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E. Wolfe, J. T. Schriempf and Jason Singh The Applied Research Laboratory, The Pennsylvania State University, University Park, PA 16804. Abstract: Metallic and ceramic coatings including chromium, molybdenum, titanium carbide (TIC), and yttria partially stabilized zirconia (YSZ) coatings deposited by electron beam-physical vapor deposition (EB-PVD) will be presented along with their potential applications. Coatings are often applied on a variety of materials to extend the life of components under severe thermal, corrosion, wear, and oxidation environments. Interest in replacing chromium electroplating has sparked the use of EB-PVD technology for the repair of navy landing gear due to the high deposition rates of the EB-PVD process. The surface morphology, microstructure, and texturing of TiC films produced by reactive ion beam-assisted, EB-PVD will also be discussed for wear resistant applications in the cutting tool industry. YSZ has also been grown by EB-PVD resulting in a columnar microstructure for thermal barrier applications (TBC). Significant improvements in the life of turbine components are obtained over plasma sprayed YSZ due to the quality and microstructure of EB-PVD coatings. Scanning electron microscopy, X-ray diffraction, and electron probe microanalysis (EPMA) was used to characterize the films. In summary, this paper gives a broad overview of the various ceramic-metallic coatings deposited by EB-PVD at the Applied Research Laboratory, The Pennsylvania State University.
Introduction
Electron beam-physical vapor deposition (EB-PVD) is a derivative of the electron beam melting technique. [Records reveal the first U.S. patent was issued to M. Von Pirani in EB melting and refining of materials in March 1907.] Perhaps the most consequential growth phase in EB technology began in the early 80s and is still in progress. This significant progress was driven by three factors: (1) much improved vacuum generation technology, (2) significant advances in computers, and (3) availability of high-quality EB guns. Since then, EB coating technology is constantly gaining reputation and confidence in a wide range of applications including thermal barrier ceramic coatings and wear-resistant hard coatings. The role of coatings is significant in the advancement of technologies for applications in the optics, auto, and aerospace industries. A high percentage (75%) of aircraft engine components is coated by metallic or ceramic coatings for the purpose of enhancing performance and reliability. Thus, there is a continuous effort to engineer surface properties to enhance the life of components under severe environmental conditions where corrosion, high-temperature oxidation, and wear are concerns. Similarly, multilayered ceramic and metallic films are used in the fabrication of microelectronic components. Processes to control thin film properties are also extremely important in the microelectronic industry. Before proceeding, three questions need to be answered: 1. What are coating processes? 2. What is the uniqueness of the EB-PVD process? 3. What are ideal applications for EB-PVD coatings?
Coating Processes
Industrial coating techniques (exclusive of painting and electroplating) can be broadly classified into three groups: physical vapor deposition (PVD), chemical vapor deposition (CVD), and spray processes. Each process can again be sub-classified based on the source of energy used for the deposition of coatings as shown in Table 1. Each of these processes has advantages and disadvantages. Chemical and physical conditions during the deposition reaction can strongly affect the composition, residual stresses, and microstructure (i.e., amorphous, polycrystalline, epitaxial, and textured) of the product. The effect of these conditions must be understood to control the process. Coating thickness, desired properties (including microstructure, physical, and mechanical properties), and the application will determine the coating process to be used. In the spray process, pre-alloyed powder is injected along with a carrier gas through a highenergy source. The coating material is transported in the form of molten or semi-molten droplets and directly deposited onto the components. The principle of the process is to feed powder into the plasma where the particles are rapidly heated to their melting point and accelerated to speeds on the order of 300 m/sec. After a few milliseconds, the molten powder particles strike and flatten on the object surface and rapidly solidify. The adhesion of the particles to the substrate is mainly a mechanical bond. The rate of coating deposition and the quality of the coatings (density) depends upon the spray process selected (D-gun, HVOF, plasma-transferred arc processes, etc.), the processing parameters, and the coating and substrate materials used. A significant advantage of this process is the high deposition rate (100-1,000 pm/minute) and the fact that various metallic and oxide coatings can be applied. A disadvantage of the spray processes is the inability to obtain homogenous, high-quality, and dense coatings.
Spray Deposition processes Thermal spray High-velocity-oxy-fuel (HVOF) Detonation gun (D-gun) Chemical Vapor Deposition Processes (CVD) Low pressure CVD Plasma enhanced CVD Photochemical and laser-CVD Physical Vapor Deposition Processes (PVD) Thermal evaporation Electron beam evaporation Sputtering -Balanced and unbalanced magnetron sputtering -Direct current diode sputtering -Radio frequency sputtering -Triode-assisted PVD
Some of the difficulties of the spray process can be overcome by the chemical vapor deposition (CVD) process. The term CVD is defined as a process whereby a reactant gas mixture is passed in a high-temperature reactor to form a solid product in the form of a thin film at the substrate surface. The CVD coating process takes place between temperatures of 800 and 1200 0C. Various metallic and ceramic (oxides, carbides, and nitrides) coatings have been deposited at rates of 5-10 pm/hour. The disadvantages of the CVD process are: they often require high-deposition temperatures (>10000C); they produce chemical waste (such as acids) that is environmentally unacceptable; deposition rates are usually slow (40 u/minute) for high-quality coatings.
Some of the shortcomings of the CVD process can be addressed by the physical vapor deposition (PVD) process. The term PVD denotes those vacuum deposition processes where the coating material is evaporated by various mechanisms (resistance heating, high-energy ionized gas bombardment, or electron gun) under vacuum, and the vapor phase is transported to the substrate, forming a coating. PVD is a line-of-sight process in which atoms travel from the source material to the substrate in a straight path. The PVD coating process takes place between temperatures of 100-600 C. Sputtering is one of the most versatile PVD processes available for thin film preparation. Various metallic and ceramic (carbides and nitrides) coatings can be applied by this process typically at a rate of a few um or less per hour. Unlike the CVD process, PVD processes are clean and pollution free. The main disadvantages of PVD processes (with exception of EB-PVD) are the low deposition rates (1-5 pm per hour) and the difficulty in applying oxide coatings efficiently. In spite of significant advancements in the various PVD processes (such as cathodic-arc and DC and RF unbalanced-magnetron sputtering), there are still drawbacks in coating quality. For example, the cathodic-arc PVD process produces liquid droplets or macro-particles of metals, 1 um to 15 um in size, during the evaporation of the target material. These molten particles can be entrapped in the growing film, resulting in nonhomogeneity in the microstructure and detrimental physical properties. In sputtering processes, an applied electric field produces plasma of inert-gas ions, which strike the cathode composed of the source material, and ejects atoms from it. Atoms from the source material are deposited on the surface of the substrate, where they can also combine with reactive gases to form ceramic coatings (e.g., TIN, NbN, etc.). Ion implantation is not a deposition process, but rather a surface modification process in which appropriate atoms are embedded in a material through high-energy beams. High-energy ions are produced in an accelerator and directed on the surface of the substrate. A high-energy ion implanter (1-10 MeV) is required for deep penetration (-5 pm). Ionized particles enter into the substrate with kinetic energies four to five orders of magnitude greater than the binding energy of the solid by a collision mechanism. The principal application of ion implantation has been in the electronic industries. The disadvantage of the ion implantation process is the limited depth of penetration into the substrate (< 5um). Ion plating is a derivative of ion implantation in which the substrate is made the cathode and the source material is thermally evaporated before being partially ionized and accelerated to the substrate (cathode). By the proper selection of materials and gas, carbides, nitrides, and oxides can be deposited. Potential applications of ion plating are in tool industries and certain aircraft components. Disadvantages of the above mentioned PVD processes can be addressed by the EB-PVD.
sight process, therefore uniform coatings of complex parts (such as turbine blades) can be accomplished by continuously rotating the part during the coating process.
Vertical Rotary
Drive
4 6 kW/G
Load Lock
Vacuum Pumps Part Manipulator 0-14 rpm, 2 rotary 0-1000mm/mln translatlon axis
Chamber Dimenslons Depth: 91Omm Width: 896mm Height: 726mm Maximum Substrate Dimenslonas/Weight Horizontally Fed Cylinder: 200mm dia. x 289mm/20kg Vertically Held Disc: 400mm dia. /100 kg
THREE INGOT FEEDERS 70mm dir. x 500mm long Ingots 0.16 to 15mm/min Feedrate
Many coating materials are used both in the microelectronics and heavy manufacturing industries. For example, metal oxides and nitrides are used in microelectronic industries as an insulator, buffer layer, or diffusion barrier layer. The thickness of coatings for such applications is <1um. On the other hand, in the aerospace and auto industries, oxide coatings are used for enhancing the performance of components under severe environmental conditions such as corrosion, oxidation, and wear. The coating thickness for such applications is typically > 10 um. Such coatings are often called thermal barrier coatings (TBCs). Multilayered metallic or ceramic coatings are often applied on the components to achieve desired properties. Properties and performance of the coating also depends upon the coating thickness. It has been well established that multilayered coatings with layer thickness cl pm offer superior structural and physical properties due to refined microstructure in the coating. In summary, the choice of deposition technique is determined by the application for the coating, the desired coating properties, cost or production rate available from the process, temperature limitation of the substrate, uniformity or consistency of the process, and its compatibility with subsequent processing steps. Chemical and physical conditions during the deposition reaction can strongly affect the resultant microstructure of the coating (i.e., singlecrystalline, polycrystalline, amorphous, epitaxial).
components of aircraft and helicopters. IBAD, EB-PVD process offers additional flexibility in repairing localized damage in landing gears which cannot be done by any other processes
Figure 2. Low (a) high (b) magnification SEM micrographs of WC-Co coatings deposited by HVOF showing non-uniform microstructure and porosity. without affecting the physical and mechanical properties of the base material. The significant advantage of using IBAD along with EB-PVD is enhancing metallurgical bonding of the coating with the substrate at a relatively low temperature. For instance, EB-PVD chromium coatings were flaking or debonding from the landing gear when deposited below 280 0C (<550 OF). This was perhaps due to poor metallurgical bonding and high residual stresses in the deposit. When, the same Cr coating was applied on the landing gear along with argon ion bombardment (Table 2), the resulting coating had a dense microstructure with good metallurgical bonding between the base material as well as the electroplated chromium (region b of Figure 38). Figure 3A is a photograph of a helicopter landing gear showing localized surface damage that needs to be repaired. The current repair process is the chemical stripping of the chromium coating followed by re-plating, baking, and machining of the entire component. Localized refurbishment of the landing gear (Figure 3b) was successfully demonstrated by applying Cr in the ion beam assisted, EB-PVD chamber. The SEM micrograph shows that the EB-PVD Cr deposit is relatively denser than the electroplated Cr which has spacings/voids between the grains (region a and b, respectively shown in Figure 38). Unlike thermal spray coatings, these deposits had a dense microstructure with good metallurgical bonding with the base metal. In addition, microcrack sealers are not required. The cost saving is expected to be more than 20-30% with improved component life and performance.
Figure 3. Photograph showing a helicopter landing gear having localized surface damage (A) and SEM micrograph of the refurbished region (B) showing good metallurgical bonding of the Cr deposited by EB-PVD (region a) on the electroplated Cr (region b) and base material (region c).
Table 2. Process parameters used in depositing Cr by Sciaky IBAD, EB-PVD. 17 EB-voltage (kV) 900 EB-Current (mAmp) 15 Deposition rate (um/hour) 0 <280 Substrate temperature ( C) 2 Deposition time (hours) 250 volts, 75 mAmp, 10 sccm Argon gas Ion gun parameters:
Figure 4. SEM micrograph of the fractured TBC coated button showing columnar grains.
Properties
Thermal Conductivity (W/mK) Surface roughness (um) Adhesive strength (MPa) Youngs modulus (Gpa) Erosion Rate (Normalized to EB-PVD) Microstructure
EB-PVD
1.5 1.0 400 90 1 Columnar
Plasma sprayed
0.8 10 20-40 200 7 laminated
presence of porosity between the laminated grains. In contrast, the thermal conductivity of TBCs applied by EB-PVD is higher than the plasma spray coatings. The higher thermal conductivity in the EB-PVD TBCs is due to limited porosity present in the individual columnar grains. The porosity in TBCs is mainly present between the columnar grains (Figure 4). In spite of higher thermal conductivity, TBCs applied by EB-PVD is preferred over the plasma spray process due to smooth surface finish, better strain tolerance, better erosion-resistance properties, and improved metallurgical bonding with the substrate. The typical process parameters used in producing TBCs are listed in Table 4. Table 4. Process parameters used in depositing TBCs by Sciaky EB-PVD 18 EB-voltage (kV) 1.7 EB-Current (Amp) 3.4 Deposition rate (um/min) <1000 Substrate temperature (0C) Deposition time (hours) 1 In spite of significant advancement in the EB-PVD coating technology, there are still challenges in producing low thermal conductivity EB-PVD TBCs. Future thrusts are in producing a lowconductivity EB-PVD TBC by altering the microstructure and creating micro-porosity within the columnar grains. or in providing new materials with different compositions and functional gradient coatings [6-11]. Past, present and future thrusts of TBCs are summarized in Figure 5.
Lamellar TBC Laser Grooved
- Low Modulus/Strength TBC + Alloyings EB-PVD: Textured Columnar Structure (001 growth direction) l Columnar Porosity
Gradient Coating
Graded Coating
Figure 5. Schematic diagram showing the evolution of past, present, and future microstructure of TBCs.
Figure 6: SEM micrograph showing the surface morphology of TiN coating deposited on stainless steel substrate by IBAD, EB-PVD.
Several TiC coatings were deposited by RIBA, EB-PVD under identical processing conditions with the exception of the level of ion bombardment (27 uA/cm2 - 163 uA/cm2). The hardness values ranged from 1721 to 3504 VH 0.050. The general trend shows that the hardness of the TiC coating increases with increasing levels of ion bombardment as shown in Figure 7. The generally accepted bulk hardness value of TiC is 2200-2800 VHN. The TiC coating deposited with 162 uA/cm2 (3504 VH O.050) showed over 25% improvement in the hardness value. This increase in hardness can be attributed to a more dense film, texturing, and/or stress. Comparing the hardness of the films to the titanium/carbon ratio, no general trends exist. This is quite surprising, yet very informative as it strongly suggests that the composition was not the determining factor in the degree of hardness in the films and that the hardness values are directly related to the structure properties of the films such as degree of texturing and density. Although the coatings were deposited under identical conditions, compositional variations can occur resulting from the equipment itself or due to sputtering of the growing film during deposition. 4000 3500 3000 2500 2000 1500 20
I I I I I I I
40
60
80
100
120
140
160
180
Figure 7. Plot showing hardness increase in TiC coatings produced by IBAD, EB-PVD as a function of ion beam current density. Table 5: Typical process parameters used in depositing TiC and TiB2 coatings on WC-Co inserts by Denton IBAD, EB-PVD. EB Current (Amp) Deposition rate (A /min) Substrate temperature (0C) Deposition time (hours) Substrate bias (- volts) Ion beam process parameters 0.12 - 0.17 500 200-650 1 -100 to -630 current 500 m Amp, voltage 150 volts
To improve the cutting performance of WC-Co cutting tools during the machining of titanium and nickel-based alloys, TiB2-x coatings were deposited by direct evaporation under various processing conditions. The hardness of the coatings is shown in Figure 8. Direct evaporation of TiB2 yielded a TiB2-x coating with a hardness of 2940 VH 0.050. The hardness of the coating was increased to 3041 VH 0.050by argon ion beam assist deposition. The hardness was still further increased by applying both a negative bias and bombarding the TiB2-x growing
film with argon ions during deposition. The resulting surface morphology shows a uniform, finegrained surface with an average grain size less than 100 nanometers as shown in Figure 9. Typical process parameters for TIC and TiB2-x coatings are listed in Tables 5 and 6. Table 6. Process parameters used in depositing by TiB2-x Sciaky EB-PVD EB-voltage (kV) EB-Current (mAmp) Deposition rate (um/min) Substrate temperature (0C) Ingot diameter (mm) 18 900 0.07 <750 49.5
Sample2Number
Figure 8: Plot showing increase in hardness of TiB2-x as a function of processing parameters (direct evaporation, negative bias and argon ion bombardments).
Figure 9. SEM micrographs showing fine grained TiB2 coatings deposited on Si substrate by Sciaky EB-PVD at 750 0C. Lastly, Figure 10 shows the fractured surface of a TiB2-x / TIC multilayer deposited on a WC-Co cutting tool. The TIC (grown by RIBA, EB-PVD) serves as a bond coat as well as to
prevent chemical reactions between the TiB2-x and substrate material. The interface between the TiC and TiB2-x looks very good. The TiC has columnar structure whereas the TiB2-x shows a very fine-grained microstructure. Similarly, multilayered coatings composed of TiC/Cr3C2, have been successfully produced by the co-evaporation of the Ti, Cr, and graphite ingots in the EBPVD chamber (Figure 1). The future thrust is in developing superhard multilayered coatings composed of AI2O3/TiC and of TiB2/Tic/Cr3C2, by the ion beam-assisted EB-PVD.
Figure 10: SEM micrograph of a fractured surface of the TiB2-x /Tic coating deposited on WC-Co tool showing excellent interface between the coatings.
Deposition by low temperature evaporation and sputtering has been found to lead to low density regions at steps due to a misalignment of the columnar grains growing from the substrate surface with the those growing from the step. These regions are extremely susceptible to attack by wet etchants which leads to occurance of line breakages during interconnect patterning. If the film is deposited under conditions favoring an isotropic rather than columnar morphology this type of defect can be prevented. Molybdenum films have been deposited using EB-PVD at high and low substrate temperature and with and without argon ion bombardment to determine what conditions are
suitable for suppression of the columnar microstructure and what films are suitable for use as interconnects. The stress states of these films were also investigated to determine the effect of temperature and bombardment on film stress. Figures 11-15 show the interconnect lines etched from EB-PVD MO films deposited under various conditions.
Of these films, the ones showing the least amount of preferential etching were those deposited under high bombardment and concurrent substrate heating as shown in Figures 14 and 15. The film evaporated with no substrate heating or bombardment is particularly poor due to weak adhesion of the film to the substrate (Figure. 11). It appears that bombardment or temperature alone is unable to sufficiently alter the microstructure of the MO film as shown by Figs. 12 and 13; however, the combination of the two is sufficient to suppress the formation of the columnar microstructure leading to step induced defects. Figures 16 and 17 show the TEM micrographs of evaporated MO deposited at 600 0C with and without ion bombardment respectively. It is clear that the bombardment has changed the microstructure from a fine-grained columnar morphology to a roughly broken isotropic structure. This is done through a combination of increasing surface mobility of the depositing atoms through energy transfer from the bombarding ions [19] and by causing subsurface lattice damage and atomic rearrangement [20]. Figure 18 shows the results of the bulk film x-ray stress analysis of these films and films sputtered under various RF powers. This shows that through ion bombardment the stress state can be varied from highly compressive to tensile.
Figure 16 X-sectional TEM image of 600 0C, ion assist. sample shown in Figure 15.
Summary
Electron beam-physical vapor deposition offers high flexibility in depositing ceramic and metallic coatings for a wide variety of applications ranging from microelectronic to turbine industry. Attachment of an ion source to the EB-PVD unit offers additional benefits in depositing coatings at a relatively lower temperature. Processing parameters control the microstructure, physical and mechanical properties, and residual stresses present within the coating. Chromium was successfully deposited at a relatively low temperature (< 550 OF) on a damaged landing gear. The hardness of TiC and TiB2-x was increased by 35% and 15 %, respectively by controlling the process parameters and bombarding the growing film with ionized gas. Similarly, both residual stress and microstructure of the molybdenum films were altered by ion beam assisted deposition which suppressed preferential etching that is undesirable for interconnects applications.
Acknowledge
Authors would like to express their sincere thanks to laboratory staff members (Dale D. Donner, Thomas Medill, Dennis Mcgregor, and Tad Rimmey) for their support during the course of experiments. Special thanks to Navy ManTech office for their financial support.
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