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Chapter 2

Size Dependency in Nanostructures

2.1 Introduction
Nanostructures are some 0, 1, 2 or 3 dimensional materials which are mostly composed of one dimensional and zero dimensional nanomaterials such as nanopowders, nano-particles, nano-wires, and etc. Nanostructures consist of twodimensional nano-materials arrangement or thin layers, called nano-coatings or nanostructured coatings. For instance, nano-powders can be served as raw materials to produce nano-coatings in processes such as thermal spraying (plasma spraying and high velocity oxygen fuel spraying) [18]. In this chapter, at rst, various types of nanostructures (especially nanocoatings) and their producing methods, including thermal spraying coatings, transitional metal nitride coatings, super-hard coatings, multi-layers, nano-composite and environmental coatings will be analyzed. Then, the role of electrochemistry in production of nano-composites and also electrodeposited coatings characteristics will be explained, and nally nano-composites application will be examined. Finally the effect of size on the properties of nanostructures will be discussed.

2.2 Nanocomposites and Their Production Methods 2.2.1 Thermal Spraying Nano-Composites
Thermal spraying involves particles quick surface melting and freezing. Thermal spraying nano-composites are of higher abrasive resistance in comparison with micro-coatings. For their high hardness, thermal stability, cosmetic appearance, and chemical neutrality, transitional metal nitride coatings are of a great interest among researchers. In normal circumstances, these coatings are produced through chemical vapor deposition (CVD) and physical vapor deposition (PVD), although their nano-structural coatings can be obtained using ion beam. Mentioned

M. Aliofkhazraei, Nanocoatings, Engineering Materials, DOI: 10.1007/978-3-642-17966-2_2, Springer-Verlag Berlin Heidelberg 2011



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nano-coatings are of a great hardness. This increase in hardness of multi-layers and multi-grids (two-layers) are more intense. Spraying of transition metal nitride nano-particles in an amorphous nitride matrix gives a rise to development of grains with dimensions lower than one nanometer, which makes them efcient for uses such as enhancement of abrasive resistance in copper cutting tools. Thermal spraying method is a suitable method for production of hard coatings on selected matrixes. Coating material is heated in a gaseous environment and is sprayed toward matrix surface in melted drops form, in a high velocity. Due to hits, the drops are settled in a homogenous form on the surface and convey their initial heat to cold matrix and rapidly change into solid state. Applicable raw materials in these methods include powder, rod, and wire. Regarding these materials and efciency of regarded coatings, there are different processes based on thermal spraying, such as plasma spraying, high velocity oxy fuel (HVOF), ame spraying, and etc. In traditional plasma spraying, there is a high-temperature plasma jet in the gun. Powder particles, with dimension of several microns are injected into plasma jet, which changes them into a melted state. Then this combination is sprayed toward matrix. For quick heating and accelerating to coating process, combustion process is fairly common in HVOF method. Gaseous fuels, such as acetylene, propane, propylene or hydrogen, are mixed with oxygen. Then this gaseous combination is combusted, and produces a ame with approximate velocity of 2,000 m/s. powder particles inter into a combustion container, which involves a noble gas such as Ar, and are heated. Then particles are accelerated within a uid under supersonic velocity toward matrix. Micro-crystalline ceramic and metallic coatings are obtained through low pressure plasma and HVOF spraying. During last decades, availability of different processes for providing nanopowders, including aerosol process, solgel process, chemical production, alloying, and mechanical grinding have made some progresses in producing nano-coatings. Thermal spraying methods, using nano-powders, give rise to production of coatings with higher hardness, strength, and abrasive resistance, in comparison with traditional method. It is revealed that HVOF and metallic and ceramic nano-powders plasma spraying is a useful method for creating nano-structured coatings. Since its higher velocity, drops moving, and lower thermal energy quantities, HVOF, compared with plasma spraying, produces a more compacted structure and higher cohesion between coating and matrix [912]. Oxide ceramics such as alumina, chromia, titania, and zirconia, are widely used as surface coating materials for improvement of abrasive resistance, wearing, and cavity. Coatings made from zirconia are used for cylinder head and piston crown at internal combustion engines to improve thermal efciency, output force, and fuel efciency. These coatings involve cavities which are characteristics of plasmasprayed coatings. Nano-crystalline zirconia coatings show lower porosity (8%) in comparison with micro-crystalline coating (12%). TEM test exhibits ne structure of nano-crystalline coatings at presence of co-axis grains (60120 nm) and columnar grains (150350 nm). Fine co-axis grains are cooled because of homogenous germination of mentioned melt, while columnar grains growth is due

2.2 Nanocomposites and Their Production Methods


to heterogeneous germination in boundaries, where there is a higher cooling gradient. For efcient melting of nano-zirconia source at plasma jet, boundaries are very thin and their interface is fairly narrow. This leads to an improvement of cohesion between coating and matrix, then nano-zirconia coatings indicate lower abrasion rate, compared with its micro micro-coatings (Fig. 2.1). Over the past few years, hydroxyapatite (HAP) has been introduced as a porous layer on metallic substrates to provide easier in-growth of bony tissues. Dey et al. [13] studied the size effect on these kinds of coating that were fabricated by microplasma spray. The excellent biocompatibility and bio-stability of HAP layers have become well established and the usages of this material for prosthetic applications have been rapidly popularized recently. Plasma spraying (PS) with a high power (e.g. 2040 kW) is the most popular and commercially accepted method of coating. However, due to the high temperature of plasma jet, the degradation of HAP occurred during spraying, which involved the formation of unwanted tetracalcium phosphate (TTCP), tricalcium phosphate (TCP) and calcium oxide phases. In addition, due to the rapid cooling of sprayed particles, amorphous calcium phosphate also appears in the HAP coatings on Ti6Al4V substrates. The degree of crystallinity (Xc) of PS-HAP coatings usually lied less than 70%. To tackle these problems, recently the microplasma spraying (MPS) process with a low power (e.g. 14 kW) has been used because it can provide a higher degree of crystallization, e.g. Xc * 90% and phase purity than those provided by conventional plasma spraying method. Dey et al. [13] used the metallic substrate from a surgical grade, biocompatible austenitic stainless steel (SS316L). The choice was done in accordance to better corrosion resistance properties, mechanical properties and lower cost of SS316L than those of the conventional Ti6Al4V alloy. The stability and reliability of the coated implant in vivo depend mainly upon the local mechanical properties of the layer. Dey et al. [13] used a low plasmatron power (*1.5 kW), i.e. microplasma was used to coat HAP on SS316L and the local mechanical properties, e.g. nano-hardness (H) and Youngs modulus (E) of the MPS-HAP coating were examined by the well established nanoindentation technique. The local mechanical properties, e.g. H and F of HAP and/or HAP

Fig. 2.1 Changes of abrasion with applied load for plasmasprayed zirconia coating a micro-crystalline coating, b nano-crystalline coating


2 Size Dependency in Nanostructures

composite coating as well as global mechanical properties, e.g. microhardness have not been discussed to a great detail in literature. Most of the researchers used nanoindentation data with a Berkovich indenter for plasma sprayed HAP coating on Ti6Al4V substrate. The reported values on H and E spanned a range of &45 and 83123 GPa, respectively as one proled from the coating-substrate interface to the free coating side across the coating cross-section. The nanoindentation data revealed further, that Youngs modulus value of amorphous zone was much lower than that of the crystalline zone of HAP coating. On the other hand, for HAP coating fabricated by using Nd-YAG laser on titanium, the nanoindentation measurements with a Vickers diamond pyramidal indenter along the coating cross-section showed that both H and E values were lower at the coating side than at the coating-substrate interface. Nano-hardness and Youngs moduli data have also been reported for functionally graded coating (FGC) of HAP/glass composite and HAP/a-TCP composite. Others have evaluated Vickers microhardness and nano-hardness of different composite coating systems, e.g. (a) plasma sprayed 50 vol.% HAP/50 vol.% Ti6Al4V composite coating on Ti6Al4V substrate, (b) plasma sprayed HAP/YSZ/Ti6Al4V composite coating, (c) HAP/carbon nanotube (CNT) composite coating and (d) biomimetic HAP coating deposited on Ti6Al4V and Ti13Nb11Zr alloy substrates. Most of these reports involve a Ti6Al4V or Ti or Ti alloy substrate and thus the amount of information on micro- or nanomechanical properties of microplasma sprayed HAP coating on SS316L substrate is almost insignicantly small. Dey et al. [13] prepared phase pure and owable HAP granule from the conventional wet chemical route. HAP coatings of thickness near 200 lm were prepared by microplasma spraying on SS316L substrates. The degree of crystallization for MPS-HAP was found to be high (near 91%). The statistical validity of their data was established through the application of Weibull statistics, because of the porous and heterogeneous nature of the coating. For both H and E values of the coating, the values of the Weibull modulus (m) showed an overall increasing trend with respect to load although some occasional deviations were observed. Such deviations might have risen due to the presence of pores and cracks in different layers of the coating. It was assumed that higher scatter of data at lower load could be linked to stochastic nature of interaction between the indenter that penetrated a very shallow depth and the aws that scale with the size/depth of the indentation and which possessed a highly statistical size distribution in the surface and in the close vicinity of sub-surface region. At higher load, it was suggested that due to a larger indentation zone of inuence, an averaging out effect of indenter-aw interaction predominated to affect a reduction in data scatter. At a low load of 10 mN, the coating demonstrated a hardness value of about 5 GPa at a depth of about 170 nm which dropped by 60%, e.g. near 2 GPa at a depth of about 3 microns for a higher load of 1,000 mN. These data recommended the presence of a strong indentation size effect in the nano-hardness behaviour of the coatings. Figure 2.2 illustrates the SEM images of the polished cross-section of the MPSHAP coating taken at progressively higher magnications: (a) at 91 K; (b) 96 K; (c) 910 K.

2.2 Nanocomposites and Their Production Methods


Fig. 2.2 SEM images of the polished cross-section of the MPS-HAP coating taken at progressively higher magnications: a at 91 K; b 96 K; c 910 K, reprinted with kind permission from Mukhopadhyay [13]

2.2.2 Transitional Metal Nitride Coatings

Using hard coatings for protection of structure constituents against abrasion is of a great interest. Due to their high hardness, nitride coatings, such as titanium nitride, titanium carbo-nitride, titanium boro-nitride, and titanium aluminide nitride, are very suitable for cutting tools and drilling machines. In addition transitional metal nitrides are among important materials in decorative coating industry since they create beautiful colors within the range of visible wavelength. Hard coatings of titanium nitride, produced by PVD and CVD methods are used for a long time on industrial scale. For practical apply these hard coatings must be efciently stuck with context. In spite of those mentioned above, PVD is a linear method and coatings cohesion to matrix is less than CVD method. This is caused by diffusion of coating material during CVD thermal process. The most important drawback of CVD method is corrosive nature of applied gasses, such as SiCl4, and TiCl4 which may jeopardize health of operators. In addition, it is possible for matrix to be deformed due to imposing in high temperature of the environment. For these applications, drills, and gears it is required to a low deposition temperature to prevent deformation of coated constituents and loss of their mechanical properties. These objectives are difcult to obtain in thermal CVD. On the other hand, a lower deposition temperature (480560C) is needed to develop titanium nitride coatings. However, this technology is not very handy and


2 Size Dependency in Nanostructures

only a limited number of commercial and industrial equipment are produced through this method. Hence, there has been an effort to produce nano-crystalline coatings with better cohesion, using PVD method with ions contributions. Atomic bombardment of developed layer can delay grain growth and cause development of nano-crystalline layers. Through IBAD there it is a strongly expectation for development of metallic nitride coatings with a noticeable improvement in abrasion, corrosion, electrical strength, and optical properties with a change in deposition parameters, such as atomic ux, ionic energy, matrix temperature, and etc. IBAD is addressed for a process through that a thin layer is developed simultaneously using PVD method, using an independent ionic beam. Though IBAD method it is possible to control ionic ux and energy. IBAD method is mostly used because of a need for independent control of layer composition and better cohesion between matrix and coating. Through changing deposition parameters, such as atom ux, ion energy, matrix temperature, and etc. it is predicted to be a particular improvement in coatings characteristics. Production of hard coatings with transitional metal nitrides, through IBAD method is an extensive study area. These nitrides include titanium nitride, chromium nitride, vanadium nitride, zirconium nitride, and aluminum nitride. Also, their obtained coatings have different mechanical and chemical properties. For example, titanium nitride has a structure similar to that of NaCl, but titanium nitride have more hardness, higher chemical stability, and efcient cohesion to matrix, which makes it most famous coating for cutting tools. Titanium nitride is oxidized at temperatures higher than 500C. This causes development of pure titanium oxide, attached to titanium nitride, which leads to reduce of abrasive resistance of titanium nitride coatings. Due to development of a passive and compacted oxide layer, chromium nitride indicates a higher resistance against oxidization in comparison with chromium oxide, which limits next oxidization. Aluminum nitride is among substances which can be applied at higher temperatures, where nitrogen and aluminum atoms are bonded with strong covalent bonds. Once, this coating is subjected to high temperatures, aluminum move to surface and compose aluminum oxide layer, which is an extremely efcient barrier to prevent later oxidization reactions. IBAD method is more applied in practical investigations. At thin layers, low rate of energy (less than 100 eV) for ionic uid is applied at lower temperatures to control ne structures of the layers. When matrix temperature is lower than 15% of coatings materials melting point, the layer includes co-axis ne grains, ranged 2050 nm. This is caused by low mobility of deposited atoms at lower temperatures of the matrix. Next zone is ne transitional zone of the ne structure between columnar zones, where temperature varies between 3 and 15% of matrix melting point. Atoms can migrate at higher temperatures of matrix due to surface diffusion. In next zone one can observe columnar structure since deposited atoms have enough surface mobility to diffusion and increase of grain size. In nal zone grain growth is controlled by volumetric diffusion and obtained when matrix temperature is higher than 50% of melting temperature [1418].

2.2 Nanocomposites and Their Production Methods


2.2.3 Super Rough and Super Hard Nanocrystalline Coatings

At industrial applications there is an increasing demand for coatings having higher resistance against oxidation, higher hardness, and longer life than those of single layer coatings. To supply industrial needs for development of improved coatings, there has been many efforts to design and produce super consolidated coatings. Some researchers proposed notion of designing solids with strong coatings, using two alternative layers with high and low elastic constants. Each layers thickness must be in nano range and there must be no dislocation source between layers. If dislocations could be created in the zone of materials with lower modulus, they must be overcome to the noticeable stress diffused from the phase with higher modulus, before creep phenomenon (along the layers). Thus they must prohibit the creep along the layers. Such multilayer coatings are called super-lattice and their two layers can be metallic, carbide, and nitride. A multilayer includes different piled materials on atomic scale. During multilayer coatings designing both related structural and constitutional factors must be considered. These factors are: Grain size, layers individual thickness, combination module, the number materials interfaces (assuming the last layer is resistant against abrasion) [1921]. Physical and mechanical properties of some hard materials can be combined in multilayer coatings, leading to optimization of materials properties. Abrasion is one of most important factors for destruction of engineering equipment. For instance, cutting tools are subjected to great loads, high temperatures, and inefcient lubrication; hence during mechanisms such as scratching, cohesion, thermal softening, and chemical abrasion there will be an overall abrasion on them. Then, to improve their characteristics it is recommended to use some multi-constituents coatings such as titanium nitride, aluminum/titanium nitride and aluminum/chromium/nickel nitride. Succeeding progresses leads to bring on development of multi-layer coatings such as titanium-aluminum nitride, chromium nitride and aluminum-titanium nitride and vanadium nitride. It seems that these multi-layers are of a higher potential for improving cutting tools lifetime. According performed studies, multilayer coating of aluminum-titanium nitride/chromium nitride have highest abrasive resistance and hardness, in comparison to other coatings. Besides, multilayer lm of titanium nitride/aluminum nitride also enjoys both high mechanical and anti-oxidation properties. When it comes to compare multilayer coatings with single layer one, there reveals to be some advantages and disadvantages including: 1. A multilayer lm may have a better hardness and ductility, comparing with all layers one by one. 2. A multilayer lm with limited thickness has equal or higher mechanical stability with each of single layers. 3. A multilayer with desirable constituents from different single layer lms can be adapted with practical needs. 4. There is an increase in cohesion between multilayer lm and matrix. 5. Remained stress in multilayer lm decreases. 6. Multilayer lms have a more compact structure.


2 Size Dependency in Nanostructures

There are different methods for producing these multilayers but the most common way is through evaporation, due to its highest efciency among the other methods for controlled preparation of high quality structures on atomic scale. On the other hand, electrochemical methods are also very efcient, for their low costs and possibility for mass production. As well as abrasive properties, which are initial reasons for using multilayer coatings, reaching to suitable magnetic properties it is suggested to use such nano-multilayers. For multilayer coatingwhere growth conditions are decentit is possible for magnetic stabilization at one direction (vertical to layer plain). Particularly, some multilayer lms based on Co, such as Co/Pd, Co/Pt, and Co/Au, indicate a high magnetic anisotropy at vertical directions. Tri-layers of Co/Cu/Co have same situations [2234]. It has been proved that this anisotropy of the properties is due to Co layer thickness. When its thickness decreases (up to 0.4 nm) its magnetic properties have an increase and magnetic direction of multilayer lm changes from parallel to coating layer to vertical on Co layer thickness. Current advances in coating technology, using PVD and CVD plasma methods, lead to deposition of multilayer coatings with more preferable mechanical and chemical properties. As an example for these multilayer structures, one can name Al/Cu and Al/Ag. Once dual layers constant reaches to 5 nm, hardness of vanadium nitride/titanium nitride and niobium nitride/titanium nitride coatings reaches to 50 GPa. Super-lattice coatings enjoy higher hardness than that of single-layer coatings such as titanium nitride, vanadium nitride, and niobium nitride. Increasing hardness in super-lattice coating was investigated, based on examination of dislocations mixed movements within and into the layers. The model implies a maximum peak, where there is a difference in shear modulus between two materials and their sharp interface. Here, once super-lattice constant is more than 5 nm its hardness declines to 14 Gpa. Super-lattices physical properties have made them suitable to be used in Micro Electromechanical Systems (MEMS), as a small tool for protection against abrasion. Layers in super-lattice should be amorphous; as amorphous can connect the lattice more conveniently. Hard singlelayer nano-composite coatings were designed, using plasma CVD process. This is occurred at high frequency under direct current. Through this process a hard transitional metal nitride and a covalent nitride (e.g. silicon nitride or bore nitride) are simultaneously deposited to obtain immiscible phases with interfaces and high cohesion energy. In the other words, the coating includes transitional metal nitride, where nano-crystalline with 46 nm size is located in an amorphous matrix with thickness of less than 1 nm. Such a coating is called nano-composite layer [3547]. As an interesting example of size dependency, plasma electrolysis has been used for fabrication hard nanocrystalline layers. The usage of nanocrystalline plasma electrolytic saturation by applying pulsed current in an organic electrolyte based on Glycerol has been studied. Response Surface Methodology was applied to optimize the operating conditions for small nanocrystallite sizes of coatings. The levels studied were peak of applied cathodic voltage range between 500 and 700 volts, peak of applied anodic voltage between 200 and 400 volts and the ratio

2.2 Nanocomposites and Their Production Methods


Fig. 2.3 SEM nanostructure for treated samples by cathodic plasma electrolysis with average size of a 32.6 nm and b 95.1 nm [48]

of duty cycle of cathodic direction to duty cycle of anodic direction of 0.250.35. The usage of high applied cathodic voltages and low anodic voltages and also low ratio of duty cycle of cathodic direction to duty cycle of anodic direction is more suitable for achieving lower sizes of complex nanocrystallites. The samples with high height to width ratio of distribution curves of nanocrystallites have simultaneously, smaller average sizes and lower length to diameter ratio of nanocrystallites [48]. Response surface methodology proved to be fairly accurate in predictive modeling and optimization of conditions for minimizing the average sizes of nanocrystallites obtained in pulsed bipolar nanocrystalline plasma electrolytic carbo-boriding, and that the average sizes of nanocrystallites to be reasonably approximated by quadratic non-linearity. In this process, the samples with high height to width ratio of distribution curves of nanocrystallites have smaller average sizes of nanocrystallites and lower length to diameter ratio of nanocrystallites. Figure 2.3 illustrates SEM images of treated samples with different effective factors. These samples have different average size of nanocrystallites. Narrower distributions for lower average size of nanocrystallites were observed for these samples. Figure 2.4 illustrates the distribution curves of these samples [48].

2.2.4 Nanocomposite Coatings

The rst investigations on composite coatings were performed in 1962. In 1970 for the rst time Ni-SiC composite coating was used to improve engines abrasive resistance. This composite is yet applied for some panels in automobile industry. Composite coatings are obtained through simultaneous deposition of tiny neutral particles in a metallic matrix. Due to its competence for producing lms with excellent mechanical properties such as abrasive resistance, wear strength, hardness, and lubrication, this method is matter of great interest. Simultaneous deposition of non-metallic and metallic phases for development of composite layers has


2 Size Dependency in Nanostructures

Fig. 2.4 Distribution curves of nanocrystallites for mentioned treated samples in a Fig. 2.3a and b Fig. 2.3b [48]

a signicant improvement in most of mechanical and physical properties of the coating. Such properties depend on neutral particles morphology in composite coating. Furthermore, metallic matrix of nano-composite coatings exhibit unique optical and magnetic properties and are promising for production of materials for ne tools. Applied ceramic particles mostly include aluminum oxide, carbide, chromium oxide, titanium oxide, molybdenum oxide, tungsten carbide, and etc. Besides, polymeric particles such as polyethylene and polytetrauoroethylene are used to decrease friction ratio and achieve a nonstick composite surface. According to performed studies, ne-grained Ni-SiC composite has a smoother surface and there

2.2 Nanocomposites and Their Production Methods


is stronger bond between SiC and Ni. Once SiC particles are bigger than 0.1 lm, usually there develops an oxide layer on SiC particles which have a weak bond with nickel matrix, which leads to development of cavities and cracks in grains boundary. On the other hand, interface of a very ne SiC and mixed Ni is free of any defect. In the same volumetric fraction very ne particles are more abundant, which prevent grains growth at higher temperatures. However, investigations show a decrease in particles size leads to decrease of simultaneous deposition of the particles. It was showed that concentration of SiC (with dimension of 0.1 lm), obtained from spinning wheel test, in a nickel sulphamate solution is less than 0.7 weight percentage, which is very close to thresholds scale obtained from EDS analysis. In contrary, concentration for carbide, where grain size is 0.2 and 2.8 lm, is 2 and 6 volumetric percentage, respectively. In general, concentration changes of polyethylene particles surrounded in the matrix on an electrode of a spinning plain is obtained basically from throw analysis. According this model, the required amount for simultaneous deposition of 5 lm particles is 10 time less than that of 20 lm particles. Although it is long time since hard metallic coatings application through plating deposition has a drastic advancement, but mechanisms of simultaneous deposition have not completely been solved, yet [4961]. Guglielmi was the rst who proposed successful two-staged absorption mechanism. Through this mechanism he suggests that the results depend on volumetric fraction of co-deposited particles with Langmuir absorption isotherm. The rst step of this free absorption mechanism is where particles from metallic ion coating on the cathode have a considerable amount of free physical absorption. In this step there is a layer of absorbed ions and solvent molecules; and also there is a reaction between electrodes and particles. The rst step is a strong absorption which seems to be with contributed to electrical eld, as a strong electrochemical reaction causes strong absorption of the powder on the electrolyte. Absorbed particles progressively are surrounded by metallic layer. This mechanical model can be expressed as equation below:   C Mi 1 expA Bg C a nFqm V0 k 2:1

where: M: deposited metals atomic weight, io: exchanged current density, n: deposited metal capacity, F: Faraday constant, qm: density of deposited metal, g: extra voltage of electrode reaction, and k: Langmuir isotherm constant, which is determined by intensity of the reaction between particles and cathode. B and V0 parameters are dependent on particles deposition and both play the same role with A and i0, which are dependent on metallic deposition. Guglielmi models parameters changes with deposition system changes, such as SiC and titanium oxide particles with nickel in sulphate bath or alpha aluminum oxide particles with copper in CuSiO4 plating bath. The mechanism shows a simple effective method to analyze direct effect of basic parameters on composite plating [6268].


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Recently, electrodeposition of tertiary Al2O3/Y2O3/CNT nanocomposite by using pulsed current has been studied. Coating process has been performed on nickel sulphate bath and nanostructure of obtained compound layer was examined with high precision gure analysis of SEM images. The effects of process variables, i.e. Y2O3 concentration, treatment time, current density and temperature of electrolyte have been experimentally studied. Statistical methods were used to achieve the minimum of corrosion rate and average size of nanoparticles. Finally the contribution percentage of different effective factors was revealed and conrmation run show the validity of obtained results. Also it has been revealed that by changing the size of nanoparticles, corrosion properties of coatings will change signicantly in same trend. AFM and TEM analysis have conrmed smooth surface and average size of nanoparticles in the optimal coating. The Taguchi method for the design of experiment has been used for optimizing tertiary nanocomposite electrodeposited coating process parameters for the corrosion protection of treated samples. The contribution of Y2O3 concentration is more than the sum of the contributions of all the other three factors. It is evident that, among the selected factors, Y2O3 concentration has the major inuence on the corrosion rate of performed coatings. It can be seen that the current density is second important factor that affects on corrosion rate of the treated substrates. Furthermore, it can be assumed that treatment time and temperature of electrolyte have almost the same effect on corrosion rates of coatings because of the minor difference in the contribution percentages among these two factors. By ranking their relative contributions, the sequence of the four factors affecting the corrosion rate is Y2O3 concentration, current density, treatment time and temperature of electrolyte. In the case of average size of nanoparticles ranking of effective factors by their relative contributions is as same as for corrosion rate which show strong relation among these two measured properties of coatings. AFM and TEM analysis have conrmed smooth surface and average size of nanoparticles in the optimal coating. Figures 2.5 and 2.6 illustrate the SEM and AFM images of optimal coating, respectively [69]. Nitride Nano-Composite Coatings These coatings have typical structure of nc-MnN/a-Si3N4, where c and n are, respectively, crystalline and amorphous phases and Mn stands for transitional metals such as Ti, W, V, and Zr. In nano-composite coatings, transitional metalnitride phase is hard enough to bear exerted load while, on the other hand, amorphous nitride provides exibility of the structure. Based on computer simulations plastic deformation in nano-crystalline materials, where particle size is less than 10 nm, can be corresponded with particle boundary. Here, grains boundaries slipwhich is controlled by diffusion of grain boundarymay be responsible for plastic deformation in nano-crystalline materials. Slip is caused by atomic movements and stress induced from 3D free migration; in the other words, once nano-crystalline materials are extremely tiny indicate soft behaviors.

2.2 Nanocomposites and Their Production Methods Fig. 2.5 SEM nanostructure of optimal nanocomposite coating [69]


Fig. 2.6 AFM surface prole of optimal nanocomposite coating [69]

Hence, an increase of hardness is required locking in grains slip boundaries. Indeed, this is the reason for increase of hardness in nc-MnN/a-Si3N4 system, for nanocomposite coatings of nc-TiN/a-Si3N4 and nc-W2N/a-Si3N4, where particles size decreases up to 4 nm. It was declared that these developed nano-composite coatings by CVD method, will reach to diamond hardness (7080 MPa), where grain size is about 2 nm. Achieving a high hardness, nitride phase concentration must be around 1723 molar percentage. The reason for hardness increase is progress of submerged nitrides nano-structure. nc-MnN/a-Si3N4 system shows noticeable thermal stability until 1,000C. CVD plasma process provides high chemical activity for gas and controlled surface mobility, as well as ionic bombardment. Other methods such as PVD can be used for preparation of other nano-crystalline/ amorphous coatings, such as titanium carbide in a carbon matrix or tungsten carbide


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in carbon matrix, which are of a unique combination of hardness and ductility. Carbon serves as a hard, ductile, and lubricating matrix; while nano-particles act as crystals which enhance hardness and other mechanical properties. As nc-MnN/aSi3N4 with high elasticity typically shows brittle behavior, some researchers designed nano-grain coatings (where grain size is 1050 nm) with high ductility in an amorphous matrix. This state leads to development of dislocations; however they are too small for expansion of cracks. Segregation of larger grains leads to adjustment of non-apparent strains and development of nano-cracks between crystals, which nally results in plasticity behavior. According to this state, titanium carbide coatings in a carbon matrix include: hardness of 30 GPa, fraction coefcient: 0.150.2, and ductility: 4 times greater than nano-crystalline titanium carbide. According to above, super-lattice or multilayer coating is materials which can be applied in MEMS method. All in all, silicon and other electronic materials are used for production of mechanical miniature panels (micro-machines), such as membranes, cantilever, gears, engines, and valves, using standard process of concentrated circuit industry instead of surface machining. Surface machining is a process for creating surface structures from tiny deposited layers. Surface ne-structures thickness varies from 0.1 to several micrometer to nal size of 10500 micrometer. Currently, some researchers produced super-nano-crystalline coatings of diamond with CVD method, by short waves using unique chemical such as CAr or methane-Ar. Hence carbon couples are obtained from methane through following reactions. 2CH4 ! C2 H2 3H2 C2 H2 ! C2 H2 2:2 2:3

There is a very small amount of hydrogen in atmosphere. Through traditional CVD method, developed diamond lm constitutes: methane (1%) and hydrogen (99%), and an extra hydrogen contained gaseous mixture. This extra mixture solves diamond phase and develops columnar morphology with larger grain size and higher surface roughness. Final rough surface of diamond microstructure can cause extra scratches along slip plain. It was applied the term of super-nano-diamond coatings to make a distinction among these materials, micro-structures of diamond with grain size of 110 micrometer, and nanocrystalline diamond (50100 nm). AFM studies for thin lms of super-nano and micro diamond showed that super-nano diamond coating has s smoother surface. These coatings hardness is about 88GPa and their modulus is close to that of mono-crystalline diamond (70GPa). Besides, their fracture strength is too much more than that of silicon, silicon carbide, pseudo-diamond carbon, and mono-crystalline diamond. This lms fracture coefcient is comparable with that of natural diamond and its abrasion against hard materials is a minimum amount, due to smooth appearance of the surface. Thus, in these layers with improved mechanical and tribological properties, are ideal materials for MEMS applications [30, 7079].

2.2 Nanocomposites and Their Production Methods

43 Nanocomposite Coatings of Ni/Al2O3 Nano-composites coatings of Ni/Al2O3 are used to enhance abrasive resistance of metals surface in micro-tools. Although micro-composite coating of Ni/Al2O3 has had a signicant advancement, but there are some difculties during their preparation. Volumetric amount of alumina particles in Ni/Al2O3 composite coating is not controllable in quantitative sense and particles in composite coating are persistent. Some researchers recorded that alumina particles can easily stick to each other in electrolyte. This causes weak mechanical properties in the coatings. Alumina weight in composite coating can be increased between 3.5 and 14.6%, using inverse pulse electrical deposition, which results in improvement of mechanical properties. In spite of that distribution of tiny alumina particles is yet a problem during coating preparation. Putting smaller neutral particles in sediment layer is more difcult, due to problem of neutral particles distribution. Volumetric amount of nano-particles within the composite coating under work circumstances is very few. Distributed particles in an electrolyte solution are persistently moving. Once one particle reach to another one, their energy content denes weather they are separated or connected. Particles connection occurs when their absorption energy is higher than detractive energy. The pure energy in a continuous structure rests upon nature and condition of the system. Information about structure of interface zone is an important factor to perceive stability of solid particles dispersion in an electrolyte. For creating decent dispersion for alumina particles in a nickel sulfamate bath chemical and physical methods, which change particles size in interface zone, are necessary. Chemical effect occurs once particles involve absorbed surfactants or macro molecules for development of electrostatic interference in internal particles. Under particular circumstances this interference results in increase of absorbed layer rejection and situational entropy release at internal particles. On the other hand, chemical effect occurs once particles absorb a destructive energy such as ultrasonic. Creation of ultrasonic waves in liquid environment results in an extraordinary pressure (100 atm), which induces huge stress and destruction of cohesive energy between internal particles. Through previous investigations, the average size of continuous alumina in deionized water, and nickel sulfamate bath were 183 and 1,109 nm, respectively. It seems that effect of solutions ionic stability on particles accumulation in nickel bath is not negligible. Average dimensions of continuous alumina using physical dispersion by ultrasonic energy decreases up to 280 nm, while this reduction is 448 nm when it comes to use chemical dispersion released from surface factors in nickel bath. Although chemical and physical dispersion are considered at electrochemical preparation of nano-composite coating, these methods, to some extent, impede dispersion of neutral alumina particles in nickel sulfamate bath since electrolyte ionic concentration is an important factor in effective distribution of aluminum particles. Alumina particles distribution in a dilute nickel sulfamate bath, along using ultrasonic dispersion, is an effective method to prevent continuity of alumina particles [8093].


2 Size Dependency in Nanostructures Al Based Composite Nano-Coatings Al based composites with aluminum borate whiskerswhich are created using high pressure castingindicate a comparable strength and modulus with those of aluminum composites with SiC or silicon nitride whiskers. However, they have a lower thermal expansion and higher abrasive resistance. Besides, another priority of these whiskers is their very low costs in comparison with those of SiC1/20 of SiC whiskers. Hence, aluminum borate whisker is of great qualications for expansion of aluminum based composite applications. Also, based on existed theoretical and empirical studies, it was revealed that aluminum borate whisker is unstable in Al alloys, and the reaction occurs in their interface. To control reaction in interface, nitriding process of these whiskers, based on thermodynamic calculations, was suggested. To reach a continuous and homogenous phase nitrided nano-coating must be used. Phase analysis implies presence of BN and alumina on nitrided surface. Nitrided nano-coating with thickness of 4060 nm isolates the whisker from surrounding matrix and aluminum/coating interface will be free reaction productions [60, 94104]. Al/TiO2 Nanocomposite Coatings Titanium oxide is of abundant usage in gas sensors and photo-catalysts. For example, it is used in gas sensors to detect explosion released gases such as natural gas and hydrogen. Due to their crystalline structure, surface area, their cavity types (in terms of opening and closure), and their size distribution, photo-catalysts are used for segregation of air pollutants and organic contaminator in waters. It has been currently shown that TiO2 nano-coatings are of a greater sensation compared with that of micro-structure ones. The easiest and simplest way to achieve a nano-coating with thermal spray method is using raw materials with nano-size. However, directly adding such nano-powders during spray process is difcult. Moreover, plasma or gas ame leads to melting and removing its initial structure. Therefore, it was achieved that better characteristics through simultaneous spray of the other substance which prevents development of Ti-O2 powder in the furnace. Thus particles of metallic Al, which are of a lower temperature and higher reactivity in comparison with TiO2, are added to Al/TiO2 composite powders to enhance spraying efciency. Al particles have signicant role to create homogenous sediment. They lead to reach to unique characteristics of nano-structures, maintaining nanometric structure during spraying process [105115]. Al/Al2O3 Nanocomposite Coating Useful effect of alumina nano-particles was recorded in 1990s. It is found that development of nano-size dual metallic phases in alumina can noticeably enhance its thermal and mechanical characteristics. Metallic phase exhibits higher thermal

2.2 Nanocomposites and Their Production Methods


conductivity and resistance against thermal shock in comparison with alumina ceramic. Also, metallic phase can increase ceramics ductility as metallic particles deform plastically. In performed operations on metallic/alumina nano-composites, metals such as Cr, Ni, Fe, W, titanium carbide were used, which leads to 23 times increase of ductility. Second phase has been added through mechanical combining of alumina and metallic powders, and their under-pressure sintering of graphite crucibles. The main problem of mechanical combination method is to nd out how to reach to second phases ne dispersion and favorite thermal expansion difference between alumina and metal. Thus, a chemical coating method was used for preparation of ceramic/metallic nano-composites, which has variant advantages compared with mechanical combination method. The obtained powder in this method is more homogenous and of a higher cohesion between metal and ceramic. Preparing nano-composite coating of Al2O3/Al wet chemical coating method was applied. Aluminum nano-particles are solved in appropriate solution, then Al2O3 is added, and nally considered composite is deposited in the solution. Through occurred reactions, there develops a thick Al(OH)3 layer on aluminum particles surface which, after calcication, is converted to alpha alumina nano-particles (with grain sizes of 1020 nm) and distributed Al particles. The advantage of Al2O3/Al composite is development of a thin transition layer between Al and Al2O3, which is able to improve their bond [110, 116127]. Nanostructured Coatings of Tungsten Carbide/Ni-Co Although tri-valence chromium ions, and particularly hexa-valence ones, are very poisonous, chromium plated coatings are widely used to enhance surface abrasive resistance. Another problem of plated chromium coatings is their decrease in thermal mobility with increase of temperature, so hardness and abrasive resistance of plated layers reduces. Hereabout there have been many studies in surface engineering to nd a suitable substitute for this coating, leading to promising results. First choice is tungsten carbide or tungsten-carbide/cobalt. As it previously mentioned nano-crystalline materials show unusual chemical, physical, and mechanical properties, in comparison with amorphous ones. This is caused due to nano-crystalline materials noticeable decrease in grain size and volumetric ratio of grains boundary, and triple connections. Here, a decrease in tungsten carbide grain size up to 70 nm in tungsten-carbide/Co composite leads to a two-time increase in abrasive resistant. Nano-crystalline nickel with grain sizes of 1020 nm, created with electrical deposition method, has abrasive resistance of 100170 times and friction ratio of 4045% higher than that of multi-crystalline nickel, where grain size is 10100 lm. it was found that nano-composite coating of diamond in nickel matrix under effect of distributed nano-diamond strength indicates less internal stress and higher ne-hardness. Mentioned nano-composite shows excellent abrasive


2 Size Dependency in Nanostructures

characteristics at room and even higher temperatures. Anti-abrasive properties of this composite coating are 4 times more than that of pure nickel coating [128130].

2.3 Electrochemistry Role in Production of Nano-Coatings

Electrochemistry is an advanced technology in production of nano-particles. Before studying use of different electrochemical methods for nano-coatings production, rst it should be dened that how colloidal chemical state leads to creation of nano-particles. This leads to better understanding of electrochemistry concept and its effect on nano-coatings. In colloid science, nano-particles mostly obtained from surfactant contained saturated solutions. The rst rule of organic ligands is inactivation of surface and development in suspending state. This preparation technique of nano-particles is called engaged sedimentation. Similar methods for development of nano-particles on conductive matrix have dramatically advanced in electrochemistry. It has been proved that adding surface intermediates can lead to deposition of nano-particles during plating. Additives prevent particles growth and maintain particles size to be approximately constant. A more common method is creating changes in plating parameters, e.g. voltage or current. However, there is another two-step method including a high extra voltage in a short time for germination of metallic particles on surface and then slow growth of particles in a lower extra voltage. Low extra voltage results in minimum change (about 7%) in particle size. this stops diffusion of mixed layers and decrease in growth rate. particles shape produced by engaged electro-deposition depends on applied matrix and extra voltage. Metals such as Au, Ag, Ni, and polymeric nano-particles with spherical geometry on graphite matrixes, are created by this method. Palladium nano-wires with 55 nm diameter and length of several hundred meters were created through this method, which are used in a polymeric matrix as hydrogen sensor. It is worthy to say this wires strength decrease when they are subjected to hydrogen [80, 131140].

2.3.1 Electro-Deposition Using Porous Templates

Electro-deposition is one of the effective methods in nano-composite production. For its low costs and high production potential, it is of a great interest. The only way to produce nano-coatings through this method is changing parameters such as current, voltage, bath composition, pH, and etc. It is also found that in most cases created coatings properties with electro-chemical method is preferable, compared with the other methods; because most compacted coating without any pre-stress is produced through this method. Material development using porous templates to control size and shape is a common method to create nano-particles. Despite, there are many problems of using templates in sedimentation methods, due to

2.3 Electrochemistry Role in Production of Nano-Coatings


heterogeneity and pores block; however grain growth in electro-deposition can only occur suing a template. Template electrodes are constituted from materials such as etched Mica and porous alumina membrane. Electro-deposition is applied using a template for preparation of nano-wire made of different materials. Through an advance initiative in production, using templates, nano-wires are created by periodic movements of wording electrode in a solution including Au ions and a solution including Ag ions. Difference in Au and Ag cross sections creates wires with nanobarcodes. Electro-deposition method with template, for preparation of materials with high surface area includes used nano-pores. Spherical poly-styrene nanoparticles are created on an Au matrix of a colloidal cell. In electro-deposition a metal develops on an electrode, a metal-polystyrene develops, and then polystyrene particles are solved and a metallic layer with nano-pores will create. Currently, so many researchers have had focus on common plating methods with direct current as deposition methods for creation of nano-crystalline materials. In most cases, electro-deposition is a product with no porosity on it and there are no integration processes, compared with other methods for producing nanocrystalline materials. Through this method one can either create coating on surface or make a denite shape (such as foil, sheet, or regular shapes). Using this method, some special metals (e.g. Ni, Co, Pd), dual alloys (such as NiP, Co-W, Ni-Zn, and Ni-Mo), and triple alloys (like NiFeCr) can be produced. Basically, electrodeposition results in production of nano-structural material whenever process parameters (such as bath composition, pH, temperature, extra voltage, and etc.) are selected in a way that electro-crystallization induced by germination is in a high rate and grain growth has a low rate. Electro-crystallization occurs under effect of two competitive reactions: production of new crystals and growth of existed crystals, under effect of different factors. Two main steps determining the rate are: charge transition step on electrode surface and surface diffusion of extra ions on crystal surface. Grain growth occurs at low extra voltages and high surface diffusion rate. On the other hand, high extra voltages and low surface diffusion lead to development of new grains [141153].

2.3.2 Nano-Coatings Properties

Determined properties associated with crystalline nano-coatings reveals that these properties can be categorized in two groups: 1. Coating properties which are strongly depended on grain size including: abrasive resistance, strength, malleability, hardness, friction coefcient, electrical resistance, solid solubility, hydrogen solubility, permeability, local wear resistance, stress corrosion cracking, and thermal stability. 2. Properties which are weakly inuenced by grain size, including: bulk density, thermal expansion, Young modulus, and coercivity.


2 Size Dependency in Nanostructures

2.4 Mechanical Properties

As it is expected plastic deformation behavior of nano-crystalline materials is strongly depended on grain size. Most performed tests are related to determination of ne-hardness at room temperature on samples with thickness of 0.10.5 lm; where rst they are plated on Ti matrix and then Ti is used to determine nehardness. The results of hardness measurement for plated NiP whiskers at room temperature were reported. Same results were obtained for Pd and Cu produced from neutral gas evaporation method. An increase in grain size is accompanied with considerable decrease of hardness in range of lower than 20 nm. These observed reductions of hardness are not corresponded with HallPetch behavior. Recently, performed investigations on tensional strength of Ni nano-crystal at room temperature have shown a behavior similar to that of determined with hardness. It is found that grain boundary diffusion in creep phenomenon is not an efcient factor to determine mechanical behavior of Pd and nano-crystalline Cu at room temperature. Start point for hardness decrease, i.e. deviation from HallPetch behavior, occurs once triple lines occupy a high ratio of sample volume. This phenomenon is generally in accordance with softening effect of triple lines. Through electrochemical grinding of wires to sizes lower than grains average size, triple connections can be displaced in ne structures. At all cases this transition, increase of strength, and decrease of malleability is shown from co-axis state to columnar one. Modied theory of dislocation locking with fewer numbers of dislocations can be used to explain deviational behavior from HallPetch equation. It was shown that there is a considerable decrease in HallPetch gradientobtained in critical circumstancesdue to presence of a spread dislocation cycle. Some researchers state that dislocation mechanism is not used for nano-crystalline material with grain size lower than a critical limit, for example 10 nm, for FCC metals. A combined model, based on above geometric assumptions for matrix, volumetric ratio of intra-crystalline and crystalline constituents, were proposed to determine nano-crystalline materials strength. It has been proved that the model can be applied for interpretation of different approaches including deviation from Hall Petch equation and negative gradient of HallPetch curve. This analysis includes quadric nodes where triple lines meet each other, as well as grain binderies and triple connections. Strength distribution for grain boundaries (rgb), triple links (rtl), and triple nodes (rqn), as: rqn [ rtl [ rgb Researchers also, reached to an analytical explanation to examine creep rate of nano-crystalline materials for a diffusion mechanism involving triple lines. General rate of the creep is sum of creep rate due to network diffusion, grain boundary diffusion, and triple line diffusion. It has been proved that, due to triple line diffusion, creep speed has stronger association with grain size compared with grain

2.4 Mechanical Properties


boundary diffusion. For instance, distribution of triple line diffusion in creep speed at stable stage seems to be inverse power of four, which is one order more than that of grain boundary diffusion and two orders more than that of grain-size-depended network diffusion in matrix. Besides, in comparison with dislocation mechanism, where applied stress power is more than 3, secondary creep rate, yet, is linearly related with tensional stress. Conclusion was that at higher stresses, grain boundary slip is main deformation mechanism at room temperature for pure electro-deposited nano-crystalline nickel. There was recorded a negative gradient of HallPetch, where grain size was less than 10 nm. One can claim that deviation from HallPetch equation might be for dynamic creep process induced from diffusion mechanisms [154164]. Thanks to advancements in applications of electro-deposited nano-crystalline materials, recently a comprehensive investigation was carried out on their mechanical properties. Also yield strength and tensional strength increase with grain size decrease, well as considerable increase in hardness. It is interesting to know that work coefcient of hardness decrease to around zero where grain size reduces up to 10 nm. For typical materials, material malleability with reduction in grain size up to 50% of length to fracture in tension decreases to 15 and 1%, where grain size is 10 and 1 nm, respectively. It is found that in most of cases there is more malleability in buckling. For grain sizes of 10 nm, a slow return in malleability was recorded. Compared with multi-crystalline Ni, abrasion rate of electrodeposited nano-crystalline Ni is intensely decreased and its friction ratio is fairly low. In contrary with recent calculation about nano-crystalline materials, carried out with methods with homogenizing stage, electrodeposited nanocrystalline Ni shows no signicant decrease in Young modulus. This approves the previous obtained results which mention a drop in Young modulus in nanoprocesses is due to high value of remained porosity. Numerous investigations have been performed on the formation of nanocomposite layers during recent years, such as papers about NiP-TiO2 as lubricious layer, Ni-SiC and Ni-Co-SiC as wear and corrosion-resistant coatings, Ni-TiO2 as photocatalytic layer, and Ni-SiO2 as corrosion-resistant layer. The most important features of a well-performed layer are constant concentration along the nanocomposite layer and uniform distribution of nanoparticulates in matrix. Some modications in electrodeposition such as using pulsed current and ultrasonic bath were usually employed for better dispersion of nanoparticulates in obtained nanocomposite layer. Some papers reported usage of ultrasonic bath during nanocomposite electrodeposition process. Results about the effect of the ultrasonic condition outside of the cell during electrodeposition demonstrated that the ultrasonic condition increases uniform distribution of Al2O3 nanoparticulates but decreases their concentration in the metallic matrix. Also, some reports were published about the effect of pulsed current on electrochemical coating process. It has been revealed that usage of pulsed current will lead to fabrication of harder nanocomposite layers. Pulse generator has been utilized for fabricating nanocomposite layer in order to achieve more concentration of carbon nanotubes and to increase the uniform distribution of nanoparticulates in deposited layer [137].


2 Size Dependency in Nanostructures

There is no wide study on specic nickel-tungsten/carbon nanotube (Ni-W/ CNT) nanocomposite layer formation by electrodeposition. Ni-W/CNT nanocomposite layer was performed by pulsed current and study the concentration of nanoparticulates and process effective parameters on the electrochemical and mechanical properties of coated samples. Distribution of nanoparticulates in nanocomposite layers has also been investigated. The effect of duty cycle on distribution of carbon nanotubes in nanocomposite layers shows strong attendance but does not change the W content in the metallic matrix. Microhardness increased for different nanocomposite layers with different amounts of carbon nanotubes. Microhardness of nanocomposite layers did not change signicantly by changing the duty cycle. Figure 2.7 illustrates the nanostructures of nanocomposite layers formed by different (low, medium, and high) duty cycles of pulsed current. Comparison of nanostructures of obtained nanocomposite layers shows that increasing duty cycle signicantly alters the distribution and content percentage of carbon nanotubes in nanocomposite layers. It has been revealed that carbon nanotube content will increase from 4.3 to 13.1 wt% by increasing duty cycle from 20 to 80%, respectively, and agglomeration of nanoparticulates will decrease in higher duty cycles. The rst mentioned result was predictable since in higher duty cycles the

Fig. 2.7 Nanostructures of Ni-W/CNT nanocomposite layers formed by different duty cycles of pulsed current: a 20% (AFM); b 50% (AFM); c 50% (TEM); d 80% (AFM) [137]

2.4 Mechanical Properties


electrochemical reaction for deposition of the metallic matrix has longer times for its occurrence; hence, deposition of nanoparticulates in layer has longer times to occur (in each cycle of pulsed current). By considering ideal distributed nanoparticulates in electrolyte, it can be concluded that increasing duty cycle will lead to longer on times (of applied pulsed current in each cycle) and lower applied potential (for obtaining constant average current density), which means lower power for embedment of nanoparticulates into nanocomposite layer, so agglomeration is less than that in lower duty cycles that act in the opposite manner. Figure 2.8 shows that the W content in the metallic matrix did not change signicantly by increasing duty cycle of pulsed current. Changing trend of the W content is the same as carbon nanotube content. W content increased from 10.8 to 12.1 wt%. It can be assumed that the interaction of nanoparticulates and pulsed current has an inuence on the W content in the metallic matrix. It can easily be concluded that effect of carbon nanotubes is much more than duty cycle, and decreasing carbon nanotube content will also lead to a decrease in the W content of the metallic matrix [137]. Microhardness of Ni-W and nanocomposite layers with respect to different concentrations of carbon nanotubes as well as different applied duty cycles is reported in Table 2.1, which increases from 522 HV for Ni-W alloy to 779 HV for nanocomposite layer with 13.1 wt% of carbon nanotubes. Also, the W content in nanocomposite layer will not change by changing the duty cycle of pulsed current, so increasing microhardness of the obtained different nanocomposite layers with the applied different duty cycles should be concerned by the presence of carbon nanotubes. As mentioned before, there is less carbon nanotube in nanocomposite layers, which are formed by lower duty cycles, but the microhardness of nanocomposite layers will not change signicantly by changing the applied duty cycles (Table 2.1). Thus, increasing duty cycle will lead to mutual effect of higher contents of carbon nanotubes in the metallic matrix with simultaneous less normal distribution, which in total will lead to approximately constant microhardness of the obtained layer. Figure 2.9 illustrates the distribution of carbon nanotubes in a 500 nm 9 500 nm area of analyzed SEM nanostructures. Changing trend of distribution in this gure conrms our conclusions.

Fig. 2.8 Inuence of duty cycle of pulsed current on CNT nanoparticulate contents in obtained nanocomposite layers and W contents in the metallic matrix of nanocomposite layers [137]

52 Table 2.1 Microhardness of Ni-W/CNT nanocomposite electrodeposited layers [137] Sample Ni-W Ni-W/CNT

2 Size Dependency in Nanostructures Duty cycle/% 20 35 50 65 80 HV 522 725 739 754 767 779

2.5 Corrosion Properties

In general, corrosion resistance of nano-crystalline materials in aqueous solutions is of great importance in an extensive area for future applications. There performed few studies in this area. Both improved and disadvantageous results for development of nano-crystalline in corrosion process have been recorded for corrosion behavior of nano-crystalline produced by amorphous materials crystallization. Obtained results are highly inuenced by weak characteristics of crystallized amorphous materials. In the other words, during last few years, there have been considerable advancements in perception of ne structures effect on corrosion properties for materials produced by electrodeposition process. In previous studies, polarization at both constant and changing potentials, with deaerated 2 N sulfuric acid (pH = 0) were performed on bulk pure Ni nano-crystals with grain sizes of 50, 32, and 500 nm and compared with pure multi-crystalline Ni with grain size of 100 lm. Nano-crystalline specimens show the same active-inactive-trance-passive behavior; and differences are between passive current density and open circuit potential. Nano-crystalline specimens indicate more intense current in passive zone, implying higher corrosion rate. This current density is mostly because of more grain boundaries and triple connections in nano-crystalline samples, creating electrochemically active spots. This density difference in current density decreases for higher potentials (1,100 mV versus Calomel reference electrode). At this potential difference, nal dissolve rate overcome to structurally control dissolve rate, existed at low potentials. Another obvious difference in polarization result, in varying potential of nano-crystalline and multi-crystalline samples, is open circuit potential. It seems that positive transition of open circuit potential for nanocrystalline samples is due to catalyst properties of hydrogen releasing reaction. Both samples show extensive corrosion; however this corrosion is more homogenous nano-crystalline Ni, while sample with grain size of 100 lm reveals more developed local corrosion across grain boundary and triple connections. XRD analysis of polarized samples for passive zone suggests that created passive layers on nano-samples are less developed. This porous layer allows nano-crystalline sample for a more homogenous destruction; while, on the other hand, for coarse Ni, destruction of passive layer rst happens at grains boundary and triple connections rather than crystal surface, leading to preferred invasion in these zones. There has been obtained similar approaches for corrosion behavior of

2.5 Corrosion Properties


Fig. 2.9 Distributions of CNT nanoparticulates in the metallic matrix of nanocomposite layers for different applied duty cycles of pulsed current: a 20%; b 50%; c 80% [137]


2 Size Dependency in Nanostructures

nano-crystalline stainless steel (304) with grain size of 25 nm, in HCl, obtained through spraying process. A decrease of sensitivity against local corrosion is due to ne-grained micro-structure, conducts in an even distribution of Cl ions. Recently, corrosive behavior of Ni nano-crystals, in 30 weight percentage KOH solution and a solution with normal pH of 3 weight percentage of NaCl, has been studied which produced results similar to those of sulfuric acid. Compared with Ni multi-crystal, overall corrosion has an increase; however, nano-crystalline materials are more protected against this local destruction which leads to catastrophic fracture. Using salt spraying test, it was found that under electrochemical conditions e-structure of Ni has a few effect on nal corrosive performance. Both micro-crystalline and nano-crystalline coatings reveal similar corrosive protection on steel samples. Another corrosion study was performed on nano-crystalline Ni according to existed conditions on steam generator alloy, as a part of electro-sleeve development program. Tests of sensitivity against intra-granular invasion and stressaccompanied sensitivity against corrosion were performed on polytonal acids and MgCl2, while alternative emerging test was carried out in NaCl. The results show that electrodeposited nano-crystalline Ni with grain size of 100 nm is resistant against intra-granular phenomena such as grain boundary invasion and corrosion with grain boundary stresses. This material is resistant against local pitting attacks and shows just a negligible sensitivity against crevice corrosion. Second group of tests are concentrated on particular environments, where steam generator materials are imposed. These environments include alkaline, acidic, and a compound of oxidizing and reducing particles ones. Tests have shown excellent strength of nano-crystals in base and reducing acidic environments. Resistance against corrosion is limited in acidic and oxidizing environments [165174].

2.6 Hydrogen Transition and Sensitivity

Hydrogen transition behavior in thin sheets of nano-crystalline Ni, with average size of 17 nm at temperature of 293K, is determined using electrochemical dual storage. Based on determined permeability, permitted ux values, and surface fraction (i.e. given volume), these changes are due to hydrogen transition across distinct triple connections, grains boundary, and network paths. Permeability of triple connection is about 3 and 70 times quicker than grain boundary and network diffusion, respectively. This shows effect of triple connections defects. Moreover, diffusion from triple connection zones in nano-crystalline Ni implies importance of triple connection defect on bulk properties of nano-crystals. Nano-crystalline Ni with average size of 20 nm shows more electro-catalytic behavior, in comparison with cooled, ne grained, and completely annealed Ni. Another study on hydrogen transition behavior of Ni, using electrolytic charging method, shows that an essential increase in permeability of hydrogen and its capacity is obtained whenever Ni is in nano-crystalline form. Collecting

2.6 Hydrogen Transition and Sensitivity


hydrogen in dual electrodes of Ni with same thickness has this following order: nano-crystal, ne grain, mono-crystalline structures. Besides, apparent concentration of hydrogen in a 20 nm sample is around 60 times more than that of monocrystalline structure, based on allowed exchanges. Hydrogen permeability and capacity is due to its more amounts of intra-crystalline spaces, offering these following features: 1. High density from short circle diffusional paths 2. More free volumes, resulting in more segregation of hydrogen

2.7 Magnetic Characteristics and Ionic Conductivity

Many experiments suggest that magnetic characteristics depend on material size. Although understanding magnetic structure of nano-structure materials is far away from its complete state, there is a clear imagination from saturated magnetism; as recent contradictory results about chemical and physical structure of nano-crystalline materials is justiable. According rst studies, nano-crystalline materials show a great deal of decrease in saturated magnetism with decrease in grain size. Approximately 40% of decrease in saturation magnetism was obtained in comparison with bulk alpha Fe for nano-crystalline Fe with grain size of 6 nm, developed by simultaneous deposition of nano-particles obtained from consolidation of pure gas. This behavior is due to differences in magnetism ne-structure of nano-crystal and common multi-crystalline Fe. In a same way, strong effects of particle size on saturation magnetism were obtained during study of super tiny unconsolidated particles produced through gas evaporation. For super tiny particles (1050 nm) of Ni, Co, and Fe, an intense decrease was observed in saturated magnetism with grain size reduction, which was accompanied with nonmagnetic oxidized layers on particle. Another study on these super tiny particles has shown magnication is negatively associated with decrease of particles size. Decrease in saturation magnetism is accompanied with surface effectswhich are more important than grain size. Also, decrease of saturation magnetism rate in Ni powder, due to evaporation of produced gas resulted from structural disorder in interface, was recorded. Measured magnetic momentum of interface atoms is about half of that of atoms in coarse grain material. Further, it was found that super tiny Ni particles saturation magnetism considerably reduces with grain size decrease. It was recorded that accidental magnication of nano-crystalline gallium (Ga) samples produced by gas consolidation and dimensional compaction is about 75% of its multicrystal. It must be added all mentioned samples are created using gas consolidation method resulting in production of materials with high internal porosity, which creates a big deal of surface area for oxide development after posing to free air. On the other hand, it was recorded that saturation magnetism is not signicantly associated with grain size. Ni grains size has been declined from 10 to 100 nm;


2 Size Dependency in Nanostructures

then for Ni samples with tiniest grain size observed magnetism is just 10% less than that of multi-crystalline Ni. These results were observed for bulk nanocrystalline Ni created with electro-deposition method and its creation mechanism was said to be unavoidable development of porous oxide. Obtained results are coordinated with recent calculations, implying effect of structural disorder. At these studies, grain boundary size is a source for different disorder states. Measurements show that magnetic momentum is not really sensitive to magnitude of structure disorder from grain boundaries. Once material structure is amorphous, average momentum is only 15% of decrease; hence, for nano-crystalline Ni with grain sizes of 10 nm, where grain boundary atoms occupy 30% space, nal effect of structural disorder on medium momentum would be negligible. Other recent records prove these results. For instance, for nano-crystal created by rolling, there is no signicant difference in saturation magnetism for material with grain sizes of 1 nm and 50 lm. similar results have recorded for Ni nano-crystals. Also, for nano-crystalline Ni created from gas consolidation method, before posing it to free air saturation magnetism is independent from grain size, but as soon as its pose to free air saturation magnetism declines to 80% of its original value. Recently Ishihara et al. [175] fabricated thin lms of La1.61GeO5-d as a new oxide ionic conductor, on dense polycrystalline Al2O3 substrates by a pulsed laser deposition (PLD) method and studied the effect of the lm thickness on the oxide ionic conductivity on the nanoscale. The effective deposition parameters were optimized to obtain La1.61GeO5-d thin lms with stoichiometric composition. Annealing was found necessary to get crystalline La1.61GeO5-d thin lms. It was also found that the annealed La1.61GeO5-d lm exhibited extraordinarily high oxide ionic conductivity. Due to the nano-size effects, the oxide ion conductivity of La1.61GeO5-d thin lms increased with the decreasing thickness as compared to that in bulk La1.61GeO5-d. In particular, the improvement in conductivity of the lm at low temperature was signicant.The electrical conductivity of the La1.61GeO5-d lm with a thickness of 373 nm is as high as 0.05 (log (r/S cm-1) = -1.3) at 573K. The oxide ion conductor is an important functional material applied in different elds such as fuel cells, oxygen sensors, oxygen pumps, water electrolysis, and oxygen separating ceramic membrane. Among these application areas, the electrolyte of fuel cell is attracting much interest. Several numbers of new oxide ion conductors such as strontium and magnesium doped lanthanum gallate (LSGM) and La10Si6O27 apatite oxide and were reported recently. Among the new oxide ion conductors fabricated recently, La-decient La2GeO5, is highly interesting, because of its high oxide ion conductivity over a wide range of oxygen partial pressure and unique structure. In La2GeO5 based oxides, La deciency leads to the formation of oxygen vacancies and oxide ion conductivity in La1.61GeO5-d is the highest in La2GeO5 based oxides. The transport number of the oxide ion is nearly unity in the O2 partial pressure range 110-21 atm and the conductivity is comparable to that of well-known fast oxide ion conductors, e.g., La0.9Sr0.1Ga0.8Mg0.2O3-d and Gd-doped CeO2. Recently, nano-size effects on ionic

2.7 Magnetic Characteristics and Ionic Conductivity


conductivity have been attracting much interest because of improved ion conductivity. Some researchers reported that the uoride ionic conductivity in CaF2 and BaF2 hetero-layered lms, prepared by molecular-beam epitaxy, increases proportionally with increasing interface density, namely, decreasing thickness, when the interface spacing is larger than 50 nm, which is in agreement with the semi-innite space-charge calculation. In contrast, due to the positive charge at grain boundary, negative nano-size effects were reported for the oxide ion conductivity in CeO2 based oxides. On the other hand, it is reported that the oxide ion conductivity in the laminated lms consisting of ZrO2 and Gd doped CeO2 (GDC) thin lm increases with decreasing number of lamination. The effects of nano grain size on the ionic conductivity on La2GeO5 based oxide lm and it was found that the conductivity was improved by decreasing lm thickness of La2GeO5. However, in the conventional study, nano-size effects are not studied systematically and so, the nano-size effects are still not clear. New oxide ion conductor of La1.61GeO5-d lm of various thicknesses was fabricated as thin lms of varying thickness on dense polycrystalline Al2O3 substrates by using pulsed laser deposition. The obtained La1.61GeO5-d lm by Ishihara et al. [175] exhibited almost the pure oxide ionic conductivity and the oxide ion conductivity increased with the decrease of the lm thickness. In particular, increase of conductivity at low temperature was more signicant. Considering the stable valence number of La and variable valence of Ge (3+ and 4+), the amount of oxygen vacancies can be determined by the composition of the lm. Since the composition of the prepared La1.61GeO5-d lms is almost the same, it is generally considered that the increased conductivity may not be explained by the change in the amount of oxygen vacancy but by the improved mobility of oxide ion by the local stress caused by the mismatch in lattice parameter between the lm and the substrate. Figure 2.10 illustrates arrhenius plots of La1.61GeO5-d thin lms and

Fig. 2.10 Arrhenius plots of La1.61GeO5-d thin lms and that of bulk La1.61GeO5-d sample, reprinted with kind permission from Tatsumi Ishihara [175]

58 Fig. 2.11 PO2 dependence of the electrical conductivity in La1.61GeO5-d thin lm with various thicknesses at 873K, reprinted with kind permission from Tatsumi Ishihara [175]

2 Size Dependency in Nanostructures

that of bulk La1.61GeO5-d sample. PO2 dependence of the electrical conductivity in La1.61GeO5-d thin lm with various thicknesses at 873K can be seen in Fig. 2.11.

2.8 Thermal Stability

Thermal stability of nano-crystals is of a great importance in high temperature applications. For electro-deposited nano-crystals thermal stability is examined through TEM and an indirect method, involving determination of thermal stability using harness measurements as a function of annealing time. For synthetic growth of grains there are some preventing factors for grain boundary movements leading to their thermal stability. There is a slowing dual force in nano-crystals due to triple connections. It can be easily shown that grain growth for ned multi-crystal materials is controlled by inherent movement of triple connections. For thermal stability of nano-structures, extra distributions of triple connections lead to preferred dissolve in these spots. Such a dissolve was observed in nano-crystals in triple connections using TEM method. Ni stability with grain sizes of 10 and 20 nm was investigated, using TEM. Degradation temperature for these materials is 353K. This lack of stability is due to unusual germination after annealing.

2.9 Nanocoatings Applications

Nano-crystalline structures made of electro-deposition have some commercial applications, due to these following reasons: 1. Electro-shaping and electroplating are recognized industries with extensive usage.

2.9 Nanocoatings Applications


2. Their low cost: Nano-crystals can be created using a simple modication in bath electrical parameters applied for electroplating and electro-shaping current. 3. High potential of producing materials, alloys, and composites with metallic matrix in different forms at one stage (i.e. coatings, complicated shapes, and etc.). 4. Capability of producing nano-structures with high density and no porosity.

2.9.1 Structural Applications

As it is expected from HallPetch assumptions, there are different practical applications for nano-crystals based on existed criteria for development of resistant coatings. Preferential mechanical properties of electro-deposited nano-structures are among their most important industrial applications. Electroplating process is applied for in situ maintenance of nuclear steam generator tubes. This process is successfully applied in aqueous reactors in US and Canada and registered as a standard method for repairing pressure tube. Through this application, Ni with grain size of 100 nm, is created on interior walls of steam generator tubes to perform a complete structural maintenance in places where primary homogeneity of tube structure is mitigated. High strength and convenient malleability of these 100 nm grains result in application of a thin plate (0.51 mm) which minimizes uid current and heat transition in steam generator. Recent geometrical models and empirical achievements have shown that nano-structural materials can have a high resistance against creep and inter-granular cracking. Different applications of nano-structural materials, where their inter-granular properties of resistance against cracking are used, include: positive plates of Acid-Pb batteries and load shaped lines (made of Cu, Pb, and Ni) for industrial applications.

2.9.2 Functional Applications

One of the most successful applications of nano-structural materials is in soft magnetic materials for engines, transformators, and etc. Predicted decrease in anisotropy of magnetic crystal during grain size decrease, compared to its predened thickness, has been investigated. Electro-deposited nano-crystals would have a low coordination without causing any damage to saturation magnetism. Hence, application of these ferromagnetic materials with high efciency in engines, transformators, anti-attack applications, has been enhanced due to recent advancements in electroplating technology. Through this technology it is possible to economically mass production of plates, thin sheets, and wires. Another important application of electroplated nano-crystalline materials is for production of thin copper-made sheets for print circuit sheets.


2 Size Dependency in Nanostructures

Etching rate increases when grain size declines and grain sizes of 50100 nm provide optimum etching with maintaining convenient electrical conductivity. At it previously mentioned, high density of intra-crystalline defects is present in bulk state and cutting free surface of nano-structure materials offers a good chance for hydrogen and catalyst storage applications. There are many different applications for usage of these materials in both electrodeposited and electro-shaping methods for battery systems and alkaline fuel cell electrodes.

2.9.3 Classication of Applications

Improved hardness, wear and corrosion resistances, as well as decrease of saturation magnetism, acceptable thermal range, elastic properties, and electrical resistance make nano-crystal coatings an ideal candidate for protecting and associated coatings (such as in contact of hard and soft surface, coatings with less abrasive resistance, electronic conductivity, and alternative coatings for Cr and Cd in aerospace applications). Once such thin coatings are used, sediment nestructural changes with coating thickness increase of a great importance. Most previous studies on electrodeposited metals, not necessarily on their nanocrystalline form, have shown that increase of coating thickness causes to increase of grain size. For electrodeposited nano-crystalline Ni, it is found that rst the sediment was amorphous with transition to nano-crystalline state and then there is an increase in grain size. In contrary, electrodeposited nano-crystals of Ni suggest that in most cases nano-crystals are exactly settled on interface with matrix and grain size is basically dependent from coating thickness. For distinct electrochemical conditions there is a thin transition layer made of coarser grains. Finally it has been proven that at initial layer with thickness of 200 nm grain sizes is independent from thickness [155, 176185]. Table 2.2 introduces some applications of nano-coatings.

2.10 Key Points for Development 2.10.1 Environment and Stability

In most cases surface engineering leads to economically use of materials and, consequently, protability in many applications. For instance, increasing service lifetime there will be a decrease in wastes and energy consumption, which caused to retrieve improvement. Many advanced surface engineering processes have negligible environmental effects. One of developing activities in this led is recoating of high-cost panels. Environmental rules, limiting each one of these panels wear, have a big share in progress of these industries.

2.10 Key Points for Development 61

Table 2.2 Applications of some size affected nano-coatings Industrial applications of Coatings resistant against scratch, wear, corrosion, and environmental Coatings resistant against scratch, abrasion, corrosion, nano-coatings factors and environmental factors Using alumina as a scratch, abrasion resistant coating Manufacturing light resistant panels for airplane structure Nano-metric corrosion protector coating Using nano-particles for coating in transportation industry Using nano-metric coating of ceramics in navy force Using nano-metric coating for strength increase Using nano-metric coating for clothes Manufacturing nano-metric coating of WC/CoNi through electrodepositing method Various types of optical coatings including antireection, mist Using light-resistant layers of UV resistant coating and protective coatings Surface improvement for making mist and steam resistant layers Making panels with nano-metric coating Self-cleaner glasses Coatings with medical, biologic, and environmental applications Nano-metric coating of inorganic particles for medical applications Using nano-particles in masks Using nano-metric coating of hydroxyl-apatite for making prosthesis Using nano-composite coating for food packing Anti-pollution materials in shipping industry Nano-composite coating for dealing with viruses Using Ag nano-particles as an anti-bacterial coating Using TiO2 nanoparticles to decrease environmental pollutions (continued)


Table 2.2 Continued Coatings with electrical and electronic applications Making transparent conductor coatings using carbon nano-tubes Using nano-metric coating in solar cells Nano-metric coating of Ni particles with oxides Using nano-metric polarizer layers in production of LCD monitors Manufacturing transparent electrically conductor nano-metric coating Increasing storage capacity by magnetic nano-layers Development of nano-metric coating for lubrication of surfaces

2 Size Dependency in Nanostructures


Key Points for Development


2.10.2 Weight and Volume Reduction

From this viewpoint, applied panelsespecially ones used in vehicleare considered. Al, Ti, and Mg alloys are required for improvement of surface corrosive and abrasive resistance. In these cases a mixture of two or several processes are needed in surface engineering. Also, polymers surface engineering has a great potential for development in structural applications.

2.10.3 Smart Layers and Structures

Application of enhanced structures is of suitable accountability for increasing environmental conditions. This can conduct in more development in technological application of sensors which are able to create a revolution in applications such as intelligent anti-oxide layers in steam turbines, self-watching structures, and packing food products. At all of these cases surface engineering plays a key role.

2.10.4 Processes Understanding

Surface engineering processes and relationship between processes features should be better understood. This adequate perception leads to improvement of process control quality and trustable quality and more insurance of the buyer. Modeling has a key role at these processes and generating convincing data is preferable. Some of important technologies of surface engineering must be improved through development of processes to increase rate of marked layer or change step by step processes to a continuous ones.

2.10.5 Training
Engineers must mainly be aware of surface engineering potential and its exact role on designing; also mechanical engineering courses should involve these points. For instance, surface engineering must be created as a major in manufacturing engineering. Lack of harmony and compatibility between industrial needs and academic works will create some problems. This has been examined in various cases. Surface engineering programs will nally cause to a development in university and industry, which should be better emphasized.


2 Size Dependency in Nanostructures

2.11 Surface Engineering Share in Key Industry Sections

Building planes and vehicles comprehensively depend on surface-engineered panels. About 80% of these industries make use of coating. England has rst position in eld of steam turbines coating and annually obtains 1 billion pound bonus. Advanced coating of panels has considerably increased during last decades. In 1997, 23% of quick machining components for steel and 67% of monolithic carbide panels are coated by physical and chemical evaporation. Coating with Physical Vaporization Detector (PVD) method involves 5 billion pounds annual revenue. PVD coating in production of multi-layers for high efciency cutting tools has made dry machining possible, which needs a cooler coating with no decrease in protability. Surface engineering of dual compounds and light alloy panels are used in special vehicles and advance applications such as coast equipment, medicine, and sports. Continuous manufacturing and performance of packaging industry is widely associated with surface engineering. Thanks to surface engineering, 44 billion drink cans are annually produced in Europe. Coating role for improvement of productions and their packaging is vital; especially in preventing air and moisture diffusion on potato chips and prepared food, or as a protector against crashing or cracking for thin glasses. Multilayer sputtering magnetron of a coating with low diffusion on construction glasses decreases thermal waste to 60% during winters, which amounts to a signicant annual gure of fuel/m2 of glass. It is expected that 50% of buildings use these glasses till 2005. Plasma improvement of polyethylene surface with high molecular weight causes its durability against slight shakes, which is applied in medicine. For tissue recovery with advanced bio-sensors, all attached plastic biomedical panels to substrates use engineered surfaces to create efcient and compatible performance with human body. All electronic panels and advance sensors, optical coatings, and etc. also are beneted from surface engineering technology during building process [186188].

2.12 Estimation of Corrosion and Erosion Costs

During last 10 years, due to educations for improvement of awareness from corrosion related issues, there was a 515 million pounds saving in England. Studies show similar values of total gross products for India, China, and United States. For United States decay costs exceeds 100 billion dollars annually. This is 1,300 million pounds for England, which is 3.5% of State gross product, where 3.0 million pounds is saved. This amount is 4850 billion dollars in United States, which compose 4% of per capita gross production. As it previously remarked, this amounts to 10% of national gross production in developing countries.


Surface Engineering in Automobile Industry


2.13 Surface Engineering in Automobile Industry

There are nearly 27 million cars and 3.3 commercial vehicles in England roads. Car sale in Europe was about 12 million in 1997, where England share was about 1.7 million. It is estimated that car manufacturing will be 17% of Englands surface engineering. Surface engineering has a signicant role in this industry; since 6% of engine building costs and power transfer is for coating technology. Total produced color for this industry exceeds 300 million pounds. Protective steel and body panels, as infrastructures, need to be repaired; so, many of them are galvanized and prepared for painting with another suitable coating. While metals mostly are coated by organic painting, plastics should be initially metalized. Here, application of wet processes competes with advancements in PVD and CVD methods. Market is not the only effective factor on technology progress, but there are some environmental and legislation concerns which are considered as a powerful encouragement in this eld. Painting just involves about 2 kg of vehicles weight, while painting process emits about 5 kg Volatile Organic Compounds (VOC) to the atmosphere. Efforts for reduction of this effect led to development of powder technology advancement. Most of coatings changes involve using the CrVI, where some substitute are being made for that. Automobile industry is directed to reaching products with higher compatibility with environment; as in their producing method application of CrVI is avoided. Mentioned cases are only a small part of coating applications.

2.14 Surface Engineering in Power Generation Industry

Here, power generation is addressed to high efciency engines for aerospace industry, marine gas turbines, and electric generating turbines. Gas turbines are considered as a part of combinational cyclic developed machinery. Gas turbines have some advantages compared with equipment of power generating from fossil fuels, such as higher efciency, lower constructing costs and using different fuels. This equipment work at higher temperatures and combustion and hot gas pass occurs within them. Here, creep, oxidization, and corrosion are regarded among important factors. Achieving ideal conditions, coating is of a great importance. Coating system is widely applied in gas turbines to protect gas pass route and increase system lifetime. The following objectives are supposed to be achieved during 5 coming years: 1. 2. 3. 4. A 50C increase in work temperature 10,000 h increase of panels lifetime One hundred percent Increase in system visitation time A wide increase of applied fuels, natural gas, heavy fuels originated from coal, biomass, and etc.


2 Size Dependency in Nanostructures

Achieving these objectives, coating systems should be developed. There are so many researches in this eld. Regarding various ndings all studies are directed on intelligent corrosion resistant coatings. These coatings can be appropriate answer for corrosive environments, in order to avoiding panels oxidization. This state is achievable through plasma spray technology, CVD, development in platinum aluminate, and new insulating materials (layering and staining where both have low electrical conductivity). As well as above-mentioned applications, use of composite surfaces as a substrate for main layer of ceramicswhich of a good thermal compatibility with the layer as well as stability against corrosionis also progressing. Nowadays, there are comprehensive investigations at this area.

1. Arranz, M.A., Colino, J.M.: Nanoscale ripple formation in Co/Si(100) thin lms with Ar+ beam etching. J. Phys. Conf. Ser. 200, 14 (2010) 2. Aubry, A., Lei, D.Y., Maier, S.A., Pendry, J.B.: Broadband plasmonic device concentrating the energy at the nanoscale: the crescent-shaped cylinder. Phys. Rev. B Conden. Matter Mater. Phys. 82 (2010) 3. De Arruda Rodrigues, C., De Tacconi, N.R., Chanmanee, W., Rajeshwar, K.: Cathodic electrosynthesis of niobium oxide one-dimensional nanostructures with tailored dimensions. Electrochem. Solid State Lett. 13, B69B72 (2010) 4. Krzeminski, M., Molinari, M., Troyon, M., Coqueret, X.: Characterization by atomic force microscopy of the nanoheterogeneities produced by the radiation-induced cross-linking polymerization of aromatic diacrylates. Macromolecules 43, 81218127 (2010) 5. Liang, H.W., Liu, S., Yu, S.H.: Controlled synthesis of one-dimensional inorganic nanostructures using pre-existing one-dimensional nanostructures as templates. Adv. Mater. 22, 39253937 (2010) 6. Liang, S., Fang, X., Xia, T.L., Qing, Y., Guo, Z.X.: Self-assembled magnetic nanohead-FeSi nanowire epitaxial heterojunctions by chemical vapor deposition. J. Phys. Chem. C 114, 1618716190 (2010) 7. Rinaldi, A., Correa-Duarte, M.A., Salgueirino-Maceira, V., Licoccia, S., Traversa, E., Davila-Ibaez, A.B., Peralta, P., Sieradzki, K.: Elastic properties of hard cobalt boride composite nanoparticles. Acta Materialia 58, 64746486 (2010) 8. Xiao, X., Sachdev, A.K., Haddad, D., Li, Y., Sheldon, B.W., Soni, S.K.: Stress-induced Sn nanowires from SiSn nanocomposite coatings. Appl. Phys. Lett. 97 (2010) 9. Enz, T., Sieger, H., Fasel, C., Hahn, H.: Nanocomposite formation through thermal decomposition of mixed samarium and magnesium citrate-derived gels formed by spray pyrolysis. J. Am. Ceram. Soc. 91, 30663073 (2008) 10. Bobzin, K., Ernst, F., Zwick, J., Schlaefer, T., Cook, D., Nassenstein, K., Schwenk, A., Schreiber, F., Wenz, T., Flores, G., Hahn, M.: Coating bores of light metal engine blocks with a nanocomposite material using the plasma transferred wire arc thermal spray process. J. Therm. Spray Tech. 17, 344351 (2008) 11. Gregory, O.J., Wnuk, S., Downey, M.A., Wnuk, V.: Improved thermal spray instrumentation using intermediate nanocomposite coatings. In: Proceedings of the International Instrumentation Symposium, pp. 223233. (2004) 12. Gregory, Q.J., Wnuk, S., Downey, M.A., Wnuk, V.: Improved thermal spray instrumentation using intermediate nanocomposite coatings. In: Technical Papers of ISA, pp. 223233. (2004)



13. Dey, A., Mukhopadhyay, A.K., Gangadharan, S., Sinha, M.K., Basu, D., Bandyopadhyay, N.R.: Nanoindentation study of microplasma sprayed hydroxyapatite coating. Ceram. Int. 35, 22952304 (2009) 14. Grigore, E., Ruset, C., Li, X., Dong, H.: The inuence of carbon content on the characteristics of VCN coatings deposited by combined magnetron sputtering and ion implantation (CMSII). Surf. Coat. Technol. 204, 20062009 (2010) 15. Fox-Rabinovich, G.S., Yamamoto, K., Kovalev, A.I., Veldhuis, S.C., Ning, L., Shuster, L.S., Elzy, A.: Wear behavior of adaptive nano-multilayered TiAlCrN/NbN coatings under dry high performance machining conditions. Surf. Coat. Technol. 202, 20152022 (2008) 16. Ii, J., Kim, I., Dost, S.: Texture evolution in TiN, TaN and W2N thin lms, In: Materials Science Forum, pp. 15911596. (2002) 17. Solodukhin, I.A., Khodasevich, V.V., Uglov, V.V., Brizuela, M., Oate, J.I.: The use of preliminary ion implantation and heating on the substrate for modifying TiN coating properties and TiN/substrate interface. Surf. Coat. Technol. 142144, 11441147 (2001) 18. Ji, H.B., Xia, L.F., Ma, X.X., Sun, Y., Sun, M.R.: Comparison of surface properties of Ti 6Al4V coated with titanium nitride, TiN+TiC+Ti(C,N)/DLC, TiN/DLC and TiC/DLC lms by plasma-based ion implantation. Acta Metallurgica Sinica (English Letters) 13, 967 973 (2000) 19. Olszyna, A.R., Biesiada, K., Smolik, J.: Super-hard carbon layers produced on the Al2O3/ Al2O3+x%SiC (whiskers) ceramic cutting edges. Plasma Process. Polym. 4, S278S281 (2007) 20. Guo, Y., Ma, S., Xu, K.: Effects of carbon content and annealing temperature on the microstructure and hardness of super hard TiSiCN nanocomposite coatings prepared by pulsed d.c. PCVD. Surf. Coat. Technol. 201, 52405243 (2007) 21. Reie, G., Weimantel, S., Rost, D.: Preparation of super-hard coatings by pulsed laser deposition. Appl. Phys. A Mater. Sci. Process. 79, 12751278 (2004) 22. Zhou, J., Walleser, J.K., Meacham, B.E., Branagan, D.J.: Novel in situ transformable coating for elevated-temperature applications. J. Therm. Spray Tech. 19, 950957 (2010) 23. Tsotsos, C., Baker, M.A., Polychronopoulou, K., Gibson, P.N., Giannakopoulos, K., Polycarpou, A.A., Bbel, K., Rebholz, C.: Structure and mechanical properties of low temperature magnetron sputtered nanocrystalline (nc)Ti(N,C)/amorphous diamond like carbon (aC:H) coatings. Thin Solid Films 519, 2430 (2010) 24. Abad, M.D., Muoz-Mrquez, M.A., El Mrabet, S., Justo, A., Snchez-Lpez, J.C.: Tailored synthesis of nanostructured WC/aC coatings by dual magnetron sputtering. Surf. Coatings Technol. 204, 34903500 (2010) 25. Garcia-Torres, J., Gmez, E., Valls, E.: Modication of magnetic and structural properties of Co and CoAg electrodeposits by sulphur incorporation. Mater. Chem. Phys. 122, 463 469 (2010) 26. Fabrizi, A., Cabibbo, M., Cecchini, R., Spigarelli, S., Paternoster, C., Haidopoulo, M., Kiryukhantsev-Korneev, P.V.: Thermal stability of nanostructured coatings. In: Materials Science Forum, pp. 122. (2010) 27. Wang, Y., Li, Z., Du, J., Wang, B.: Mechanical properties of the plasma-enhanced magnetron sputtering SiCN coatings. Appl. Surf. Sci. 257, 15 (2010) 28. McCrea, J.L.: Industrial implementation of nanostructured cobalt as an alternative to hard chrome. Surf. Eng. 26, 149152 (2010) 29. Zhao, J., Peng, X., Wang, F.: Fabrication of a nitrided coating on a novel NiCr nanocomposite with increased surface hardness. Mater. Res. Bull. 45, 420424 (2010) 30. Abu Samra, H., Staedler, T., Aronov, I., Xia, J., Jia, C., Wenclawiak, B., Jiang, X.: Deposition and characterisation of nanocrystalline Mo2N/BN composite coatings by ECR plasma assisted CVD. Surf. Coat. Technol. 204, 19191924 (2010) 31. Weston, D.P., Harris, S.J., Capel, H., Ahmed, N., Shipway, P.H., Yellup, J.M.: Nanostructured CoW coatings produced by electrodeposition to replace hard Cr on aerospace components. Trans. Inst. Met. Finish. 88, 4756 (2010)


2 Size Dependency in Nanostructures

32. Maury, F., Douard, A., Delclos, S., Samelor, D., Tendero, C.: Multilayer chromium based coatings grown by atmospheric pressure direct liquid injection CVD. Surf. Coatings Technol. 204, 983987 (2009) 33. Kumar, A., Kaur, D.: Nanoindentation and corrosion studies of TiN/NiTi thin lms for biomedical applications. Surf. Coatings Technol. 204, 11321136 (2009) 34. Ziebert, C., Albers, U., Stber, M., Ulrich, S.: Constitution and mechanical properties of nanocrystalline reactive magnetron sputtered VAlCN hard coatings as a function of the carbon content. Plasma Process. Polym. 6, S560S565 (2009) 35. Modi, S.H.H., Aliofkhazraei, M., Rouhaghdam, A.S., Ghobadi, E., Mohsenian, E.: Improvement of surface characteristics by electroplating hard chromium coating post treated by nanocrystalline plasma electrolytic carbonitriding. Plasma Process. Polym. 6, S297S301 (2009) 36. Tsyntsaru, N., Dikusar, A., Cesiulis, H., Celis, J.P., Bobanova, Z., SidelNikova, S., Belevskii, S., Yapontseva, Y., Bersirova, O., Kublanovskii, V.: Tribological and corrosive characteristics of electrochemical coatings based on cobalt and iron superalloys. Powder Metall. Met. Ceram. 48, 419428 (2009) 37. Fox-Rabinovich, G.S., Kovalev, A.I., Aguirre, M.H., Beake, B.D., Yamamoto, K., Veldhuis, S.C., Endrino, J.L., Wainstein, D.L., Rashkovskiy, A.Y.: Design and performance of AlTiN and TiAlCrN PVD coatings for machining of hard to cut materials. Surf. Coat. Technol. 204, 489496 (2009) 38. Krause, M., Bedel, L., Taupeau, A., Kreissig, U., Munnik, F., Abrasonis, G., Kolitsch, A., Radnoczi, G., Czigany, Z., Vanhulsel, A.: Structural and mechanical characterization of BCxNy thin lms deposited by pulsed reactive magnetron sputtering. Thin Solid Films 518, 7783 (2009) 39. Zeng, Z., Zhou, Y., Zhang, B., Sun, Y., Zhang, J.: Designed fabrication of hard Cr{single bond}Cr2O3{single bond}Cr7C3 nanocomposite coatings for anti-wear application. Acta Mater. 57, 53425347 (2009) 40. Stueber, M., Holleck, H., Leiste, H., Seemann, K., Ulrich, S., Ziebert, C.: Concepts for the design of advanced nanoscale PVD multilayer protective thin lms. J. Alloys Compd. 483, 321333 (2009) 41. Boonyongmaneerat, Y., Saengkiettiyut, K., Saenapitak, S., Sangsuk, S.: Effects of WC addition on structure and hardness of electrodeposited NiW. Surf. Coat. Technol. 203, 35903594 (2009) 42. Gupta, G., Mondal, K., Balasubramaniam, R.: In situ nanocrystalline FeSi coating by mechanical alloying. J. Alloys Compd. 482, 118122 (2009) 43. Bobanova, Z.I., Dikusar, A.I., Cesiulis, H., Celis, J.P., Tsyntsaru, N.I., Prosycevas, I.: Micromechanical and tribological properties of nanocrystalline coatings of irontungsten alloys electrodeposited from citrate-ammonia solutions. Russ. J. Electrochem. 45, 895901 (2009) 44. Vojtech, D.: Properties of hard NiPAl2O3 and NiPSiC coatings on al-aased casting alloys. Mater. Manufact. Process. 24, 754757 (2009) 45. Jung, A., Natter, H., Hempelmann, R., Lach, E.: Nanocrystalline alumina dispersed in nanocrystalline nickel: enhanced mechanical properties. J. Mater. Sci. 44, 27252735 (2009) 46. Mishra, S.K.: Nano and nanocomposite superhard coatings of silicon carbonitride and titanium diboride by magnetron sputtering. Int. J. Appl. Ceramic Technol. 6, 345354 (2009) 47. Krella, A., Czyzniewski, A.: Cavitation resistance of CrN coatings deposited on austenitic stainless steel at various temperatures. Wear 266, 800809 (2009) 48. Aliofkhazraei, M., Sabour Rouhaghdam, A., Heydarzadeh, A., Elmkhah, H.: Nanostructured layer formed on CPTi by plasma electrolysis (effect of voltage and duty cycle of cathodic/ anodic direction). Mater. Chem. Phys. 113, 607612 (2009) 49. Ranjith, B., Paruthimal Kalaignan, G.: NiCoTiO2 nanocomposite coating prepared by pulse and pulse reversal methods using acetate bath. Appl. Surf. Sci. 257, 4247 (2010)



50. Guo, Y., Wang, Q.: Facile approach in fabricating superhydrophobic coatings from silicabased nanocomposite. Appl. Surf. Sci. 257, 3336 (2010) 51. Antonello, A., Brusatin, G., Guglielmi, M., Martucci, A., Bello, V., Mattei, G., Mazzoldi, P., Pellegrini, G.: Hybrid organic-inorganic ZnSloaded nanocomposite lms for stable optical coatings. Thin Solid Films 518, 67816786 (2010) 52. Moskalewicz, T., Wendler, B., Czyrska-Filemonowicz, A.: Microstructural characterisation of nanocomposite ncMeC/aC coatings on oxygen hardened Ti6Al4V alloy. Mater. Charact. 61, 959968 (2010) 53. Liu, X.W., Devaraju, M.K., Yin, S., Sato, T.: Calcium-doped ceria/titanate tabular functional nanocomposite by layer-by-layer coating method. J. Solid State Chem. 183, 15451549 (2010) 54. Heidarian, M., Shishesaz, M.R., Kassiriha, S.M., Nematollahi, M.: Characterization of structure and corrosion resistivity of polyurethane/organoclay nanocomposite coatings prepared through an ultrasonication assisted process. Prog. Org. Coat. 68, 180188 (2010) 55. Sharif, M., Faghihi-Sani, M.A., Golestani-Fard, F., Saberi, A., Soltani, A.K.: Coating of graphite akes with MgO/carbon nanocomposite via gas state reaction. J. Alloys Compd. 500, 7477 (2010) 56. Mge-Revil, A., Steyer, P., Cardinal, S., Thollet, G., Esnouf, C., Jacquot, P., Stauder, B.: Correlation between thermal fatigue and thermomechanical properties during the oxidation of multilayered TiSiN nanocomposite coatings synthesized by a hybrid physical/chemical vapour deposition process. Thin Solid Films 518, 59325937 (2010) 57. Vartiainen, J., Tuominen, M., Nttinen, K.: Bio-hybrid nanocomposite coatings from sonicated chitosan and nanoclay. J. Appl. Polymer Sci. 116, 36383647 (2010) 58. Guo, Y., Jiang, D., Zhang, X., Zhang, Z., Wang, Q.: Room temperature synthesis of waterrepellent polystyrene nanocomposite coating. Appl. Surf. Sci. 256, 70887090 (2010) 59. Wo, P.C., Munroe, P.R., Zhou, Z.F., Li, K.Y., Xie, Z.H.: Effects of TiN sublayers on the response of TiSiN nanocomposite coatings to nanoidentation and scratching contacts. Mater. Sci. Eng. A 527, 44474457 (2010) 60. Abdul Samad, M., Sinha, S.K.: Nanocomposite UHMWPE-CNT polymer coatings for boundary lubrication on aluminium substrates. Tribol. Lett. 38, 301311 (2010) 61. Mulligan, C.P., Blanchet, T.A., Gall, D.: CrNAg nanocomposite coatings: hightemperature tribological response. Wear 269, 125131 (2010) 62. Bahadormanesh, B., Dolati, A.: The kinetics of NiCo/SiC composite coatings electrodeposition. J. Alloys Compd. 504, 514518 (2010) 63. Fan, Y., Chen, D.: Control-steps and inuence factors of SiO2 electrodeposition process with Zn coatings. In: Advanced Materials Research, pp. 14161419. (2010) 64. Rudnik, E.: Inuence of Cs+ ions on codeposition of SiC particles with NiCo alloy. Trans. Inst. Metal Finish. 87, 239245 (2009) 65. Liu, H., Chen, W.: Electrodeposited NiAl composite coatings with high Al content by sediment co-deposition. Surf. Coat. Technol. 191, 341350 (2005) 66. Hu, F., Chan, K.C.: Electrocodeposition behavior of NiSiC composite under different shaped waveforms. Appl. Surf. Sci. 233, 163171 (2004) 67. Ramesh Bapu, G.N.K., Thiruchelvam, T.: Validity of adsorption mechanism for electrodeposited zinc composites. Bull. Electrochem. 17, 405408 (2001) 68. Chang, Y.C., Chang, Y.Y., Lin, C.I.: Process aspects of the electrolytic codeposition of molybdenum disulde with nickel. Electrochim. Acta 43, 315324 (1998) 69. Mirzamohammadi, S., Kiarasi, R., Aliov, M.K., Sabur, A.R., Hassanzadeh-Tabrizi, A.: Study of corrosion resistance and nanostructure for tertiary Al2O3/Y2O3/CNT pulsed electrodeposited Ni based nanocomposite. Trans. Inst. Metal Finish. 88, 9399 (2010) 70. Ulrich, S., Ye, J., Stber, M., Ziebert, C.: Cubic boron nitride based metastable coatings and nanocomposites. Thin Solid Films 518, 14431450 (2009) 71. Popov, C., Bliznakov, S., Kulisch, W.: Inuence of the substrate nature on the properties of nanocrystalline diamond lms. Diam. Relat. Mater. 16, 740743 (2007)


2 Size Dependency in Nanostructures

72. Perez-Mariano, J., Lau, K.H., Sanjurjo, A., Caro, J., Casellas, D., Colominas, C.: TiSiN nanocomposite coatings by chemical vapor deposition in a uidized bed reactor at atmospheric pressure (AP/FBR-CVD). Surf. Coat. Technol. 201, 22172225 (2006) 73. Kulisch, W., Popov, C., Vorlicek, V., Gibson, P.N., Favaro, G.: Nanocrystalline diamond growth on different substrates. Thin Solid Films 515, 10051010 (2006) 74. Li, Y.S., Kiyono, H., Shimada, S., Lu, X., Hirose, A.: Mechanical and eld emission properties of CGed Si(C,N) lms synthesized by PECVD from HMDS precursor. Diam. Relat. Mater. 15, 17271731 (2006) 75. Lattemann, M., Sell, K., Ye, J., Persson, P.A.O., Ulrich, S.: Stress reduction in nanocomposite coatings consisting of hexagonal and cubic boron nitride. Surf. Coat. Technol. 200, 64596464 (2006) 76. Li, Y.S., Shimada, S., Kiyono, H., Hirose, A.: Synthesis of TiAlSiN nanocomposite lms using liquid injection PECVD from alkoxide precursors. Acta Mater. 54, 20412048 (2006) 77. Winkelmann, A., Cairney, J.M., Hoffman, M.J., Martin, P.J., Bendavid, A.: ZrSiN lms fabricated using hybrid cathodic arc and chemical vapour deposition: structure vs. properties. Surf. Coat. Technol. 200, 42134219 (2006) 78. Yoon, J.K., Kim, G.H., Han, J.H., Shon, I.J., Doh, J.M., Hong, K.T.: Low-temperature cyclic oxidation behavior of MoSi2/Si3N4 nanocomposite coating formed on Mo substrate at 773 K. Surf. Coat. Technol. 200, 25372546 (2005) 79. Polini, R., Amar, M., Ahmed, W., Kumashiro, S., Sein, H., Colligon, J.S.: A study of diamond synthesis by hot lament chemical vapour deposition on nanocomposite coatings. Thin Solid Films 489, 116121 (2005) 80. Aliofkhazraei, M., Rouhaghdam, A.S., Ghobadi, E., Mohsenian, E.: Electrodeposition and mechanical and corrosion resistance properties of tertiary Ni-W/Al2O3/CNT nanocomposite coatings. In: Advanced Materials Research, pp. 1216. (2010) 81. Ciubotariu, A., Benea, L., Lakatos-Varsanyi, M., Dragan, V.: Electrochemical impedance spectroscopy and corrosion behaviour of Al2O3Ni nano composite coatings. Electrochim. Acta 53, 45574563 (2008) 82. de Hazan, Y., Werner, D., ZGraggen, M., Groteklaes, M., Graule, T.: Homogeneous NiP/ Al2O3 nanocomposite coatings from stable dispersions in electroless nickel baths. J. Colloid Interf. Sci. 328, 103109 (2008) 83. Feng, Q., Li, T., Teng, H., Zhang, X., Zhang, Y., Liu, C., Jin, J.: Investigation on the corrosion and oxidation resistance of NiAl2O3 nano-composite coatings prepared by sediment co-deposition. Surf. Coat. Technol. 202, 41374144 (2008) 84. Feng, Q., Li, T., Yue, H., Bai, F., Qi, K., Jin, J.: Sediment co-deposition of nanostructured Ni-Al2O3 composite coatings. In: Key Engineering Materials, pp. 244247. (2008) 85. Feng, Q., Li, T., Zhang, Z., Zhang, J., Liu, M., Jin, J.: Preparation of nanostructured Ni/ Al2O3 composite coatings in high magnetic eld. Surf. Coat. Technol. 201, 62476252 (2007) 86. Liu, Y., Ren, L., Yu, S., Han, Z.: Inuence of current density on nano-Al2O3/Ni+Co bionic gradient composite coatings by electrodeposition. J. Univ. Sci. Technol. Beijing Min. Metallurg. Mater. (Eng Ed) 15, 633637 (2008) 87. Liu, Y., Yu, S.R., Ren, L.Q., Han, Z.W.: Nano-Al2O3/Ni + Co gradient composite coating by electrodeposition. Jilin Daxue Xuebao (Gongxueban)/J. Jilin Univ. (Engineering and Technology Edition) 39, 154158 (2009) 88. Mirzamohammadi, S., Aliov, M.K., Sabur, A.R., Hassanzadeh-Tabrizi, A.: Study of wear resistance and nanostructure of tertiary Al2O3/Y2O3/CNT pulsed electrodeposited ni-based nanocomposite. Mater. Sci. 46, 7686 (2010) 89. Wu, B., Xu, B.S., Zhang, B., L, Y.H.: Preparation and properties of Ni/nano-Al2O3 composite coatings by automatic brush plating. Surf. Coat. Technol. 201, 69336939 (2007) 90. Zhang, H., Zhou, Y., Hu, H.: Preparation and oxidation performance of an-Al2O3-modied chromizing coating. Xiyou Jinshu Cailiao Yu Gongcheng/Rare Metal Mater. Eng. 38, 1655 1658 (2009)



91. Zheng, H.Y., An, M.Z.: Electrodeposition of ZnNiAl2O3 nanocomposite coatings under ultrasound conditions. J. Alloys Compd. 459, 548552 (2008) 92. Zheng, H.Y., An, M.Z., Lu, J.F.: Surface characterization of the ZnNiAl2O3 nanocomposite coating fabricated under ultrasound condition. Appl. Surf. Sci. 254, 1644 1650 (2008) 93. Zhou, Y.B., Chen, H.Y., Zhang, H.J., Wang, Y.D.: Oxidation of Al2O3-dispersion chromizing coating by pack-cementation at 800C. Trans. Nonferrous Metals Soc. China (English Edition) 18, 598602 (2008) 94. Wang, H., Zuo, D., Chen, G., Sun, G., Li, X., Cheng, X.: Hot corrosion behaviour of low Al NiCoCrAlY cladded coatings reinforced by nano-particles on a Ni-base super alloy. Corros. Sci. 52, 35613567 (2010) 95. Barshilia, H.C., Acharya, S., Ghosh, M., Suresh, T.N., Rajam, K.S., Konchady, M.S., Pai, D.M., Sankar, J.: Performance evaluation of TiAlCrYN nanocomposite coatings deposited using four-cathode reactive unbalanced pulsed direct current magnetron sputtering system. Vacuum 85, 411420 (2010) 96. Chatterjee, S., Shariff, S.M., Padmanabham, G., Majumdar, J.D., Choudhury, A.R.: Study on the effect of laser post-treatment on the properties of nanostructured Al2O3TiB2TiN based coatings developed by combined SHS and laser surface alloying. Surf. Coat. Technol. 205, 131138 (2010) 97. Tang, F., Alam, T., Moody, M.P., Gault, B., Cairney, J.M.: Challenges associated with the characterisation of nanocrystalline materials using atom probe tomography. In: Materials Science Forum, pp. 23662369. (2010) 98. Wang, H., Zuo, D., Yan, J., Huang, M., Li, X.: Effects of nanometer Al2O3 particles on oxidation behaviors of laser cladding low Al NiCoCrAlY coatings. Oxid. Met. 74, 4960 (2010) 99. Masanta, M., Ganesh, P., Kaul, R., Roy Choudhury, A.: Microstructure and mechanical properties of TiB2TiCAl2O3SiC composite coatings developed by combined SHS, solgel and laser technology. Surf. Coat. Technol. 204, 34713480 (2010) 100. Lu, H., Zhang, W., Zhang, R., Xu, H., Wang, H., Chen, D., Yang, D.: Preparation of Fe coating Al2O3 nanometer composite powder and its mechanical properties after hot press sintering. Preparation of Fe coating Al2O3 nanometer composite powder and its mechanical properties after hot press sintering. In: Advanced Materials Research, pp. 1619. (2010) 101. Gao, J., He, Y., Wang, D.: Fabrication and high temperature oxidation resistance of ZrO2/ Al2O3 micro-laminated coatings on stainless steel. Mater. Chem. Phys. 123, 731736 (2010) 102. Olszowka-Myalska, A., Myalski, J., Botor-Probierz, A.: Microstructural characteristics of an AZ91 matrix-glassy carbon particle composite. Adv. Eng. Mater. 12, 609616 (2010) 103. Wang, L., Wan, S., Wang, S.C., Wood, R.J.K., Xue, Q.J.: Gradient DLC-based nanocomposite coatings as a solution to improve tribological performance of aluminum alloy. Tribol. Lett. 38, 155160 (2010) 104. Yin, B., Liu, G., Zhou, H., Chen, J., Yan, F.: Microstructures and properties of plasma sprayed FeAl/CeO2/ZrO2 nano-composite coating. Appl. Surf. Sci. 256, 41764184 (2010) 105. Han, Y., Wu, G., Li, H., Wang, M., Chen, H.: Highly efcient ultraviolet photodetectors based on TiO2 nanocrystal-polymer composites via wet processing. Nanotechnology 21 (2010) 106. Labille, J., Feng, J., Botta, C., Borschneck, D., Sammut, M., Cabie, M., Auffan, M., Rose, J., Bottero, J.Y.: Aging of TiO2 nanocomposites used in sunscreen. Dispersion and fate of the degradation products in aqueous environment. Environ. Pollut. 158, 34823489 (2010) 107. Lu, Z., Ren, M., Yin, H., Wang, A., Ge, C., Zhang, Y., Yu, L., Jiang, T.: Preparation of nanosized anatase TiO2-coated kaolin composites and their pigmentary properties. Powder Technol. 196, 122125 (2009) 108. Dinh, N.N., Chi, L.H., Long, N.T., Thuy, T.T.C., Trung, T.Q., Kim, H.K.: Preparation and characterization of nanostructured composite lms for organic light emitting diodes. J. Phys. Conf. Ser. 187 (2009)


2 Size Dependency in Nanostructures

109. Dinh, N.N., Chi, L.H., Chung Thuy, T.T., Trung, T.Q., Truong, V.V.: Enhancement of current-voltage characteristics of multilayer organic light emitting diodes by using nanostructured composite lms. J. Appl. Phys. 105 (2009) 110. Yang, S.M., Chang, Y.Y., Lin, D.Y., Wang, D.Y., Wu, W.: Thermal stability of TiAlN and nanocomposite TiAlSiN thin lms. J. Nanosci. Nanotechnol. 9, 11081112 (2009) 111. Dinh, N.N., Chi, L.H., Thuy, T.T.C., Thanh, D.V., Nguyen, T.P.: Study of nanostructured polymeric composites and hybrid layers used for light-emitting diodes. J. Korean Phys. Soc. 53, 802805 (2008) 112. Oliveira, J.C., Manaia, A., Cavaleiro, A.: Hard amorphous TiAlN coatings deposited by sputtering. Thin Solid Films 516, 50325038 (2008) 113. Abdel Aal, A.: Hard and corrosion resistant nanocomposite coating for Al alloy. Mater. Sci. Eng. A 474, 181187 (2008) 114. Zhai, C.S., Wang, J., Li, F., Tao, J.C., Yang, Y., Sun, B.D.: Thermal shock properties and failure mechanism of plasma sprayed Al2O3/TiO2 nanocomposite coatings. Ceram. Int. 31, 817824 (2005) 115. Parlinska-Wojtan, M., Karimi, A., Coddet, O., Cselle, T., Morstein, M.: Characterization of thermally treated TiAlSiN coatings by TEM and nanoindentation. Surf. Coat. Technol. 188 189, 344350 (2004) 116. Zahmatkesh, B., Enayati, M.H.: A novel approach for development of surface nanocomposite by friction stir processing. Mater. Sci. Eng. A 527, 67346740 (2010) 117. Pourhosseini, J., Zakeri, M., Rahimipour, M.R., Salahi, E., Pourhosseini, G.R.: Preparation of FeAlAl2O3 nanocomposite via mechanical alloying and subsequent annealing. Mater. Sci. Technol. 26, 11321136 (2010) 118. Zhitomirsky, V.N., Kim, S.K., Burstein, L., Boxman, R.L.: X-ray photoelectron spectroscopy of nano-multilayered ZrO/AlO coatings deposited by cathodic vacuum arc plasma. Appl. Surf. Sci. 256, 62466253 (2010) 119. Lv, H., Zhao, W., An, Q., Nie, P., Wang, J., Chu, P.K.: Nanomechanical properties and microstructure of ZrO2/Al2O3 plasma sprayed coatings. Mater. Sci. Eng. A 518, 185189 (2009) 120. Chen, C.H., Li, H.Y., Chien, C.Y., Yen, F.S., Chen, H.Y., Lin, J.M.: Preparation and characterization of a-Al2O3/Nylon 6 nanocomposite masterbatches. J. Appl. Polym. Sci. 112, 10631069 (2009) 121. Kulkarni, T., Wang, H.Z., Basu, S.N., Sarin, V.K.: Phase transformations in mullite-based nanocomposites. Int. J. Refract Metal Hard Mater. 27, 465471 (2009) 122. Stber, M., Albers, U., Leiste, H., Seemann, K., Ziebert, C., Ulrich, S.: Magnetron sputtering of hard CrAlNO thin lms. Surf. Coat. Technol. 203, 661665 (2008) 123. Wang, S.C., Tseng, C.H.: Effects of Al2O3 nanoparticle on the microstructure and magnetic properties of Co/Al2O3 coatings prepared by composite plating. In: Advanced Materials Research, pp. 131139. (2008) 124. Chang, Y.Y., Chang, C.P., Wang, D.Y., Yang, S.M., Wu, W.: High temperature oxidation resistance of CrAlSiN coatings synthesized by a cathodic arc deposition process. J. Alloys Compd. 461, 336341 (2008) 125. Du, X., Xu, Y.: Formation of Al2O3BaTiO3 nanocomposite oxide lms on etched aluminum foil by sol-gel coating and anodizing. J. Sol Gel. Sci. Technol. 45, 5761 (2008) 126. Balani, K., Bakshi, S.R., Chen, Y., Laha, T., Agarwal, A.: Role of powder treatment and carbon nanotube dispersion in the fracture toughening of plasma-sprayed aluminum oxidecarbon nanotube nanocomposite. J. Nanosci. Nanotechnol. 7, 35533562 (2007) 127. Hannula, S.P., Turunen, E., Keskinen, J., Varis, T., Flt, T., Gustafsson, T.E., Nowak, R.: Development of nanostructured Al2O3Ni HVOF coatings. In: Key Engineering Materials, pp. 539544. (2006) 128. Vida-Simiti, I., Jumate, N., Negrea, G., Sechel, N., Coman, C.: Structure of some composite materials for excessive wear applications. Metalurgia Int. 14, 137140 (2009) 129. Lin, W.S., Qian, S.Q., Xu, M.M.: Wear behavior of electro-brush plating Nano-WC/PTFENi composite coatings. Mocaxue Xuebao/Tribology 27, 442446 (2007)



130. Chen, H., Xu, C., Qu, J., Hutchings, I.M., Shipway, P.H., Liu, J.: Sliding wear behaviour of laser clad coatings based upon a nickel-based self-uxing alloy co-deposited with conventional and nanostructured tungsten carbide-cobalt hardmetals. Wear 259, 801806 (2005) 131. Mangam, V., Bhattacharya, S., Das, K., Das, S.: Friction and wear behavior of CuCeO2 nanocomposite coatings synthesized by pulsed electrodeposition. Surf. Coat. Technol. 205, 801805 (2010) 132. Zanella, C., Lekka, M., Bonora, P.L.: Effect of ultrasound vibration during electrodeposition of NiSiC nanocomposite coatings. Surf. Eng. 26, 511518 (2010) 133. Zhou, Z.F., Pan, Y., Lei, W.X.: Ni nanocomposite lms formed by Ni nanowires embedded in Ni matrix using electrodeposition. Trans. Nonferrous Metals Soc. China (English Edition) 20, 637642 (2010) 134. Frade, T., Bouzon, V., Gomes, A., da Silva Pereira, M.I.: Pulsed-reverse current electrodeposition of Zn and ZnTiO2 nanocomposite lms. Surf. Coat. Technol. 204, 35923598 (2010) 135. Xue, Y.J., Liu, H.B., Lan, M.M., Li, J.S., Li, H.: Effect of different electrodeposition methods on oxidation resistance of NiCeO2 nanocomposite coating. Surf. Coat. Technol. 204, 35393545 (2010) 136. Wang, G., Zhang, K.: Superplastic Properties of Al2O3/NiMn nanocomposite fabricated by electrodeposition. J. Mater. Sci. Technol. 26, 625628 (2010) 137. Aliofkhazraei, M., Ahangarani, S., Sabour Rouhaghdam, A.: Effect of the duty cycle of pulsed current on nanocomposite layers formed by pulsed electrodeposition. Rare Metals 29, 209213 (2010) 138. Tsai, Y.C., Hong, Y.H.: Electrodeposition of platinum and ruthenium nanoparticles in multiwalled carbon nanotube-naon nanocomposite for methanol electrooxidation. J. Nanomater. 2009 (2009) 139. Ramalingam, S., Muralidharan, V.S., Subramania, A.: Electrodeposition and characterization of CuTiO2 nanocomposite coatings. J. Solid State Electrochem. 13, 17771783 (2009) 140. Hosseini, M.G., Abdolmaleki, M., Sadjadi, S.A.S., Boroujen, M.R., Arshadi, M.R., Khoshvaght, H.: Electrodeposition of Ni-WndashB nanocomposite from tartrate electrolyte as alternative to chromium plating. Surf. Eng. 25, 382388 (2009) 141. Wang, P., Gao, L., Wang, L., Zhang, D., Yang, S., Song, X., Qiu, Z., Murakami, R.I.: Magnetic properties of feni nanowire arrays assembled on porous AAO template by AC electrodeposition. Int. J. Modern Phys. B 24, 23032307 (2010) 142. Hu, F., Chan, K.C., Yue, T.M., Surya, C.: Dynamic template assisted electrodeposition of porous ZnO thin lms using a triangular potential waveform. J. Phys. Chem. C 114, 5811 5816 (2010) 143. Xia, X.H., Tu, J.P., Xiang, J.Y., Huang, X.H., Wang, X.L., Zhao, X.B.: Hierarchical porous cobalt oxide array lms prepared by electrodeposition through polystyrene sphere template and their applications for lithium ion batteries. J. Power Sour. 195, 20142022 (2010) 144. Ma, B., Li, Y., Zhao, J., Li, X., Xin, W.: Novel structural functional lms based on selfassembly template and electrodeposition: synthesis and characterization of porous Ni/YSZ lms. Thin Solid Films 517, 51725175 (2009) 145. Ibrahim Khan, M., Xu, W., Xiaoye, J., Bozhilov, K.N., Ozkan, C.S.: Study of a single insb nanowire fabricated via DC electrodeposition in porous templates. J. Nanosci. Nanotechnol. 9, 26392644 (2009) 146. Deng, M.J., Leong, T.I., Sun, I.W., Chen, P.Y., Chang, J.K., Tsai, W.T.: Fabrication of porous tin by template-free electrodeposition of tin nanowires from an ionic liquid. Electrochem. Solid-State Lett. 11, D85D88 (2008) 147. Phok, S., Rajaputra, S., Singh, V.P.: Copper indium diselenide nanowire arrays by electrodeposition in porous alumina templates. Nanotechnology 18 (2007) 148. Gelves, G.A., Murakami, Z.T.M., Krantz, M.J., Haber, J.A.: Multigram synthesis of copper nanowires using ac electrodeposition into porous aluminium oxide templates. J. Mater. Chem. 16, 30753083 (2006)


2 Size Dependency in Nanostructures

149. Yan, H., Yang, Y., Fu, Z., Yang, B., Xia, L., Fu, S., Li, F.: Fabrication of 2D and 3D ordered porous ZnO lms using 3D opal templates by electrodeposition. Electrochem. Commun. 7, 11171121 (2005) 150. Gerein, N.J., Haber, J.A.: Effect of ac electrodeposition conditions on the growth of high aspect ratio copper nanowires in porous aluminum oxide templates. J. Phys. Chem. B 109, 1737217385 (2005) 151. Yan, H., Yang, Y., Fu, Z., Yang, B., Wang, Z., Xia, L., Yu, S., Fu, S., Li, F.: Fabrication of 2D ordered porous ZnO lms using 3D opal templates by electrodeposition. Chem. Lett. 34, 976977 (2005) 152. Wu, M.T., Leu, I.C., Yen, J.H., Hon, M.H.: Novel electrodeposition behavior of Ni on porous anodic alumina templates without a conductive interlayer. J. Phys. Chem. B 109, 95759580 (2005) 153. Kumar, S., Kumar, S., Chakarvarti, S.K.: SEM morphology and XRD characterization of Ni microstructure arrays synthesized by dc electrodeposition in porous polycarbonate templates. J. Mater. Sci. 39, 32493251 (2004) 154. Hou, K.H., Chang, Y.F., Chang, S.M., Chang, C.H.: The heat treatment effect on the structure and mechanical properties of electrodeposited nano grain size NiW alloy coatings. Thin Solid Films 518, 75357540 (2010) 155. Bhanvase, B.A., Sonawane, S.H.: New approach for simultaneous enhancement of anticorrosive and mechanical properties of coatings: application of water repellent nano CaCO3-PANI emulsion nanocomposite in alkyd resin. Chem. Eng. J. 156, 177183 (2010) 156. Han, B., Lu, X.: Effect of nano-sized CeF3 on microstructure, mechanical, high temperature friction and corrosion behavior of NiW composite coatings. Surf. Coat. Technol. 203, 36563660 (2009) 157. Ballarre, J., Jimenez-Pique, E., Anglada, M., Pellice, S.A., Cavalieri, A.L.: Mechanical characterization of nano-reinforced silica based sol-gel hybrid coatings on AISI 316L stainless steel using nanoindentation techniques. Surf. Coat. Technol. 203, 33253331 (2009) 158. Lekka, M., Koumoulis, D., Kouloumbi, N., Bonora, P.L.: Mechanical and anticorrosive properties of copper matrix micro- and nano-composite coatings. Electrochim. Acta 54, 25402546 (2009) 159. Zanella, C., Lekka, M., Bonora, P.L.: Inuence of the particle size on the mechanical and electrochemical behaviour of micro- and nano-nickel matrix composite coatings. J. Appl. Electrochem. 39, 3138 (2009) 160. Dhoke, S.K., Bhandari, R., Khanna, A.S.: Effect of nano-ZnO addition on the siliconemodied alkyd-based waterborne coatings on its mechanical and heat-resistance properties. Prog. Org. Coat. 64, 3946 (2009) 161. Fedorischeva, M.V., Sergeev, V.P., Popova, N.A., Kozlov, E.V.: Temperature effect on microstructure and mechanical properties of the nano-structured Ni3Al coating. Mater. Sci. Eng. A 483484, 644649 (2008) 162. Wilson, G.M., Saied, S.O., Field, S.K.: Mechanical and physical properties of C and CCr sputter coatings measured at the nano-scale. Thin Solid Films 515, 78207828 (2007) 163. Park, S.Y., Kim, M.C., Park, C.G.: Mechanical properties and microstructure evolution of the nano WCCo coatings fabricated by detonation gun spraying with post heat treatment. Mater. Sci. Eng. A 448451, 894897 (2007) 164. Jiang, L., Lam, Y.C., Tam, K.C., Li, D.T., Zhang, J.: The inuence of fatty acid coating on the rheological and mechanical properties of thermoplastic polyurethane (TPU)/nano-sized precipitated calcium carbonate (NPCC) composites. Polymer Bull. 57, 575586 (2006) 165. Pinto, E.M., Ramos, A.S., Vieira, M.T., Brett, C.M.A.: Brett, A corrosion study of nanocrystalline copper thin lms. Corros. Sci. 52, 38913895 (2010) 166. Saha, G.C., Khan, T.I.: The corrosion and wear performance of microcrystalline WC 10Co4Cr and near-nanocrystalline WC17Co high velocity oxy-fuel sprayed coatings on steel substrate. Metallurg. Mater. Trans. A Phys. Metallurgy Mater. Sci. 41, 30003009 (2010)



167. Liu, L., Li, Y., Wang, F.H.: Pitting corrosion behavior of a sputtered nanocrystalline thin lm of austenitic stainless steel in 3.5 mass% NaCl solution. Corros. Sci. Protect. Technol. 22, 283288 (2010) 168. Luo, W., Xu, Y., Wang, Q., Shi, P., Yan, M.: Effect of grain size on corrosion of nanocrystalline copper in NaOH solution. Corros. Sci. 52, 35093513 (2010) 169. Chandrasekar, M.S., Shanmugasigamani, M.S., Malathy, P.: Synergetic effects of pulse constraints and additives in electrodeposition of nanocrystalline zinc: corrosion, structural and textural characterization. Mater. Chem. Phys. 124, 516528 (2010) 170. Xu, J., Zhou, C., Jiang, S.: Investigation on corrosion behavior of sputter-deposited nanocrystalline (MoxCr1-x)5Si3 lms by double cathode glow plasma. Intermetallics 18, 16691675 (2010) 171. Nie, F.L., Zheng, Y.F., Cheng, Y., Wei, S.C., Valiev, R.Z.: In vitro corrosion and cytotoxicity on microcrystalline, nanocrystalline and amorphous NiTi alloy fabricated by high pressure torsion. Mater. Lett. 64, 983986 (2010) 172. Okouchi, H., Seki, Y., Sekigawa, T., Hira, H., Kawamura, Y.: Nanocrystalline LPSO Mg ZnYAl alloys with high mechanical strength and corrosion resistance. In: Materials Science Forum, pp. 14761481. (2010) 173. Lee, H.B., Wuu, D.S., Lee, C.Y., Lin, C.S.: Study of the corrosion behavior of nanocrystalline NiP electrodeposited coating. Metallurg. Mater. Trans. A Phys. Metallurg. Mater. Sci. 41, 450459 (2010) 174. Sousa, C.C., Kiminami, C.S.: Corrosion of Fe-based nanocrystalline alloys with soft magnetic properties. J. ASTM Int. 7, 112 (2010) 175. Ishihara, T., Yan, J., Matsumoto, H.: Extraordinary fast oxide ion conductivity in La1.61GeO5-[delta] thin lm consisting of nano-size grain. Solid State Ionics 177, 1733 1736 (2006) 176. Ravi, S., Ganesh, K.V., Ramanathan, A., Annamalai, J., Jaiswal, P.K.: Development of nano crystalline nickel coating for engineering applications. In: Key Engineering Materials, pp. 487492. (2010) 177. Koleva, D.A., Boshkov, N., Bachvarov, V., Zhan, H., de Wit, J.H.W., van Breugel, K.: Application of PEO113-b-PS218 nano-aggregates for improved protective characteristics of composite zinc coatings in chloride-containing environment. Surf. Coat. Technol. 204, 37603772 (2010) 178. Wang, R.M., Wang, B.Y., He, Y.F., Lv, W.H., Wang, J.F.: Preparation of composited nanoTiO2 and its application on antimicrobial and self-cleaning coatings. Polym. Adv. Technol. 21, 331336 (2010) 179. Seong, M.R., Kwon, J., Lee, G.Y., Kim, D.K., Kim, Y.S., Lee, C.S.: Optimization of surface coating condition using vapor form of alkanethiol on Cu nano powders for the application of oxidation prevention. Appl. Surf. Sci. 256, 23322336 (2010) 180. Wang, J.E.: Application of nano-titatium polymer coating to the coolers in oil rene factory. Corros. Protect. 30, 933935 (2009) 181. Izumi, T., Izumi, K., Kuroiwa, N., Senjuh, A., Fujimoto, A., Adachi, M., Yamamoto, T.: Preparation of electrically conductive nano-powder of zinc oxide and application to transparent lm coating. J. Alloys Compd. 480, 123125 (2009) 182. Tian, Z., Wang, X., Shu, L., Wang, T., Song, T.H., Gui, Z., Li, L.: Preparation of nano BaTiO3-based ceramics for multilayer ceramic capacitor application by chemical coating method. J. Am. Ceram. Soc. 92, 830833 (2009) 183. Shibli, S.M.A., Jayalekshmi, A.C.: A novel nano hydroxyapatite-incorporated NiP coating as an effective inter layer for biological applications. J. Mater. Sci. Mater. Med. 20, 711718 (2009) 184. Lewis, F., Mantovani, D.: Methods to investigate the adhesion of soft nano-coatings on metal substratesapplication to polymer-coated stents. Macromol. Mater. Eng. 294, 1119 (2009)


2 Size Dependency in Nanostructures

185. Zhang, X., Cheng, X., Yin, H., Yuan, J., Xu, C.: Preparation of needle shaped nano-copper by microwave-assisted water system and study on its application of enhanced epoxy resin coating electrical conductivity. Appl. Surf. Sci. 254, 57575759 (2008) 186. Jacquot, P., Andreux, C., Stauder, B.: Effect of industrial surface nishes on heat treatment and surface engineering of steel. Int. Heat Treat. Surf. Eng. 4, 110116 (2010) 187. Stevenson, P., Ata, S., Evans, G.M.: Erratum: the behavior of an oscillating particle attached to a gasliquid surface (Industrial and Engineering Chemistry Research 48 (8025)). Ind. Eng. Chem. Res. 49, 3504 (2010) 188. Kaufmann, H.: Industrial applications of plasma and ion surface engineering. Surf. Coat. Technol. 7475, 2328 (1995)