Surface Technology For Automotive Engineering

CIRP Annals - Manufacturing Technology 58 (2009) 608627
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CIRP Annals - Manufacturing Technology

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Surface technology for automotive engineering

K. Bewilogua a, G. Brauer a, A. Dietz a, J. Gabler a, G. Goch (1)b, B. Karpuschewski (1)c,*, B. Szyszka a
a b c
Fraunhofer-Institute for Surface Engineering and Thin Films (IST), Braunschweig, Germany Bremen Institute for Metrology, Automation and Quality Science (BIMAQ), Germany Institute for Manufacturing Technology and Quality Management (IFQ), University of Magdeburg, Universitaetsplatz 2, 39106 Magdeburg, Germany
A R T I C L E I N F O
A B S T R A C T
Keywords: Coating Chemical vapour deposition (CVD) Physical vapour deposition (PVD)
The presented paper describes the role of surface technologies in the automotive industry. Various hard coatings like nitrides, diamond and cBN are used on tools for the manufacturing process. Due to their high hardness and low coefcient of friction, diamond-like carbon lms will be indispensable for engine and power train components. The improvement of automotive glazings by optimization of optical and thermal properties of the glass is an ongoing development task. Coatings with switchable transmission, thin lm solar cells as self-cleaning and self-healing surfaces will be features in the car of the future. Various atmospheric pressure and low pressure deposition processes are available. In this paper low pressure plasma and electrochemical deposition are in focus. 2009 CIRP.
1. Introduction In general surfaces are not perfect. However, in our daily life we communicate with objects mainly through their surfaces. Surface and coating technologies on one hand improve existing materials and products; on the other hand they are indispensable for the realization of innovative products based on particular properties of thin lms. Tailored coatings allow the adjustment of mechanical (wear, friction); chemical (corrosion, permeation, temperature insulation, biocompatibility, wettability); electrical (conductivity); optical (transmission, reection, absorption, colour). properties of surfaces. Surface technology means modication, structuring or coating of materials and components. In case of coatings, one may distinguish between thick and thin lm technology. We shall talk about thick lm technology for lm thicknesses above 10 mm and thin lm technology for lm thicknesses between 0.1 nm and 10 mm. However, this division is not xed. According to the Organisation Internationale des Constructeurs dAutomobiles (OICA) in 2007 around 53 million cars and 20 million commercial vehicles have been produced. The automotive industry is one of the most important users of modern surface technologies. Besides lacquer for decoration and long term corrosion protection, tribological coatings on drive components or various functional coatings on car glazing are the most popular applications. Hard coatings with low coefcients of friction are an effective way to reduce wear and friction as well as lubricants. Coatings on glass may
reduce disturbing reections or minimize the thermal load to the passenger compartment. Thin lms also will play a decisive roll for many kinds of novel sensors adding more intelligence to the car. This holds for the components themselves as well as for the tools to manufacture them. Fig. 1 shows typical applications for functional coatings in automotive engineering. A huge variety of basic processes and related modications exists for the deposition of coatings or modication (e.g. hardening) of surfaces. The most important are lacquering, electrochemical deposition, thermal spraying, and low pressure plasma based processes like physical vapour deposition (PVD), plasma assisted chemical vapour deposition (PACVD) or plasma diffusion treatment. In the frame of this keynote paper the authors want to focus on electrochemical and plasma processes as well as a few key applications. The paper concludes with some visions for the car of the future. 2. Coatings on tools for automotive engineering 2.1. Recent developments in coating systems for cutting tools Increasing demands on production processes lead to the need of continuous improvement in cutting technologies. Especially due to the need for continuously improving the productivity, decreasing the processing costs and increasing demands on products, machining operations like hard machining, dry machining, high speed machining and precision machining have experienced signicant growth, while continuously imposing higher stresses on tools. Advanced coating systems are aimed at improving the tool wear behaviour signicantly and to enhance the tool performance [60]. Thus the requirements on the wear resistance of cutting tools are essential. Hard coatings, e.g. TiN, TiC, and Al2O3 deposited on cutting tools have been used since 1960 to increase tool lifetime [22]. Current trends in the tool industry are moving away from conventional standard tools into the direction of high quality specic tools. Today manufacturers
* Corresponding author. 0007-8506/$ see front matter 2009 CIRP. doi:10.1016/j.cirp.2009.09.001
K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627
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Fig. 1. Examples for the application of surface technologies in a modern car.
and end users focus on conguring individual coatings and coated tools [50]. However, due to the rising variability of coating systems for cutting tools, a careful selection of a suitable coating system is becoming more important. In this chapter recent developments in cutting tool coating systems, like cubic boron nitride (cBN) based coatings, supernitride coatings, diamond coatings and nanocomposite coatings, are documented. 2.2. Properties of coatings In order to select or develop a suitable tool coating, it is necessary to identify the primary wear mechanisms inherent in the specic machining task. The ability of a coating system to reduce wear sufciently is the criterion for choosing it [103]. Wear on cutting tools during machining is caused by a complex interaction of surface effects like adhesion, abrasion, diffusion and tribooxidation or volume effects like crack initiation, scoring and plastic deformation (Fig. 2). Tool coatings are used to increase wear resistance and to vary contact conditions to the effect that wear of the tool is reduced [106]. Besides the properties of the coating itself, interactions between coating and substrate, especially the bonding, are very important for the tribological and wear behaviour of coated tools. Therefore different methods for pre-treatment of the substrate, for example micro-blasting, brushing, water peening or magnetoabrasive machining after grinding, can be applied to improve coating substrate adhesion [18,42,97,172]. With the trend towards individual coated tools it is becoming increasingly important to treat the tool manufacturing as a complex system. This system is inuenced by many different process parameters which have to be optimized for the special coating process and machining task. 2.3. Recent cutting tool coating systems 2.3.1. Cubic boron nitride Cubic boron nitride (cBN) is a material with great technological importance through its high hardness and chemical inertness against ferrous materials.
Thanks to the ability to coat tools with complex geometries, such as chip-breakers on inserts, cBN based coatings on carbide inserts are complementary to widely used polycrystalline cubic boron nitride (PCBN) compact tools for nish hard turning applications [91]. Various physical and plasma assisted chemical vapour deposition processes (PVD, PACVD) have succeeded in cBN lm deposition as reviewed, e.g. by Bello et al. [10]. However, mostly the achievable thickness range of cBN lms on silicon substrates was limited to <500 nm. This thickness limit is mainly caused by an enormous residual intrinsic compressive stress (up to 20 GPa) and a pronounced sensitivity to humid air. In the last few years there has been impressive progress in the eld of thick (>1 mm) cBN coatings. Some research groups succeeded in deposition of thicker cBN, up to 20 mm [10,99,175,192]. In spite of the impressive results reported and several techniques which were described for deposition of thicker cBN lms, no successful transfer of cBN deposition processes to industrial coating machines could be realized so far. Thick cBN coatings (up to 2 mm) were deposited as top layers on cemented carbide cutting inserts pre-coated with TiAlN [99,136]. The deposition processes were done by reactive sputtering using a boron carbide target. In hard turning tests the cBN layers deposited on the TiAlN-interlayers resulted in lifetime enhancement,
Fig. 2. Inuence of coatings on wear mechanisms and contact conditions.
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Fig. 5. Phase diagram of the metastable system TiNAlN [51]. Fig. 3. A comparison of tool wear between TiAl and TiAlN + cBN top layer coated cemented carbide cutting inserts for different cutting speeds [99].
especially at higher cutting speeds compared to a TiAlN reference coating (Fig. 3). However, in hard milling tests the performance of TiAlN could not be achieved by cBN coating system [99]. Because of the difculty in terms of depositing thicker layers from vapour phase, a hybrid deposition process was developed, which allows deposition of a thick (520 mm) cBNTiN composite coating using electrostatic spray coating (ESC) and chemical vapour inltration (CVI) [118]. Before this deposition process starts, the tool inserts were cleaned by washing them in a mild detergent solution, rinsing with deionised water and dried with hot air. Subsequently the electrostatic spray process (ESC) is carried out, used to deposit a uniform layer (Fig. 4, left) of CBN particles ( 2 mm) [146]. These cBN particles are only loosely bound (by static forces) to each other and to the substrate and built up pores (Fig. 4, middle) [146]. These built up pores are important for the following CVI process. At this point, the pores were inltrated with TiN as shown in the right picture in Fig. 4. The CVI process is a spin-off of chemical vapour deposition (CVD) and it is used to convert the ESC coated particulate porous surface into a hard composite coating including strong bonding with the substrate surface [146]. More et al. [126] investigated the tool wear performance of cBNTiN coated WCCo in comparison to PCBN compact inserts in turning AlSi 4340 hardened steel. Although the tool life of approximately 1820 min per cutting edge of the cBN carbide inserts is lower compared to the PCBN tool with a produced tool life of 32 min, the cBNTiN coated carbide tools are considered to be an important complement to PCBN compact tools for hard turning applications. This conclusion is based on the investigation of total machining costs per part for both variants. It indicates that the savings in machining costs using cBNTiN coated inserts is between 12% and 30%. A critical assessment of both vapour phase and hybrid processes was recently given by Richter [143]. 2.3.2. Supernitrides One of the most promising state-of-the-art coatings is still the metastable solid solution phase (Ti,Al)N in cubic B1 structure. These coatings offer a superior oxidation and chemical resistance and hardness as compared to conventional TiN or Ti(C,N) [50].
Fig. 6. Microstructure of Ti46Al54N coating and nanostructured supernitride (SNTR) one [51].
With increasing aluminium content the oxidation resistance of (Ti,Al)N coatings increases, however a barrier is set to the PVD process technology by the deposition of insulating lms at a lm composition of approximately 6567 mol% AIN (Fig. 5) [51]. Besides the improved mechanical properties, further signicant coating parameters for their effective application on cutting tools especially at elevated cutting temperatures are the lm oxidation resistance and thermal conductivity [48]. Erkens et al. [51] investigated the cutting performance of the supernitride coatings. Therefore they compared a characteristic (Ti,Al)N based supernitride variant, the SNTR (with AlN content 67 mol%) deposited on cemented carbide inserts and cutting inserts, which were coated with using the same parameters with an effective state-of-the-art (Ti46Al54)N wear protective lm. The microstructure of both coatings is illustrated in Fig. 6. The structure of the supernitride is distinguished by a more ne grained, nanocrystalline structure in comparison to the conventional coating. The wear performance in milling of the supernitride SNTR can be observed in Fig. 7. It is demonstrated that the nanostructure and the increased AlN content act more positively on the behaviour of the supernitride SNTR coating at higher cutting speeds [51]. 2.4. CVD diamond Due to its extreme hardness and resistance to wear, diamond is the ideal coating material for cutting tools, designed for difcult-
Fig. 4. Cross-section of ESC deposited CBN, pores in the cBN layer and cross section of cBNTiN coating [92].
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Fig. 8. Surface structure of micro- (left) and nanocrystalline (right) CVD-diamond layer [5].
Fig. 7. Cutting performance of the applied coatings in milling 42CrMo4-hardened steel [51].
to-machine materials, like carbon bre-reinforced plastics, graphite, wood based materials and metal matrix composites (MMC). Three industrial applications have been established up to now, where CVD diamond coated tools demonstrate their potential in series production: When a large graphite electrode for EDM is produced, no tool change can be accepted during the machining of the workpiece since this would lead to a mark on the surface due to the larger tool diameter of the new tool. Diamond coated endmills [28,105] have lifetimes when machining graphite of 15 h and more and thus enable the production of these large electrodes. In the production of printed circuit boards (PCBs) diamond coated microrouters prolong the tool life signicantly, save time for changing tools and thus increase the productivity of this manufacturing step, which is mostly the bottle-neck in the production of PCBs [109]. For bre-reinforced plastic parts, which are increasingly used in aircraft design, complex shaped shaft mills are used advantageously [83]. With these tools the strong requirements for delamination and dimension tolerances can be met compared to simple shaped tools with massive diamond (PCD) inserts. Several chemical vapour deposition (CVD) processes have been developed for depositing diamond lms on cutting tools. Hot lament CVD (HFCVD), microwave plasma CVD (MWPACVD) and plasma arc CVD are the most widespread techniques used for thin lm deposition of diamond on cemented carbide cutting tools [148,180]. Due to the effect of Co on favouring the formation of C-sp2 and the resulting limited adhesion of the coating, the cemented carbide substrate surface has to be treated before coating. Therefore a chemical etching can dissolve Co particles at the surface and increase substrate roughness. Alternatively interlayer systems are being developed to prevent the diffusion of Co and the resulting catalyzed formation of graphite [27]. Uhlmann et al. found that the performance of diamond coated tools depends strongly on the properties of tungsten carbide substrates as well as on the pre-treatment [174]. During highly frequent mechanical load, the diamond coating adheres better, if a higher hardness, a lower cobalt-content of the substrate and a lower surface roughness are given. A deeper etching during the pre-treatment in order to remove cobalt from the sub-surface as well as a thicker layer also have a positive inuence on the adherence of the layers. The inuence of the layer morphology could not be proven clearly in that case. The friction behaviour of diamond coated tungsten carbide tools is inuenced by the surface condition and the substrate properties only to a small degree. Hu et al. [89] studied the properties of nanocrystalline diamond (NCD), produced by MWPACVD, in comparison with HFCVD microcrystalline coatings and PCD tools. Fig. 8 shows the surfaces of nanocrystalline and microcrystalline diamond coatings. It is
clear that a nanocrystalline coating has a much smoother surface compared to a microcrystalline diamond coating because of the ultrane crystallites. In Fig. 9 the ank wear development is demonstrated in machining Al20 wt% SiC composite. The result of the cutting performance of the nanocrystalline tool is comparable to the PCD one and much better than the microcrystalline tool. The stronger built-up of the workpiece material on the rough, microcrystalline diamond layer leads to stronger adhesive wear and can be regarded as the reason for the much shorter tool life compared to the smooth nanocrystalline diamond coating. Further researches [3] in turning EDM graphite electrodes with micro- and nanocrystalline CVD diamond coated Si3N4 ceramic inserts tools showed the potential of both coating types and the ceramic tool material for this special machining task, with an achieved machined length of at least 10 km per tool edge. No delamination of diamond lm was remarkable due to the use of silicon nitride ceramic as substrate for the coating. 2.4.1. Nanocomposites The development of nanocomposites provides enormous potential for the improvement of coatings. The structure of TiAlN based nanocomposite lms depends on deposition of very different kinds of materials, the components (like Ti, Al, Cr in the rst group and Si in the other) are not mixed completely, and 2 phases are created. The nanocrystalline TiAlN- or AlCrN-grains are embedded in an amorphous Si3N4-matrix (Fig. 10) [35]. The industrial and economical property for deposition of nanocomposites is provided by the advanced LARC1 and CERC1 technology (Lateral Rotating Cathodes and CEntral Rotating Cathodes) [36]. The main advantages of these novel coatings are the higher hardness compared to other conventional coatings and especially the enormous improvement of heat resistance. The spinodal segregation and the resulting loss of hardness tend to appear much later than with non-nanocomposites (Fig. 11) [35]. The comparison of the lifetime of coated tapping tools is illustrated in Fig. 12. At the standard machining rate of 25 m/min the performance of the nanocomposites is only a little better than the best TiAlCN coating and about two-times better than the TiCN
Fig. 9. Flank wear in machining Al20 wt% SiC composite [89].
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Fig. 10. Nanocomposite structure.
Fig. 14. Performance improvement of nanocomposite coating in gear hobbing.
Fig. 11. Inuence of nanocomposite structure on spinodal segregation [36,86].
surface speed and feed-rate are signicantly higher. The facility of faster machining results in an increase of the productivity by about 56% [182]. Nanocomposite coatings are also expected to be capable for use in gear hobbing processes. These operations are characterized by dynamical load and discontinuous wear attack on the coated tool. Therefore the coating system must satisfy special requirements. Karpuschewski et al. studied the performance of state-of-the-art coatings compared with newly developed AlCrN based nanocomposite coating in gear hobbing [96]. The resulting improvement is shown in Fig. 14. The experimental tests were carried out using PM-HSS and HM tools. In both cases the nanocomposite coating performed better than the conventional coating. A proper improvement could be achieved in the case of using HM tools. Nanocomposites will play a major role in future developments to enhance performance of cutting tools, especially for dry cutting operations, due to their hardness at elevated temperatures [37]. 2.5. Coatings for forming tools Forming tools, e.g. for punching or deep drawing, are widely used in the automotive industry. Actual developments in forming processes are focussed on light materials like Ti, Al or Mg. For many years it has been known that chromium nitride CrN or titanium based coatings like TiN, TiCN or TiB2, prepared both by PVD as well as by CVD techniques, can considerably increase the tool lifetime [87,85]. Modern coating designs for forming tools show a tendency towards multilayer composites. Such composites, e.g. can consist of hard base layers covered by relatively soft low friction top layers like MoS2 or amorphous carbon [85]. Diamond-like carbon (DLC), known in several modications with a large spread of properties, is an attractive coating material for forming tools [169]. However, for many years the applicability of DLC coated forming tools was limited because the achievable coating adhesion was insufcient under real high load operation conditions. Recently, a considerable improvement of the DLC adhesion has been realized by preparing special interlayer systems designed for high shear stress applications [186,187]. There the complete optimized coating system consists of the following single layers: rst chromium layer (Cr); chromium nitride (CrN); second Cr layer; tungsten containing amorphous hydrogenated carbon (a-C:H:W or W-DLC).
Fig. 12. Comparison of the lifetime of tools for dry tapping [182].
Fig. 13. Comparison of coatings on drills made of cemented carbide (drilling GGG40) [182].
coating. However at a high cutting speed, the nanocomposites lose only about 12% of the lifetime whereas TiAlCN coatings lose more than 50% and the other both coatings performed poorly. In this case the excellent performance of the nanocomposite coatings arises not only from the higher hardness and oxidation resistance, but also from the smoother surface [182]. Fig. 13 shows the comparison of the lifetime in drilling of cast iron GGG40. The lifetime of nanocomposite coated tools is slightly higher than that with state-of-the-art (Ti1xAlx)N ones, although the applied
The corresponding coatings have been used in several industrial applications [186].
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Further improvements of the tool performance can be expected if the tools can be treated in a plasma diffusion process, e.g. nitriding, before starting the coating deposition. The continuous developments in coating technology for cutting and forming tools allow fullling the increasing demands of industrial applications with regards to economical and ecologically benign processes. It is considered that in the future the coating technology will be furthermore an important aspect for enhancements of cutting tool performance related to the enclosing treatment and research of the coating system with all its inuencing parameters. 3. Coatings for engine and power train components 3.1. Coating materials and applications Today several components of engines and power trains in automobiles are coated with wear and friction-reducing materials to increase their lifetime, reduce fuel consumption and prevent corrosion [183]. Since more than 10 years for the base materials of these components there is an increasing trend to lightweight materials like aluminium or magnesium [135]. Here aluminium alloy engine blocks should be mentioned [6,117]. It is noteworthy that besides coating processes also other surface treatments like nitriding, especially plasma nitriding, can considerably improve the performance of automobile components [113]. The potential of plasma nitriding will be considered more detailed below. Examples for coatings used for automotive applications are: Piston ringscoated with hard chrome, deposited by galvanic processes, with chromium nitride, prepared by PVD techniques [183], mostly arc evaporation, or with a metal matrix composite (MMC) produced by thermal spray techniques [52]. Typical coating thicknesses are in the range of some 10100 mm. Cylinder bores of aluminium cast engine blockscoatings consisting of carbon steel partly reinforced by ceramic particles, prepared by thermal spraying [6,113,17]. Older variants of such coatings are nickel based composites or hard chrome [117]. Crankshaft bearingstypical materials are AlSn, AlSnBi alloys or steel-bronze. Brewe [19] presented an assessment of several slider bearing materials considering different operation conditions. Ball pivotsa signicant reduction of corrosion combined with improved wear behaviour and lower friction coefcients could be achieved by combining plasma nitriding and oxidation [183]. Injector needles in diesel enginescoated with diamond-like carbon (DLC) coatings [173]. Just the last mentioned DLC based coatings became more and more important for the friction and wear reduction of several automobile components. In the last years, DLC based coatings were at least in discussion also as candidates for all other above mentioned application elds. The term DLC describes a coating material class covering a broad range of physical and chemical properties. Well dened combinations of coating properties can be adjusted using different deposition processes and parameters. Due to the extremely high pressures of 2000 bar and more in diesel injection systems [173], DLC coatings are indispensable for these components. Other applications of DLC coatings in serial car production concern tappets and piston pins. Furthermore DLC coatings will be used nearly in 100% of high performance applications in racing car engines, e.g. on camshafts and valves [178]. The annual market value of DLC coated components has been continuously increasing since the last decade of the last century with the trend towards 600 Ms in the next few years [178]. In the following sections classication and properties, preparation techniques and applications of DLC based coatings shall be discussed in detail.
3.2. DLC based coatings 3.2.1. Classication and properties of DLC coatings Diamond-like carbon (DLC) coatings are well known for their high hardness and wear resistance as well as low friction coefcients and sometimes low surface energies. Commonly a distinction is drawn between hydrogen free (a-C or ta-C) and hydrogen containing (a-C:H) lms. Both types can be modied by incorporation of additional elements like metals (a-C:H:Me) or non-metallic elements (a-C:H:XX: additional elements). Other properties of DLC based coatings which could be rather interesting for technical applications are: a broad range of electrical resistivity, transparency in the infrared spectral range, chemical inertness or variable wetting behaviour (corresponding to different surface energies). Especially a-C:H and metal containing a-C:H:Me coatings are today established in industrial practise, mainly for automotive applications. The combinations of excellent mechanical and tribological properties have been well known for several years. Low friction coefcients (m 0.2 against steel under dry, lubricant free conditions) were measured for a-C:H and also for metal-containing amorphous hydrogenated diamond-like carbon lms (a-C:H:Me or Me-DLC) [46,102]. In the following discussion the abbreviations aC:H and a-C:H:Me shall be used. In the last 10 years a-C:H coatings displaced the metal containing a-C:H:Me coatings more and more in the eld of highly stressed automotive components. The background of this substitution is that the metal free a-C:H is considerably harder and more wear resistant than a-C:H:Me [173,13]. Fig. 15 shows this relation for tungsten containing a-C:H:W and three different a-C:H coatings. Furthermore, adhesion problems of a-C:H coatings limiting their reliable application, could be resolved even in industrial scales by appropriate interlayer systems between substrates and aC:H top coating (e.g. [79]). Hydrogen free tetrahedral amorphous carbon (ta-C) lms with a dominating content of sp3 bonded carbon atoms (>50%) can be still harder (>50 GPa, [133]) than aC:H (see Fig. 15). Recently large scale laser-arc deposition techniques for ta-C were developed and transferred to industrial batch coaters [151]. Such ta-C coatings should be potential candidates for highly loaded automobile components. Very interesting and promising coatings properties can be achieved by modifying with non-metal elements: a-C:H: X (X: Si, O, F, N). Silicon containing a-C:H:Si lm are known to have still lower friction coefcients than a-C:H [132]. Films containing both silicon and oxygen (a-C:H:Si:O) are characterized by rather low surface energies which are comparable to those of Teon1 [72]. Low surface energies lead to a decreasing wettability and to a lower susceptibility to adhesion of materials, e.g. of powders on pressing tools. Fig. 16 shows the water contact angles and the surface energies for different modied DLC coatings. Compared to pure a-C:H both lower and higher surface energies can be
Fig. 15. Abrasive wear rates and hardness of a-C:H:W and a-C:H coatings prepared by PACVD (r.f.: radio frequency excited plasma, m.f.: mid-frequency excited plasma) and C-DLC (see preparation of DLC based coatings).
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Fig. 16. Water contact angles and surface energies (polar and disperse components are shown) for a-C:H and modied a-C:H:X coatings as well as for PTFE (Teon1) as reference.
realized. However, an optimization of one property mostly leads to a deterioration of other properties. Thus highly hydrophobic lms commonly have a relatively low wear resistance. To illustrate this, Table 1 gives an overview on characteristic values for plastic hardness (HUplast/GPa), abrasive wear rate (wr/ 1015 m3/Nm), water contact angle (WCA/18) and surface energy (SE/mN/m) of different amorphous carbon lms and of Teon1 as reference. To overcome this drawback, multilayer coatings were prepared to combine the best properties of single layers. For example a combination of a-C:H and a-C:H:Si allows to synthesize lms with both extremely low friction and low wear rates [123]. In an ambient atmosphere under dry, lubricant free conditions nearly all amorphous carbon lms have low friction coefcients 0.2 against steel. An exception is a-C:H:Si:O (see Table 1). However, the friction behaviour under dry conditions does not allow predictions on typical machine operation conditions in a lubricated state. On the other hand, low dry friction coefcients can prevent scufng if the lubricant is insufcient or fails. Friction under lubricated conditions is a complex process depending on the type of lubricant, additives, coating type, operating temperature and contact conditions. Generally, compared to steel, the most DLC based coatings reduce the friction coefcients under lubricated conditions [137,40,150]. More details on a general classication and nomenclature of carbon based coatings can be found in a recently developed guideline [180]. 3.2.2. Preparation of DLC based coatings The most widely applied method to deposit a-C:H lms is based on the glow discharge of hydrocarbon gases with substrate electrodes excited by radio frequency (r.f.13.56 MHz) or medium frequency (m.f.some 10 to some 100 kHz) power [80]. In the m.f. range both harmonic a.c. and pulsed d.c. voltages have been successfully applied. These techniques often will be named as PACVD (plasma assisted chemical vapour deposition). Beside pure a-C:H also modied a-C:H:X coatings (X: Si, O, F or other elements) normally will be prepared by PACVD methods. Examples for the different precursors to be used are: a-C:H: methane (CH4) or acetylene (C2H2); a-C:H:Si: tetramethylsilane TMS (SiC4H12) (+CH4 to vary the Si content); a-C:H:Si:O: hexamethyldisiloxane HMDSO (Si2OC6H18).
Metal containing a-C:H:Me coatings are prepared mostly by reactive d.c. magnetron sputtering in industrial batch coaters [79,161] or in multi-chamber in-line machines [76]. Sputtering belongs to the so called PVD (physical vapour deposition) techniques (see chapter 6). The used targets consist of metal or metal carbide and the working gas is an argonhydrocarbon mixture [161,14]. The magnetron sputter technique has high potential for scale-up, for deposition of complex coating systems like multilayer lms and also for realization of in-line deposition processes. Using graphite instead of metal targets, also metal free a-C:H coatings can be prepared by reactive d.c. magnetron sputtering [13]. In order to emphasize the similarity of the deposition process to that for a-C:H:Me the name C-DLC was introduced for this a-C:H coating material. Working with well dened special process parameters in an unbalanced magnetron (UBM) mode causing high plasma densities, very hard (up to 50 GPa, compare with data in Fig. 15) C-DLC coatings can be deposited [129]. The structural reason for these high hardness values obviously is the relatively low hydrogen content (near 10 at%) compared to about 15 at% for standard aC:H like cognizable from Fig. 17. In serial productions of a-C:H coatings, e.g. for automotive components, today in many cases a hybrid process consisting of a sputter deposition of an adhesion improving metal based layer (Cr, CrN) and a PACVD process (m.f.) for the a-C:H top layer is used [79]. 3.2.3. Potential future application elds of DLC based coatings The promising properties of DLC coatings have led to a continuously increasing number of application areas for machine and engine components [121,113,173,178] as well as for forming and cutting tools [121,43]. The different modications of DLC based coatings result in a broad spectrum of properties (see Table 1). Gradient or multilayer arrangements combining the different layer materials allow realizing even a still wider range of coating properties. Except for the extraordinary coating properties it is important that diamond-like carbon can be deposited at low substrate temperatures (<200 8C), e.g. on temperature sensitive materials like ball bearing steel or even plastics. On the other hand, if the base materials to be coated have a stable microstructure up to higher temperatures like, e.g. high speed or cold working steels, a plasma nitriding process or a duplex process (plasma nitriding combined with subsequent coating deposition) can considerably improve the tribological properties of automobile components [183,113]. In the case of DLC based top coatings duplex processes result in higher surface hardness, lower friction coefcients and particularly improved adhesion [125,59]. Furthermore, the following application perspectives, today still in a development phase, should be noted: Gears: DLC coatings of gear surfaces seem to be very promising with respect to further reduction of friction and to operation under lubrication loss conditions. However, this application is not widely established so far [178]. On the other hand there are some research results indicating a potential benet. Murakawa et al. [130] revealed that WC/C (a-C:H:W) coatings enlarged the lifetime of test gears three times. Furthermore, it was reported by these authors that a micro-shot peening pre-treatment process modied the ground surface and increased the lifetime of the
Table 1 Some essential properties of different DLC based coatings and of Teon1. Outstanding properties are highlighted. Hardness [GPa] a-C:H a-C:H:Si a a-C:H:Si:O a-C:H:W Teon1
a
Friction coeff. m vs. steel (ambient air) 0.150.2 <0.1 0.40.6 0.2 0.1
Abrasive wear [1015 m3/Nm] 0.51 24 1015 14 )
Water contact angle [8] 7075 7580 95105 6570 110120
Surface energy [mN/m] 40 38 24 42 19
2535 20 810 1520 <0.5
Si/C % 0.2.
615
Fig. 17. Hardness of C-DLC (a-C:H) coatings vs. hydrogen content, measured for samples prepared in two different plants both using reactive sputter techniques with graphite targets. As reference the eld typical for a-C:H from PACVD processes is marked.
Fig. 19. Radial bearing ring with DLC force sensor structures (for details see [16]).
Fig. 18. Part of tire mold coated with a anti-sticking a-C:H:Si:O coating.
shows a radial bearing with DLC force sensors. One obstacle on the way to a reliable operation in bearings seems to be that the resistivity of these sensors depends not only on the force, but also on the temperature [16]. Before introducing such technical solutions into a broad application many problems need to be solved, as excellently summarized by Lampe et al. [113] generally for the plasma surface engineering in automotive industry. As examples the long time for scale up processes to industrial dimensions, a high reliability, the cost effectiveness, the available production capacity and the patent situation should be mentioned. 4. Coatings for automotive glazing, lighting and information display 4.1. Automotive glazing 4.1.1. Recent developments in coatings for automotive glazing Automotive glazings are multifunctional devices [115]. They protect against wind, cold and rain and also against thermal load from the sun and environmental noise. Comfort and safety functions such as sun-control [53], deicing [71], antireex and easy-to-clean properties [74] are realized by functional coatings [120,166] which are deposited using advanced thin lm technologies. Coatings are applied as soft or hard coatings. Soft coatings are based on thin metal lms embedded in dielectric layers for optical reasons. These soft and sensitive stacks have to be protected and thus, they are integrated in laminated glazings. Hard coatings on the other hand consist of more robust ceramic materials or thicker metal lms. They withstand mechanical wear and corrosive attack to a certain extent and can be applied on the inside or outside of the glazing. Prominent examples for outside coatings are hydrophobic easyto-clean coatings [74] for enhanced optical performance while driving in rain. The use of light weight complex shaped polycarbonate glazings will be possible with appropriate UV protective [147] anti-scratch coatings [152]. These examples are just the starting point for future developments. Future car generations will be equipped with transparent [144] or head-up displays [165,179] in order to magnify trafc signs and other critical events according to eye tracking systems.
coated gears. Yao et al. [194] concluded from tests with coated and uncoated rollers that coatings (a-C:H:W) can only enhance the durability if both partners in the tribosystem are coated. The effects described here obviously are related to relatively rough, not polished gear surfaces. Indeed the polishing of gear components is clearly too expensive to be done in serial production. Lubricated components: So called lubricant or oil pockets, consisting of dimples in the surfaces of friction partners, can considerably inuence the behaviour of lubricated tribological systems of forming tools [7] or components [107]. It is to expect that combinations of such topographically modied surfaces with suitable coatings, e.g. a DLC modication, could further reduce friction losses in engine components. Today, different techniques for modications of surface topographies are known and will be widely used [21]. Anti-sticking coatings: As described above, modied a-C:H coatings like a-C:H:Si:O are characterized by low surface energies causing low wettability with liquids and low sticking of various solid materials [81]. This property could be used to reduce the sticking of carbon-particulate matter, e.g. on intake valves of engines. Fig. 18 shows a car tire molding tool where aC:H:Si:O coatings were found to have a potential to reduce the tire material deposition, improve demolding and cleaning behaviour. The anti-sticking and low wetting effect can be considerably enhanced by combining surface roughness in micro- and nanometer length scales with hydrophobic top layers [54,101] like the well-known lotus-effect in nature. However, these super-hydrophobic surface structures seem to be mechanically less stable than smooth surfaces coated, e.g. with a-C:H:Si:O or a similar hydrophobic coating. Thin lm sensors: In the recent years DLC based coatings became more and more interesting because of their piezoresistive properties. Under mechanical pressure the resistance of DLC coatings decreases reproducibly. This allows the use of such coatings as force sensors, e.g. on washers or bearings [16]. Fig. 19
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Fig. 20. Strategies for sun-control windshield manufacture, e.g. coating on glass or lamination of coated PET (left) and layout of double silver sun-control coatings (right) [56].
Smart coatings will be used to adjust the transmittance of the glazing to minimize the heat load [66] and to protect the drivers and passengers privacy. 4.1.2. Properties of coatings on automotive glass There are four well known factors which disturb the drivers vision and which cause severe discomfort: (i) light scattering from water droplets during rainy weather, (ii) light reection from the dashboard, (iii) light reection from the mirrors and (iv) the thermal overheat due to sun load [84]. Modern automotive glazings make use of coated glass in order to handle these problems. The most important coatings on automotive glass are suncontrol coatings for laminated windshields. They are deposited either on the curved glass or on the at glass prior to glass bending or on the polymeric web prior to lamination. The layout of the coating is similar for all those cases as shown in Fig. 20. It contains two thin silver layers embedded in antireective dielectric layers. These coatings exhibit more than 75% transmittance in the visible range while the infrared part of the sun spectrum is blocked, as shown in Fig. 21. Compared to conventional tinted glass, decrease of maximum interior temperature of more than 11 8C from more than 100 to 89 8C is achieved for extreme climate tests [104] and more important, the time needed for the air conditioning to reach comfortable temperature levels is decreased by 40% [82]. The market penetration for these types of windshields is about 30% for car production in Europe in 2002. For single glass sun roofs and side or back windows, the concept of lamination of insulatormetalinsulator stacks is not feasible. Dielectric layer stacks can be used for this application [164]. Currently, however there are no products on the market utilizing this technique. Another important eld of application is the control of surface energy in order to achieve water repellant easy-to-clean layers without droplet formation during rainy weather. Organic hydro-
phobic layer systems exhibit lifetime of about 3 years on the windshield [74]. Also hydrophilic layers are used to improve the drivers vision during rain. These coatings are applied on the mirrors in order to spread the water lm and to minimize the scatter [167]. The use of hydrophilic layers is a new eld of application compared to the use of water repelling hydrophobic coatings, which are applied by wet chemical deposition [128]. Antireective layer stacks are used to minimize the reection from the dashboard. Sufcient results have been obtained for glazings which have been coated only on the inner side of the glass. These windshields exhibit reectance smaller than 10% at an angle of incidence of 608 [74]. UV protective TiO2:CeO2 lms are deposited by solgel coating on glass to minimize the interior UV load [127]. At night time, the drivers vision is impaired due to intense reection from the mirrors. This problem can be minimized by dielectric or metallic front side mirrors [62] in contrast to standard Ag plated back side mirrors. The problem of image distortion by rain droplets can be solved using a photo induced hydrophilic TiO2 coating of the mirror surface [78]. Furthermore, switchable electrochromic coatings are used for coating on inside and outside rearview mirrors which are controlled by photodiodes [116]. 4.1.3. Substitution of mineral glass by polycarbonate Mineral glass has shown to be an excellent material for automotive glazing due to its excellent optical performance, its long term durability and low production costs. However, demands for light weight glazing, more complex shapes and the ability for more modular construction opened up the pathway for substitution of mineral glass for automotive glazing by polycarbonate [11]. The polycarbonate allows weight reduction on the order of 50%, in contrast to PMMA, it is non-brittle and the parts can be manufactured by injection molding. However, the scratch resistance is inferior to glass and the material is not UV stable. Both problems can be solved by coatings. The rst crucial point is the scratch resistance of the coating which is measured with the Taber Abraser test. The stray light (Haze) level has to be smaller than 2% after 1000 revolutions of the Taber wheel. The second aspect is the UV stability which is checked by outdoor exposure. For accelerated tests, the criteria are stability for QUV-B for more than 1000 h and for xenon arc light for more than 2250 h. An early paper on that technology is the SAE report from 1993 [77]. Several applications came up where wet coatings with a primer lm ($2 mm) and a thick silica lled organo-polysiloxane top coat ($5 mm) were used. The haze level after Taber Abraser testing is in the order of 7% after 100 revolutions compared to mineral glass with 2% after 1000 revolutions. To compensate these drawbacks limiting the use of coated PC in the rear part of automotive body behind the b-pillar, a new process technique has been developed in the 1990s. The plasma enhanced deposition of transparent scratch protecting coatings by e-beam evaporation [98] or chemical vapour deposition (PACVD) [152]. A commercial product with a plasma based hard coating in the thickness range of 46 mm and an underlying wet chemical UV blocker and primer was announced in 2003, the Exatec 500 [134]. A modied version came up in 2006, the Exatec 900, where lifetime tests predict stability for more than 10 years. Degradation is due to failure of the UV absorber and the maximum UV dose correlates with the thickness of the UV absorber. The 10-year lifetime goal is met with an UV absorber thickness of 65 mm deposited by wet chemical methods. The thickness of the plasma deposited abrasion resistant coating is in the order of 3 mm [147]. 4.1.4. Potential for new developments Functional coatings on the outer side: new functions such as low emissivity outside coating to protect against condensation of water and ice formation in combination with fast cost effective full size heating units, durable easy-to-clean coatings and low reectance layers can be realized as soon as ultra durable
Fig. 21. Optical spectra of uncoated, tinted sun-control glass and double silver coated sun control glass [55]. The sun spectrum for air mass 1.5 is also shown.
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Fig. 22. Self-regenerating coating for long term hydrophobic coating based on nanostructured surface which is covered with a hydrophobic agent supplied by the underlying replenishment layer [142].
functional layers for outside coating are available. An important aspect is the development of ultra durable conductive optical layers with low emissivity. When the emissivity of the uncoated glass of e = 84% is decreased to e < 20%, the radiation cooling is minimized to an extent that prevents the condensation of water over night and thus, neither tarnishing of the glass nor ice formation occurs. Early work dates back to 1980s where SnO2:F lms deposited by spray pyrolysis had been investigated [75]. However, the durability of the coating was not sufcient since the high roughness of the SnO2:F gave rise to extensive wear in the Taber test. The new technology of high power pulse magnetron sputtering opens up a pathway for solving that problem: crystalline ITO (In2O3:Sn) lms with thickness of 140 nm can be deposited on unheated glass substrates. This transparent and conductive coating allows for glass bending and is extremely durable. Both the scratch and wear characteristics are improved with respect to the bare mineral glass [88]. A new concept for durable hydrophobicity are self-regenerating water repelling layers [142]: self-healing of super hydrophobicity is due to a polymeric replenishment layer, which releases a voltatile wax-like polymer through a porous, nanostructured metal oxide top coat, as shown in Fig. 22. Super hydrophobicity is due to the morphology of the metal oxide lm plus the low surface energy of the wax lm. A worn wax lm recovers due to diffusion of polymer out of the reservoir. This material transport process is stable over long terms and it protects the surface in a well dened manner. 4.1.4.1. Electronics. Bright self-emitting displays based on organic light emitting diodes (OLEDs) offer new possibilities to adopt exible displays on the dashboard. Future generations will integrate transparent OLEDs as a part of the glazings in order to present information for driver and passenger in a variable manner. This allows for the implementation of new safety features, for example for the magnied presentation of trafc signs, which are recognized by eye-trackers and which are displayed on the glazing by camera systems. Head-up displays and touch-screen interfaces will allow for the presentation of a small subset of information and thus, the control of the car will be much easier and safer [144]. 4.1.4.2. Illumination. Glazings will be used for full size illumination of the interior. This comfort feature will be achieved in short term by SMD-LEDs mounted in the sun roof, but future generations will implement full size illumination using transparent OLEDs integrated in the glazing. 4.1.4.3. Switchable transmission. Blinds will be replaced by fast switching optical layers in such a way, that only the illuminated part of the glazing will be shaded. Also full size shading of the glazing will be possible in order to minimize the thermal load on parking cars and to protect the drivers privacy on demand. 4.1.4.4. Photovoltaics. Semi-transparent thin lm solar cells will be integrated as a part of the optical design for sun roof elements. Air control units and security devices will be powered by these elements without any load for the storage battery. 4.2. Lighting The front, back and side lights of a car are crucial for all safety aspects. Besides this, they are also important design elements.
Up to the mid-80s, mineral glass was used for the front lights exclusively. From design and construction viewpoint, however, it was very attractive to substitute mineral glass by other materials allowing for complex shapes, ease of production and light weight solutions. In respect to these demands, polycarbonate headlights entered the market. The ford continental from 1984 was the rst car where mineral glass was replaced by polycarbonate [61] and nowadays, the market share of coated polycarbonate headlights is almost 100%. The technology for PC headlight coating is similar to the PC glazing. However, the demands on optical quality and low defect density of the coating are not as stringent as those for the automotive glazing. Stateof-the-art is silicone based hard coatings for scratch and UV protection [158]. Plasma [166] and hot-wire CVD processes allow for excellent performance, the costs, however are higher than for wet chemical deposition in this case. The reector of the headlight is coated with sputtered high reective aluminium and covered by SiO2 for corrosion protection [73]. Inorganic LEDs open up new pathways for headlight design and construction. Due to the reduced heating of the headlight antifogging layers on the inner side of the transparent housing [153] will be necessary for proper operation. Thin and low energy OLEDs will enable arbitrary shaped automotive lighting [131]. 4.3. Information display AR coatings are applied on the instrumental cluster and accessories such as navigation systems to minimize unwanted reections disturbing the drivers view [156]. Besides this, all aspects of display and touch screen technologies are important for automotive information display [160]. New developments address all aspects for OLED technology [139], such as OLEDs with a transparent active driver matrix [70] and exible OLED displays [1]. 5. Process and production technology 5.1. Plasma processes Thin lm deposition and surface treatment processes based on low pressure plasmas are still the key to realize many innovative surfaces in automotive engineering. The two basic families are physical vapour deposition (PVD) and plasma assisted chemical vapour deposition (PACVD). Evaporation and sputtering are the most important PVD processes. They require vacuum, since single particles have to be transported over a distance of several tens of cm from the coating source to the substrate without signicant energy loss. The coating material is solid, thin lms are deposited via the transition solidliquidvapoursolid in case of evaporation or solidvapour solid in case of sputtering. Evaporation is the oldest PVD process. Materials with an appreciable vapour pressure at temperatures up to 1500 8C (this holds for many metals) may be evaporated by resistive heating, for materials with a higher melting point (e.g. metal oxides) electron beam evaporation is used [9]. Evaporation is a rather fast process with deposition rates in the range of several mm/s. However, lm quality and adhesion to the substrate may suffer from the low energy (around 0.2 eV) of evaporated particles. More sophisticated evaporation processes therefore make use of an additional plasma (Fig. 23). The evaporated particles crossing the plasma zone are activated and ionized and consequently can form a much denser lm [124]. Plasma activated electron beam evaporation is nowadays the preferred process for manufacturing of antireective coatings on lenses for optical instruments or spectacles [197]. Sputtering is often called a billiard game with ions and atoms. Positive ions (in industrial processes mainly argon is used as process gas) are generated in a plasma which is ignited between a
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Fig. 25. The principle of magnetron sputtering. Electrons are trapped by the Lorentz force K ey B in an inhomogeneous magnetic eld, resulting in an enhanced ionisation of argon atoms. Fig. 23. The principle of plasma assisted electron beam evaporation.
Fig. 24. The sputter process on an atomic scale.
cathode (sputter target) and an anode (substrate). They are accelerated in the electric eld, hit the target surface and transfer their energy to the target atoms which are ejected and form a thin lm on the substrate (Fig. 24). If a reactive gas (e.g. oxygen or nitrogen) is added to the argon, metal oxides, nitrides or various compound lms can be deposited. Compared to other deposition technologies, sputtering is a rather slow process (deposition rates in the range of nm/s). However, since the energy of sputtered atoms is around 10 times higher than the energy of evaporated particles, dense and smooth thin lms with a high quality can be obtained. With the introduction of the planar magnetron cathode in the late seventies [30] sputtering began to conquer all industrial branches needing thin lm technologies for the realization of new or improvement of existing products. The main advantages of magnetron sputtering are: Low plasma impedance and thus high discharge current in the range of 1100 A (depending on target length) at typical voltage around 500 V; Deposition rates ranging from 1 nm/s to 10 nm/s (in some cases up to 50 nm/s) and thus suitable for economic mass production; Low thermal load on the substrate (made the lm deposition on temperature sensitive substrates possible); Excellent plasma and coating homogeneity even for cathodes with a length of several meters; Dense and well adherent lms; Huge variety of coating materials. The operation of a magnetron cathode is based on the trapping of electrons in a magnetic eld according to Fig. 25. An industrial sputter coater for the deposition of DLC or Me-DLC on tools or components is shown in Fig. 26. The most severe inherent problems of planar magnetron sputtering were the poor target material utilization of around 25% and the process instabilities accompanying the reactive deposition of insulating materials like SiO2 or Al2O3 in DC powered discharges. Both problems have been solved through intensive R + D work during the last two centuries.
Fig. 26. Industrial coating equipment for sputter deposition of DLC (from graphite targets) or Me-DLC. Two magnetron cathodes are shown in the left side of the picture.
Fig. 27. The principle of sputtering with a rotatable magnetron (C-MAG).
In 1985 Wright and Beardow [189] reported on a tubular magnetron which was industrialized as C-MAG [122] several years later. According to Fig. 27 the target is a tube rotating around a xed magnetic eld. With such rotatable magnetrons a material utilization of 90% and a target lifetime of several weeks may be achieved. Pulse magnetron sputtering operated by power supplies in a frequency range from 10 kHz to 100 kHz has been introduced for the long term stable high rate deposition of insulating oxides or nitrides in particular on large areas. Fig. 28 illustrates the principle of a dual magnetron unit. At any time, one of the identical plasma source acts as sputter cathode, while the other one acts as anode. Process instabilities during deposition of insulating materials are almost eliminated. In 1999, Kouznetsov et al. [108] reported on lm deposition using high power pulse magnetron sputtering (HPPMS) at target power densities up to 2800 W/cm2 (conventional DC discharges are operated at 2050 W/cm2).
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Fig. 28. The principle of pulse magnetron sputtering from a dual magnetron unit. Fig. 30. DLC formation with PACVD (schematic).
Thin lm transistors that control the individual pixels in an active matrix liquid crystal display or absorber lms in Si-based thin lm solar cells consist of amorphous silicon. From these examples it is obvious that PACVD is a key manufacturing process for innovative products. Hot lament activated chemical vapour deposition (HFCVD) is a vacuum based thermal CVD process using an array of tungsten wires which are heated to temperatures between 2000 8C and 3000 8C [149,119]. The coating of large two-dimensional plates (size up to 500 mm 1000 mm) or substrates with a cylindrical geometry is possible in different reactors, as shown in Fig. 31. HFCVD has been used for the deposition of polycrystalline diamond on large areas. The feasibility of manufacturing amorphous silicon, microcrystalline silicon, and silicon nitride has been demonstrated. HWCVD may be an important step on the way to cost effective solar cell production. 5.2. Electrochemical processes
Fig. 29. High power pulse magnetron sputtering in an industrial hard coating machine. Due to the high power the light emission is much more intensive than in the conventional magnetron plasma. (Source: SVS Vacuum Coating Technologies.)
At typical pulse duration of 50 ms and frequencies around 50 Hz the mean power dissipated in such a discharge is similar to the DC case. In an HPPMS process a high amount of the lm forming species is ionized (5090%) which results in dense lms. DeKoven et al. [41] report on HPPMS deposited DLC lms with a density of 2.7 g/cm3 (2.0 g/cm3 are usually obtained with DC sputtering [122]). HPPMS processes are already established in industrial coaters, an example is shown in Fig. 29. In CVD processes thin lms are formed directly from the gas phase. The source material, a so called precursor, is a vapour. Liquid materials may be employed, but they have to be transferred to the vapour phase. There are vacuum based CVD processes and those taking place under atmospheric pressure. The energy supplied to the precursor gas in the CVD reactor is used to break bonds, the lm is formed from the fragments. Depending on the method of energy supply we distinguish between thermal CVD and plasma assisted or PACVD. Thermal CVD requires rather high process temperatures (up to 1000 8C) and therefore is limited to heat resistant substrates, while PACVD is a rather cold process and thus suitable even for plastics. The deposition rates of CVD processes are in the range of several to several tenth of nm/s. A typical application of PACVD is the deposition of DLC, this process is schematically shown in Fig. 30. Suitable precursor gases are acetylene (C2H2) or methane (CH4). At deposition rates of 12 mm/h and a required thickness of several micrometers the deposition time is in the range of a few hours. A further important PACVD process is the deposition of amorphous silicon from silane (SiH4), a silicon containing gas.
Electrochemical processes (electroplating, electroless plating, electrophoretic painting) are the most important surface technologies in the automotive industry. The most important properties are an increased corrosion resistance, tribological functions like wear resistance or reduced friction properties and decorative aspects. About 40% [90] of the products of the electroplating industry are intended for the automotive industry, primarily for corrosion resistance. 5.2.1. General technical process The most important deposition metals in a car are zinc, nickel and chromium. Typical of these metals, the equation for the electro-deposition of nickel is shown in the following equation: cathode : Ni2 2e ! Ni (1)
On the other side, metallic nickel will be dissolved according to the following equation: anode : Ni ! Ni2 2e (2)
The process works in a so called Watts electrolyte, based on a solution of Nickel sulphate with small amounts of Ni-chlorides. In order to keep the pH-value constant at 34, boric acid is added. The average current density is about 5 A/dm2. Organic additives can inuence the grain renement and levelling of the coating in order to achieve a dense, bright shining surface [20]. The deposition of the metal can be performed either in a rack plating process for larger parts or in a so called barrel plating process, where small parts like screws are placed in a barrel, which is rotating in the electrolyte bath during the deposition process.
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Fig. 31. HFCVD reactors for at and cylindrical substrate geometries.
5.3. Corrosion protection 5.3.1. Electrodeposition of zinc and zinc alloys The most important coating metal is zinc in combination with conversion layers and/or cathodic dip painting layers for corrosion protection (see below). The main reasons for choosing zinc for corrosion protection are the relatively low price and the ability to provide cathodic protection to steel, while maintaining a low zinc corrosion rate in non-aggressive environment, due to the formation of passive layers of zinc hydroxide. Zinc plating is realized by two different electroplating processes. Single parts are coated by a so called batch process, either a rack process or a barrel process; larger parts can be produced from steel which is coated with zinc in an endless coil-tocoil plating process and then subsequently formed to car doors or engine hoods. To an increasing extent, the pure zinc layer is being replaced by a zincnickel alloy with a nickel content of about 1015%. The corrosion resistance is increased compared to a pure zinc layer, however, the costs are higher [63,26,57,58]. Generally, the zinc (alloy) layer is only a part of a complex corrosion protection system consisting of the metallic layer, the hexavalent chromium free conversion layer and the painting system. 5.3.2. Hot dip galvanizing Hot-dip galvanizing (HDG) is the process where steel coils in a continuous process or metal parts (batch galvanizing) are immersed in a bath of molten zinc, resulting in a well-adhered zincsteel alloy coating that protects the steel from corrosion. The temperature of the molten zinc is about 460 8C and the thickness layer varies from about 8 mm for coil coating processes and 15 20 mm for the coating of single parts. Both processes, electroplating of zinc and hot dip galvanizing are well known processes on usual steel, however, the upcoming of new types of steel with a high strength like the TRIP steel (transformation-induced plasticity) causes some problems. The addition of certain alloying metals like Al or Mn passivates the surface of this steel and reduces the wettability during the hot dip galvanizing process resulting in a lower adhesion [8]. The electroplating of zinc on the TRIP-steel reduces the dynamic tensile strength [191]. 5.3.3. Conversion layers The so called directive on End-of life vehicles (ELV) [33] bans the application of certain heavy metals like lead, cadmium, mercury and hexavalent chromium in the automotive industry from July 2007. However, hexavalent chromium was one of the most efcient corrosion protective coatings on zinc plated steel and aluminium. This was not only because of the relatively high coating thickness of about 200400 nm but also due to the so called self-healing effect. This effect, not yet really understood, covers a small crack, caused for example by a mechanical damage, again with hexavalent chromium and saves the surface against corrosion attack.
Commercially available are technical solutions based on trivalent chromium (passivation) which is considered to be nonhazardous [39,184,141]. Depending on the coating thickness, such processes are known as thin layer passivation (about 50 nm) and thick layer passivation (about 200500 nm). Additionally, a Sibased seal coating can further improve the corrosion protection. 5.3.4. Cathodic dip painting: (CDP) The priming of a car body is carried out nearly completely with the cathodic dip painting process. In a bowl which is lled with the priming paint based on an epoxy resin the car body is connected as the cathode, while a stainless steel sheet is the anode. A voltage of about 320360 V is applied. However, there is no direct electrodeposition but an electrocoagulation: due to the water electrolysis, the pH-value at the cathode increases and causes the discharge of the positively charged particles according to: R3 N insoluble R-COOH ! R3 NH soluble R-COO 4 H2 O 4e ! 2H2 4OH R3 NH soluble OH ! R3 N H2 O precipitation on the car body where R3N is the lm former (insoluble amine salt); R-COOH the (solubilising acid); R3NH+ + R-COO the solubilised positively charged polymer. The dissolved positively charged polymer precipitate on the surface and form a dense, electrical insulating layer. The coating thickness of this process is very homogenous. Cathodic dip painting is possible on steel, zinc-plated steel, aluminium and magnesium. The process is usually combined with inorganic conversion layers like zinc phosphate in order to improve the adhesion or hexavalent chromium free layer for an additional corrosion protection. CDP is an optimal priming process for the combination with powder- or conventional coating [29]. A scheme of the CDP-process of car bodies is shown in Fig. 32. 5.4. Plastic metallisation and decorative plating 5.4.1. Plastic metallisation Due to the fact that weight saving in automotive industry is a critical objective, the substitution of metallic parts with plastic parts is still going on. A lot of parts are visible and therefore, they need an attractive surface. The market for the plastic metallisation is about 60 million s p.y. only for the automotive industry [136]. The most common polymers are acrylonitrilebutadienestyrene (ABS) and related blends with polycarbonate (PC) and polyamide, which are used for mirror frames, door knobs, electrical switches and more (see Fig. 33). Compared to the metallisation of metal substrates, the adhesion of a metallic layer on polymers is completely different, due to the fact that polymers are electrical insulators. The adhesion is not
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Fig. 32. Scheme of the CDP-process with car bodies.
inhomogeneous and thus, the coating thickness is much higher than the target value. The correct value is subsequently obtained by grinding and polishing processes. A very special layer is a chromium composite coating with embedded hard particles like diamond or alumina. Normally, chromium based composites are not possible due to the strong hydrogen evolution, however it succeeds with a special pulseplating process [23,24]. For some special applications in racing cars and motor-bikes a composite coating based on electroless nickelphosphorus alloy with embedded particles of SiC are used. 5.6. Outlook and latest developments Although the electroplating industry is well established, new developments are necessary to meet the demands of automotive industry. These are in particular weight saving, improved corrosion protection and legal requirements. Magnesium is a light metal which is more and more interesting, but it suffers from corrosion susceptibility. Up to now, there are only few magnesium parts mounted in a car. New processes for electrodeposition on magnesium as well as new chromium free conversion layers offer an opportunity to develop new corrosion resistant magnesium systems [45,176]. In order to improve the corrosion protection of steel with zinc coatings, the steel industry has developed a new coating system, based on electroplated (ZEMg) or hot dip plated zinc (ZMg) with an additional thin layer of PVD-deposited magnesium. The Mg-layer shifts the electrochemical potential to more negative values and reduces the corrosion on steel [154,155,157]. This system should be applied for coil coating processes. Legal requirements ban the use of hexavalent chromium as a conversion layer and trivalent chromium is for most applications a technical adequate solution. However, there is concern about the general use of chromium, and thus, new passivations with completely chromium-free conversion layers, based on various materials like cerium, vanadium, molybdenum or molybdatezinc have been developed. The corrosion protection will be further increased in combination with paintings [188,159]. The process of composite plating requires insoluble and chemical inert particles in the electrolyte. With the so called microencapsulation it is possible to transfer liquid or chemical active substances into a solid phase which is inert in the electrolyte. With this technique it is possible to embed for example microencapsulated oil (see Fig. 34) or molybdenum sulphide in metallic coatings for low friction applications or
Fig. 33. Chromium-plated door knob of polyamide.
caused by a metalmetal bond but by a mechanical bonding. The coating process can be described in following steps: (1) Etching with Cr6+ containing sulphuric acid in order to get a rough, hydrophilic surface; (2) Treatment with catalytic active palladium nuclei; (3) First metallisation step with a thin autocatalytic electroless deposited nickel layer; (4) Reinforcement of the thin layer with an electrodeposited coating of copper and/or nickel. Usual, the metallisation of plastic parts is intended for decorative applications, thus the main top coating is a thin chromium layer [38]. 5.4.2. Decorative plating The favourite metal for decorative metallisation is chromium in several versions like bright or dull chromium. The coating thickness is about 0.5 mm; however, the kind of chromium coating depends from the nickel interlayer which is about 1020 mm thick. For a bright chromium layer, the nickel layer needs a strong levelling effect which can be achieved by the addition of organic additives (leveller, grain rener). For a dull chromium layer some oil drops will be added to the nickel electrolyte which will be adsorbed and cause a velvety surface. However, the resulting chromium layer will not inuence the surface, but only the colour. Although metallic chromium is not considered to be hazardous, it will be deposited from a hexavalent electrolyte which is acutely toxic and can cause cancer. Thus, more and more electrolyte suppliers and job-coaters try to substitute the Cr(VI)-electrolyte with a non-toxic trivalent electrolyte. In former times, Cr from trivalent baths suffers from a brownish colour, but recent successes show that it is possible to deposit the same bluish tint as occurs with hexavalent chromium baths [114,177,48]. 5.5. Wear resistance A lot of wear resistant parts are used in cars, e.g. cam shafts, valves, shock absorber, piston rods and rings, bearings and others. Most of them are coated with a hard chromium layer which is a very popular layer with a high hardness of about 1100 HV and a good corrosion resistance. The layer thickness varies from about 10 mm to more than 100 mm [114]. However; the coating is very
Fig. 34. SEM-picture of an oil containing nickel composite coating.
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corrosion inhibitors for an improved corrosion protection (selfhealing effect) [44]. 6. Coating characterization The development of new coating technologies requires novel measuring techniques, particularly non-destructive inspection methods, in order to ensure the desired coating properties like layer thickness, hardness, homogeneity and others. In most cases, they are restricted to certain materials or are applicable only within a limited range of coating parameters. Some measuring methods have been successfully transferred into industrial environments. The most important methods to analyse coating properties are discussed in the following sections. 6.1. Photothermal measuring techniques Photothermal techniques form a class of different measuring methods. Their common feature is the generation of thermal waves within a specimen. This is usually realized by exposing the surface to intensity modulated laser radiation. The partial absorption of this radiation means a periodical energy deposition. Mathematically, such a situation is described by the thermal diffusion equation [69], which is given for a one-dimensional heat propagation by @ @ @T kz Tz; t rzcz z; t Hz; t (3) @t @z @z The source term H(z,t) expresses the density of heat sources along the z-axis and its time dependence. In order to analyse coating properties, those solutions of the thermal diffusion equation are important which represent strongly damped temperature waves [69]: z p Tz; t T 0 ez=m cos vt (4) m 4 T0 is the temperature amplitude at the coating surface. For Eq. (4) it is assumed that all radiation energy is absorbed directly at the surface and that the heat propagates only one-dimensionally in z-direction. This condition is often fullled, at least approximately. The quantity m is called the thermal diffusion length, which is coupled to the thermal wavelength lth:
Fig. 35. Phase differences depending on the normalized layer thickness x for different values of the thermal reection coefcient R.
lth 2pm
(5)
Eq. (5) together with (4) show that a thermal wave is damped out nearly completely within a propagation distance of one thermal wavelength. If a thermal wave encounters an interface to a substrate with different thermal properties, a fraction of it is reected and propagates back to its origin, where it will interfere with the initial thermal wave. The thermal reection coefcient R of the interface has the form [12] R 1 eS =eL 1 eS =eL (6)
where eS, eL are the thermal effusivities of the substrate (S) and the layer (L), which depend on the thermal conductivity k, the density r and the heat capacity c of the corresponding material: p e krc (7) Commonly, multiple reections between the layer surface and its interface to the substrate occur, resulting in a surface temperature oscillation T(t) which shows modied amplitudes and phase differences with respect to the excitation radiation. In contrast to the amplitude of the thermal wave, its phase difference is not inuenced by the absorption of the excitation energy. The dependence of the photothermal phase on the coating thickness d (here normalized to the thermal diffusivity m) is shown in Fig. 35 for different values of the thermal reection coefcient R. For the
phase curve of R = 0.9, a straight line indicates an almost linear relationship of the phase for a certain range of layer thickness. This range is often used for the photothermal thickness analysis of coatings. The surface temperature T(t), from which amplitude and phase signals can be analysed using lock-in techniques, is most often measured by infrared sensors [93]. Special techniques had been developed to reduce the time required for surface scans [25,190]. Alternative detection methods like thermo reection and the mirage technique [111,112] are preferred for instance, if the infrared emissivity is low. The measurement of layer thicknesses and the detection of defects are the most important applications of the photothermal analysis [12,34]. They are used, e.g. within industrial production lines to measure the thickness of powder coatings. Not only single coatings, but also multilayer coatings can be analysed by multiple frequency measurements [95,185]. Another application is the determination of thermal parameters, which requires the knowledge of the coating thickness and the thermal parameters of the substrate [15,140,68,138]. Due to the fact that delaminations have a strong impact on the thermal contrast of coating interfaces, such defects have a signicant inuence on the photothermal signals. No simple rule can be elaborated to decide whether or not a certain coating parameter can be measured using thermal waves. However, some conditions will be advantageous: a thermal reection coefcient close to +1 or 1 promises a strong measuring contrast. Surface absorption and emission allow applying a simplied photothermal model [145]. The analysis of semitransparent coatings is considerably more complicated [49]. The thermal diffusion length m should be in the same order as the layer thickness. This can often be achieved, because m is a function of the modulation frequency. The coating thicknesses which can be analysed approximately range from 1 mm to 400 mm for organic coatings and from 10 mm to 10 mm for metallic coatings. 6.2. Acoustic microscopy Another non-destructive method to analyse coatings and other near surface zone structures is acoustic microscopy. This is based on the generation of high frequency sound waves with piezoelectric transducers, which are focussed by an acoustic lens into the examined specimen. Structures within the specimen reect a portion of the sound energy. A part of the reected acoustic wave is then collected by the lens and converted into an electric signal by the same transducer. If the lens is scanned in rows and columns over the specimen, the signals for all measured points form an acoustic image, where structures indicate the presence of possible defects [100].
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The acoustic reection coefcient Ra of an interface can be dened as [2] Ra Z2 Z1 Z2 Z1 (8)
where the acoustic impedance Z is the product of the density r and sound velocity ys : Z r ys . The acoustic wave is reected at the lens surface if no coupling medium like water is used, because the acoustic impedance of the lens material, which is commonly sapphire, is considerably different from the acoustic impedance of air. For propagation time measurements, the transducer cannot emit and receive acoustic waves simultaneously. Hence, only short pulses of ultrasound waves are emitted and the transducer is then switched into the detection mode. The next ultrasound pulse is emitted if no more echoes are expected. The signal amplitude yields information about the acoustic impedance of the structure which caused the echo. If the sound velocity is known, the time from the emission of the pulse to the detection of its reection allows calculating the distance from the lens to the structure. If microscopic defects like blisters within a coating or delaminations of the interface have to be analysed [193,47], the resolution of the acoustic microscope becomes an important parameter. It can be shown that the lateral resolution increases with the lens aperture and with the frequency of the acoustic wave. Unfortunately, the absorption of the acoustic waves increases with the square of the frequency. This circumstance limits the detection depth. In practise, one has to nd a compromise between penetration depth and lateral resolution. 6.3. Micromagnetics Magnetic measuring principles are based upon the correlation between the surface zone parameters of a workpiece and the corresponding change of the electromagnetic material properties. Thus, these methods are restricted to materials with reasonable electrical conductivity (e.g. eddy current measuring methods) and ferromagnetic properties (magnetic and micromagnetic methods) [4]. Nevertheless, all ferromagnetic and antiferromagnetic materials show a strong interaction between the magnetic dipoles and Weiss domains. Since they cover a large spectrum of technically very important workpieces, micromagnetics have gained a substantial progress during the last 20 years, due to intensive research work [69]. Some of the most important magnetic measuring methods are the eddy current method, the Barkhausen effect, the superposition permeability and the harmonic analysis, all non-destructive testing methods [162]. The eddy current principle is based on the impedance analysis of a sample. Depending on interactions between the magnetic eld generated by a coil and an object, conductivity and permeability related changes in the impedance occur. For the Barkhausen effect, a stationary electromagnet applies an alternating magnetic eld to a ferromagnetic sample. The alternating magnetization of the sample is stimulated by changing magnetic domain sizes through jumps of the domain-separating Bloch walls [163]. The micromagnetic testing methods enable the microstructure characterization, detection of micro-failures and evaluation of the local distribution of residual stresses, adhesion strength, mechanical hardness and coating thickness [171,4,170,65]. 6.4. X-ray diffraction X-ray scattering techniques are non-destructive methods for the analysis of the crystallographic structure, chemical composition and physical properties of materials and thin lms. These techniques are based on the measurement of the scattered
intensity, caused by an X-ray beam irradiating a sample, as a function of incident and scattered angle, polarization and wavelength or energy. Thin lm diffraction and grazing incidence X-ray diffraction are used for the characterization of crystallographic structures and preferred orientation of substrate-anchored thin lms. Highresolution X-ray diffraction enables the characterization of thickness, crystallographic structure and stress in thin epitaxial lms [168,32,195]. In the case of coatings and lms, the substrate and the deposition process may result in very high residual stress elds which can affect both performance and surface integrity, since adhesion or cracking resistance can be strongly altered [64]. In the case of very thin coatings, the lm contribution to the diffraction pattern can be hidden by that of the substrate. In these cases, a glancing incidence X-ray diffraction (GIXRD) technique is preferred, since the penetration depth can be strongly reduced by choosing incident angles close to the critical angle [196]. In this geometry the diffracting planes are generally not parallel to the sample surface and it is possible to study the structure of the coatings as a function of the X-ray penetration depth [64]. 6.5. Surface metrology The surface geometry of functional coatings can be characterized in different ways. The prevalent methods work either in a tactile or non-contact mode. A classical tactile measuring system is the prolometer traditionally called stylus instrument and it works like a phonograph. For the atomic force microscope [31], however, the contact to the surface is caused by atomic interactions. Non-contact methods can be divided into vertical and lateral scanning procedures. In most cases, they are based on optical measuring principles. But also acoustic measuring methods can be applied [67]. Some examples for vertical scanning devices are the white light interferometer and the confocal microscope [110]. Two cases for lateral scanning systems are fringe projection and laser scanning. With the procedures specied above it is possible to assess the surface geometry via standardized roughness and waviness parameters. Apart from these standardized characterizations of surface geometry, laser optical light scattering methods like the angle resolved scattering (ARS) and other speckle techniques are very convenient, since the objective areal roughness parameters are integrally determined. 7. Summary and visions The most important aspects of surface technologies for automotive engineering have been discussed in this paper. Tribological coatings on tools nowadays are the key for efcient manufacturing processes. Several families of such coatings have been developed during the past 30 years, ranging from different metal nitrides like TiN, TiAlN or CrN to various carbon based lms. Superhard c-BN is on the way to industrialization, bridging the gap between nitrides and diamond and with a temperature stability superior to that of diamond. Due to their high hardness and low coefcient of friction, diamond-like carbon lms are of great interest for various drive components. Introduced on high performance injection nozzles around 15 years ago, today their application in automotive technology is still limited, but will substantially grow in the future, being pushed by the need for reduction of fuel consumption and the desire for longer lifetime of components. The ultimate dream is the engine that runs without any lubricants. Even today the car driver has to suffer from all the disadvantageous optical and thermal properties of glass. Together with a substantial increase of glazed area there is an increasing demand to eliminate these disadvantages and add more functionality to the glass by suitable coatings. The basic desire of the driver is certainly
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more comfort through a simple de-icing procedure in winter as well as a substantially reduced heat transfer during hot summer days. Further visions are self-cleaning instead of easy-to-clean glass surfaces and the integration of sensors or semi-transparent displays into the windscreen. Many coatings which can full abovementioned desires already do exist. Highly selective sun control lms with a transmission of more than 90% in the visible and a high reection in the near infrared part of the solar spectrum can easily be realized, but their manufacturing costs are still prohibitive for use in automobiles. Electrochromic coatings with variable transmission will replace mechanical blinds in sunroofs in the future and they will also be used on side and rear windows for privacy reasons. For 20 years there have also been strong efforts to replace mineral glass by polycarbonate (PC), where weight reduction and increased safety are the main reasons. Highly scratch resistant surface coatings are necessary to protect the soft PC, and an additional UV blocker has to be integrated in order to avoid its degradation. To realize such complex lms in an industrial scale and at reasonable costs is an ongoing challenge. Improved corrosion protection of steel strips used for the car body is a further object of current research and development activities. Zinc magnesium alloys or SiOx deposited by plasma activated evaporation will most probably replace conventional corrosion protection in the near future. The combination of the high hardness and wear resistance of DLC lms and its piezoelectric properties are the basis for realization of novel temperature and force sensors, which can be used even in harsh environments and thus add more comfort and safety to the car. Finally, automotive industry and drivers dream of surfaces that repair themselves, even after mechanical degradation. Electroplated composite lms containing capsules with corrosion inhibitors is one of the approaches on the way to such intelligent surfaces. In conclusion, surface manufacturing technologies are one of the keys to add more safety and comfort to future cars. References
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CIRP Annals - Manufacturing Technology

Surface technology for automotive engineering

* Corresponding author. 0007-8506/$ see front matter 2009 CIRP. doi:10.1016/j.cirp.2009.09.001

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

Fig. 1. Examples for the application of surface technologies in a modern car.

Fig. 2. Inuence of coatings on wear mechanisms and contact conditions.

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

Fig. 9. Flank wear in machining Al20 wt% SiC composite [89].

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

Fig. 10. Nanocomposite structure.

Fig. 14. Performance improvement of nanocomposite coating in gear hobbing.

Fig. 11. Inuence of nanocomposite structure on spinodal segregation [36,86].

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

Abrasive wear [1015 m3/Nm] 0.51 24 1015 14 )

Water contact angle [8] 7075 7580 95105 6570 110120

Surface energy [mN/m] 40 38 24 42 19

2535 20 810 1520 <0.5

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

Fig. 24. The sputter process on an atomic scale.

Fig. 27. The principle of sputtering with a rotatable magnetron (C-MAG).

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

Fig. 31. HFCVD reactors for at and cylindrical substrate geometries.

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

Fig. 32. Scheme of the CDP-process with car bodies.

Fig. 33. Chromium-plated door knob of polyamide.

Fig. 34. SEM-picture of an oil containing nickel composite coating.

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

K. Bewilogua et al. / CIRP Annals - Manufacturing Technology 58 (2009) 608627

The acoustic reection coefcient Ra of an interface can be dened as [2] Ra Z2 Z1 Z2 Z1 (8)

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