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Surface & Coatings Technology 202 (2008) 4438 4443 www.elsevier.com/locate/surfcoat

Thermal spraying of cylinder bores with the Plasma Transferred Wire Arc process
K. Bobzin a , F. Ernst a , K. Richardt a , T. Schlaefer a,, C. Verpoort b , G. Flores c
a

Surface Engineering Institute, RWTH Aachen University, Aachen, Germany b Ford Forschungszentrum Aachen GmbH, Germany c Gehring GmbH & Co. KG, Ostfildern, Germany Available online 8 April 2008

Abstract Engine blocks of passenger cars made of hypoeutectic AlSi-alloys are generally equipped with cast iron liners in order to provide cylinder running surfaces that meet the tribological requirements. Thermally sprayed cylinder running surfaces are a promising alternative to cast iron liners. APS sprayed cylinder running surfaces made from low alloyed C steel have already proven their ability to reduce friction losses within the engine. Additional potential to reduce friction losses is offered by novel, and highly alloyed iron based surface building materials. This work describes the development of such materials and their application by the Plasma Transferred Wire Arc internal diameter coating process. The feedstocks lead to partially amorphous coatings with embedded boridic nanoscale precipitations if processed by thermal spraying. The coatings were applied onto the inner diameters of test liners made of aluminium EN AW 6060 and onto cylinder bore walls of an in-line 4 cylinder engine. Prior to coating, all surfaces to be coated were pre-treated by a novel fine boring process in order to create a surface topography which enables the adherence of the coatings. The coatings microstructures were analysed by light optical microscopy, hardness measuring and transmission electron microscopy. Furthermore the oil storage capacities of the honed surfaces were determined. 2008 Elsevier B.V. All rights reserved.
Keywords: Plasma Transferred Wire Arc; Nanocomposite coating; Cored wire feedstock; Engine block

1. Introduction One of the most important objectives of the automotive industry within the next years lies within the reduction of emissions and as well the reduction of the fuel consumption. Both are objectives that depend on lowering the engines weight but also the frictional resistance within the drive train and especially the engine. Decreasing the engines weight is reached by the use of light-metal alloys. Grey cast iron, which once was the standard material in the production of engine blocks, is now replaced more and more by, mostly hypoeutectic, aluminiumsilicon (AlSi) alloys. Not only for gasoline-operated, but also for diesel engines. Engine blocks made of these alloys save between 35 and 50% in weight

Corresponding author. Tel.: +49 241 16602 11; fax: +49 241 16602 17. E-mail address: schlaefer@iot.rwth-aachen.de (T. Schlaefer). 0257-8972/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2008.04.023

compared to grey cast iron engine blocks [1]. The mechanical properties such as Young's modulus, tensile strength and hardness of aluminium based alloys used for engine blocks are significantly lower than those for grey cast iron. Particularly due to the low hardness, hypoeutectic AlSi-alloys (e. g. AlSi8Cu3: 115135 HB) do not meet the tribological requirements in the contact area between the piston ring and the cylinder bore wall [2]. Due to the low wear resistance of hypoeutectic AlSi-alloys, the surface in this contact area has to be modified or substituted. Generally the material at the surface is being substituted by pressed in or cast in cylinder liners made of grey cast iron. Grey cast iron has a sufficient hardness and the embedded graphite lamellas serve as a solid lubricant, especially in the bottom and top dead centre where the piston speed is near zero (mixed friction). Besides the high costs and an increase of the engines weight and size, the use of cylinder liners exhibits further problems. The different thermal expansion coefficients of grey

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cast iron and the engine block material can cause a deformation of the liner and also local heat transfer problems (heat pockets) if the liner disengages from the engine block [3]. Particularly the deformation of the liner leads to an increased oil and fuel consumption and increasing emissions. A newer approach to produce iron based cylinder running surfaces on engine bore walls is to apply thermally sprayed coatings onto the bore walls. The presented investigations are part of the joint project Nano-crystalline composite coatings for cylinder bores with nano-structured surface and wear forecast for highly loaded gasoline and diesel engines NaCoLab, promoted by the German Federal Ministry for education and research in the range of the program Nano-mobil. The objective of the research project is to comply with all the requirements in order to produce engine blocks of aluminiumsilicon alloys with thermally sprayed cylinder running surfaces. 2. Thermal spraying of cylinder bores The coating of bores by thermal spraying requires special thermal spraying systems. To enable the application of thermally sprayed coatings onto cylinder bore walls, on the one hand the gun heads dimensions have to be small compared to the bore. Typically the diameters of cylinder bores in modern passenger car engines are smaller than 100 mm. On the other hand, in order to avoid having to rotate the engine block to be coated, the gun head has to be able to rotate coaxially to the bore. Hence, these systems are typically characterized by a rotating spindle. The gun head with the plasma generator or the combustion chamber and the nozzle are mounted to the bottom of the spindle. Due to the axial feed combined with the rotation of the spindle a spiral spray pattern is created on the bore wall. At the moment at least four thermal spraying systems designed for this special purpose are either commercially available or in the stage of research. One system uses powder feedstock while three of them use wire as feedstock:

Fig. 1. Picture of the PTWA system, (left) and a schematic of the PTWA process (right).

Rotary powder plasma process (APS) Rotating twin wire arc system (TWA), both systems, APS and TWA, are in serial production, High velocity oxygen fuel system (HVOF), in the stage of research, Plasma Transferred Wire Arc system (PTWA), in serial production for engine remanufacturing.

In high volume manufacturing facilities, the handling of wire is considered easier than the handling of powder, since no complex and also no costly powder feeding equipment is required. Within the frame of this work the Plasma Transferred Wire Arc technology was applied. The plasma generator or gun head consists of a tungsten cathode, an air-cooled pilot nozzle made of copper and an electrically conductive consumable wire which is the anode (Fig. 1). The gun head is mounted to a rotating spindle, which rotates with up to 600 rpm. The wire is fed perpendicularly to the centre orifice of the nozzle. To start the

process, a high voltage discharge is initiated, which ionizes and dissociates the gas mixture between the cathode and the nozzle. Due to a constricting orifice in the pilot nozzle the plasma is forced to exit the nozzle at supersonic velocity. The elongated plasma is transferred to the consumable anode, the wire, completing the electric circuit. A constant current power supply maintains the plasma from the cathode to the wire with an arc voltage of 100120 V and a current of 60100 A. This melts the tip of the wire and then the high pressure plasma gas together with the atomizing gas strips the molten particles from the end of the wire. Thereby a jet of finely atomized particles is created, which is accelerated towards the substrate at high speed. The atomizing gas can be any non-combustible gas. In this work a mixture of argon and hydrogen is used as the plasma gas and compressed air is used to atomize and accelerate the molten particles. The system is suitable to coat cylinder bores with a diameter of 35 to 360 mm. Due to the high speed of the spray particles of 100130 m/s very dense coatings with a porosity of less than 2% can be applied with the PTWA system. The particle temperature thereby reaches a value of approximately 2100 C. Because of the consumable wire anode and the design of the gun head, no water cooling is required, which minimises the systems dimensions and improves its reliability. The process chain in the production of coated cylinder bores consists of four steps. The first steps are machining the cylinder bore to a certain diameter, and machining the surface to be coated as mentioned later, so the coating is able to adhere. Next steps are the thermal spraying process and the honing of the coated bore to generate a surface that meets the tribological requirements. The thickness of the coating after the honing operation is typically 100150 m. Because of the as sprayed roughness of the coating and the required machining allowance, the thickness of the as sprayed coating is typically around 200300 m. 2.1. Pre-treatment of the substrates The substrate pre-treatment in the production of engine blocks with thermally sprayed cylinder running surfaces can be carried

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respectively mechanically roughened liners. The bond strength was determined with the PAThandy pull off adhesion tester (DfD Instruments, Kristiansand, Norway), which enables bond strength testing of curved surfaces. 2.2. Surface building materials Within the work presented, two materials systems are under development. As reference materials low alloyed carbon steels are used as feedstock. These steels contain 0.10.82 wt.% carbon. However, special iron based alloys are being developed within the NaCoLab project by the company DURUM GmbH, Willich, Germany. The aim of this work was to develop iron based feedstocks that, when processed by thermal spraying, form wear resistant, friction optimized coatings with embedded boridic precipitations. Thermally sprayed coatings in general contain a certain amount of porosity. For this specific application, it was found that the coating porosity can have a positive effect on the frictional behaviour of the coating, if the pores are machined open by the following honing process. The open pores in the functional surface of the cylinder bore work as micro cavities, which are able to store a certain amount of oil in addition to the oil storage capacities of the honing grooves [7]. This additional oil storage capacity improves the frictional behaviour of the surface. The oil storage capacities of some coatings were analysed. The recommended oil storage capacities for low carbon PTWA-sprayed steel coatings are between 0.050 and 0.070 mm3/cm2 for the pores and 0.0140.018 mm3/cm2 for the honing topography (honing grooves) [8]. The optimum values for nanocrystalline coatings are subject to current investigations. All materials were sprayed onto liners made from EN AW 6060 (AlMgSi0.5) with an inner diameter of 83.3 mm and a height of 120 mm. The substrates were mechanically roughened with the dove tail like profile. Cross sections of the coatings were prepared to evaluate the microstructure. To gain further information on the coating, especially on the size of the precipitations, transmission electron microscopy (TEM) investigations were carried out by the Institut fr Produkt Engineering of DuisburgEssen University, Germany.

Fig. 2. Schematic of the mechanical roughening process (dove tail like topography) and the cutting tool 0(source IWF, Braunschweig, Germany).

out by grit blasting. Coatings applied onto grit blasted bore walls show bond strength values of more than 30 MPa which is considered to be the minimum required value [4]. The process though requires additional grit blasting equipment. Hence, the procedure is not considered to be the optimum solution for the production of engine blocks with thermally sprayed cylinder running surfaces. Besides grit blasting, there are other processes which can be utilized to activate the bore surface, such as high pressure water jet blasting or the NiAl/Flux procedure. With the latter, a flux agent is applied on the non-roughened surface. A coating of nickelaluminium (NiAl) of approximately 50 m in thickness is applied onto the flux. The flux strips the oxide from the aluminium and allows for chemical bonding of the NiAl coating to the aluminiumsilicon alloy. The functional steel coating is then sprayed onto the as sprayed NiAl coating [5,6]. The need for a pre-treatment process that leads to high bond strength values and which can be easily integrated in the serial production of engine blocks has led to different mechanical roughening processes (MRP). One process was developed by the Institute of Machine Tools and Production Technology of Braunschweig University (IWF) within the framework of this project. With this mechanical roughening process, a tool with one or two geometrically defined cutting edges is used to produce topographies that provide undercuts in order to enable the mechanical interlocking of substrate and coating. Thereby the overlay of the rotary motion and the axial infeed of the tool leads to a helix, similar to thread cutting, Fig. 2. Within the scope of this project, different profiles were developed and evaluated. The same machining centers which are used to bore up the cylinder bores of the engine blocks, can be employed to roughen the bore walls. Hence, the process provides, contrary to grit blasting, good integrability into the process chain. The cutting process was developed as a lube oil free process, which means, that no excessive cleaning after the operation is required. Early attempts of a mechanically roughened surface (liner made from EN AW 6060) led to a bond strength of 40 MPa, which is significantly higher than the recommended value of 30 MPa. The most successful out of the evaluated profiles is a dove tail like profile which leads to bond strengths of up to 58 MPa. Fig. 3 compares the bond strengths of 0.82% C steel coatings which were sprayed onto high pressure water jet blasted,

Fig. 3. Bond strength of PTWA-sprayed 0.82% C steel coatings on aluminium EN AW 6060 substrates.

K. Bobzin et al. / Surface & Coatings Technology 202 (2008) 44384443 Table 1 Typical spray parameters for the application of C steel coatings by PTWA-spraying Ar [slpm] 067 H2 [slpm] 29 Current [A] 65 Wire feed rate [m/s] 0.072 Air flow [slpm] 1100 Revolution speed (spindle) [1/min] 400

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2.2.1. Carbon steel coatings When low carbon steel is used with the PTWA thermal spraying process and compressed air is used as the atomizing gas, the iron in the alloy reacts with the oxygen of the atomizing gas and forms FeO (wuestite) a high temperature oxide, which, due to the high cooling rates, is frozen at room temperature. Wuestite is a hard oxide phase which serves as a solid lubricant and is responsible for the good tribological properties of Fe/FeO-coatings [9], especially in both dead centres. PTWA-sprayed carbon steel coatings typically include less than 2% porosity, determined by optical image analysis. Typical spray parameters for producing steel coatings are given in Table 1. To produce a coating with approximately 300 m in thickness, 16 passes are required, whereas the material throughput is 4 kg/h. The deposition efficiency was determined to be 92% for the parameters given in the table. Fig. 4 shows a micrograph of a PTWA thermal spray coating made from 0.82% C steel. The micrograph shows some porosity within the coating, and some finely distributed wuestite, which appears darker than the iron matrix in the figure. The hardness of these coatings is significantly higher than for the 0.1% C steel coatings. The values range from 550 to 620 HV 0.1. The coating shown was produced with optimised coating parameters. It was found that an increase in the revolution speed from 400 to 600 min 1 leads to a better distribution of the oxides within the coating. 2.2.2. Nano-structured coatings In order to produce nano-structured coatings with embedded boridic hard phases, besides other alloying elements such as Cr, Si, W, the wires contain between 1.9 wt.% and 5 wt.% boron.

Fig. 5. Micrograph of a coating made from early SUNA 3 wire (Hardness 1200 HV 0.1).

Because of the high content of alloying elements (approx. 25%), the wires, called SUNA, were produced as cored wires. The powder fillings were made of either crushed powders of coarse grain ( 350 m) or a mixture of crushed and gas-atomized powders of a smaller grain size distribution ( 180 m, + 45 m). Due to the rapid solidification, the crystallites (MxBy) are finely distributed within the amorphous coating and often show a grain size lower than 100 nm. The first developments of these feedstocks, called SUNA 2 and 3, were made from coarse (grain size 350 m) crushed powders in an iron sheath with a high content of boron (~5 wt.%). The coatings made from this feedstock show a very high hardness of 1200 HV 0.1 but also numerous micro cracks and disruptions, as shown in Fig. 5. One SUNA 3 sample was honed to determine the oil storage capacities caused by the honing grooves and the machined open pores. It was shown that, due to the brittle behaviour, many particles were ripped out and left behind a surface with the oil storage capacities being too high. Hence, the surfaces did not meet the requirements of a cylinder running surface. For the second batch (SUNA 6) the content of boron was adjusted (1.9 wt.%), which led to dense coatings free of micro

Fig. 4. Micrograph of a PTWA-sprayed 0.82% C steel coating.

Fig. 6. Honed coating made from SUNA 6 wire.

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Fig. 7. TEM bright field pictures of a PTWA-sprayed SUNA 6 coating. In the picture to the left an amorphous structure is shown while the picture on the right hand side shows nanoscale precipitations (by courtesy of M. Hahn, Institut fr Produkt Engineering, DuisburgEssen University, Germany).

Fig. 8. PTWA-sprayed SUNA 6-3 coating. Light optical image of the micrograph (left) and SEM-image of the honed surface (right).

cracks. A cross section of such a coating is given in Fig. 6. The oil storage capacities of the honed surface were within the required range. Fig. 7 shows two TEM bright field images of this coating. The picture on the left hand side indicates a predominantly amorphous matrix, whereas the picture to the right shows nanoscale (Fe, Cr)23B6-precipitations in an amorphous matrix. To produce more homogeneous coatings, with the next batch (SUNA 6-3) the powder filler made of crushed material was replaced by a mixture of gas-atomized and crushed powders of a different grain size distribution ( 180, + 45 m). Fig. 8 gives a cross section of a SUNA 6-3 coating and a SEM-image of the honed surface. The bright field image and the diffraction pattern given in Fig. 9 show, that the precipitations are nanoscale. Two phases were found; MxBy and M3O4 (M = metal, B = boron, O = oxygen). The analysis of the precise composition of both phases is subject to current investigations. The SUNA 6-3 feedstock was already successfully applied onto the bore walls of an in-line engine block. From the SUNA 6 as well as from the SUNA 6-3 feedstock crack free coatings could be produced, even if thick coatings of 600 m were produced. The results on the oil storage capacities for SUNA 3, 6 and 6-3 coatings are given in Fig. 10. As shown in the picture, the oil

storage capacities of the pores in the SUNA 6-3 coating are below the recommended values. Besides test liners, two Ford Zetec in-line 1.4 l engines were coated with the reference material 0.1% C steel and the SUNA

Fig. 9. TEM picture of a SUNA 6-3 coating.

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Acknowledgements The authors would like to thank the German Federal Ministry of Research and Education for funding the NaCoLab project (grant ID 03X0003). References
[1] R. van Basshuysen, F. Schfer (Eds.), Handbuch Verbrennungsmotor (Compendium of Combustion Engines), Friedrich Vieweg & Sohn Verlag, Wiesbaden, Germany, 2007, (in German), ISBN: 978-3-8348-0227-9. [2] Aluminium-Motorbloecke (Aluminium engine blocks), sv corporate media, Munich, Germany, ISBN 3-937889-18-3, 2005 (in German). [3] T. Kuhn, Messung der Zylinderverformung von Aluminiumkurbelgehusen fr Dieselmotoren (Measuring the Distortion of Cylinders in Aluminum Diesel Engine Blocks), PhD thesis, Hannover University, 2001 (in German). [4] G. Barbezat, S. Keller, G. Wuest, Internal plasma spray process for cylinder bores in automotive industry, Proceedings of the 15th International Thermal Spray Conference, C. Coddet, May 2529, 1998 (Nice), ASM International, Materials Park, Ohio, USA, ISBN: 0-87170-659-8, 1998, p. 963979. [5] D. Cook, Processing, Structure, Property and Performance Relationships for the Thermal Spray of the Internal Surface of Aluminum Cylinders, PhD thesis, State University of New York at Stony Brook, USA, 2001. [6] E. Lugscheider, R. Dicks, K. Kowalsky, D. Cook, K. Nassenstein, C. Verpoort, A materials system and method of its application for the wear protection of aluminium engine cylinder bore surfaces, in: E. Lugscheider (Ed.), Proceedings of the International Thermal Spray Conference 2004, DVS-Verlag, Duesseldorf, Germany, 2004, p. 334340, May 1012, 2004 (Osaka). [7] G. Barbezat, J. Schmid, Plasmabeschichtungen von Zylinderkurbelgehusen und ihre Bearbeitung durch Honen, MTZ Motortechnische Zeitschrift 62 (2001) 4, Vieweg Verlag / GWV Fachverlage, Mnchen, Germany, 2001, p. 314320, (in German). [8] C. Verpoort, W. Blume, M. Broda, F. Orlamuender, K. Holdik, S. Kollinger, K. Bobzin, F. Ernst, J. Zwick, T. Schlaefer, F. Schreiber, T. Wenz, A. Schwenk, G. Flores, in: R. van Basshuyen, W. Siebenpfeiffer (Eds.), Thermisches Beschichten von Aluminium-Zylinderlaufbahnen mit nanokristallinen Schichten im Rahmen des BMBF-NanoMobil-Projektes (Thermal spraying of cylinder running surfaces within the framework of the BMBF NanoMobile Project, MTZ Konferenz Motor 2007, Vieweg Verlag / GWV Fachverlage, Mnchen, Germany, 2007, May 2223, 2007 (Neckarsulm), (in German). [9] G. Barbezat, Thermal spray coatings for tribological applications in the automotive industry, in: B.R. Marple, M.M. Hyland, Y.-C. Lau, R.S. Lima, J. Voyer (Eds.), Proceedings of the 2006 International Thermal Spray Conference, ASM International, Materials Park, Ohio, USA, 2006, May 1518, 2006 (Seattle), ISBN: 10: 0-87170-836-1. [10] Q. Zhou, unpublished data, Jaguar Cars. Ltd., Whitley, United Kingdom, 2007.

Fig. 10. Oil storage capacities of coatings made from different SUNA wires.

6-3 feedstock. Friction tests were carried out with a strippeddown engine for the 0.1% C steel coating. Thereby the engine, with or without the cylinder head, is driven by an electric motor. The torque required to rotate the crankshaft with the pistons is recorded. For the engine with the mounted cylinder head, the friction was determined to be 6.8% below the values measured for the standard engine with liners made from grey cast iron. Without the cylinder head, the friction was 14% lower compared to the standard engine. The SUNA 63 coated engine has not been tested yet. However, a decrease in friction of 10% was calculated for the stripped-down engine with the mounted cylinder head, also compared to the standard engine [10]. 3. Conclusions Within this study it could be shown, that substrate roughening by fine boring with a geometrically defined cutting edge provides a good alternative to the commonly used grit blasting process in the automotive industry. Bond strength values of nearly twice the required value of 30 MPa could be proved. Furthermore iron based wire feedstocks were developed, that, when processed by thermal spraying, lead to coatings with embedded, nanoscale boridic precipitations. In order to evaluate the SUNA feedstocks with regard to their tribological behaviour, at the moment honed coatings are being tested on a reciprocating and on a rotating sliding wear tester against nitrided and also against electroplated, alumina reinforced chromium coated (CKS) piston rings. In order to further improve the process stability as well as the homogeneity of the coatings, future SUNA feedstocks will be produced with FeCr- instead of Fe-sheaths.