liquid in cryogenic tank.

**Figure 22.** Comparison of volumetric density of different systems to store hydrogen (Schlapbach & Zuttel, 2001)

In another set of research, the efforts are focused on physical entrapping of hydrogen in porous materials. Physisorption of H2 allows fast loading and unloading. Nanostructured materials are the sole candidates for this purpose. Carbon nanomaterials (Dillon et al., 1997) and metal organic framework (MOFs) (Ce´te et al., 2005; Zhou et al., 2007) are two dominate studied classes of materials with the goal of solid-phase storage of H2. By the advent of carbon nanotubes at early 90s (Iijima, 1991; Iijima & Ichihashi, 1993), great deal of attention was attracted to this novel nanomaterial. Dillon *et. al.* (Dillon et al., 1997) for the first time reported high capability of single-walled carbon nanotubes (SWNTs) as porous media for H2 uptake, reporting 5 to 10wt% of H2 adsorbtion at ambient conditions. Chen *et. al.* (Chen et al., 1999) later reported significant enhancement of H2 uptake (20wt%) of multi-walled carbon nanotubes (MWNTs) upon doping with alkali metals at 300K and 0.1MPa. These results were beyond the requirements that have been established by Department of Energy (DOE) of US where gravimetric density of H2 must be at least 6wt%. However, subsequent studies revealed that CNTs are not promising candidates for H2 uptake. The results indicate metal doping of CNTs can enhance the H2 uptake of nanotubes, but hardly exceeds 4wt% (Liu et al., 1999; Béguin & Frackowiak, 2006).

30 New Advances in Vehicular Technology and Automotive Engineering

and oxygen stored in super-cooled liquid in cryogenic tank.

Zuttel, 2001)

exhaust water. Hydrogen supplication, refuelling infrastructure and storage of hydrogen are still ongoing challenges (Chan, 2007). Although hydrogen has very high gravimetric energy density, its' application hindered due to low volumetric energy density. Storing hydrogen in liquid state require employing highly expensive cryogenic tanks (Fig. 21). Compressing hydrogen gas also urges using costly storage facilities. There has been considerable research to develop new materials enabling storage of hydrogen at high enough concentration at not too high pressure and too low temperature. Initial interest was focused on metal hydrides through chemisorptions of hydrogen (Fig. 22). However, efforts were quite unsuccessful to synthesis metal alloys reaching to theoretical limit (~8wt%) unless some promising results were reported for nanosized metal (oxide) composites (Arico et al., 2005). Metal alloys such as LaNi, TiFe, MgNi are generally expensive and in all cases are heavy which makes

commercialization of products dealing with mobile applications problematical.

**Figure 21.** GM ElectroVAN, the first hydrogen fuel cell powered car introduced at 1966. The hydrogen

**Figure 22.** Comparison of volumetric density of different systems to store hydrogen (Schlapbach &

In another set of research, the efforts are focused on physical entrapping of hydrogen in porous materials. Physisorption of H2 allows fast loading and unloading. Nanostructured Novel nano-porous materials, MOFs, have been centre of attention for gas adsorbtion. These materials are product of reaction of metals ions with rigid organic molecules (Ce´te et al., 2005). Due to exceptionally high surface area and tunable chemical structure of MOFs, high potential for high enough H2 uptake is envisioned. In September 2011, Daimler introduced a concept vehicle, Mercedes-Benz F125!, which was pictured to be derived by 2025 (http://media.daimler.com). The most interesting technology of this conceptual car is its source of energy which is hybrid of Li-S battery (See below for more details) and hydrogen fuel cell. Despite current technology used in available fuel cell vehicles, liquid or compress hydrogen, storage facility of hydrogen is based on MOFs materials in this concept vehicle. The manufacturer claims one will be able to derive up to 1000km with maximum speed of 220km.h-1 before it is needed to be refilled.

Although interest to fabricate solid-phase hydrogen reservoir using CNTs are now quenched, emergence of the carbon-based thinnest materials, *i.e.* graphene, again revived hopes to have carbon-based hydrogen storage tanks (Park et al., 2007; Dimitrakakis et al., 2008; Burress et al., 2010). In fact, as the H2 storage mechanism in carbon nanostructures relies on physisorption on graphenic surface, the hydrogen uptake is proportional to specific surface area of nanostructure which reaches ultimate value for carbon nanostructures in graphene (2630 m2.g-1) (Dimitrakakis et al., 2008). Researches on developing high surface area graphene-based materials are ongoing and more time requires confirming whether graphene-based nanoporous materials are able to solve the mystery of the hydrogen storage or not (Subrahmanyam et al., 2011).

Another major issue which hinder widespread application of fuel cell vehicles, is high cost associated with manufacturing them (Fig. 23). The expensive constituents of fuel cells including the catalyst and electrolyte membrane are the origin of high cost of fuel cells (Steele & Heinzel, 2001). In addition, performance and life time of these classes of fuel cells (PEFC, DMFC) can be remarkably improved by nano-engineering of the catalyst and electrolyte membrane. In fact, the commercialization of fuel cells will very much rely on the ability to reduce the cost and improve the performance of catalyst, membrane and other

expensive parts to launch a fuel cell powered vehicle at a competitive cost and driving capabilities (Arico et al., 2005). To reach this goal, nanotechnology plays a dominant role.

The Role of Nanotechnology in Automotive Industries 33

more active than Pt which consists of cores made of a Cu-Pt alloy and Pt-rich outer shell (Mayrhofer et al., 2009). Such structure is obtained through a controlled dealloying the hybrid nanoparticles. However, many challenges associated with using precious Pt-based catalyst still remain untouched through these strategies. For instance, General Motor's fuelcell set-up used around 80 grams of platinum as electrocatalyst to split hydrogen into electrons and protons which costs roughly 5000\$ (Tollefson, 2010). Although General Motors's officials hope to reduce the Pt loading to 30 grams in near future and less than 10 grams in the next decade, the price of catalyst would still be high considering the fact that

**Figure 24.** Basic structure of hydrogen fuel cell in which hydrogen split into electron and proton at

With the goal of achieving inexpensive catalyst for fuel cells' application, tremendous attempts have been done since 60s decade (Jasinski, 1964). Despite quite ineffective early catalysts, recent developments through nanoscale engineering of nanostructured catalysts revive the hopes to have non-precious replacement of Pt catalysts. Catalysts based on thermally annealed precursors comprising nitrogen, carbon and transition metals, especially Fe and Co (Fe (or Co)/N/C), have attracted more attention due to high activity and performance (Lefevre et al., 2009; Bashyam & Zelenay, 2006; Proietti et al., 2011). This class of catalysts consists of metal nanoparticles embedding in nanostructured nitrogen-doped graphenic carbon (Wu et al., 2011). Metal free catalysts have been also synthesized and evaluated as catalyst. Among them, carbon-based nanostructures are the most studied systems. At 2009, Dai's group (Gong et al., 2009) at Case Western University showed gas phase N-doping of CNTs would result in a metal free electrocatalyst. After that, many studies revealed promising performance of N-doped carbon nanomaterials such as SWNTs (Zhang & Dai, 2012), graphene (Qu et al., 2010), mesoporous graphitic array (Liu et al., 2010) and carbon quantum dots (Li et al., 2011), for replacing Pt-based catalysts (Gong et al., 2009; Chen et al., 2012; Wang et al., 2011). Findings in Fe (or Co)/N/C systems and N-doped carbon nanomaterials may be combined possibly through using CNTs or graphene as

anode and at cathode protons reduce oxygen exhausting water finally (Tollefson, 2010).

the Pt is so scarce.

**Figure 23.** The challenges associated with implementing hydrogen as the next generation green fuel including hydrogen source and production, storage infrastructure, fuel tank and high efficient fuel cells (Tollefson, 2010).

Principally, fuel cells (PEFCs and DMFCs) operate with a polymer electrolyte membrane which is sandwiched between cathode and anode that separate the fuel (hydrogen) from the oxidant (air or oxygen) (Fig. 24). The performance of these low-temperature fuel cells is mostly limited by oxygen reduction reaction (ORR) (Arico et al., 2005). The current generations of fuel cells are utilized platinum (Pt)-based catalyst for both the oxidization of fuel and reduction of the oxygen (Greeley et al., 2009). Several factors are motivating researchers to replaces Pt which the high cost of this precious metal (40-70 \$.g-1) is one them. In addition, this metal is so scarce (less than 0.005 p.p.m in the Earth's crust) and about 90% of the world's Pt supply comes from just two countries, South Africa and Russia (http://en.wikipedia.org/wiki/Platinum). A few approach are being actively pursued with the goal of improving the electro-catalyst activity plus lowering the overall cost. However, these efforts have dominantly followed three major strategies including: i) improving the Ptbased catalyst ii) developing new class of non-precious catalyst using other transition metals and finally iii) metal-free catalyst materials.

Today Pt-carbon catalyst which are widely used in PEFCs and DMFCs, are nanoparticles of Pt decorated on carbon support (*e.g.* carbon black) (Greeley et al., 2009). Pt nanoparticles' activity increases as the particle size decreases reaching a minimum of ~3nm (Arico et al., 2005). Rational nano-engineering of Pt alone or with other metal atoms into specific arrangement of nanostructured alloys such as core-shell nanoparticles or nanowire (Koenigsmann et al., 2011; Koenigsmann et al., 2012; Hong et al., 2012; Lim et al., 2009) is a highly effective tool to synthesis new generation of catalyst if fundamentals of governing the performance of catalyst are understood. Core-shell nanoparticles of Pt-Cu, for example, are more active than Pt which consists of cores made of a Cu-Pt alloy and Pt-rich outer shell (Mayrhofer et al., 2009). Such structure is obtained through a controlled dealloying the hybrid nanoparticles. However, many challenges associated with using precious Pt-based catalyst still remain untouched through these strategies. For instance, General Motor's fuelcell set-up used around 80 grams of platinum as electrocatalyst to split hydrogen into electrons and protons which costs roughly 5000\$ (Tollefson, 2010). Although General Motors's officials hope to reduce the Pt loading to 30 grams in near future and less than 10 grams in the next decade, the price of catalyst would still be high considering the fact that the Pt is so scarce.

32 New Advances in Vehicular Technology and Automotive Engineering

(Tollefson, 2010).

and finally iii) metal-free catalyst materials.

expensive parts to launch a fuel cell powered vehicle at a competitive cost and driving capabilities (Arico et al., 2005). To reach this goal, nanotechnology plays a dominant role.

**Figure 23.** The challenges associated with implementing hydrogen as the next generation green fuel including hydrogen source and production, storage infrastructure, fuel tank and high efficient fuel cells

Principally, fuel cells (PEFCs and DMFCs) operate with a polymer electrolyte membrane which is sandwiched between cathode and anode that separate the fuel (hydrogen) from the oxidant (air or oxygen) (Fig. 24). The performance of these low-temperature fuel cells is mostly limited by oxygen reduction reaction (ORR) (Arico et al., 2005). The current generations of fuel cells are utilized platinum (Pt)-based catalyst for both the oxidization of fuel and reduction of the oxygen (Greeley et al., 2009). Several factors are motivating researchers to replaces Pt which the high cost of this precious metal (40-70 \$.g-1) is one them. In addition, this metal is so scarce (less than 0.005 p.p.m in the Earth's crust) and about 90% of the world's Pt supply comes from just two countries, South Africa and Russia (http://en.wikipedia.org/wiki/Platinum). A few approach are being actively pursued with the goal of improving the electro-catalyst activity plus lowering the overall cost. However, these efforts have dominantly followed three major strategies including: i) improving the Ptbased catalyst ii) developing new class of non-precious catalyst using other transition metals

Today Pt-carbon catalyst which are widely used in PEFCs and DMFCs, are nanoparticles of Pt decorated on carbon support (*e.g.* carbon black) (Greeley et al., 2009). Pt nanoparticles' activity increases as the particle size decreases reaching a minimum of ~3nm (Arico et al., 2005). Rational nano-engineering of Pt alone or with other metal atoms into specific arrangement of nanostructured alloys such as core-shell nanoparticles or nanowire (Koenigsmann et al., 2011; Koenigsmann et al., 2012; Hong et al., 2012; Lim et al., 2009) is a highly effective tool to synthesis new generation of catalyst if fundamentals of governing the performance of catalyst are understood. Core-shell nanoparticles of Pt-Cu, for example, are

**Figure 24.** Basic structure of hydrogen fuel cell in which hydrogen split into electron and proton at anode and at cathode protons reduce oxygen exhausting water finally (Tollefson, 2010).

With the goal of achieving inexpensive catalyst for fuel cells' application, tremendous attempts have been done since 60s decade (Jasinski, 1964). Despite quite ineffective early catalysts, recent developments through nanoscale engineering of nanostructured catalysts revive the hopes to have non-precious replacement of Pt catalysts. Catalysts based on thermally annealed precursors comprising nitrogen, carbon and transition metals, especially Fe and Co (Fe (or Co)/N/C), have attracted more attention due to high activity and performance (Lefevre et al., 2009; Bashyam & Zelenay, 2006; Proietti et al., 2011). This class of catalysts consists of metal nanoparticles embedding in nanostructured nitrogen-doped graphenic carbon (Wu et al., 2011). Metal free catalysts have been also synthesized and evaluated as catalyst. Among them, carbon-based nanostructures are the most studied systems. At 2009, Dai's group (Gong et al., 2009) at Case Western University showed gas phase N-doping of CNTs would result in a metal free electrocatalyst. After that, many studies revealed promising performance of N-doped carbon nanomaterials such as SWNTs (Zhang & Dai, 2012), graphene (Qu et al., 2010), mesoporous graphitic array (Liu et al., 2010) and carbon quantum dots (Li et al., 2011), for replacing Pt-based catalysts (Gong et al., 2009; Chen et al., 2012; Wang et al., 2011). Findings in Fe (or Co)/N/C systems and N-doped carbon nanomaterials may be combined possibly through using CNTs or graphene as

support in Fe (or Co)/N/C catalysts instead of carbon black. However, it seems that carbon nanomaterials would have much more contribution in the next generation of catalyst in fuel cells than what they have in current Pt/C commercial catalysts. Rational design of nanostructure of the so-called upcoming catalyst would be the key issue.

The Role of Nanotechnology in Automotive Industries 35

al., 2002; Kang & Ceder, 2009). In fact, conventional Li-ion batteries equipped with cobalt oxide which are prone to catch fire due to thermal runaway, phosphates can be used to fabricate larger Li-ion batteries much more suitable for automobiles. For example, Volvo 3CC concept car, because of limitations associated with using cobalt oxide based batteries, is equipped with 3000 Li-ion cells with AA size. The safety issue can be overcome by employing phosphate-based cathode, the technology which is being commercialized by A123 Systems (co-founded by Dr. Chiang) which is collaborating with GM on a plug-in hybrid car, Chevy Volt (Fig. 26) (http://www.economist.com/sciencetechnology/tq/PrinterFriendly.cfm?story\_id=10789409).

**Figure 25.** Basic structure of a Li-ion battery in which lithium ion intercalation into anode and cathode during charge and discharge process, respectively, is employed to store electrochemical energy

Nanosizing the cathode and anode materials are now tremendously followed in different battery materials (Fig. 27). Silicon, one of the most promising anode materials, may find somewhere in market if researchers could overcome instability of this materials during charge-discharge process through the nanostructuring of this element (Armand & Tarascon, 2008). Different nanostructures of Si such as nanoparticles (Lee et al., 2010), nanowire (Chan et al., 2008), nanotube (Wu et al., 2012), hierarchical nanoporous structures (Magasinski et al., 2010) and their composites with nanocarbons (Lee et al., 2010; Cui et al., 2009), have shown to have exceptionally high capacity and stability raising hopes to have commercial

In the realm of cathode materials for Li-based batteries, sulfur boosts the capacity of Li-ion batteries with one order of magnitude higher theoretical capacitance (Peramunage & Licht, 1993). Therefore, the Li-S batteries may succeed Li-ion batteries as their energy density is extremely high plus low cost and density of sulfur (Kang et al., 2006). However, its capacity fades away during charge-discharge of the cell due to polysulfide ions (the reaction intermediates) dissolution in electrolyte causes irreversible loss of active materials diminishing the capacitance few times lower than theoretical value. At 2009, by employing

(Tarascon & Armand, 2001).

batteries with Si-based anode.

#### *3.7.2. Batteries*

Although fuel cell powered cars have been driven since more than 45 years ago (Fig. 21), the current efficiency as replacing the internal combustion engines hinders widespread use of FCV (additionally lack of hydrogen storage infrastructures and cost are real barriers) (Turner, 2004). In addition, from practical point of view, because of low power density of FCs, FC powered automobiles require an energy storage device to deliver required energy in power-peak demands. As a result, currently automakers have come to this decision to launch new versions of hybrid cars before FC cars, which has resulted to introduction of new generation of automobiles with considerably low gasoline combustion reaching to record less than one litre per 100 km (Demirdeven & Deutch, 2004). Therefore, at the heart of the upcoming automobiles, energy storage devices play a key role. Batteries are blooming in different markets and automobile industry is not an exemption. Among different classes of batteries, lithium ion batteries have higher potential for employing in the next generation of cars due to higher energy density, unless in the first generation of electric cars even leadacid batteries (for example the EV1, GM introduced 1996) and Ni-MeH (Prius, Toyota) were used (http://www.economist.com/sciencetechnology/tq/PrinterFriendly.cfm?story\_id= 10789409).

Similar to other batteries, Li-ion batteries also consist of cathode, electrolyte and anode (Fig. 25). Due to principles governing the electrochemistry of Li-ion batteries wide ranges of materials can be used in this class of devices which significantly affect the cell potential, energy density and safety of batteries (http://www.economist.com/sciencetechnology/tq/ PrinterFriendly.cfm?story\_id=10789409). Therefore, huge amount of attention has been attracted towards developing high performance Li-ion batteries from both academic communities and industrial firms. The efforts are focused on improving the capacity, safety and the charging rate. Nanoscopic materials are presumed to have great contribution in the world's \$56 billion battery market in near future (Serrano et al., 2009).

The cathode and anode materials must be able to be intercalated with Li ions having high Li hosting capacity and also high electron conduction (Tarascon & Armand, 2001). Among the various materials employed as cathode for Li-ion batteries, iron (or other metal) phosphate is a promising and safe replacing candidate for conventional cathode material, cobalt oxide (Padhi et al., 1997). This case is interesting as nanoengineering helped a lot to see marketable version of this material. In fact, due to the low electrical conductivity of FePO4, the energy charging rate is very low. Unless it is found that doping with other transition metals can enhance the material's conductivity, FePO4-based materials found their way in marketplace when Chiang's group at MIT uncovered that nanosized FePO4 particles can store and deliver energy much faster than usual size (~10 μm) due to higher surface area which facilitate intercalation of Li ions (Chung et al., 2002; Kang & Ceder, 2009). In fact, conventional Li-ion batteries equipped with cobalt oxide which are prone to catch fire due to thermal runaway, phosphates can be used to fabricate larger Li-ion batteries much more suitable for automobiles. For example, Volvo 3CC concept car, because of limitations associated with using cobalt oxide based batteries, is equipped with 3000 Li-ion cells with AA size. The safety issue can be overcome by employing phosphate-based cathode, the technology which is being commercialized by A123 Systems (co-founded by Dr. Chiang) which is collaborating with GM on a plug-in hybrid car, Chevy Volt (Fig. 26) (http://www.economist.com/sciencetechnology/tq/PrinterFriendly.cfm?story\_id=10789409).

34 New Advances in Vehicular Technology and Automotive Engineering

*3.7.2. Batteries*

10789409).

support in Fe (or Co)/N/C catalysts instead of carbon black. However, it seems that carbon nanomaterials would have much more contribution in the next generation of catalyst in fuel cells than what they have in current Pt/C commercial catalysts. Rational design of

Although fuel cell powered cars have been driven since more than 45 years ago (Fig. 21), the current efficiency as replacing the internal combustion engines hinders widespread use of FCV (additionally lack of hydrogen storage infrastructures and cost are real barriers) (Turner, 2004). In addition, from practical point of view, because of low power density of FCs, FC powered automobiles require an energy storage device to deliver required energy in power-peak demands. As a result, currently automakers have come to this decision to launch new versions of hybrid cars before FC cars, which has resulted to introduction of new generation of automobiles with considerably low gasoline combustion reaching to record less than one litre per 100 km (Demirdeven & Deutch, 2004). Therefore, at the heart of the upcoming automobiles, energy storage devices play a key role. Batteries are blooming in different markets and automobile industry is not an exemption. Among different classes of batteries, lithium ion batteries have higher potential for employing in the next generation of cars due to higher energy density, unless in the first generation of electric cars even leadacid batteries (for example the EV1, GM introduced 1996) and Ni-MeH (Prius, Toyota) were used (http://www.economist.com/sciencetechnology/tq/PrinterFriendly.cfm?story\_id=

Similar to other batteries, Li-ion batteries also consist of cathode, electrolyte and anode (Fig. 25). Due to principles governing the electrochemistry of Li-ion batteries wide ranges of materials can be used in this class of devices which significantly affect the cell potential, energy density and safety of batteries (http://www.economist.com/sciencetechnology/tq/ PrinterFriendly.cfm?story\_id=10789409). Therefore, huge amount of attention has been attracted towards developing high performance Li-ion batteries from both academic communities and industrial firms. The efforts are focused on improving the capacity, safety and the charging rate. Nanoscopic materials are presumed to have great contribution in the

The cathode and anode materials must be able to be intercalated with Li ions having high Li hosting capacity and also high electron conduction (Tarascon & Armand, 2001). Among the various materials employed as cathode for Li-ion batteries, iron (or other metal) phosphate is a promising and safe replacing candidate for conventional cathode material, cobalt oxide (Padhi et al., 1997). This case is interesting as nanoengineering helped a lot to see marketable version of this material. In fact, due to the low electrical conductivity of FePO4, the energy charging rate is very low. Unless it is found that doping with other transition metals can enhance the material's conductivity, FePO4-based materials found their way in marketplace when Chiang's group at MIT uncovered that nanosized FePO4 particles can store and deliver energy much faster than usual size (~10 μm) due to higher surface area which facilitate intercalation of Li ions (Chung et

world's \$56 billion battery market in near future (Serrano et al., 2009).

nanostructure of the so-called upcoming catalyst would be the key issue.

**Figure 25.** Basic structure of a Li-ion battery in which lithium ion intercalation into anode and cathode during charge and discharge process, respectively, is employed to store electrochemical energy (Tarascon & Armand, 2001).

Nanosizing the cathode and anode materials are now tremendously followed in different battery materials (Fig. 27). Silicon, one of the most promising anode materials, may find somewhere in market if researchers could overcome instability of this materials during charge-discharge process through the nanostructuring of this element (Armand & Tarascon, 2008). Different nanostructures of Si such as nanoparticles (Lee et al., 2010), nanowire (Chan et al., 2008), nanotube (Wu et al., 2012), hierarchical nanoporous structures (Magasinski et al., 2010) and their composites with nanocarbons (Lee et al., 2010; Cui et al., 2009), have shown to have exceptionally high capacity and stability raising hopes to have commercial batteries with Si-based anode.

In the realm of cathode materials for Li-based batteries, sulfur boosts the capacity of Li-ion batteries with one order of magnitude higher theoretical capacitance (Peramunage & Licht, 1993). Therefore, the Li-S batteries may succeed Li-ion batteries as their energy density is extremely high plus low cost and density of sulfur (Kang et al., 2006). However, its capacity fades away during charge-discharge of the cell due to polysulfide ions (the reaction intermediates) dissolution in electrolyte causes irreversible loss of active materials diminishing the capacitance few times lower than theoretical value. At 2009, by employing

an innovative technique through the nanostructuring the sulfur inside the mesoporous carbon, capacitances near the theoretical limits were attained (Ji et al., 2009). After that, different carbon nanostructures such as hollow carbon nanofibers (Zheng et al., 2011), graphene oxide (Ji et al., 2011) and pyrolzed PAN/graphene (Yin et al., 2012) were used to immobilize sulfur. This class of batteries (Li-S) would find market in automobile industries as also claimed by Daimler in its concept vehicles, Mercedes-Benz F125! having exceptional high range of 1000km (Fig. 28) (http://media.daimler.com).

The Role of Nanotechnology in Automotive Industries 37

**Figure 28.** Mercedes-Benz F125! the concept vehicle introduce by Daimler at 2011 equipped with advanced technology in energy storage including high performance Li-S batteries having power density of 350 Wh.kg-1 (energy capacity 10 kWh) and revolutionary ultra-porous MOFs technology (104 m2.g-1) making it possible to store 7.5 kg of H2 in a flexible framework. All these technologies owe a lot to

Despite of advantages of using batteries as energy storage device in hybrid cars including high energy density, challenges associated with employing batteries especially timely recharging, safety and lifetime bring the another electrochemical storage device as candidate for the same purpose, i.e. supercapacitors. Supercapacitors store energy by forming a double layer of electrolyte ions on the surface of conductive electrodes, called EDLCs (Miller & Simon, 2008). The widespread applications of supercapacitors are limited by their low energy density (1-5 Wh/kg) comparing to batteries (10-500 Wh.kg-1) and as a result high cost of energy storage. But the fact that supercapacitors can be charged and discharged in less than a minute over a million cycles motivates scientific communities to enhance energy density of supercapacitors (Simon & Gogotsi, 2008; Chmiola et al., 2006). It is envisioned at energy density of 40 Wh/kg, the supercapacitors would be an improvement over the batteries used in some hybrid vehicles. In addition, the concept of supercapacitor powered urban bus which recharge at each bus stop in a minute is another intriguing idea (Fig. 29,

At the heart of the current EDLCs, nanoporous carbon acts as electrode. To improve the energy density of supercapacitors, different nanomaterials such as MWNTs (Frackowiak et al., 2000), SWNTs (Kaempgen et al., 2009), metal oxide nanoparticles (Hu et al., 2006) and conducting polymers (Zhang et al., 2010) (two later cases are classified as pseudocapacitors), have been used but high cost of nanotubes and some metal oxide (*e.g.* RuO2) and

poor stability of pseudo-capacitors render them not enough efficient storage device.

nanoscience and technology (http://media.daimler.com).

*3.7.3. Supercapacitors*

left side).

**Figure 26.** Chery Volt, a plug-in hybrid car, was introduced by GM. The automaker is trying to use safer nanophosphate-based batteries

(http://www.economist.com/sciencetechnology/tq/PrinterFriendly.cfm?story\_id=10789409).

**Figure 27.** Nanotechnology will make batteries with higher energy density which charge faster than current Li-ion batteries (Serrano et al., 2009).

**Figure 28.** Mercedes-Benz F125! the concept vehicle introduce by Daimler at 2011 equipped with advanced technology in energy storage including high performance Li-S batteries having power density of 350 Wh.kg-1 (energy capacity 10 kWh) and revolutionary ultra-porous MOFs technology (104 m2.g-1) making it possible to store 7.5 kg of H2 in a flexible framework. All these technologies owe a lot to nanoscience and technology (http://media.daimler.com).

#### *3.7.3. Supercapacitors*

36 New Advances in Vehicular Technology and Automotive Engineering

high range of 1000km (Fig. 28) (http://media.daimler.com).

safer nanophosphate-based batteries

current Li-ion batteries (Serrano et al., 2009).

an innovative technique through the nanostructuring the sulfur inside the mesoporous carbon, capacitances near the theoretical limits were attained (Ji et al., 2009). After that, different carbon nanostructures such as hollow carbon nanofibers (Zheng et al., 2011), graphene oxide (Ji et al., 2011) and pyrolzed PAN/graphene (Yin et al., 2012) were used to immobilize sulfur. This class of batteries (Li-S) would find market in automobile industries as also claimed by Daimler in its concept vehicles, Mercedes-Benz F125! having exceptional

**Figure 26.** Chery Volt, a plug-in hybrid car, was introduced by GM. The automaker is trying to use

**Figure 27.** Nanotechnology will make batteries with higher energy density which charge faster than

(http://www.economist.com/sciencetechnology/tq/PrinterFriendly.cfm?story\_id=10789409).

Despite of advantages of using batteries as energy storage device in hybrid cars including high energy density, challenges associated with employing batteries especially timely recharging, safety and lifetime bring the another electrochemical storage device as candidate for the same purpose, i.e. supercapacitors. Supercapacitors store energy by forming a double layer of electrolyte ions on the surface of conductive electrodes, called EDLCs (Miller & Simon, 2008). The widespread applications of supercapacitors are limited by their low energy density (1-5 Wh/kg) comparing to batteries (10-500 Wh.kg-1) and as a result high cost of energy storage. But the fact that supercapacitors can be charged and discharged in less than a minute over a million cycles motivates scientific communities to enhance energy density of supercapacitors (Simon & Gogotsi, 2008; Chmiola et al., 2006). It is envisioned at energy density of 40 Wh/kg, the supercapacitors would be an improvement over the batteries used in some hybrid vehicles. In addition, the concept of supercapacitor powered urban bus which recharge at each bus stop in a minute is another intriguing idea (Fig. 29, left side).

At the heart of the current EDLCs, nanoporous carbon acts as electrode. To improve the energy density of supercapacitors, different nanomaterials such as MWNTs (Frackowiak et al., 2000), SWNTs (Kaempgen et al., 2009), metal oxide nanoparticles (Hu et al., 2006) and conducting polymers (Zhang et al., 2010) (two later cases are classified as pseudocapacitors), have been used but high cost of nanotubes and some metal oxide (*e.g.* RuO2) and poor stability of pseudo-capacitors render them not enough efficient storage device.

Emergence of graphene has revolutionized this field, as this material is the thinnest imaginable carbon allotrope (Fig. 29, right side) (Stoller et al., 2008). The graphene-based pseudo-capacitors are still in infancy stage, but initial results confirm high capacity of graphene-based EDLCs having improved energy density. At May 2011, Ruoff's group (Zhu et al., 2011) at university of Texas-Austin claimed they have developed graphene-based EDLCs through an industrial viable method having energy density of 75 Wh.kg-1 which is more than one order magnitude higher than conventional supercapacitors. It is foreseen by 2020, half of graphene's market (~ \$675 million) belongs to supercapacitors which clearly illustrate the impact of graphene-based materials on this field (http://www.bccresearch.com/report/AVM075A.html). It should be noted that hybrid systems of batteries and supercapacitors are indentified as the most effective and reliable solution for applications where lifecycle and reliability are vital including cars (http://www.grapheneenergy.net/applications.html).

The Role of Nanotechnology in Automotive Industries 39

electricity and helps industries to reduce fuel consumption. In recent years, research to find new sources of energy in automobiles are being carried out (Levitsky et al., 2010, Ong et al., 2010).

It has been found that solar cells can be used as an additional source of energy supporting some of electronic devices used in an automobile. Silica-based solar system is a conventional system for producing electricity from sunlight. However, production and large scale use of this system is complicated and costly. Therefore, attempts have been carried out to produce new solar system usable for automobile economically. In silicon based solar cells, the electron needed will be supplied by silicon after exposure to sunlight. The produced electron can be transferred to semiconductors from electrodes. In solar cells, an organic material like chlorophyll can be used as substrate. A large surface area layer based on nanoporous titanium oxide is used for the transmission to the electrodes. This system as shown in Fig. 30 consists of two glass plates each of them have a transparent electrode

As it can be seen in Fig. 30, one of the plates covered with layer of dye-sensitive titanium oxide and another one is coated with platinum as catalyst. However, in conventional siliconbased solar cells, the efficiency is low due to light reflection at the solar glass pan. The reduction is approximately 10 percent for even high efficiency solar cells. This problem has been solved in new generation of solar cells using sol-gel method. Using this technique, a coating layer is applied over the glass pans. This coating could reduce light reflection from glass pans resulting in an increase in solar cell efficiency up to 6 percent. The sol used for this purpose includes a mixture of silica balls at two different sizes. To obtain best antireflective properties from coating, mixture of particles with diameter of 10 nm and 30 nm should be used. In order to apply coating layer over the cells, the glass pans should be immersed in the tank containing nano SiO2 sol. The optimum antireflective properties can be obtained at 120 nm thickness. The sol becomes dry using gel and nanoporous layer can be obtained after hardening glass coated pans at 600-700 °C. This novel coating layer has very low refractive index (of only 1.25) resulting in light reflection at 400-2500 nm. In this way, solar transmission will be increased from 90 percent for conventional one to 95 percent for

(Levitsky et al., 2010, Ong et al., 2010).

**Figure 30.** Solar cells based on nanotechnology for modern cars.

this solar cell (Levitsky et al., 2010, Ong et al., 2010).

**Figure 29.** Left side: Sinautec's Ultracapacitor Bus, an urban bus powered by on-board supercapacitors and batteries which charged at bus stop. Right side: a conventional set-up for supercapacitors in which forming a double layer of electrolyte ions on the surface of high surface area conductive electrodes store energy (Stoller et al., 2008).

At June 2010, researchers at MIT introduced new concept of energy storage device, having both high density (comparable to Li-ion batteries) and power density (even higher than supercapacitors) (Lee et al., 2010). Again nanocarbons did excellent as electrode. The whole idea was to exchange Li ions between the surfaces of two nanostructured carbon electrode having functional groups (Jang et al., 2011). In fact, charging of Li-ion batteries is timely because Li ions must intercalate into cathode and anode which takes time. This strategy to store energy may be implemented in next generation of automobiles but further investigation are required to clarify the exact chemistry governing the device and also confirm feasibility and other issues.

#### **3.8. Nanotechnology in solar cell in automobile**

Solar cells are used to produce electricity from sunlight. This system has been gradually developed in different industries as it is an environmentally benign method of producing electricity and helps industries to reduce fuel consumption. In recent years, research to find new sources of energy in automobiles are being carried out (Levitsky et al., 2010, Ong et al., 2010).

It has been found that solar cells can be used as an additional source of energy supporting some of electronic devices used in an automobile. Silica-based solar system is a conventional system for producing electricity from sunlight. However, production and large scale use of this system is complicated and costly. Therefore, attempts have been carried out to produce new solar system usable for automobile economically. In silicon based solar cells, the electron needed will be supplied by silicon after exposure to sunlight. The produced electron can be transferred to semiconductors from electrodes. In solar cells, an organic material like chlorophyll can be used as substrate. A large surface area layer based on nanoporous titanium oxide is used for the transmission to the electrodes. This system as shown in Fig. 30 consists of two glass plates each of them have a transparent electrode (Levitsky et al., 2010, Ong et al., 2010).

**Figure 30.** Solar cells based on nanotechnology for modern cars.

38 New Advances in Vehicular Technology and Automotive Engineering

(http://www.grapheneenergy.net/applications.html).

energy (Stoller et al., 2008).

confirm feasibility and other issues.

**3.8. Nanotechnology in solar cell in automobile**

Emergence of graphene has revolutionized this field, as this material is the thinnest imaginable carbon allotrope (Fig. 29, right side) (Stoller et al., 2008). The graphene-based pseudo-capacitors are still in infancy stage, but initial results confirm high capacity of graphene-based EDLCs having improved energy density. At May 2011, Ruoff's group (Zhu et al., 2011) at university of Texas-Austin claimed they have developed graphene-based EDLCs through an industrial viable method having energy density of 75 Wh.kg-1 which is more than one order magnitude higher than conventional supercapacitors. It is foreseen by 2020, half of graphene's market (~ \$675 million) belongs to supercapacitors which clearly illustrate the impact of graphene-based materials on this field (http://www.bccresearch.com/report/AVM075A.html). It should be noted that hybrid systems of batteries and supercapacitors are indentified as the most effective and reliable solution for applications where lifecycle and reliability are vital including cars

**Figure 29.** Left side: Sinautec's Ultracapacitor Bus, an urban bus powered by on-board supercapacitors and batteries which charged at bus stop. Right side: a conventional set-up for supercapacitors in which forming a double layer of electrolyte ions on the surface of high surface area conductive electrodes store

At June 2010, researchers at MIT introduced new concept of energy storage device, having both high density (comparable to Li-ion batteries) and power density (even higher than supercapacitors) (Lee et al., 2010). Again nanocarbons did excellent as electrode. The whole idea was to exchange Li ions between the surfaces of two nanostructured carbon electrode having functional groups (Jang et al., 2011). In fact, charging of Li-ion batteries is timely because Li ions must intercalate into cathode and anode which takes time. This strategy to store energy may be implemented in next generation of automobiles but further investigation are required to clarify the exact chemistry governing the device and also

Solar cells are used to produce electricity from sunlight. This system has been gradually developed in different industries as it is an environmentally benign method of producing As it can be seen in Fig. 30, one of the plates covered with layer of dye-sensitive titanium oxide and another one is coated with platinum as catalyst. However, in conventional siliconbased solar cells, the efficiency is low due to light reflection at the solar glass pan. The reduction is approximately 10 percent for even high efficiency solar cells. This problem has been solved in new generation of solar cells using sol-gel method. Using this technique, a coating layer is applied over the glass pans. This coating could reduce light reflection from glass pans resulting in an increase in solar cell efficiency up to 6 percent. The sol used for this purpose includes a mixture of silica balls at two different sizes. To obtain best antireflective properties from coating, mixture of particles with diameter of 10 nm and 30 nm should be used. In order to apply coating layer over the cells, the glass pans should be immersed in the tank containing nano SiO2 sol. The optimum antireflective properties can be obtained at 120 nm thickness. The sol becomes dry using gel and nanoporous layer can be obtained after hardening glass coated pans at 600-700 °C. This novel coating layer has very low refractive index (of only 1.25) resulting in light reflection at 400-2500 nm. In this way, solar transmission will be increased from 90 percent for conventional one to 95 percent for this solar cell (Levitsky et al., 2010, Ong et al., 2010).

### **3.9. Nanotechnology based catalyst for reduction of exhaust emission**

Todays, environmental regulations forced car producers to reduce exhaust emission of automobiles. Using new generations of fuels can be one way achieving this target. However, at this time, technology needed for large scale production of fuel has not been developed maturely. Use of catalysts is a conventional approach reducing exhaust emission. These catalysts are made of high-grade steel housings containing catalytically active materials. These active materials are able to convert exhaust pollutants to nitrogen, steam, and carbon dioxide. Three most important polluting elements that exhaust included carbon monoxide, hydrocarbons and nitric oxides. To eliminate or reduce these pollutants emission from exhaust gas, three kinds of catalysts are needed. Nanotechnology can play an important role in converting toxic pollutants to non-toxic gases. It is well known that increasing surface area of catalyst enhance its catalytic activity. Designing catalytic materials to absorb nitric oxides from exhausted gas has become a big challenge for car manufacturers. To solve this problem, new generation of catalyst with high capability of NOx-absorbing are developed. The mechanism by which this system works is presented in Fig. 31 (Hvolbk et al., 2007, Kim et al., 2006, Nilsson et al., 2005, Zhou et al., 2010).

The Role of Nanotechnology in Automotive Industries 41

sized Au particles. The most important of them are the quantum size effects, charge transfer to or from the support or support induced strain, oxygen spill-over to or from the support, oxidation state of Au and the role of very low-coordinated Au atoms in nanoparticles. The metal nobility depends on the metal surface ability to oxidize or chemisorption of oxygen. From periodic table of elements, Au is the only metal with endothermic chemisorption energy. Because of this behavior, Au is a metal which could not bind with oxygen at all. Au is a very good catalyst for oxidation of carbon monoxide (CO) presented in exhausted gas in automobile. The activity of Au depends on particle size as the best activity can be seen at

New generation of mirrors and headlights used in cars are based on glass and polymer components with high optical quality and efficiency. Nanotechnology is employed to achieve these unique properties. To this end, ultra-reflecting thin layer (with thickness lower than 100 nm) based on aluminum oxide can be applied over the surface of mirrors or headlights. Applying ultra-thin layers over the mirrors can also help us to equip surfaces with fat, dirt water and repellent features. Using chemical vapor deposition (CVD) technique, nanometric hydrophobic and oelophobic layers can be applied over the surface of mirrors. It has been found that fluoro-organic materials are able to improve hydrophobicity and oelophobicity of the surface at thicknesses of 5-10 nm. This nanometric layer could also produce smooth surface which impurities like water drop, dirt, oil and fingerprints can be easily cleaned. This ultra-thin layer has high resistance against friction and makes it applicable at longer times. As it can be seen in Fig. 32, the layer could chemically bonded to the surface of mirror from the side consisting anchor groups. The chemical groups at other

particle sizes < 5 nm (Hvolbk et al., 2005).

side of the layer produce hydrophobic surface.

**Figure 32.** The composition of ultra-reflecting layers used on modern mirrors.

**3.10. Ultra-reflecting layer for automobile mirror**

*3.10.1. Mirrors with high optical and self-cleaning properties*

**Figure 31.** Three-way nano-structured catalyst for cleaning exhaust from pollutants (Hvolbk et al., 2005).

Recent researches revealed that Au nanoparticles having sizes lower than 5 nm are very effective catalysts. There are many different mechanisms indicating catalytic activity of nano sized Au particles. The most important of them are the quantum size effects, charge transfer to or from the support or support induced strain, oxygen spill-over to or from the support, oxidation state of Au and the role of very low-coordinated Au atoms in nanoparticles. The metal nobility depends on the metal surface ability to oxidize or chemisorption of oxygen. From periodic table of elements, Au is the only metal with endothermic chemisorption energy. Because of this behavior, Au is a metal which could not bind with oxygen at all. Au is a very good catalyst for oxidation of carbon monoxide (CO) presented in exhausted gas in automobile. The activity of Au depends on particle size as the best activity can be seen at particle sizes < 5 nm (Hvolbk et al., 2005).

#### **3.10. Ultra-reflecting layer for automobile mirror**

40 New Advances in Vehicular Technology and Automotive Engineering

et al., 2006, Nilsson et al., 2005, Zhou et al., 2010).

**3.9. Nanotechnology based catalyst for reduction of exhaust emission**

Todays, environmental regulations forced car producers to reduce exhaust emission of automobiles. Using new generations of fuels can be one way achieving this target. However, at this time, technology needed for large scale production of fuel has not been developed maturely. Use of catalysts is a conventional approach reducing exhaust emission. These catalysts are made of high-grade steel housings containing catalytically active materials. These active materials are able to convert exhaust pollutants to nitrogen, steam, and carbon dioxide. Three most important polluting elements that exhaust included carbon monoxide, hydrocarbons and nitric oxides. To eliminate or reduce these pollutants emission from exhaust gas, three kinds of catalysts are needed. Nanotechnology can play an important role in converting toxic pollutants to non-toxic gases. It is well known that increasing surface area of catalyst enhance its catalytic activity. Designing catalytic materials to absorb nitric oxides from exhausted gas has become a big challenge for car manufacturers. To solve this problem, new generation of catalyst with high capability of NOx-absorbing are developed. The mechanism by which this system works is presented in Fig. 31 (Hvolbk et al., 2007, Kim

**Figure 31.** Three-way nano-structured catalyst for cleaning exhaust from pollutants (Hvolbk et al., 2005).

Recent researches revealed that Au nanoparticles having sizes lower than 5 nm are very effective catalysts. There are many different mechanisms indicating catalytic activity of nano

#### *3.10.1. Mirrors with high optical and self-cleaning properties*

New generation of mirrors and headlights used in cars are based on glass and polymer components with high optical quality and efficiency. Nanotechnology is employed to achieve these unique properties. To this end, ultra-reflecting thin layer (with thickness lower than 100 nm) based on aluminum oxide can be applied over the surface of mirrors or headlights. Applying ultra-thin layers over the mirrors can also help us to equip surfaces with fat, dirt water and repellent features. Using chemical vapor deposition (CVD) technique, nanometric hydrophobic and oelophobic layers can be applied over the surface of mirrors. It has been found that fluoro-organic materials are able to improve hydrophobicity and oelophobicity of the surface at thicknesses of 5-10 nm. This nanometric layer could also produce smooth surface which impurities like water drop, dirt, oil and fingerprints can be easily cleaned. This ultra-thin layer has high resistance against friction and makes it applicable at longer times. As it can be seen in Fig. 32, the layer could chemically bonded to the surface of mirror from the side consisting anchor groups. The chemical groups at other side of the layer produce hydrophobic surface.

**Figure 32.** The composition of ultra-reflecting layers used on modern mirrors.

### *3.10.2. Anti-glare rear mirrors*

Nowadays, safety regulations for car drivers lead to produce rear view mirrors to obtain an appropriate view at dawn and dusk. This can be done by equipping glasses with functional layer composite with electrochromic properties. For the glasses equipped with this technology, the optical properties will be changed by applying a certain voltage which moves the charges to intermediate layer. The incoming light will be absorbed by color centers produced by ions at the electrodes. As a result, small quantity of light will be reflected (Fig. 33).

The Role of Nanotechnology in Automotive Industries 43

Nano-filter Conventional filter

be transported through filter easier with lower air pressure loss. This shows that the new

This technology is also applied for soot filters. Using nanofibers in soot filters, the emission of pollutants in passengers and utility cars will be reduced. Using nanofilters, the dirt particles could not adhere to the foam materials used at roof of car and prevent polluting it.

Mohsen Mohseni, Bahram Ramezanzadeh, Hossein Yari and Mohsen Moazzami Gudarzi

Amerio, E.; Fabbri, P.; Malucelli, G.; Messori, M.; Sangermano, M.; Taurino, R. (2008) Scratch

Arico, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J.-M. & van Schalkwijk, W. (2005). Nanostructured Materials for Advanced Energy Conversion And Storage Devices. Nat.

Bashyam, R. & Zelenay, P. (2006). A Class of Non-Precious Metal Composite Catalysts for

Armand, M. & Tarascon, J. M. (2008). Building Better Batteries. nature 451, 7179, 652-657 Banerjee, A.N. (2011) The design, fabrication, and photocatalytic, utility of nanostructured semiconductors: focus on TiO2-based nanostructures, Nanotechnology, Science and

resistance nano-silica reinforced acrylic coatings. Prog. Org. Coat. 62., 129.

filter work at lower level of energy.

**Figure 34.** Nano-filters for air cleaning in car interior.

*Amirkabir University of Technology, Iran*

**Author details**

**4. References**

Mater. 4, 5, 366-377

Applications, 4, 35-65.

Fuel Cells. nature 443, 7107, 63-66

**Figure 33.** The conventional mirrors (a) and modern anti-glare rear mirrors for cars (b).

Like charging and discharging of a car battery, the glass can get back to its original properties as the pole changes. This glass equipped by a rear sensor which could measure and control the glaring light of following vehicles. As soon as the glaring light disappears, the mirror gets back to original state.

#### **3.11. Nano-filters for air cleaning**

In addition to safety improvement and fuel consumption reduction, the enhancing comfort for customers is of importance. The air quality inside the car is an important factor affecting customers comfort. The air inside cars contains particles and gaseous pollutions which need to be filtered. Achieving this target needs equipping cars with high quality interior air filters with high efficiency of pollens, spores and industrial dusts filtration. This filter could be used at variable temperature (-40 °C to 100 °C) and humid conditions. Nanofibers are utilized to produce novel filters with superior properties compared with conventional filters (Fig. 34).

For the fibers in nanometric range size the classical fluid dynamic laws is not true anymore. Because of the lower air resistance of nanofibers compared with micron-sized fibers, air can be transported through filter easier with lower air pressure loss. This shows that the new filter work at lower level of energy.

This technology is also applied for soot filters. Using nanofibers in soot filters, the emission of pollutants in passengers and utility cars will be reduced. Using nanofilters, the dirt particles could not adhere to the foam materials used at roof of car and prevent polluting it.

**Figure 34.** Nano-filters for air cleaning in car interior.

### **Author details**

42 New Advances in Vehicular Technology and Automotive Engineering

Nowadays, safety regulations for car drivers lead to produce rear view mirrors to obtain an appropriate view at dawn and dusk. This can be done by equipping glasses with functional layer composite with electrochromic properties. For the glasses equipped with this technology, the optical properties will be changed by applying a certain voltage which moves the charges to intermediate layer. The incoming light will be absorbed by color centers produced by ions at the electrodes. As a result, small quantity of light will be

**Figure 33.** The conventional mirrors (a) and modern anti-glare rear mirrors for cars (b).

Like charging and discharging of a car battery, the glass can get back to its original properties as the pole changes. This glass equipped by a rear sensor which could measure and control the glaring light of following vehicles. As soon as the glaring light disappears,

In addition to safety improvement and fuel consumption reduction, the enhancing comfort for customers is of importance. The air quality inside the car is an important factor affecting customers comfort. The air inside cars contains particles and gaseous pollutions which need to be filtered. Achieving this target needs equipping cars with high quality interior air filters with high efficiency of pollens, spores and industrial dusts filtration. This filter could be used at variable temperature (-40 °C to 100 °C) and humid conditions. Nanofibers are utilized to produce novel filters with superior properties compared with conventional filters (Fig. 34).

For the fibers in nanometric range size the classical fluid dynamic laws is not true anymore. Because of the lower air resistance of nanofibers compared with micron-sized fibers, air can

*3.10.2. Anti-glare rear mirrors*

(a)

(b)

the mirror gets back to original state.

**3.11. Nano-filters for air cleaning**

reflected (Fig. 33).

Mohsen Mohseni, Bahram Ramezanzadeh, Hossein Yari and Mohsen Moazzami Gudarzi *Amirkabir University of Technology, Iran*

### **4. References**

Armand, M. & Tarascon, J. M. (2008). Building Better Batteries. nature 451, 7179, 652-657

Barletta, M.; Bellisario, D.; Rubino, G.; Ucciardello, N. (2010). Scratch and wear resistance of transparent topcoats on carbon laminates. Prog. Org. Coat. 67., 209.

The Role of Nanotechnology in Automotive Industries 45

Chinas-Castillo. F.; Spikes, H.A. (2003). Mechanism of action of colloidal solid dispersions,

Chmiola, J.; Yushin, G.; Gogotsi, Y.; Portet, C.; Simon, P. & Taberna, P. L. (2006). Anomalous Increase in Carbon Capacitance at Pore Size Less Than 1 Nanometer. Science 312, 5794,

Cho,S.I.; Kwon,W.J.; Choi, S.J.; Kim, P.; Park, S.A.; Kim,J.; Son, S.J.; Xiao, R.; Kim, S.-H.; & Lee, S. B. (2005) Nanotube-Based Ultrafast Electrochromic Display, Advanced Materials,

Chung, S.-Y.; Bloking, J. T. & Chiang, Y.-M. (2002). Electronically Conductive Phospho-

Cui, L.-F.; Yang, Y.; Hsu, C.-M. & Cui, Y. (2009). Carbon-Silicon Core-Shell Nanowires as High Capacity Electrode for Lithium Ion Batteries. Nano Lett. 9, 9, 3370-3374 Cole, G.S.; Bin, F. (1993) Proceed. ASM, Mater. Cong. Pittsburg, PA, October 17–21 ASM

Courter, J.L. (1997). Mar resistance of automotive clearcoat: I. Relationship to coating

Cummins, D.; Boschloo, G.; Ryan, M.; Corr, S.D.; Rap, N. & Fitzmaurice, D. (2000). Journal

Dahotre, N.B.; Nayak, S. (2005). Nanocoatings for engine application. Surface & Coatings

Das, A.; et al. (2008). Modified and unmodified multiwalled carbon nanotubes in high performance solution‐styrene‐butadiene and butadiene rubber blends. Polymer. 49., 24.,

Dastjerdi, R. & Montazer, M. (2010). A review on the application of inorganic nanostructured materials in the modification of textiles: Focus on anti-microbial properties.

Demirdeven, N. & Deutch, J. (2004). Hybrid Cars Now, Fuel Cell Cars Later. Science 305,

Dillon, A. C.; Jones, K. M.; Bekkedahl, T. A.; Kiang, C. H.; Bethune, D. S. & Heben, M. J. (1997). Storage of Hydrogen in Single-Walled Carbon Nanotubes. nature 386, 6623, 377-

Dhoke, S.K.; Khanna, A.S. (2009). Electrochemical behavior of nano-iron oxide modified

Dimitrakakis, G. K.; Tylianakis, E. & Froudakis, G. E. (2008). Pillared Graphene: A New 3-D Network Nanostructure for Enhanced Hydrogen Storage. Nano Lett. 8, 10, 3166-3170 Ebisawa, M.; Hara, T.; Hayashi, T.; Ushiko, M. (1991). Production Process of Metal Matrix

Frackowiak, E.; Metenier, K. & Bertanga, V. (2000). Supercapacitor Electrode from

Fujishima, A.; Zhang, X. & Tryk. D.A. TiO2 photocatalysis and related surface phenomena,

Garcia-Heras, M.; Jimenez-Morales, A.; Casal, B.; Galvan, J. C.; Radzki, S.; Villegas, M. A.

Olivines as Lithium Storage Electrodes. Nat Mater 1, 2, 123-128

Colloids and Surfaces B: Biointerfaces, 79 (1), August 2010, 5-18.

alkyd based waterborne coatings. Mater. Chem. Phys. 117., 550-556.

Multiwalled Carbon Nanotubes. Appl. Phys. Lett. 77, 15, 2421-2423

Composite (MMC) Engine Block. SAE Paper No.-910835.

Surface Science Report 63 (2008) 515-582.

(2004). J. Alloys Compd. 219., 219.

Trans. ASME. 125., 552–557.

International Materials Park, OH 13.

Technology. 194., 58– 67.

5276.

379

5686, 974-976

of Physical Chemistry B, 104, 2000, 11449.

mechanical properties. J. Coat. Technol. 69., 866., 57.

1760-1763

17 (2), 171-175.

Chinas-Castillo. F.; Spikes, H.A. (2003). Mechanism of action of colloidal solid dispersions, Trans. ASME. 125., 552–557.

44 New Advances in Vehicular Technology and Automotive Engineering

4.,178-185.

9386-8, Florida

5751, 1166-1170

35

93

processing. Academic Press, San Diego.

Proceedings of the IEEE 95, 4, 704-718,

paraffin. Wear. 218., 153–158.

Results. Angew. Chem. Int. Ed. 49, 47, 8902-8904

Barletta, M.; Bellisario, D.; Rubino, G.; Ucciardello, N. (2010). Scratch and wear resistance of

Bautista, Y.; Gómez , M.P.; Ribes, C.; Sanz, V. (2011). Correlation between the wear resistance and the scratch resistance for nanocomposite coatings. Prog. Org. Coat, 70.,

Béguin, F. & Frackowiak E. (2006). Nanotextured Carbons for Electrochemical Energy Storage, In: Carbon Nanomaterials, Gogotsi Y, (1st ed.), 295-319, CRC Press, 0-8493-

Bellayer, S.; Bourbigot, S.; Flambard, X.; Rochery, M.; Gilman, J.W. & Devaux, E.

Bourbigot, S.; Le Bras, M.; Flambard, X.; Rochery, M.; Devaux, E. & Lichtenhan, J.D. Polyhedral oligomeric silsesquioxanes: applications to flame retardant textiles. In: Fire retardancy of polymers: new applications of mineral fillers. Le Bras, M.; Wilkie, C.A.; Bourbigot, S.; Duquesne, S. & Jama, C. editors. p. 189-201, Royal Society of Chemistry; 2005, London:. Ce´te, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keeffe, M.; Matzger, A. J. & Yaghi, O. M. (2005). Porous, Crystalline, Covalent Organic Frameworks. Science 310,

Brinker, CJ., Scherer, GW. (1990). Sol-gel science: the physics and chemistry of sol-gel

Brooman, E.W. (2002). Modifying Organic Coatings to Provide Corrosion Resistance: Part II-

Brooman, E.W. (2002). Modifying Organic Coatings to Provide Corrosion Resistance--Part II1: Organic Additives and Conducting Polymers. Met. Finish. 100 (2002) 104. Burress, J. W.; Gadipelli, S.; Ford, J.; Simmons, J. M.; Zhou, W. & Yildirim, T. (2010). Graphene Oxide Framework Materials: Theoretical Predictions and Experimental

Chan, C. C. (2007). The State of the Art of Electric, Hybrid, and Fuel Cell Vehicles.

Chan, C. K.; Peng, H.; Liu, G.; McIlwrath, K.; Zhang, X. F.; Huggins, R. A. & Cui, Y. (2008). High-Performance Lithium Battery Anodes Using Silicon Nanowires. Nat Nano 3, 1, 31-

Chen, S; Liu, W.; Yu, L. (1998). Preparation of DDP-coated PbS nanoparticles and investigation of the antiwear ability of the prepared nanoparticles as additive in liquid

Chen, P.; Wu, X.; Lin, J. & Tan, K. L. (1999). High H2 Uptake by Alkali-Doped Carbon Nanotubes under Ambient Pressure and Moderate Temperatures. Science 285, 5424, 91-

Chen, P.; Xiao, T.-Y.; Li, H.-H.; Yang, J.-J.; Wang, Z.; Yao, H.-B. & Yu, S.-H. (2012). Nitrogen-Doped Graphene/ZnSe Nanocomposites: Hydrothermal Synthesis and Their Enhanced

Cheng, K.C.; Chen, F.R. & Kai, J.J. (2007) Electrochromic property of nano-composite

Electrochemical and Photocatalytic Activities. ACS Nano 6, 1, 712-719

Prussian Blue based thin film. Electrochimica Acta, 52, 2007, 3330–3335.

transparent topcoats on carbon laminates. Prog. Org. Coat. 67., 209.

Proceedings of the 4th AUTEX conference. Roubaix: ENSAIT; 2004. 3.

Inorganic Additives and Inhibitors. Met. Finish. 100 (2002) 42.

Gong, K.; Du, F.; Xia, Z.; Durstock, M. & Dai, L. (2009). Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction. Science 323, 5915, 760-764

The Role of Nanotechnology in Automotive Industries 47

Jasinski, R. (1964). A New Fuel Cell Cathode Catalyst. nature 201, 4925, 1212-1213

Cathode for Lithium-Sulphur Batteries. Nat Mater 8, 6, 500-506

Cells. J. Am. Chem. Soc. 133, 46, 18522-18525

AMPTIAC Newsletter. 6., 1., 37.

nature 458, 7235, 190-193

Surf. Coat. Technol. 140., 11.

Nano Lett. 12, 4, 2013-2020

Society Proceeding 21, 564-575

Advanced Materials, 18, 2006, 763–766.

Ji, L.; Rao, M.; Zheng, H.; Zhang, L.; Li, Y.; Duan, W.; Guo, J.; Cairns, E. J. & Zhang, Y. (2011). Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur

Ji, X.; Lee, K. T. & Nazar, L. F. (2009). A Highly Ordered Nanostructured Carbon-Sulphur

Kabacoff, L.T. (2002). Nanoceramic coatings exhibit much higher toughness and wear resistance than conventional coatings. Materials Science and Technology, The

Kaempgen, M.; Chan, C. K.; Ma, J.; Cui, Y. & Gruner, G. (2009). Printable Thin Film Supercapacitors Using Single-Walled Carbon Nanotubes. Nano Lett. 9, 5, 1872-1876 Kakac, S.; Pramuanjaroenkij, A. (2009) Review of convective heat transfer enhancement with nanofluids. International Journal of Heat and Mass Transfer. 52., 13-14.,3187–3196. Kang, B. & Ceder, G. (2009). Battery Materials for Ultrafast Charging and Discharging.

Kang, K.; Meng, Y. S.; Breger, J.; Grey, C. P. & Ceder, G. (2006). Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries. Science 311, 5763, 977-980 Kasten, L. S.; Grant, J. T.; Grebasch, N.; Voevodin, N.; Arnold, F. E.; Donley, M. S. (2001).

Kiliaris, P. & Papaspyrides, C.D. (2010). Polymer/layered silicate (clay) nanocomposites: An

Kim, J., et al. (2006). Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV. Surf. Sci. 600 (2006) 4622. Kimura, G. & Yamada, K. (2009). Electrochromism of poly(3,4-ethylenedioxythiophene)

Koenigsmann, C.; Santulli, A. C.; Gong, K.; Vukmirovic, M. B.; Zhou, W.-p.; Sutter, E.; Wong, S. S. & Adzic, R. R. (2011). Enhanced Electrocatalytic Performance of Processed, Ultrathin, Supported Pd-Pt Core-Shell Nanowire Catalysts for the Oxygen Reduction

Koenigsmann, C.; Sutter, E.; Chiesa, T. A.; Adzic, R. R. & Wong, S. S. (2012). Highly Enhanced Electrocatalytic Oxygen Reduction Performance Observed in Bimetallic Palladium-Based Nanowires Prepared under Ambient, Surfactant less Conditions.

Kole, M.; Dey, T. K. (2010). Thermal conductivity and viscosity of Al2O3 nanofluid based on

Kötz, R.; Müller, S.; Bärtschi, M.; Schnyder, B.; Dietrich, P.; Büchi, F. N.; Tsukada, A.; Scherer, G. G.; Rodatz, P.; Garcia, O.; Barrade, P.; Hermann, V. & Gallay, R. (2001). Supercapacitors for Peak-Power Demand in Fuel-Cell-Driven Cars. Electrochemical

Lee, S.H.; Deshpande, R.; Parilla, P.A.; Jones, K.M.; To, B.; Mahan, A.H. & Dillon, A.C. (2006) CrystallineWO3 Nanoparticles for Highly Improved Electrochromic Applications.

overview of flame retardancy, Progress in Polymer Science, 35, 902–958.

films on Au nano-brush electrode. Synthetic Metals, 159 (9-10), 914-918

Reaction. J. Am. Chem. Soc. 133, 25, 9783-9795

car engine coolant. Journal of Physics D. 43., 31., ID 315501.

Jasinski, R. (1964). A New Fuel Cell Cathode Catalyst. nature 201, 4925, 1212-1213

46 New Advances in Vehicular Technology and Automotive Engineering

morphology of coating films. Prog. Org. Coat. 40., 39.

760-764

Org. Coat. 61.,106.

http://media.daimler.com

http://en.wikipedia.org/wiki/Platinum

http://www.bccresearch.com/report/AVM075A.html

http://www.grapheneenergy.net/applications.html

Oxygen Reduction. ACS Nano 6, 3, 2410-2419

Supercapacitors. Nano Lett. 6, 12, 2690-2695

Storage Devices. Nano Lett. 11, 3785–3791

Science, 94(4), 2004, 1466-1472.

363, 6430, 603-605

Search of the Perfect Battery. The Economist. 2008.)

Gong, K.; Du, F.; Xia, Z.; Durstock, M. & Dai, L. (2009). Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction. Science 323, 5915,

Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T. P.; Hansen, H. A.; Jaramillo, T. F.; RossmeislJ; ChorkendorffI & Nerskov, J. K. (2009). Alloys of Platinum and Early

Hara, Y.; Mori, T.; Fujitani, T. (2000). Relationship between viscoelasticity and scratch

Hernandez-Padron, G.; Rojas, F.; Garcia-Garduno, M.; Canseco, M.A.; Castano, V.M. (2003). Development of hybrid materials consisting of SiO2 microparticles embedded in

http://www.economist.com/sciencetechnology/tq/PrinterFriendly.cfm?story\_id=10789409 (In

Holzapfel-Metallveredelung, Application areas of nanotechnological corrosion protection. Hong, J. W.; Kang, S. W.; Choi, B.-S.; Kim, D.; Lee, S. B. & Han, S. W. (2012). Controlled Synthesis of Pd-Pt Alloy Hollow Nanostructures with Enhanced Catalytic Activities for

Horrocks, A.R. (2011). Flame retardant challenges for textiles and fibres: New chemistry versus innovatory solutions. Polymer Degradation and Stability, 96, 2011, 377-392. Hu, C.-C.; Chang, K.-H.; Lin, M.-C. & Wu, Y.-T. (2006). Design and Tailoring of the Nanotubular Arrayed Architecture of Hydrous RuO2 for Next Generation

Huang, P.Y.; Chao, Y.C. & Liao, Y.T. (2004). Preparation of fluoroacrylate nanocopolymer by miniemulsion polymerization used in textile finishing. Journal of Applied Polymer

Hvolbk, B.; Janssens, T. V. W.; Clausen, B.S.; Falsig, H.; Christensen, C.H.; N◌ّ rskov, J.K.

Iijima, S. & Ichihashi, T. (1993). Single-Shell Carbon Nanotubes of 1-nm Diameter. nature

Jacobson, M. Z.; Colella, W. G. & Golden, D. M. (2005). Cleaning the Air and Improving

Jang, B. Z.; Liu, C.; Neff, D.; Yu, Z.; Wang, M. C.; Xiong, W. & Zhamu, A. (2011). Graphene Surface-Enabled Lithium Ion-Exchanging Cells: Next-Generation High-Power Energy

Jardret, V.; Lucas, B.N., Oliver, W. (2000). Scratch Durability of Automotive Clear Coatings: A Quantitative, Reliable and Robust Methodology. J. Coat. Technol. 72., 907., 79.

(2007). Catalytic activity of Au nanoparticles. Nanotoday. 2., 4., 14. Iijima, S. (1991). Helical Microtubules of Graphitic Carbon. nature 354, 6348, 56-58

Health with Hydrogen Fuel-Cell Vehicles. Science 308, 5730, 1901-1905

phenolic-formaldehydic resin polymer matrices. Mater Sci Eng A. 355., 338.

Transition Metals as Oxygen Reduction Electrocatalysts. Nat. Chem. 1, 7, 552-556 Groenewolt, M. (2008). Highly scratch resistant coatings for automotive applications., Prog.

Lee, J. K.; Smith, K. B.; Hayner, C. M. & Kung, H. H. (2010). Silicon Nanoparticles-Graphene Paper Composites for Li Ion Battery Anodes. Chem. Commun. 46, 12, 2025-2027

The Role of Nanotechnology in Automotive Industries 49

Mirabedini, S.M.; Sabzi, M.; Zohuriaan-Mehr, J.; Atai, M. & Behzadnasab, M. (2011). Weathering performance of the polyurethane nanocomposite coatings containing silane

Monk, P. M. S.; Mortimer, R. J. & Rosseinsky, D.R. (2007). Electrochromism and Electrochromic Devices. Cambridge University Press, ISBN:9780521822695, London. Montazer, M.; Behzadnia, A.; Pakdel, E.; Rahimi, M.K. & Bameni Moghadam, M. (2012a). Durable antibacterial and cross-linking cotton with colloidal silver nanoparticles and butane tetracarboxylic acid without yellowing, Colloids and Surfaces B: Biointerfaces,

Montazer, M.; Alimohammadi, F.; Shamei, A. & Rahimi, M.K. (2012b). synthesis of nanosilver/polypropylene plastics for antibacterial application. Current Applied Physics, In

Nilsson, A., et al. (2005). Catal. Lett. The electronic structure effect in heterogeneous

Nobel, M.L.; Picken, S.J.; Mendes, E. (2007). Waterborne nanocomposite resins for

Ong, P-L.; Euler, W. B.; Levitsky, I. A. (2010). Hybrid solar cells based on single-walled

Osborne, J. H.; Blohowiak, K. Y.; Taylor, S. R.; Hunter, C.; Bierwagen, G.; Carlson, B.;

Padhi, A. K.; Nanjundaswamy, K. S. & Goodenough, J. B. (1997). Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries. J. Electrochem. Soc.

Park, N.; Hong, S.; Kim, G. & Jhi, S.-H. (2007). Computational Study of Hydrogen Storage Characteristics of Covalent-Bonded Graphenes. J. Am. Chem. Soc. 129, 29, 8999-9003 Pawlicka, A. (2009). Development of Electrochromic Devices. Recent Patents on

Peramunage, D. & Licht, S. (1993). A Solid Sulfur Cathode for Aqueous Batteries. Science

Presting, H.; Ko¨nig, U. (2003). Future nanotechnology developments for automotive

Proietti, E.; Jaouen, F. d. r.; Lefevre, M.; Larouche, N.; Tian, J.; Herranz, J. & Dodelet, J.P. (2011). Iron-Based Cathode Catalyst with Enhanced Power Density in Polymer

Qu, L.; Liu, Y.; Baek, J.-B. & Dai, L. (2010). Nitrogen-Doped Graphene as Efficient Metal-Free Electrocatalyst for Oxygen Reduction in Fuel Cells. ACS Nano 4, 3, 1321-1326 Ramezanzadeh, B.; Mohseni, M.; Yari, H.; Sabbaghian, S. (2009). An evaluation of an automotive clear coat performance exposed to bird droppings under different testing

Ramezanzadeh, B.; Mohseni, M.; Yari, H.; Sabbaghian, S. (2010a). A study of thermal mechanical properties of an automotive coating exposed to natural and simulated bird

automotive coating applications. Progress in Organic Coatings. 58., 96–104.

carbon nanotubes/Si heterojunction. Nanotechnology. 21., 10., 105203.

treated TiO2 nanoparticles. Applied Surface Science, 257, 2011, 4196–4203.

Press, Corrected Proof, Available online 9 February 2012

Bernard, D.; Donley, M. S. (2001). Prog. Org. Coat. 41, 217.

89, 196-202.

catalysis. 100 (2005) 111.

144, 4, 1188-1194

Nanotechnology, 3, 177-181.

applications. Mater Sci Eng C. 23., 6–8., 737.

Electrolyte Membrane Fuel Cells. Nat. Commun. 2, 416

approaches. Progress in Organic Coatings, 66., 149-160

droppings. Journal thermal analysis calorimetry, 102, 13-21

261, 5124, 1029-1032

Mirabedini, S.M.; Sabzi, M.; Zohuriaan-Mehr, J.; Atai, M. & Behzadnasab, M. (2011). Weathering performance of the polyurethane nanocomposite coatings containing silane treated TiO2 nanoparticles. Applied Surface Science, 257, 2011, 4196–4203.

48 New Advances in Vehicular Technology and Automotive Engineering

electrodes. Nat. Nanotech. 5, 7, 531-537

Analysis. SAE Paper No.-930794., 129.

Chem. Int. Ed. 49, 14, 2565-2569

Mater 9, 4, 353-358

321, 5889, 651-652

3531

technologies. Energy Combust. Sci. 29., 1.,1-69.

5923, 71-74

1, 15-18

5932, 1302-1305

1127-1129

Lee, J. K.; Smith, K. B.; Hayner, C. M. & Kung, H. H. (2010). Silicon Nanoparticles-Graphene Paper Composites for Li Ion Battery Anodes. Chem. Commun. 46, 12, 2025-2027 Lee, S. W.; Yabuuchi, N.; Gallant, B. M.; Chen, S.; Kim, B.-S.; Hammond, P. T. & Shao-Horn, Y. (2010). High-power lithium batteries from functionalized carbon-nanotube

Lefevre, M.; Proietti, E.; Jaouen, F. d. r. & Dodelet, J.P. (2009). Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells. Science 324,

Levitsky, I.A. (2010). Hybrid Solar Cells Based on Carbon Nanotubes and Nanoporous

Li, Y.; Zhou, J.; Tung, S.; Schneider, E.; Xi, S. (2009). A review on development of nanofluid

Li, Y.; Zhao, Y.; Cheng, H.; Hu, Y.; Shi, G.; Dai, L. & Qu, L. (2011). Nitrogen-Doped Graphene Quantum Dots with Oxygen-Rich Functional Groups. J. Am. Chem. Soc. 134,

Lim, B.; Jiang, M.; Camargo, P. H. C.; Cho, E. C.; Tao, J.; Lu, X.; Zhu, Y. & Xia, Y. (2009). Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction. Science 324,

Lin, S.S.; Patterson, D.J. (1993). Piston-Ring Assembly Friction Modeling by Similarity

Liu, C.; Fan, Y. Y.; Liu, M.; Cong, H. T.; Cheng, H. M. & Dresselhaus, M. S. (1999). Hydrogen Storage in Single-Walled Carbon Nanotubes at Room Temperature. Science 286, 5442,

Liu, Y.Y.; Tang, J.; Wang, R.; Lu, H.; Li, L.; Kong, Y.; Qi, K. & Xin, J.H. (2007). Artificial lotus leaf structures from assembling carbon nanotubes and their applications in

Lowry, M.S.; Hubble, D.R.; Wressell, A.L.; Vratsanos, M.S.; Pepe, F.R. & Hegedus, C.R. (2008). Assessment of UV-permeability in nano-ZnO filled coatings via high throughput

Magasinski, A.; Dixon, P.; Hertzberg, B.; Kvit, A.; Ayala, J. & Yushin, G. (2010). High-Performance Lithium-Ion Anodes Using a Hierarchical Bottom-Up Approach. Nat

Mayrhofer, K. J. J.; Juhart, V.; Hartl, K.; Hanzlik, M. & Arenz, M. (2009). Adsorbate-Induced Surface Segregation for Core–Shell Nanocatalysts. Angew. Chem. Int. Ed. 48, 19, 3529-

Miller, J. R. & Simon, P. (2008). Electrochemical Capacitors for Energy Management. Science

hydrophobic textiles. Journal of Materials Chemistry, 17(11), 2007, 1071-1078. Liu, R.; Wu, D.; Feng, X. & Müllen, K. (2010). Nitrogen-Doped Ordered Mesoporous Graphitic Arrays with High Electrocatalytic Activity for Oxygen Reduction. Angew.

experimentation. Journal of Coating Technology and Research, 5 (2), 233–239. MacLean, H.L.; Lave, Lester B. (2003). Evaluating automobile fuel/propulsion system

Silicon, IEEE Nanotechnology Magazine. doi. 10.1109/MNANO.2010.938654.

preparation and characterization. Powder Technology. 196., 2., 89.

	- Ramezanzadeh, B.; Mohseni, M.; Yari H. (2010b)The role of basecoat pigmentation on the biological resistance of an automotive clear coat. Journal Coating Technology Research, DOI 10.1007/s11998-010-9254-5

The Role of Nanotechnology in Automotive Industries 51

Rapoport, L.; Feldman, Y.; Homyonfer, M.; Cohen, H.; Sloan, J.; Hutchison, J.L. (1999). Inorganic fullerene-like material as additives to lubricants: structure–function

Rashvand, M.; Ranjbar, Z. & Rastegar, S. (2011). Nano zinc oxide as a UV-stabilizer for

Rastegar, F.; Richardson, D.E. (1997). Alternative to chrome: HVOF cermet coatings for high

Sanchez, E.; Bannier, E.; Cantavella, V.; Salvador, M.D.; Klyatskina, E.; Morgiel, J.; Grzonka, J.; Boccaccini, A.R. (2007). Deposition of Al2O3-TiO2 Nanostructured Powders by Atmospheric Plasma Spraying. Journal of Thermal Spray Technology. DOI:

Sangermano, M.; Messori, M. (2010). Scratch Resistance Enhancement of Polymer Coatings.

Schlapbach, L. & Zuttel, A. (2001). Hydrogen-Storage Materials for Mobile Applications.

Schulz, U.; V. Wachtendorf, T. Klimmasch, P. Alers. "The influence of weathering on scratches and on scratch and mar resistance of automotive coatings" Prog. Org. Coat, 42

Serrano, A. K.; Jackson, C. L. & Scott, K. (2003). The Promise of Fuel Cell-Based

Serrano, E.; Rus, G. & Garcea-Martenez, J. (2009). Nanotechnology for Sustainable Energy.

Shchukin, D.G.; Mçhwald, H. (2007). Self-Repairing Coatings Containing Active

Sheffer, M.; Groysman, A.; Starosvetsky, D.; Savchenko, N.; Mandler Mandler, D. (2004).

Shen, W.; Jiang, B.; Scholten, A.; Schwenke, R.; Mi, L.; Seal, C.; Wang, P. (2004). A Quantitative Index for Mar and Scratch Resistance of Materials for Automotive Glazing Applications and Quantitative Evaluation of Damages by Different Scratching Modes.

Simon, P. & Gogotsi, Y. (2008). Materials for Electrochemical Capacitors. Nat. Mater. 7, 11,

Steele, B. C. H. & Heinzel, A. (2001). Materials for Fuel-Cell Technologies. nature 414, 6861,

Stoller, M. D.; Park, S.; Yanwu, Z.; An, J. & Ruoff, R. S. (2008). Graphene-Based

Subrahmanyam, K. S.; Kumar, P.; Maitra, U.; Govindaraj, A.; Hembram, K. P. S. S.; Waghmare, U. V. & Rao, C. N. R. (2011). Chemical Storage of Hydrogen in Few-Layer

Graphene. Proceedings of the National Academy of Sciences 108, 7, 2674-2677 Tahmassebi, N.; Moradian, S.;, Ramezanzadeh, B.; Khosravi, A.; Behdad, S. (2010) Effect of addition of hydrophobic nano silica on viscoelastic properties and scratch resistance of

an acrylic/melamine automotive clearcoat. Tribo Intern. 43., 685.

aromatic polyurethane coatings. Progress in Organic Coating, 71, 362–368.

horse power diesel engines, Surf. Coat. Technol. 90., 1–2., 156-163.

relationship. Wear. 225–229., 975–982.

10.1007/s11666-008-9181-5.

nature 414, 6861, 353-358

Corros. Sci. 46., 2975.

Tribogy Letters. 17., 3., 637-644.

(2001) 38.

845-854

345-352

Macromol. Mater. Eng. 295., 603.

Automobiles. Bull. Mater. Sci. 26, 2, 207-214

Nanoreservoirs, DOI: 10.1002/smll.200700064.

Ultracapacitors. Nano Lett. 8, 10, 3498-3502

Renewable and Sustainable Energy Reviews 13, 9, 2373-2384

Rapoport, L.; Feldman, Y.; Homyonfer, M.; Cohen, H.; Sloan, J.; Hutchison, J.L. (1999). Inorganic fullerene-like material as additives to lubricants: structure–function relationship. Wear. 225–229., 975–982.

50 New Advances in Vehicular Technology and Automotive Engineering

Journal of Polymers and the Environment, 18 (4) , 545-55

Journal of Coatings Technology Research 8 (3) , 375-387

acrylic/melamine clearcoat. Prog. Org. Coat. 72., 4., 621-631.

clearcoat "J. Coat. Technol. Res. DOI 10.1007/s11998-010-9239-4.

DOI 10.1007/s11998-010-9254-5

doi:10.1016/j.triboint.2011.10.016.

Sci, DOI 10.1007/s10853-011-5819-7.

Adhesives, 31 (7) , 775-783

89

Ramezanzadeh, B.; Mohseni, M.; Yari H. (2010b)The role of basecoat pigmentation on the biological resistance of an automotive clear coat. Journal Coating Technology Research,

Ramezanzadeh, B.; Mohseni, M.; Yari, H. (2010c). The Effect of Natural Tree Gum and Environmental Condition on the Degradation of a Typical Automotive Clear Coat.

Ramezanzadeh, B.; Moradian, S.; Khosravi, A.; Tahmassebi, N. (2010d). Effect of polysiloxane additives on the scratch resistance of an acrylic melamine automotive

Ramezanzadeh, B. & Attar, M.M. (2011a) Characterization of the fracture behavior and viscoelastic properties of epoxy-polyamide coating reinforced with nanometer and

Ramezanzadeh, B.; Mohseni, M.; Yari H. (2011c). Studying the effects of the chemical structure of an automotive clearcoat on its biological degradation caused by tree gums.

Ramezanzadeh, B.; Moradian, S.; Tahmasebi, N.; Khosravi, A. (2011d). Studying the role of polysiloxane additives and nano-SiO2 on the mechanical properties of a typical

Ramezanzadeh, B.; Moradian, S.; Khosravi, A.; Tahmasebi, N. (2011e). A new approach to investigate scratch morphology and appearance of an automotive coating containing

Ramezanzadeh. B.; Moradian, S.; Yari, H.; Kashani, A.; Niknahad, M. (2011f). The effect of basecoat pigmentation on the scratch resistance and weathering performance of an acrylic–melamine basecoat/clearcoat automotive finish.Tribology International.

Ramezanzadeh, B. Mohseni;, M.; Karbasi, A. (2011g). Preparation of sol–gel-based nanostructured hybrid coatings; part 1: morphological and mechanical studies. J Mater

Ramezanzadeh, B.; Moradian, S.; Yari, H.; Kashani, A. & Niknahad, M. (2012a). The effect of basecoat pigmentation on the scratch resistance and weathering performance of an acrylicmelamine basecoat/clearcoat automotive finish. Tribology International, 47 , 77-

Ramezanzadeh, B.; Mohseni, M.; Mohammad Rabea, A. & Yari, H. (2012b) . Attributing the resistance against simulated tree gum of an acrylic/melamine film loaded with an active silicone additive to its surface free energy. International Journal of Adhesion and

Rao, V.D.N.; Kabat, D.M.; Rose, R.; Yeager, D.; Leong, D.Y. (1997). Material Systems for Cylinder Bore Applications—Plasma Spray Technology. SAE Paper No.-970023.

micrometer sized ZnO particles. Progress in Organic Coatings, 71, 3, 242–249 Ramezanzadeh, B.; Mohseni, M.; Yari H. (2011b). On the electrochemical and structural behavior of biologically degraded automotive coatings; Part 1: Effect of natural and

simulated bird droppings. Progress in Organic Coatings 71 (1) , 19-31.

nano-SiO2 and polysiloxane additives. Prog. Org. Coat. 72., 3., 541-552.

Tarascon, J. M. & Armand, M. (2001). Issues and Challenges Facing Rechargeable Lithium Batteries. nature 414, 6861, 359-367

The Role of Nanotechnology in Automotive Industries 53

Yari, H.; Moradian, S.; Ramezanzadeh, B.; Kashani, A.; Tahmasebi, N. (2009a). The effect of basecoat pigmentation on mechanical properties of an automotive basecoat/clear coat

Yari, H.; Mohseni, M.; Ramezanzadeh, B. (2009b). Comparisons of Weathering Performance of Two Automotive Refinish Coatings: A Case Study. Journal Applied Polymer Science,

Yari, H.; Mohseni, M.; Ramazanzade, B.; Naderi, N. (2009c). Use of analytical techniques to reveal the influence of chemical structure of clear coat on its biological degradation

Yari, H.; Mohseni, M.; Ramazanzade, B. (2011). A mechanistic study of degradation of a typical automotive clear coat caused by bird droppings. Journal of coatings and

Yari, H.; Moradian, S.; Tahmasebi, N. & Arefmanesh, M. (2012a). The Effect of Weathering on Tribological Properties of an Acrylic Melamine Automotive Nanocomposite,

Yari, H.; Mohseni, M.; Ramezanzadeh, B. & Mohammad Rabea, A. (2012b). Investigating the degradation resistance of silicone-acrylate containing automotive clearcoats exposed to

Yahyaei, H.; Mohseni, M.; Bastani, S. (2011). Using Taguchi experimental design to reveal the impact of parameters affecting the abrasion resistance of sol–gel based UV curable

Yeo, S.Y.; Lee, H.J. & Jeong, S.H. (2003). Preparation of nanocomposite fibers for permanent

Yin, L.; Wang, J.; Lin, F.; Yang, J. & Nuli, Y. (2012). Polyacrylonitrile/Graphene Composite as a Precursor to a Sulfur-Based Cathode Material for High-Rate Rechargeable Li-S

Yoshino T.; Kobayashi, K.; Araki, S.; Nakamura K. & Kobayashi, N. (2012). Electrochromic properties of electrochemically fabricated nanostructure nickel oxide and manganese

Yu, M., Gu, G.; Meng, W.D.& Qing, F.L. (2007). Superhydrophobic cotton fabric coating based on a complex layer of silica nanoparticles and perfluorooctylated quaterny

Yu, W.; Xie, H.; Chen, L.; Li, Y. (2009). Investigation of thermal conductivity and viscosity of

Yu, W.; Xie, H. (2011). A Review on Nanofluids: Preparation, Stability Mechanisms, and

Yuranova, T. , Rincon, A.G.; Pulgarin, C.; Laub, D.; Xantopoulos, N.; Mathieu, H. J.& Kiwi, J. (2006). Performance and characterization of Ag-cotton and Ag/TiO2 loaded textiles during the abatement of E-coli. Journal of Photochemistry and Photobiology a-

ethylene glycol based ZnO nanofluid. Thermochimica Acta. 491., 1-2., 92.

Applications, Journal of Nanomaterials. doi:10.1155/2012/435873.

ammonium silane coupling agent. Applied surface science, 253, 2007, 3669-3673. Yu, W.; France, D. M.; Choi, S. U. S.; Routbort, J. L. (2007). Review and assessment of nanofluid technology for transportation and other applications. Tech. Rep. 78,

system during weathering. Polymer Degradation Stability, 94., 1281-1289

caused by bird-droppings. Progress in Organic Coatings, 66., 281-290

bird droppings. Progress in Organic Coatings, Accepted for publication

nanocomposite films on polycarbonate. J Sol-Gel Sci Technol. 59., 95.

Batteries. Energy & Environmental Science 5, DOI: 10.1039/c2ee03495f

antibacterial effect. Journal of Materials Science, 38(10), 2143-2147.

oxide films. Solar Energy Materials & Solar Cells, 99, 43–49.

ANL/ESD/07-9, Argonne National Laboratory.

Chemistry, 181(2-3), 363-369.

technology Research, DOI 10.1007/s11998-010-9273-2

Vol 111, Issue 6., 2946-2956

Tribology Letters, 46:123–130.

Yari, H.; Moradian, S.; Ramezanzadeh, B.; Kashani, A.; Tahmasebi, N. (2009a). The effect of basecoat pigmentation on mechanical properties of an automotive basecoat/clear coat system during weathering. Polymer Degradation Stability, 94., 1281-1289

52 New Advances in Vehicular Technology and Automotive Engineering

Batteries. nature 414, 6861, 359-367

6209

443-447

online publication

Paper No.-970016.

Physics Letters Section A. 373., 21., 1861.

diamond nanoparticles. Journal of Physics D. 42., 9.

Rev. 104, 10, 4245-4270

Tarascon, J. M. & Armand, M. (2001). Issues and Challenges Facing Rechargeable Lithium

Thorstenson, T.A.; Huang, J.B.; Urban, M.W. (1994). Mobility and distribution of silicone

Trisaksri, V.; Wongwises, S. (2007). Critical review of heat transfer characteristics of

Tzeng, S. C.; Lin, C. W.; Huang, K. D. (2005). Heat transfer enhancement of nanofluids in rotary blade coupling of fourwheel- drive vehicles. Acta Mechanica. 179., 1-2., 11.

Venkataraman, R.; Sundararajan, G. (1996). The sliding wear behaviour of Al·SiC particulate

Wang, X. Q.; Mujumdar, A. S. (2007). Heat transfer characteristics of nanofluids: a review.

Wang, X. Q.; Mujumdar, A. S. (2008). A review on nanofluids—part I: theoretical and numerical investigations. Brazilian Journal of Chemical Engineering. 25., 4., 613. Wang, S.; Yu, D.; Dai, L.; Chang, D. W. & Baek, J.-B. (2011). Polyelectrolyte-Functionalized Graphene as Metal-Free Electrocatalysts for Oxygen Reduction. ACS Nano 5, 8, 6202-

Wang, X.; Ding, B.; Yu, J. & Wang, M. (2011). Engineering biomimetic superhydrophobic

Winter, M. & Brodd, R. J. (2004). What Are Batteries, Fuel Cells, and Supercapacitors? Chem.

Wu, Y.Y.; Tsui, W.C.; Liu, T.C. (2007). Experimental analysis of tribological properties of

Wu, G.; More, K. L.; Johnston, C. M. & Zelenay, P. (2011). High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt. Science 332, 6028,

Wu, H.; Chan, G.; Choi, J. W.; Ryu, I.; Yao, Y.; McDowell, M. T.; Lee, S. W.; Jackson, A.; Yang, Y.; Hu, L. & Cui, Y. (2012). Stable Cycling Of Double-Walled Silicon Nanotube Battery Anodes through Solid-Electrolyte Interphase Control. Nat. Nanotech. advance

Wuest, G.; Barbetaz, G.; Keller, S. (1997). The Key Advantages of the Plasma-Powder Spray Process for the Thermal Spray Coating of Cylinder Bores in Automotive Industry. SAE

Xu, J,; Pang, W.; Shi, W. (2006). Synthesis of UV-curable organic–inorganic hybrid urethane

Xie, H.; Chen, L. (2009). Adjustable thermal conductivity in carbon nanotube nanofluids.

Xie, H.; Yu, W.; Li, Y. (2009). Thermal performance enhancement in nanofluids containing

additives in coatings; a spectroscopic study. Prog. Org. Coat. 24., 1994., 341.

Tollefson, J. (2010). Hydrogen: Fuel of the Future? nature 464, 1262-1264

composites—I. Macrobehaviour. Acta Mater. 40., 2., 451-460. Vreugdenhil, A. J.; Woods, M. E. (2005). Prog. Org. Coat. 53., 119.

surfaces of electrospun nanomaterials. Nano Today, 6, 510-.

lubricating oils with nanoparticle additives. Wear. 262., 819–825.

acrylates and properties of cured films. Thin Solid Films. 514., 69.

International Journal of Thermal Sciences. 46., 1., 1.

nanofluids. Renewable and Sustainable Energy Reviews. 11., 3., 512.

Turner, J. A. (2004). Sustainable Hydrogen Production. Science 305, 5686, 972-974

Zhang, K.; Zhang, L. L.; Zhao, X. S. & Wu, J. (2010). Graphene/Polyaniline Nanofiber Composites as Supercapacitor Electrodes. Chem. Mater. 22, 4, 1392-1401

**Chapter 2**

© 2012 Hintze-Bruening and Leroux, licensee InTech. This is an open access chapter distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is

© 2012 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,

**Nanocomposite Based Multifunctional Coatings**

The function of automotive coatings so far has been twofold – decoration and conservation. The former not only consists of providing a coloured and smooth surface but also to accentuate the shape of the car body via a viewing angle dependant brightness and / or colour. These optical effects mostly rely on tiny mirrors of metal flakes like aluminium or coated mica platelets that are more or less homogeneously dispersed within one coating layer; their surface normal predominantly being orthogonal to the substrates surface. The particles lateral dimensions typically are in the order of several hundred microns. The role of the coatings in the conservation of a metallic car body mainly consists in the protection of the substrate towards electrochemical degradation (= corrosion) either actively or via providing a barrier layer as well as a best possible limitation of the coatings defects produced in the wake of dramatic mechanical perturbations like impacting gravel stones. On the contrary mounted plastic parts or body panels in most cases have to be protected against chemical degradation triggered by exposure to UV light, physical erosion by swelling solvents like fuel or water depending on the nature of the polymers and the morphology of the bulk as well as towards catastrophic failure of the part upon mechanical impacts (= brittle crash behaviour). The means to achieve the latter are similar to those that are used in the

The present chapter describes the potential use of nano scaled particles based polymer composites as multifunctional constituents for novel protective as well as decorative automotive coatings. The focus lies on composites based on layered particles, namely layered double hydroxides (= LDH), their beneficial mechanical modes of action for energy dissipation, their diffusion barrier properties as well as their role in the active corrosion inhibition. For other coatings related applications of these materials we refer to a separate

and reproduction in any medium, provided the original work is properly cited.

Horst Hintze-Bruening and Fabrice Leroux

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/46853

**1. Introduction**

properly cited.

review article (Leroux et al., 2012).

design of stone chip resistant coatings for car bodies.

## **Nanocomposite Based Multifunctional Coatings**

Horst Hintze-Bruening and Fabrice Leroux

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/46853

### **1. Introduction**

54 New Advances in Vehicular Technology and Automotive Engineering

Nano Lett. 11, 10, 4462-4467

26., 12., 1127‐1132.

1541

Zhang, K.; Zhang, L. L.; Zhao, X. S. & Wu, J. (2010). Graphene/Polyaniline Nanofiber

Zhang, M. & Dai, L. (2012). Carbon Nanomaterials as Metal-Free Catalysts in Next

Zheng, G.; Yang, Y.; Cha, J. l.; Hong, S. S. & Cui, Y. (2011). Hollow Carbon Nanofiber-Encapsulated Sulfur Cathode for High Specific Capacity Rechargable Lithium Batteries.

Zhou, J.; Yang, J.; Zhang, Z.; Liu, W.; Xue, Q. (1999). Study on the structure and tribological properties of surface-modified Cu nanoparticles. Mater. Res. Bull. 34., 9., 1361–1367. Zhou, W.; Wu, H.; Hartman, M. R. & Yildirim, T. (2007). Hydrogen and Methane Adsorption in Metal Organic Frameworks: A High-Pressure Volumetric Study. The

Zhou, X., et al. (2010). New Fabrication and Mechanical Properties of Styrene-Butadiene

Zhou, X.; et al. (2010). New Fabrication and Mechanical Properties of Styrene-Butadiene Rubber/Carbon Nanotubes Nanocomposite. Journal of Materials Science & Technology.

Zhu, Y.; Murali, S.; Stoller, M. D.; Ganesh, K. J.; Cai, W.; Ferreira, P. J.; Pirkle, A.; Wallace, R. M.; Cychosz, K. A.; Thommes, M.; Su, D.; Stach, E. A. & Ruoff, R. S. (2011). Carbon-Based Supercapacitors Produced by Activation of Graphene. Science 332, 6037, 1537-

Rubber/Carbon Nanotubes Nanocomposite. J Mater Sci Tech. 26., 12., 1127.

Composites as Supercapacitor Electrodes. Chem. Mater. 22, 4, 1392-1401

Generation Fuel Cells. Nano Energy 1, advance online publication,

Journal of Physical Chemistry C 111, 44, 16131-16137

The function of automotive coatings so far has been twofold – decoration and conservation. The former not only consists of providing a coloured and smooth surface but also to accentuate the shape of the car body via a viewing angle dependant brightness and / or colour. These optical effects mostly rely on tiny mirrors of metal flakes like aluminium or coated mica platelets that are more or less homogeneously dispersed within one coating layer; their surface normal predominantly being orthogonal to the substrates surface. The particles lateral dimensions typically are in the order of several hundred microns. The role of the coatings in the conservation of a metallic car body mainly consists in the protection of the substrate towards electrochemical degradation (= corrosion) either actively or via providing a barrier layer as well as a best possible limitation of the coatings defects produced in the wake of dramatic mechanical perturbations like impacting gravel stones. On the contrary mounted plastic parts or body panels in most cases have to be protected against chemical degradation triggered by exposure to UV light, physical erosion by swelling solvents like fuel or water depending on the nature of the polymers and the morphology of the bulk as well as towards catastrophic failure of the part upon mechanical impacts (= brittle crash behaviour). The means to achieve the latter are similar to those that are used in the design of stone chip resistant coatings for car bodies.

The present chapter describes the potential use of nano scaled particles based polymer composites as multifunctional constituents for novel protective as well as decorative automotive coatings. The focus lies on composites based on layered particles, namely layered double hydroxides (= LDH), their beneficial mechanical modes of action for energy dissipation, their diffusion barrier properties as well as their role in the active corrosion inhibition. For other coatings related applications of these materials we refer to a separate review article (Leroux et al., 2012).

© 2012 Hintze-Bruening and Leroux, licensee InTech. This is an open access chapter distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2012 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

### **2. Background**

#### **2.1. Automotive coatings**

Since the industrialization of the car manufacturing process today's automotive coatings have been optimized in an evolutionary process over the past decades resulting in a typical stack of highly specialized individual coating layers (Fig. 1). This comprises an initially cathodic electrodeposited material that provides adhesion and active corrosion inhibition (ED coat) which then is covered by a spray coated layer (= primer) for the smoothening and protection of the ED coat towards UV light. On to the primer surface two layers are consecutively spray applied: first a "base coat" that provides the colour followed by a transparent top coat (= clear coat) which renders the whole system bright, smooth as well as resistant towards chemicals (bird droppings, tar, rosin, acid rain) and surface related mechanical impact like the scratching in the course of car washing. Except for the base coat itself all other layers are chemically cured after physical drying and film formation which implies that the car body has to pass three bake cycles up to 170°C (ED) or 140°C (combined base and clear layer).

Nanocomposite Based Multifunctional Coatings 57

resistance of the coating. Thus, although typically tested and introduced within one coating layer, the potential use of the described new materials concepts should not be considered to

be restricted to these prototypes, substrates and applications respectively.

**Figure 2.** Conventional automotive coating process compared to novel integrated coating.

Ramamurthy et al., 1994; Zouari & Touratier, 2002; Lonyuk et al., 2007).

Gravel stone impingement is an occasional though dramatic event in the lifetime of an automotive body or mounted part and has intensively been studied (Zehnder et al., 1993;

Regarding the physical processes occurring in a coating system there are three common basic features aside from all conceivable differences in terms of inclination angle, kinetic energy (up to 100 m/s, mass of projectiles up to several grams) as well as the shape

1. Short time scales (micro seconds) and a very limited impact area smaller than one mm² are the features of an adiabatic process which yields a local heating (up to 10²K) and a

2. A central compression area where the substrate plastically might deform and the coating material gets crunched is surrounded by a strained zone due to the lateral displacement of the coating material by the impinging projectile – thus shear stress in a

3. The volume of laterally displaced coating material reaches its maximum towards the coatings surface – thus within the highly cross linked top coat which can least accommodate by plastic flow. Hence compressive and tensile stresses (depending on the inclination angle and shape of the object) yield crack initiation within this layer and

This simplified scenario varies with different impact events as evidenced by comparing an orthogonal crush of a blunt object (infinite curvature radius) with the orthogonal "denting" of spiky or edged gravel or with the inclined "carving" by an edged impinging projectile (Dhar et al., 2005). Figure 3a shows the crater produced by a single spherical impact. Radial and concentric cracks as well as plastically flown coatings material encircle a central spot of

**2.2. Stone impact**

(curvature radius) of the projectile:

propagating shock wave.

transition zone causes coatings delamination.

crack propagation throughout the entire coating system.

**Figure 1.** Automotive coating system applied on pretreated metal.

In order to render this coating process more eco-efficient some novel coating systems recently have been introduced which comprise stacks with a reduced number of layers, e.g. without the primer (Fig. 2), (Kreis, 2008). Under critical conditions such lean coatings reveal an insufficient capability to maintain the high level of performance of their technically more mature predecessors.

This is the setting for the development of new material concepts that may provide solutions capable to overcome the constraints inherent to these recent coatings systems which are still essentially based on the conventional technologies. With respect to the automotive coatings conservation functionality it has to be pointed out that – contrary to that what is sometimes suggested by textbooks and patent claims – some features are not attributed exclusively to one single layer, e.g. the relation of the primer layers properties and the stone chip

resistance of the coating. Thus, although typically tested and introduced within one coating layer, the potential use of the described new materials concepts should not be considered to be restricted to these prototypes, substrates and applications respectively.

**Figure 2.** Conventional automotive coating process compared to novel integrated coating.

#### **2.2. Stone impact**

56 New Advances in Vehicular Technology and Automotive Engineering

**Figure 1.** Automotive coating system applied on pretreated metal.

Since the industrialization of the car manufacturing process today's automotive coatings have been optimized in an evolutionary process over the past decades resulting in a typical stack of highly specialized individual coating layers (Fig. 1). This comprises an initially cathodic electrodeposited material that provides adhesion and active corrosion inhibition (ED coat) which then is covered by a spray coated layer (= primer) for the smoothening and protection of the ED coat towards UV light. On to the primer surface two layers are consecutively spray applied: first a "base coat" that provides the colour followed by a transparent top coat (= clear coat) which renders the whole system bright, smooth as well as resistant towards chemicals (bird droppings, tar, rosin, acid rain) and surface related mechanical impact like the scratching in the course of car washing. Except for the base coat itself all other layers are chemically cured after physical drying and film formation which implies that the car body has to pass three bake cycles up to 170°C (ED) or 140°C (combined

In order to render this coating process more eco-efficient some novel coating systems recently have been introduced which comprise stacks with a reduced number of layers, e.g. without the primer (Fig. 2), (Kreis, 2008). Under critical conditions such lean coatings reveal an insufficient capability to maintain the high level of performance of their technically more