See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/281080946 Metal Deposition: Plasma-Based Processes Chapter · January 2016 DOI: 10.1081/E-EPLT-120053919 CITATIONS READS 5 7,055 4 authors: Neelesh Kumar Jain Mayur Sawant Indian Institute of Technology Indore Indian Institute of Technology Indore 171 PUBLICATIONS 2,491 CITATIONS 12 PUBLICATIONS 218 CITATIONS SEE PROFILE Sagar Hanmant Nikam Ulster University SEE PROFILE Suyog Jhavar 19 PUBLICATIONS 398 CITATIONS 17 PUBLICATIONS 102 CITATIONS SEE PROFILE SEE PROFILE Some of the authors of this publication are also working on these related projects: Development of a Process Simulation Model for Metal Additive Manufacturing View project Electrochemical Honing of Bevel Gears View project All content following this page was uploaded by Suyog Jhavar on 09 September 2020. The user has requested enhancement of the downloaded file. Metal Deposition: Plasma-Based Processes Neelesh K. Jain Mayur S. Sawant Sagar H. Nikam Suyog Jhavar Department of Mechanical Engineering, Indian Institute of Technology Indore, Indore, India Abstract Plasma-based metal deposition is one of the most promising emerging areas in surface engineering. It offers a variety of applications in thin film deposition, thick film deposition, hard facing, repairing, remanufacturing, surface modification, and complex three-dimensional (3-D) parts manufacturing. Plasma-based metal deposition processes such as physical vapor deposition and plasma-enhanced chemical vapor depositions have been used for many years but new processes, such as plasma-transferred arc (PTA) and micro-PTA (m-PTA) deposition processes capable of 3-D deposition, have attracted the interest of researchers. This entry describes various types of plasma-based metal deposition processes focusing on their working principle, types, advantages, limitations, and applications. It also highlights the developments in plasma-based metal deposition processes aimed to improve deposition rate, deposition quality, and flexibility in selection of deposition and substrate materials. The entry ends with comparative evaluation of the various plasma-based metal deposition processes described. INTRODUCTION Kelvin – Microorganisms Metal deposition is a very fast growing and demanding field due to its ability to provide high-end technical solutions for various surface treatment requirements of different products used in many industries. These requirements include the need for improving wear resistance, corrosion resistance, oxidation resistance, chemical inertness, electrical resistance, electrical conductivity, reflectivity, appearance, repairing/remanufacturing, and manufacturing of complex three-dimensional (3-D) metallic components. Metal deposition deals with a variety of materials such as metals, alloys, composites, functionally graded materials (FGMs), and shape memory materials (SMM) which require the development of diversified processes using various energy sources. Advanced materials such as nonferrous alloys (super alloys, titanium-based alloys, etc.), composites, ceramics, FGM, and SMM possess unique properties such as high melting temperature, high hardness, high strength, high toughness, brittleness, etc. making them attractive to use but difficult to process. Fig. 1 shows various categories of deposition processes for metallic materials that are commonly used in industries to process some of the advanced materials. This includes processes using laser beam, electron beam, plasma, thermal spraying, physical vapor deposition (PVD), and chemical vapor deposition (CVD). Various metal deposition processes have three major applications: 1) thin film deposition; 2) thick film deposition or hard facing; and 3) additive 722 layer manufacturing (ALM). Thin film deposition is used to modify surface characteristics according to the desired surface properties by depositing a single thin layer (thickness < 20 µm) or multiple thin layers of a metallic material. Its various applications include production of coatings for optical products, electrical appliances, and decorative items to improve properties such as wear resistance, reduce friction, corrosion resistance, hardness, etc. It can also be used in microelectronics application for semiconductor deposition, electrical insulator, antireflection coating, etc. The processes used for thin film deposition are PVD and CVD. Thick film deposition involves depositing thick layers (thickness more than 20 µm) of a harder and tougher material on the soft material. Materials such as chromium, titanium, oxides, and carbides of metallic materials are used in thick film deposition to enhance various surface properties, such as wear and corrosion resistance, which increase service life of components or can be used to repair worn out areas. Processes used for thick film deposition include thermal spraying and plasma-based deposition processes. ALM is the advanced manufacturing application of deposition processes to generate 3-D products from computer-aided design (CAD) data by depositing the material layer by layer to produce near-net-shaped components economically and with great flexibility. Each deposited layer is created by rapid solidification of the deposition material over a stationary or moving substrate. The bonding strength between the substrate and the deposition material depends on deposition energy, deposition pattern, deposition volume, and Encyclopedia of Plasma Technology DOI: 10.1081/E-EPLT-120053919 Copyright © 2017 by Taylor & Francis. All rights reserved. Metal Deposition: Plasma-Based Processes 723 heat during deposition which leads to poor metallurgical properties and inability to produce complex deposition geometries. Deposition processes, such as PVD and CVD, involve low-process temperatures and give better performance and better quality for solid material films. However, they have the major drawback of having a lower deposition rate compared to other processes. Among different categories of metal deposition processes, plasma-based processes are fast emerging as energy efficient, material efficient, and economical processes which can bridge a gap between capabilities of other deposition processes and can yield good quality metal depositions for a variety of materials. Plasma is defined as the fourth state of matter produced by energizing the gas atoms to such a level so that most of them break into free ions. It can be generated by providing external energy in the form of electric discharge, radiation, or heat to ionize the gas molecules. The energy generated by a plasma source can be used for metal deposition purposes. Plasma-based deposition is carried out by depositing layers of metallic materials over a substrate either to improve its surface properties or to add delicate 3-D features over an existing component. Metal Deposition Laser-Based Deposition Electron BeamBased Deposition Plasma-Based Deposition Chemical Vapor Deposition Thermal Spraying Fig. 1 Various categories of metal deposition processes. interaction time between the deposition and the substrate material. This enables manufacturing of highly complex structures with enhanced design freedom, better product customization, optimization, and integration of various functional features. ALM can be used to manufacture the parts made of metals, alloys, polymers, ceramics, composites, and FGMs. Processes based on laser beam and electron beam are high-energy beam processes; therefore, they are preferred for focused and low-volume deposition. They suffer from disadvantages such as high energy consumption, high investment cost, and high running cost which hinders their end applications. Thermal spraying provides great flexibility for types of materials to be deposited and provides higher deposition rate; therefore, this method is preferred for bulk deposition in large volumes. But these processes have major limitations such as the use of higher amount of PLASMA-BASED METAL DEPOSITION PROCESSES Various plasma-based metal deposition processes [i.e., PVD sputtering, plasma-enhanced CVD, plasma thermal spraying (PTS), plasma-transferred arc (PTA), and microPTA (m-PTA)] can be classified according to the type of ionization being used to form plasma, as illustrated in Fig. 2. In PVD sputtering and plasma-enhanced chemical vapor deposition (PECVD) processes, the plasma is generated by ionization caused by electric discharge in the vicinity of the deposition materials.[1] Some advantages of these processes include minimization of impurities in the thin coating, low-substrate heating, and capability to meet functional requirements economically in industrial production. These processes are used in many applications particularly in microelectronics and surface engineering. In the processes Plasma-Based Metal Deposition Processes Ionization by Electric Discharge PVD Sputtering Plasma Enhanced CVD Ionization by Thermal Energy Plasma Thermal Spray Plasma-Transferred Arc (PTA) Deposition Micro Plasma-Transferred Arc (µ-PTA) Deposition Fig. 2 Various types of plasmabased metal deposition processes on the basis of ionization. Kelvin – Microorganisms Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Physical Vapor Deposition Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 724 such as PTS, PTA deposition, and m-PTA deposition, the plasma is generated by the ionization caused by thermal energy. PTS provides higher deposition rate for wide variety of materials. It is used for the protection of new parts against wear, high temperature, and corrosion, thus improving the surface properties. Due to high-heat involvement in deposition, it leads to higher thermal distortion leading to poor metallurgical properties. PTA and m-PTA deposition processes are used to produce good quality of metal deposition giving good accessibility to the deposition area. These processes can be used for different applications such as layered manufacturing of 3-D parts, repairing and adding features to the existing components.[2] Plasma-based metal deposition processes provide wider choices in the selection of deposition and substrate materials, deposition geometry, deposition characteristics (i.e., composition, pattern, density, etc.), preprocessing conditions, and post-deposition properties. Various plasma-based metal deposition processes are described in the subsequent subsections. PVD-Sputtering Process Metal Deposition: Plasma-Based Processes and energy of the ions. Direction of striking by ions can be controlled by electric and magnetic fields. The ejected deposition material molecules move toward the substrate with or without collisions with other ejected molecules and inert gas ions depositing thin coatings on the substrate. Further nucleation and film growth occur at the substrate due to condensation of the target atoms changing composition, microstructure, residual stress, and physical properties of the deposited layers. This coated film can be influenced by bombardment of low-energy particles, ions, and energetic particles back-scattered from the target and the inert gas.[4] This enables the process to control the properties of deposition.[5] This process does not require thermal energy, hence it is also called nonthermal vaporization deposition. Consequently, this process offers advantage of low-temperature deposition for a variety of coating materials such as metals, ceramic, alloys, metal oxides, etc. Technological advances have allowed this process to be widely used in industries. Generally, DC sputtering is used for metals, while radio frequency (RF) potential is used for nonconducting materials. In some applications, separate ion beam source is convenient for the deposition of self-contained discharge with ion acceleration. Working principle Sputtering rate Fig. 3 depicts the working principle of the PVD-sputtering process in which a substrate is made as anode and the deposition or target material is made as cathodes, which are separated by a distance in the range of 5–10 cm in a chamber having vacuum in the range of 10−6 to 10−10 torr. Flow of an inert gas such as argon (Ar) is continuously provided to the vacuum chamber in which its molecules become positively charged ions ejecting electrons under applied high pressure and voltage. The ejected electrons may further ionize other gas atoms to sustain the glow discharge and create a cascading process until all the gas molecules ionize.[3] These ions strike the cathodic deposition material-ejecting molecules from its surface by transfer of their momentum. This phenomenon is known as sputtering. The interaction between inert gas ions and the target material depends on the velocity Sputtering yield is defined as the number of target atoms ejected per incident ion. It depends on the target material, binding energy of target material, relative mass of gas ions and target atoms, current density, and angle of incidence of bombarding ions. It is an important quantity in calculating sputtering rate of a target material which is given by Eq. 1: R ¼ 62:3 JSMA ðA per minuteÞ r ð1Þ where J is the ion current density (mA/cm2), S is the sputtering yield (atoms/ion), MA is the atomic weight of the target material (grams), and ρ is the density of the target material (gm/cm3). The sputtering rate can be increased by increasing the discharge current for a given applied voltage.[6] Applications Kelvin – Microorganisms PVD sputtering is advantageous for processing the materials having very high melting temperature. The major areas of application for PVD sputtering are thin film deposition for thermal insulation, thin antireflection coatings, decorative coatings, carbide coatings, and corrosion protective coatings used in various applications such as microelectronics devices, optical applications, metal cutting tool, magnetic, and optoelectronics.[7] Variants of PVD-sputtering process Fig. 3 Working principle of PVD-sputtering process. Wide ranging industrial applications of PVD-sputtering process motivated researchers to improve the basic version of Metal Deposition: Plasma-Based Processes 725 PVD-Sputtering Processes Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Balanced Magnetron Sputtering Deposition Unbalanced MagnetronSputtering Deposition TriodeSputtering Deposition Closed FieldUnbalanced MagnetronSputtering Deposition MagnetronSputtering Deposition Reactive MagnetronSputtering Deposition PVD-sputtering process to enhance sputtering rate, deposition quality, and process control. This has led to the development of different variants of PVD-sputtering process, as shown in Fig. 4, which are described in following paragraphs. Planar diode glow discharge-sputtering deposition It is the basic version of PVD-sputtering process. It finds many applications due to its ease of fabrication and applicability for wide range of materials. But it suffers from disadvantages such as substrate heating, low deposition rate, low ionization efficiency, and relatively small deposition surface areas.[8] Triode-sputtering deposition Triode-sputtering deposition process involves use of an additional heated filament to increase the electron density in plasma by thermionic emission, as depicted in Fig. 5. Ion BeamSputtering Deposition Pulsed MagnetronSputtering Deposition Biased Target Ion Beam Deposition High-Power Impulse MagnetronSputtering Deposition Fig. 4 Different variants of PVD-sputtering process. Use of triode increases ionization efficiency of plasma to generate intense sputtering discharges which enables higher discharge rates even at lower target voltages and lower pressures as compared to conventional PVD-sputtering process using DC Sometimes, filament reacts with the working gas and produces scaling that tends to erode filament rapidly during deposition thus lowering the sputter rate. Although, this process is used for thick coating, but maintaining uniformity of coating is difficult due to lack of electron path guiding mechanism to confine the plasma.[9] Magnetron-sputtering deposition The working principle of magnetron-sputtering deposition process is shown in Fig. 6. In this process, permanent magnets are arranged below the target plate so as to produce magnetic field near the target material. It concentrates the electrons and causes them to travel spirally along the magnetic flux lines near the target instead wandering Fig. 5 Working principle of triode-sputtering deposition process. Kelvin – Microorganisms Planar Diode Glow Discharge-Sputtering Deposition Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 726 Metal Deposition: Plasma-Based Processes Fig. 6 Working principle of magnetron-sputtering deposition process. Kelvin – Microorganisms around the target material. This is referred as balanced magnetron-sputtering deposition. It increases ionization efficiency due to more collisions with gas molecules. Therefore, this process can be operated at lower pressure with higher current densities and provides higher sputtering rate and generates stable plasma.[10,11] In some cases, higher current densities near the target may be undesirable because they reduce ion bombardment over the substrate which reduces the chances of desired modification of the growing film. An altered magnetic configuration can be obtained by extending the plasma region toward the substrate from vicinity of the target. This can be achieved by increasing magnetic strength of the outer magnets as compared to the middle magnet. It increases electron and ion current densities near the substrate that increases ions bombardment on the growing film.[11,12] This is known as unbalanced magnetron-sputtering deposition. This process is advantageous to produce high deposition rate, welladhered, and highly dense coatings. It has several diverse applications such as coatings of noble metals such as gold (Ag) and silver (Au) for making electrical contact,[13] niobium coatings for biological applications,[14] and electrical applications of niobium nitride coatings.[15] Despite several advantages offered by unbalanced magnetron-sputtering deposition process, it is difficult to uniformly produce coatings for complex components at a good deposition rate. Therefore, multiple magnetron systems have been introduced to develop a process known as closed field unbalanced magnetron-sputtering (CFUMS) deposition. Fig. 7 compares magnetic configuration and plasma confinement in balanced, unbalanced, and closed-field magnetron-sputtering deposition processes. In the CFUMS deposition process, multiple magnets are used to form a closed trap of electrons through multiple magnetic field lines in the plasma. Hence, electron energy losses to the chamber walls are minimized and dense plasma sustained near the substrate region lead to high ion current densities.[16] It is well suited to deposit different materials such as pure metal, nitrides, and amorphous hydrogenated carbon coatings,[17] CrAlTiN coatings for reducing the coefficient of friction,[18] and coating with graded properties. Reactive magnetron-sputtering deposition is another important variant of the PVD-sputtering process which is commonly used to deposit compound thin coatings. Here, reactive gases [i.e., nitrogen (N2) and oxygen (O2)] are intentionally added which react with the sputtered material to form a wide variety of useful compounds. The reaction can be controlled by adding the desired percentage or enough gas to ensure complete reaction of sputtered material. This process is limited to low deposition rate and sometimes produces arc-induced coating defects, i.e., arcing.[19] The arcing effect at the target leads to the ejection of droplet materials from the target which results in defects on the growing coating. The reactive gas is expected to form compound coating on substrate and cathode surface. The formation of compounds over cathode surface reduces the deposition rate which is called as poisoning effect.[20] The bipolar-pulsed technique is used in reactive magnetronsputtering process which reduces the chances of arcing and produces high deposition rate. This process has been used for the deposition of different materials such as copper (Cu)–chromium (Cr)–O thin coatings,[21] Cu(In, Ga)Se2 absorber layers on CuGa substrate,[22] and niobia (Nb2O5)/silica (SiO2)-mixed oxide thin films.[23] Pulsed magnetron-sputtering deposition utilizes RF in the range of 5–30 MHz. This RF is developed because of the 727 Fig. 7 Comparison of the magnetic configuration and plasma confinement in balanced, unbalanced, and closed-field magnetron-sputtering deposition processes. Source: From Arnell & Kelly.[11] ©1999 Elsevier. Reprinted with permission. difference in mobility between electrons and ions. This mobility difference leads to the development of negative potential on the target. This process is particularly useful for the deposition of an insulating coating or dielectric materials. It alleviates problems of poisoning and arcing associated with reactive magnetron-sputtering deposition. In this process, the charging takes place during pulse-on time only and discharging takes place during pulse-off time. This significantly reduces the arcing problem while depositing insulating materials.[11] It also reduces defects in growing coating and approaches higher deposition rate.[24] Use of this process has led to significant improvement in coating properties which can be used in different applications such as low friction titanium nitride (TiN) coating, aluminum-doped zinc oxide transparent conductive coating, and copper indium diselenide on photovoltaic devices.[25] High-power impulse magnetron-sputtering deposition is a relatively new process in which high discharge pulse power is supplied for a short period time. This results in high plasma density and highly ionized flux of the sputtered material which allows better control of the dense coating growth by controlling the energy and direction of the deposition ions and electron.[26] Pulsation of power favors diffusion and renucleation during thin film growth and avoids overheating of target.[27] The major disadvantage of this process is the typically lower deposition rate due to back-attraction of ionized sputter materials, i.e., not available for film growth. It has different applications in coatings, for example, thin films for automotive applications,[28] TiAlCN/VCN coatings for tribological applications,[29] and aluminum nitride for improving the mechanical properties.[30] target material for its sputtering and deposit it on a suitably placed substrate to form a thin coating on it, as shown in Fig. 8. Ion source such as Kaufman or duoplasmatron is used for thin film deposition by extracting a maximum amount of target material.[6] In this process, the substrate temperature, gas pressure, and ion bombardment can be independently controlled due to a separate ion source. It also reduces substrate heating. An additional secondary ion source may be used for enhancement in properties of the sputtered film growth.[31] In the IBSD process, a fraction of ions may not hit the target material but may hit the surroundings causing contamination of the coated film. Consequently, a new biased target ion beam deposition process has been developed to overcome problems of the IBSD process. In this process, a highly negative bias is applied to the target material while surroundings are grounded, so that most of ions will accelerate toward the negatively biased target material thus reducing contamination of the coating. This process Ion beam sputter deposition Ion beam sputter deposition (IBSD) is a vacuum-based deposition process that uses a separate ion source to generate a focused high-energy ion beam directed toward the Fig. 8 Working principle of ion beam-sputtering deposition process. Kelvin – Microorganisms Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Metal Deposition: Plasma-Based Processes 728 uses low energy ion sources by combining end-Hall ion and hollow cathode electron sources together for sputtering. The hollow cathode electron source is used for ejection of electrons whereas end-Hall ion source is used to maintain stable plasma. This kind of ion source produces a very high density of inert gas ions that increases deposition rate as compared to conventional IBSD.[32,33] This method enables to deposit different nonmagnetic materials such as chromium, titanium, Ag, magnetic materials such as iron, cobalt, nickel, etc., and dielectric materials such as aluminum oxide, silicon oxide, etc. Plasma-Enhanced CVD Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Working principle Fig. 9 depicts working principle of plasma-enhanced CVD process in which a mixture of an inert gas and reactant gases is supplied between the ground substrate and the cathode. Here, the inert gas ionizes to form capacitive coupling between substrate and cathode by supplying 13.56 MHz RF power to the cathode. Ionization of the inert gas molecule helps in dissociation of reactant gas which further reacts with other gas molecules or substrate material to form a new compound at the surface of the substrate.[34] The process involves chemical action, hence no subsequent heat is generated during the process. A variety of thin films can be deposited on the temperature-sensitive substrates. The temperature generated during process generally is in the range from 250°C to 350°C which is quite low as compared to the conventional CVD process. Another main advantage of PECVD is the formation of ions through inert gas which Metal Deposition: Plasma-Based Processes may bombard on the growing thin film coating. This plays an important role in growth kinetics, nucleation, stress, structure, and properties of the deposited material.[35] Highdensity power sources such as microwave (MW-PECVD) and electron cyclotron resonance (ECR-PECVD) can also be used for deposition of advanced materials.[36] Advantages and disadvantages PECVD offers many advantages such as low working temperature, uniform deposition, good deposition on corners and steps, less porosity, good adhesion with substrate, and more flexibility in working with different depositing materials. Better control of PECVD process parameters allows tailoring of mechanical, chemical, electrical, and optical properties, stoichiometry, and residual stresses of the deposition. It has some disadvantages such as generation of toxic by-products, problems in depositing pure metals, and costly process equipment.[6] Applications Materials typically deposited using PECVD include silicon carbide, silicon nitride, silicon dioxide, and amorphous silicon. Silicon nitride and silicon dioxide are the commonly used insulating materials in the fabrication of electronic devices. PECVD finds various thin film deposition applications in different fields such as microelectro-mechanical systems (MEMS) to improve optical and mechanical properties,[37] depositing superconducting materials such as niobium–germanium (Nb3Ge) and (CuMo6S8), semiconductor deposition, depositing diamond-like carbon film (DLC) as antireflection coating,[38] and microcrystalline silicon thin film for solar cells.[39] Plasma Thermal Spraying Kelvin – Microorganisms Increase in demand for coating of high temperature, corrosion, and wear-resistant materials led to the development of PTS which is a specific term for a group of coating processes used to apply metal or nonmetal coatings.[40] The first industrial plasma spray torch appeared in the 1960s. Earlier versions of PTS processes used deposition material in the form of wire which can be melted by combustion flames generated by O2/acetylene gases in a process known as high-velocity oxyfuel coating. But the use of deposition material in the powdered form necessitates plasma to generate high temperature for powder melting and deposition and accordingly modifications in the torch design. Consequently, this process is referred as PTS which is very efficient for medium-to-high velocity deposition and yields higher bonding strength.[41] Working principle Fig. 9 Working principle of PECVD process. Fig. 10 shows the concept of the PTS process using deposition material in the powdered form. Plasma is generated Metal Deposition: Plasma-Based Processes 729 Plasma Thermal Spraying Atmospheric Plasma Thermal Spraying Vacuum Plasma Thermal Sprayin Inert Gas Plasma Thermal Spraying Shrouded Plasma Thermal Spraying Under water Plasma Thermal Spraying Fig. 12 Variants of plasma thermal spraying process. Concept of plasma thermal spraying process. by feeding an inert gas such as Ar or helium (He) through the gap between the cylindrical tungsten (W) cathode and anodic Cu nozzle.[42] When the gas passes through the nozzle, the electrons coming out from the cathode ionizes the gas molecules, thus generating plasma which is accelerated toward the nozzle exit. Energy and temperature distribution of the plasma arc depends on physical properties and type of plasma gas. Deposition material in the powder form is supplied through a carrier gas. It can be supplied either externally or injected internally through a powder port into the high-energy plasma. Location and angle of powder port depend on the nozzle design of the plasma torch.[43] Different process parameters of PTS are shown in Fig. 11. Deposition characteristics are determined by the behavior of powder particles in the plasma arc (i.e., melting temperature and particle moving trajectories) which in turn is governed by condition of plasma arc (i.e., type and flow rate of plasma gas and plasma temperature), powder particle parameters (i.e., type, size, shape, and velocity), and process parameters (i.e., power supply, stand-off distance, and plasma torch velocity). Powder particle velocity depends on the feed rate of the powdered material, type of plasma gas, and other process parameters.[44] It is one of the important factors in PTS because the powder particles sprayed through various trajectories of plasma arc play Conditions of plasma arc • Type of plasma gas • Plasma gas flow rate • Plasma temperature Plasma thermal spraying Types Plasma thermal spraying process can take place under different working conditions and pressure levels. Based on these, it has five variant as listed in Fig. 12 and these are described in following paragraphs. In all these variants, the concept of plasma thermal spraying remains the same. Selection of a particular process variant can be carried out on the basis of type of coating material. Atmospheric plasma thermal spraying (APTS). This process variant is performed under atmospheric conditions which causes the surrounding air to enter into the plasma arc and interact with the molten powder particles leading to its oxidation. Therefore, it is widely used for depositing the ceramics and those metals and alloys which are insensitive toward oxidation. Many applications require coating of wear and corrosion resistance material, hence atmospheric plasma spraying process can be used for such application.[47] This process has been used for coating the mechanically alloyed nanocomposites having matrix of 6061 aluminum alloy reinforced with silicon carbide,[48] producing coating of hydroxyapatite (HA) material,[49] Process parameters • Power supply • Stand-off distance • Plasma torch velocity Behavior of powder particles in plasma arc • Melting temperature • Particle moving trajectories Powder particle parameters • Type, size, and shape of powder particles • Velocity of powder particles Deposition characteristics • Deposition geometry • Bonding strength • Deposition efficiency Fig. 11 Process parameters of plasma thermal spraying. Kelvin – Microorganisms Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Fig. 10 a vital role in melting the powder particles.[45] Deposition profile depends on the volume of material deposited per unit time and velocity of the plasma torch. Deposition thickness depends on mass flow rate of the powder, velocity of the plasma torch, and number of passes. This process can deposit high melting point materials easily due to use of high temperature generated by the plasma jet.[46] 730 nano-structured zirconia,[50] and mixture of aluminum oxide and titanium oxide.[51] Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Vacuum plasma thermal spraying (VPTS). In this variant, the coating is done in a closed vacuum chamber under a vacuum maintained in the range of 10–50 kPa. Particular value of the vacuum is selected accordingly to the quality of coating required. This avoids oxidation of the coating and heat losses which result in high-quality dense coating without porosity.[49] It has been used for tungsten carbide and cobalt coating for wear and friction resistance,[52] for nanostructured titanium oxide coating,[53] and to fabricate dense molybdenum disilicide (MoSi2) and its composite reinforced with SiC and TiB2,[54] and NiTiZrSiSn coating powder for amorphous formation.[55] Inert gas plasma thermal spraying (IGPTS). Deposition is performed in a closed chamber filled with an inert gas in the IGPTS process. The VPTS process does not provide complete protection from oxidation and sometimes presence of air due to low vacuum may cause oxidation of substrate and coating material.[40] This process is used for coating of zirconium bromide material to improve the electrical conductivity of stainless steel substrate[56] and for biomedical applications of HA and fluorapatite thin film coatings.[57] Shrouded plasma thermal spraying (SPTS). Shrouded plasma spraying is a chamber-free process to reduce the problem of oxidation by covering the plasma arc with an inert gas atmosphere, i.e., the area between the torch and the substrate is flooded with high volume of inert gases. O2 content present in plasma arc is reduced and extra addition of O2 to plasma arc is avoided by shrouding the plasma arc thus protecting the coating material against oxidation.[42] This process has been used for coating of MCrAl (where M is nickel, cobalt, and/or iron) alloys,[58] coating tungsten (W) and Cu for nuclear fusion applications,[59] nickel chromium (Ni–20Cr), and stellite-6 powders on boiler tube steels,[60] 316 L stainless steel coating.[61] Metal Deposition: Plasma-Based Processes 2) less thermal distortion of substrate due to absence of direct contact between the flame and substrate; and 3) production of cleaner and denser coating with high bonding strength.[64] Whereas its main disadvantages include 1) applicable for hard materials only; 2) difficulty in controlling the parameters of plasma arc spray; 3) loss of powder particles during passage of plasma; and 4) more expensive and complex process.[65] Applications Plasma spraying has wide variety of applications in aerospace, automotive, and structural industries particularly for coating the substrate with the wear and corrosion resistance materials.[48] Atmospheric plasma spraying is used for coating movable parts like printing rollers, steel rollers, etc. with oxide materials to increase their corrosion and abrasion resistance.[66] Some applications such as turbine blades get corroded due to atmospheric contamination, hence they should be coated with the corrosion resistance materials such as nickel and chromium but the coating process should be oxidation-free, hence vacuum, inert gas, or shrouded plasma thermal spraying process can be used.[67] Some applications such as ship-building industries and petroleum industries require underwater coating of the substrate to protect it from corrosion; in such cases, underwater plasma spraying process can be used.[62] PTA Deposition Concept Kelvin – Microorganisms Underwater plasma thermal spraying (UPTS). In this variant, coating is performed under water. A stream of an inert gas is supplied which pushes the water away from plasma arc zone and then the plasma is generated. The inert gas environment around the plasma protects: 1) the plasma from contacting the water; 2) the sprayed deposition particles from oxidation; and 3) the substrate and the coating from the corrosion.[62] This process mainly used for coating of chromium nickel compound (Cr23Ni14) and stainless steel 304 on the components of boiling water reactors.[63] PTA deposition process is an advanced form of gas W arc deposition process in which a pilot arc is produced between the negatively charged W electrode and positively charged and water-cooled Cu-constricting nozzle, as shown in Fig. 13. This pilot arc ionizes the inert gas and creates an arc between the nozzle and the substrate resulting in the generation of high power plasma which can produce an instantaneous temperature of the order of 25,000°C. This plasma is forced through a constricted nozzle, which expands and accelerates toward the substrate. The plasma jet prevents the entry of surrounding gases into the deposition zone and provides a better shield to avoid contamination.[68] Deposition material can be used either in powder or wire form depending upon the application. Energy and temperature of PTA deposition depend on the power used to generate plasma which is determined by type of power supply (i.e., continuous or pulsed), current (20–400 A), plasma gas flow rate (0.1–10.0 L/min), pulse frequency, duty cycle, and the orifice diameter. Advantages and disadvantages Advantages and limitations Major advantages offered by PTS process are: 1) flexibility in choosing high melting temperature coating material; The PTA deposition process has many advantages over arc-based process such as higher deposition rates, lesser 731 Fig. 13 Working principle of PTA deposition process. heat-affected zone (HAZ), higher heat efficiency, better quality of deposition, safer operation, potential to control the size, flux, velocity, trajectory, and thermal states of both the deposited and substrate materials. PTA deposition process yields high-strength metallurgical bond between the alloys coating and the underlying substrate. But it has some limitations such as higher cost than arc-based processes though it is cheaper than the high-energy beam (i.e., laser or electron beam)-based deposition processes, inability to produce sharper and smaller deposition which can be easily produced by high-energy beam-based deposition processes.[69] Applications PTA deposition process is well suited for coating and bulk deposition of superior mechanical properties possessing metallic materials, alloys, and composites. Some specific applications include steel coating of engine block bores,[70] thick coating of composite of ferrous nickel alloy (γ/Fe, Ni) reinforced with titanium carbide on plain carbon steel to increase in wear resistance,[71] and depositing Ti–6Al–4 V titanium alloy for ALM.[72] MICROPLASMA-BASED DEPOSITION PROCESSES Need and Concept of µ-PTA Deposition Process Arc-based deposition processes are conventional low-cost metal deposition processes, using high amount of heat and giving higher deposition rate, greater HAZ, higher dilution, and higher distortion. While high-energy beam-based processes are capital-intensive processes which can be primarily used for focused and precise deposition with low HAZ, dilution, and distortion. With the advancement in digital power supply and process control, it has become possible to develop microversion of PTA deposition process (referred as µ-PTA deposition process) which can be operated at very low current of the order of 100 mA that too with finer control and higher precision. The process has potential to bridge the gap between process capabilities of arc-based and high-energy beam-based deposition processes. The principle of plasma generation in the μ-PTA deposition process is essentially same as that in the PTA deposition process. Basis difference is the amount and control of the current used, which can be as low as 0.1 mA. This enables the µ-PTA process to generate precisely controlled and focused microplasma arc which gives almost negligible HAZ, low material distortion, deeper penetration, depositions free from porosity and inclusion, and a better appearance without any spatter marks. Additionally, it offers advantages such as improved steady arc direction, increased arc stability, and greatly reduced sensitivity to changes in arc length and has potential to be energy efficient, material efficient, economical, and environment friendly. The equipment can be automated with the use of a computer numerical controlled (CNC) machine or robotic arm and can be operated either in continuous or pulsed power mode. The μ-PTA deposition process suits best for miniature or small amount of metal depositions which is required in the repair/remanufacture of defective/damaged dies, gears, and similar engineering components. Kelvin – Microorganisms Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Metal Deposition: Plasma-Based Processes 732 Metal Deposition: Plasma-Based Processes Process variants Variants of µ-PTA deposition process can be developed depending upon the state of the deposition material used. Deposition material can be used either in the form of wire, powder, or combination of both. This affects the process parameters and produces variation in the material deposition characteristics in terms of quality, strength, and size. Preference could be made for individual characteristics and their advantages and limitations. All these details are discussed in the following paragraphs. Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 µ-PTA Wire Deposition Process In this variant, deposition material is used in the form of microsized wire. It utilizes an automatic plasma source which offers many advantages such as reduced costs and reduced lead times, fabrication of complex components, repair or remanufacture of high-value components, rapid prototyping, and low volume production. This process can also be used for ALM applications to build complex structures having multilayer and/or multimaterial and/or multitrack (i.e., depositing materials side by side) depositions. Use of wire as deposition material is advantageous to enhance quality of deposition, material and energy utilization, environment friendliness, and simplicity of the process equipment and to reduce contamination during the storage and health hazards. Small sized wires are preferred for miniaturization and small amount of metal deposition. Fig. 14 Deposition by m-PTA wire deposition process. optimum values and keep them constant throughout the deposition process. These parameters can be selected by conducting various pilot experiments. Kelvin – Microorganisms Working principle Modeling of deposition geometry Fig. 14 depicts the process of deposition by µ-PTA wire deposition process in which tracks over a substrate surface are deposited using a computer-controlled microplasma and continuous feeding micro-sized metallic wire as deposition material. The microplasma torch generates sufficient amount of heat to melt the wire allowing the formation of a strong metallurgical bond between the deposition material and the substrate. Relative motion and manipulation between the plasma torch and the substrate are required to generate the required deposition geometry. A robotic arm or CNC platform can be used to control the relative motion during deposition. The three parameters namely plasma power, travel speed, and wire feed rate influence the deposition geometry. Combination of plasma power and travel speed controls the heat available to the melt pool, which directly governs the width of deposition, while the combination of wire feed rate and travel speed governs the availability of deposition material to the melt pool, which affects the height of the deposition.[73] Various combinations of wire feeding arrangements such as front feed, back feed, and side feed are possible during this process, as shown in the Fig. 15. Type of feeding arrangement affects the metal transfer mode between the wire and the melt pool. Before deposition, it is important to set all these parameters to their In any deposition process, the geometry of deposition is mainly governed by the combination of various process parameters, i.e., power supplied, travel speed of worktable, and wire/powder feed rate.[74] A number of models predicting the deposition geometry profile have been developed for various ALM processes to understand the relationship Fig. 15 Front feed, back feed, and side feed arrangements. Metal Deposition: Plasma-Based Processes 733 between the different process parameters and the profile obtained in its cross-section. Fig. 16 depicts the schematic arrangement of the cross-section of typical single-track geometry used for modeling. The deposition geometry is described in terms of track width “w” and track height “h.” The cross-sectional area depends upon the geometric function f(x) used to describe the shape of the deposition profile. Table 1 presents the summary of various models developed using various geometric functions for predicting the single-track geometry. It is seen that the parabolic and cosine function arc geometries are more identical for the deposition profile having lower aspect ratio of the deposition (i.e., ratio of track width to track height). While circular arc-based geometry is preferred for higher aspect ratio deposition tracks.[71] A model considering deposition as an arc of ellipse was found to be closer for deposition geometry generated by µ-PTA wire deposition process. Comparative study was made in order to check the accuracy of predicted geometry considering arc of parabola, circle, cosine, and elliptical function. The model was further used to predict the distance between the two successive tracks “St” in order to minimize surface waviness, as shown in Fig. 17. The predicted distance between the two successive tracks St was used to produce multiple-track deposition. It can be seen from micrograph of Fig. 18 that surface formed by the overlapping deposition is smooth, sound, with minimum waviness, free from deposition defects, and characterizing high efficiency of the µ-PTA wire deposition process. Various modeling approaches are helpful in order to control the geometric parameters. Characterization of deposition geometry The typical geometry of a single-track deposition is defined in terms of the track height “h,” track width “w,” deposited area “A1,” and diluted area “A2,” as shown in Fig. 19. Aspect ratio and dilution are the two most Table 1 Summary of various models developed for the geometry of the deposition track. Geometry of deposition track Arc of a parabola Mathematical relations For the symmetric parabola curve passing through points B (w/2, 0) and C (0, h) y ¼ w4h2 x2 þ h Arc of a circle Arc of a cosine function Arc of an ellipse Area Ap ¼ w=2 Ð w=2 w4h2 x2 þ h dxAp ¼ 23 wh i w=2 Ð hpffiffiffiffiffiffiffiffiffiffiffiffiffiffi Aa ¼ r2 x2 þ ðh rÞ dx For an arc of a circle passing through points w=2 B (w/2, 0) and C (0, h) and having radius “r:” pffiffiffiffiffiffiffiffiffiffiffiffiffiffi Solving it gives: w wpffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi y ¼ r2 x2 þ ðh rÞ where “r” is given by: 2 r2 0:25w2 A ¼ r arcsin þ w ðh r Þ 2 a 2 2r þ h þ0:25w2 r ¼ h cos 2h w=2 Ð For a cosine function curve passes through hcos px Ac ¼ w dx w=2 point B (w/2, 0) and C (0, h) Solving it gives: y ¼ h cos px w Ac ¼ p2 wh w=2 Ð qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2 For a elliptical function curve passes through Ae ¼ 1 wx 2 h2 dx w=2 point B (w/2, and C (0, h) q0) ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 2 Solving it gives: x2 y ¼ f ðxÞ ¼ 1 w2 h Ae ¼ p4 wh Note: GMAW, Gas Metal Arc Welding. ALM process Researchers GMAW Xiong et al.;[75] Suryakumar et al.[76] Laser metal deposition shaping Zhang et al.[77] GMAW Xiong et al.[75] Metal active gas Cao et al.[78] GMAW Xiong et al.[75] µ-PTA wire deposition Jhavar et al.[74] Kelvin – Microorganisms Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Fig. 16 Schematic arrangement of the cross-section of typical single track geometry. Source: From Jhavar, Jain, et al.[74] ©2014 Taylor & Francis. Reprinted with permission. Fig. 17 Schematic representation of the cross-section of overlapped track deposition. Source: From Jhavar, Jain, et al.[74] ©2014 Taylor & Francis. Reprinted with permission. 734 Metal Deposition: Plasma-Based Processes Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Fig. 18 Optical micrograph of the successive tracks deposition based on predicted model. Source: From Jhavar, Jain, et al.[74] ©2014 Taylor & Francis. Reprinted with permission. important parameters in the single-track deposition. A favorable range of aspect ratios is essential to avoid inter-run porosity during the multitrack deposition. Dilution is the ratio of deposited area A1 to the sum of diluted area A2 and the deposited area A1 and is expressed in percentage. Dilution quantifies the relative amount of substrate material mixed with the deposited material. Jhavar et al.[73] have demonstrated that a minimum threshold of dilution is important for good metallurgical bonding between the substrate and the deposited material. But higher value of the diluted area A2 would result in higher thermal damage to the deposition, more residual stresses, and higher distortion. It was also found that smooth and regular depositions can be achieved for the aspect ratio ranging from 1.3 to 4.0 and percentage dilution ranging from 2% to 8% during deposition of AISI P20 tool steel by µ-PTA wire deposition process. Deposition of two or more successive overlapping tracks over a surface is required to create a new surface or to repair an existing surface. This can be achieved by multitrack deposition, as schematically shown in Fig. 20A. The quality of multitrack deposition can be defined by the deposition of defect-free surface, surface finish, and the surface waviness achieved. Once the optimum parameters of single-track deposition are identified for a given deposition, i.e., height, width, and area of cross-section then the overlapping distance St can be modeled which governs overlapping and Fig. 20 Multitrack deposition obtained by Ocelík et al. using (A) St < 50% of w; (B) St = 50% of w; and (C) St > 50% of w. Source: From Ocelík, Nenadl, et al.[79] ©2014 Elsevier. Reprinted with permission. valley area, as shown in Fig. 20B. Higher surface finish and surface waviness can be achieved through optimizing the value of St. Higher St can result in inter-run porosity and wavy surface. Effect of these parameters is explained by Ocelík et al.,[79] as shown in Fig. 20C. Multilayer deposition is required to deposit a new surface or to repair an existing surface of thickness more than the height of single deposition track h. Fig. 21 shows cross-section of a typical multilayer deposition. A typical Kelvin – Microorganisms Fig. 19 Cross-section of a typical single-track deposition. Fig. 21 A typical multilayer deposition. Metal Deposition: Plasma-Based Processes 735 multilayer deposition has irregular side surfaces due to inter-layer waviness and requires subsequent finishing. To evaluate these parameters, the multilayer deposition is cut in the transverse direction to the deposition. The sample has to be prepared using standard metallographic procedure for optical or scanning electron microscopy (SEM). Martina et al.[72] referred these parameters of wall width before and after the finishing as total wall width (TWW) and effective wall width (EWW), respectively. The multilayer depositions are analyzed to calculate TWW, EWW, surface waviness, and deposition efficiency. Apart from the geometrical analysis, it is important to analyze the microfeatures of deposition through which post-deposition effects like deposition errors, presence of defects, inclusions, dilution, etc. can be analyzed in detail. Jhavar et al.[80] have successfully fabricated AISI P-20 multilayer deposition consisted of fully dense structure with good surface quality using µ-PTA wire deposition process. Fig. 22A shows the geometry of wall fabricated by multilayer deposition, Fig. 22B shows the cross-section of multilayer deposition depicting various regions for SEM evaluation. Fig. 23 depicts SEM micrographs corresponding to various parameters used to judge the quality characteristics of multilayer wall deposition. The deposition above few initial layers was found to be homogeneous, and the hardness values of these zones were found near to that of the substrate. The µ-PTA wire deposition process was able to fabricate straight wall consisting of 15 layers having TWW of 2.45 mm and a EWW of 2.11 mm with a deposition efficiency of 87%. It could achieve a maximum deposition rate of 42 g/hr. Results also proved that µ-PTA wire deposition process to be Fig. 23 SEM micrographs representing various parameters used to judge the quality characteristics of multilayer wall deposition (A) region A in HAZ; (B) region B 1 mm above the substrate; (C) region C 3 mm above the substrate; and (D) region D 6 mm above the substrate. Source: From Jhavar, Jain, et al.[80] ©2014 Elsevier. Reprinted with permission. Kelvin – Microorganisms Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Fig. 22 Multilayer deposition by PTA wire deposition process (A) geometry of the wall fabricated and (B) cross-section depicting various regions for SEM evaluation. Source: From Jhavar, Jain, et al.[80] ©2014 Elsevier. Reprinted with permission. 736 cost-effective, material efficient, energy efficient, and environmental friendly process for multilayer deposition and has the potential to become an alternative ALM process for metallic materials. Downloaded by [Neelesh Kumar Jain] at 00:56 09 February 2017 Capabilities and limitations µ-PTAwire deposition process produces stable and smooth arc characterized with no sparks. The equipment is also portable and lightweight with an easy to connect torch and accessories available allow quick setup. The process is capable of making fully functional, dense, and highquality additive layer-manufactured jobs. The process was also found to be energy efficient, environmental friendly, cost-effective and an alternative to the existing deposition processes especially because of its capability to produce low volume deposition. Deposition materials in the form of wire have nearly 100% deposition efficiency and are less health hazardous than the powder deposition material. µ-PTA wire deposition process is limited to materials having good ductility, as they can be easily formed in wire shapes. Applications µ-PTA wire deposition process can be utilized for a wide range of applications from the addition of delicate features to the existing components to the making of fully functional components. The process can also be used in repair/ remanufacturing of metallic dies,[81] gears, and high-value components. Surface modification developed FGMs and processing of metal matrix composites are the upcoming applications of µ-PTA wire deposition process. This process finds its applications used in aerospace, avionics, biomedical, automotive, electronics, special purpose engineering, MEMS, repair of turbine parts, etc. Metal Deposition: Plasma-Based Processes µ-PTA Powder Deposition Process Working principle Fig. 24 depicts the generation of plasma in the μ-PTA powder deposition process. The principle of plasma generation in the μ-PTA powder deposition process is essentially same as that in the μ-PTA wire deposition process. The μ-PTA powder deposition process also work with very low plasma current (generally up to 20 A) which in turn results in comparatively low energy density and low plasma velocity. The microplasma torch generates plasma arc that creates a melt pool on the substrate surface and stream of powdered deposition material is delivered into melt pool. When the powder contacts the melt pool it is absorbed into melt pool and creates weld bead. The μ-PTA powder deposition process can greatly reduce the product development time by using the concepts and techniques of CAD/manufacturing, robotics, etc. It has the ability to manufacture net shape or near-net shape parts of very complex geometries from high quality metal materials and has potential to become an alternative to the existing ALM processes. Capabilities and limitation In this process, powder deposition of materials is advantageous during low dilution required in deposition, high metallurgical bond, deposition of FGMs, and composite materials. But it is disadvantageous from the energy and material utilization point of view. Deposition materials in the form of wire have nearly 100% deposition efficiency and less health hazardous than the powder deposition material. Kelvin – Microorganisms Fig. 24 Concept of μ-PTA powder deposition process. Metal Deposition: Plasma-Based Processes 737 Table 2 Characteristics of various plasma-based metal deposition processes. Plasma thermal spraying PTA deposition µ-PTA deposition Chemical reaction Thermal energy Thermal energy Thermal energy Processed in atmospheric or vacuum chamber Deposition in atmospheric with inert gas Deposition in atmospheric with inert gas Deposition in atmospheric with inert gas Physical Chemical and metallurgical Diffusion Diffusion Diffusion Deposition rate ● ●● ●●●●● ●●●● ●●● 5. Depositing medium Molecules and atoms Atoms Particles Particles Particles 6. Uniformity of coating ●●●●● ●●●● ● ●● ●●● 7. Heat affected zone ● ●● ●●● ●●●●● ●●●● 8. Deposition quality ●●●●● ●●●● ● ●● ●●● 9. Applications Thin film deposition of pure metal, alloy, and refractory Thin film deposition of pure metal, alloy, and refractory Hard coatings of metal, alloy, and refractory Hard coatings of metal, alloy, and refractory Micro- to milisized hard coatings Item PVD sputtering 1. Mechanism of deposition Momentum transfer 2. Working environment Processed in vacuum chamber 3. Bond type 4. PECVD Note: Lower to higher: ●, ●●, ●●●, ●●●●, and ●●●●●. Applications COMPARATIVE EVALUATION Most of the metallic materials are easily available in powder form rather than wire form because it is difficult to draw wire of hard, brittle, tough, and high strength materials. Hence, μ-PTA powder deposition process is particularly useful for those materials which can be easily powdered but difficult to be drawn as wire such as nonferrous alloys, semiconductors, composites, ceramics, FGMs, and shaper memory materials. Table 2 presents the comparative summary of various plasma-based metal deposition processes comparing mechanism of deposition, working environment, bond type, deposition rate, deposition medium, deposition quality, HAZ, uniformity of coating, and applications. Surface modification applications. μ-PTA powder deposition surface cladding is an effective process for performing surface modification on abrasion, wear, and heatsensitive materials. Variety of alloys such as tool steel, stainless steel, nickel, cobalt, and titanium alloys can be deposited using μ-PTA powder deposition process. Repair/remanufacturing. Engineering components and tools fails before the completion of their expected service life due to local impacts, thermal stresses, corrosion, erosion, fatigue, and other severe work environment. It is highly uneconomical to reject such components with minor defects much before their service life. μ-PTA powder deposition is a cost-effective process for repairing/remanufacturing them. 3-D parts manufacturing. Many industrial applications require fabrications of free-form surfaces/geometry of the metallic components. μ-PTA powder deposition process can be used for manufacturing 3-D parts with fully functional, complex geometry, long-term end-use products. It can also be used for strategically add features to forging and casting. 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