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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
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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
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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.
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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]
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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].
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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
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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].
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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
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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].
2.2.4.1 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]
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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].
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2.2.4.2 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].
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2.2.4.3 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].
2.2.4.4 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].
2.2.4.5 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
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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].
2.2.4.6 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
46
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].
47
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].
48
49
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].
50
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]
51
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
53
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]
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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].
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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
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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 S.cm-1 (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
57
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]
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.
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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.
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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.
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)
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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
2.10
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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.
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2.13
65
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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.
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