Vacuum Plasma Sprayed (VPS) Coating - Substrate System For Fundamental Study of Adhesion

AGH UNIVERSITY OF SCIENCE AND TECHNOLOGY IN CRACOW FACULTY OF MATERIAL SCIENCE AND CERAMIC
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion
MASTER THESIS Agata Sroka
Principal subject Materials Engineering Specialization Biomaterials and Composites Supervisors Prof. Elbieta Godlewska Prof. Patrik Hoffmann Dipl. Ing. Musab Hadad Cracow, 2010
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010
Content
ABSTRACT...............................................................................................................................................6 Chapter 1 INTRODUCTION 1. General information on Thermal Spray (TS) coating....................................................................7 2. The most common application of TS coatings..............................................................................9 3. Problematic issues of TS technology............................................................................................9 Chapter 2 MOTIVATION and STATE OF THE ART 1. Motivation....................................................................................................................................12 2. State of the art.............................................................................................................................12 2.1. Deposition of a continuous film...............................................................................12 2.1.1. Residual stresses................................................................................12 2.1.2. Adhesion..............................................................................................14 2.2. 3.1. Simple chemistry interface without scale roughness...............................................18 Substrate.................................................................................................................21 3.1.1. Steel....................................................................................................21 3.1.2. Aluminium............................................................................................24 3.1.3. Silicon..................................................................................................24 3.2. Coating....................................................................................................................26
3. Material system...........................................................................................................................21
4. Thermal treatment.......................................................................................................................26 5. TS techniques.............................................................................................................................26 5.1. 5.2. 5.3. 5.4. High Velocity Oxy-Feul (HVOF)..............................................................................27 Wire arc spraying....................................................................................................27 Plasma Spray (PS)..................................................................................................27 Cold spray...............................................................................................................28
6. Summary.....................................................................................................................................28 Chapter 3 MATERIALS and EXPERIMENTAL PROCEDURE 1. Coating substrate system.........................................................................................................29 2. Experimental procedure..............................................................................................................40 2.1. 2.2. Thermal spray process............................................................................................40 Investigation methods.............................................................................................43 4
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2.2.1. Morphology and chemical composition by SEM-EDX analysis...........43 2.2.2. Crystal structure by XRD analysis.......................................................48 2.2.3. Topography and bending curvature by profilometry............................50 2.2.4. Adhesion between the coating and substrate......................................54 Chapter 4 RESULTS and DISCUSSION 1. Al2O3 on Si wafer........................................................................................................................60 1.1. SEM-EDX analysis..................................................................................................60 1.1.1. Deposition of Al2O3 in one passage .................................................................64 1.1.2. Deposition of Al2O3 in multiple passages..........................................................66 1.2. 1.3. 1.4. 1.5. SEM In-situ scratch test..........................................................................................69 XRD analysis...........................................................................................................70 Topography.............................................................................................................72 Mechanism of crater formation................................................................................77 1.5.1. Erosion..............................................................................................................77 1.5.2. Corrosion..........................................................................................................78 2. Al2O3 on metallic substrate..........................................................................................................80 2.1. SEM-EDX analysis..................................................................................................80 2.2. 2.3. 2.4. 2.5. 3.1. XRD analysis...........................................................................................................80 Topography.............................................................................................................81 Interfacial indentation..............................................................................................81 Rockwell indentation...............................................................................................82 SEM-EDX analysis..................................................................................................82
3. Al2O3 on sapphire........................................................................................................................82 4. NiCr(80-20) on metal substrate...................................................................................................87 5. NiCr(80-20) on sapphire..............................................................................................................87 Chapter 5 SUMMARY.............................................................................................................................88 Literature.................................................................................................................................................91
ABSTRACT
Al2O3 sprayed on Si (001) substrate has been selected as a novel fundamental approach of studying adhesion of Vacuum Plasma Sprayed (VPS) coatings. The choice of substrate had two reasons: i) perfectly flat surface of wafers allows to avoid the mechanical anchoring effect ii) mechanical and chemical properties of Si are very well known. In result Si wafers seem not to allow thermal spraying of alumina under whatever conditions. Moreover the opposite effect substrate removal has been observed. Two possible failure mechanisms of the VPS alumina and Si wafer are investigated: i) erosion due to impact of molten alumina particles, ii) corrosion due to evaporation and melting of Si under vacuum and plasma conditions, and formation of SiO2 at the interface, which increased 5 times the cooling stress in Si.
Chapter 1
INTRODUCTION
1. General information on Thermal Spray (TS) coating Thermal spray (TS) is the most common technology for deposition of advanced thick film coatings. The process resembles spray-painting with molten coating material. Typical steps undertaken to process TS coatings are discussed below (see Figure 1.1):
Figure 1.1: Principle of thermal spray coating; ref 1: R.C. Dykhuizen in Journ. of Therm. Spr. Techn. Vol 3, No. 4 (94); ref 2: M. Vardelle et al. in Journ. of Therm. Spr. Techn. Vol 4, No. 1 (95)
In first step a suitable chemistry is selected for any given application, e.g. typically wear, corrosion or thermal resistance, or specific functional property such as electromagnetic, chemical or biological function. The composition of the feedstock (powder, wire, or rod) used in deposition is identical to the desired coating. The most popular are powders, which average particle size is broadly in range of 10-100 [m]. 7
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 However preferably, they are of narrow size distribution and equi-axial (spherical) shape as they are fed to the hot zone by compressed gas. In second step, the feedstock is melted so the initial temperature of the process must exceed its melting point, which in the case of ceramic is often over 2000 [ Commonly the feedstock C]. is fed into the hot zone of TS torch, where temperature ranges from ~ 2,000 to 15,000[ depending on the TS technique used. The melting process is controlled C] by heat transfer from hot gas (plasma) to the particles moving rapidly (more than 100[m/s]) through the hot zone with large gradient of temperature. For the hottest (plasma) torches some evaporation and loss of powder may take place. The process gasses expand in the hot zone and thus accelerate towards the nozzle. The hot process gas transfers momentum (and heat) to the particles of the feedstock, melting and in next step accelerating them towards the substrate, at the velocity of 100-1000 [m/s]. During this process some (larger) particles may melt only partially, i.e. retain solid core; alternatively, some smaller particles may evaporate. The desired first splat is round shaped and flat, which indicates strong adhesion to the surface, and consequently dense and good quality coating. Prior to deposition, the substrate, typically an alloy, is sand blasted to induce roughness and adhesion through interlocking with coating, and cleaned to remove any blasting grit and organics. Molten particles strike the substrate surface and rapidly (more than 106 [K/s]) solidify to build-up the coating. Pancakelike flow and spread is preferred for the particles building-up the coating. However, splashing or even bouncing-off does also happen, leading to undesired microstructure and powder loss. The proportion of mass solidified as coating to mass fed to the torch rarely exceeds 50% in typical TS process. However, with the optimized torch design it is possible to reach 80%. The substrate heats up during the process, typically to 200-400 [C], which is dependent on whether it is cooled or not, and how close it is to the torch. Thus the conventional TS does not significantly affect microstructure or chemistry of most metallic substrates. However, for heat-sensitive substrates cold-spray technology should be considered. Despite the microstructural defects of the coating, TS is widely used because of many advantages: the process is relatively fast and cost-effective,
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 there are not many limitations regarding the coated area, coated material, or coating material. 2. The most common application of TS coatings The applications of TS coating are diversified. Some of the most common include thermal barrier coatings (TBC) for aircraft gas turbines, abradable coatings for seals in gas turbines, thermal barrier, abradables, corrosion and wear resistant coatings for industrial gas turbines, corrosion and wear resistant coatings in pulp and paper production, bioactive coatings for implants, thermal barrier, wear and corrosion resistant coatings for automotive industry, electrical insulations, corrosion resistant coatings for bridges.
3. Problematic issues of TS technology TS process is controlled by many variables. It is therefore difficult to stabilize (i.e. to obtain coating reproducibility within narrow specifications), which is absolutely necessary in critical, such as aerospace, applications. The diagnostic tools must be supported by extensive experimentation and modeling, which include complex computer programs predicting behaviour of particle during impact on substrate, and splat formation, as a function of velocity, temperature, viscosity, etc. Evaluation and metallography of TS coatings is difficult: Porosity measurements require mercury porosimeter, on the other hand metallography must be very careful due to the easy pull-out as a result of weak cohesive bonds and high density of microcracks. Microstructure and phase composition analysis involves XRD and SEM with EDX. Wear resistance, thermal properties, and corrosion resistance is evaluated using standard (ISO, ASTM) methods. Coatings strength and stiffness is determined in tension of free-standing tubes after mandrel removal.
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 One of the most problematic issue in TS coating evaluation is to clearly determine its the adhesion mechanism. Moreover, adhesion is modified by residual stress in the coating, which measurement is also very demanding. Details on those two very important parameters are described below: a. Residual stress According to [1], residual stresses can be defined as those stresses that remain in a material or body after manufacture and processing in the absence of external forces or thermal gradients. Residual stress measurement techniques invariably measure strains rather than stresses, and the residual stresses are then deduced using the appropriate material parameters such as Young's modulus and Poisson's ratio. Often only a single stress value is quoted and the stresses are implicitly assumed to be constant within the measurement volume, both in the surface plane and through the depth. Residual stresses can be defined as either macro or micro stresses and both may be present in a component at any time. Macro residual stresses, which are often referred to as Type I residual stresses, vary within the body of the component over a range much larger than the grain size. Micro residual stresses, which result from differences within the microstructure of a material, can be classified as Type II or III. Type II residual stresses are micro residual stresses that operate at the grain-size level; Type III are generated at the atomic level. Micro residual stresses often result from the presence of different phases or constituents in a material. They can change sign and/or magnitude over distances comparable to the grain size of the material under analysis. The origin of residual stress in thermal spray coating, according to Kuroda and Clyne (1991) [2], is mainly due to: Quenching stress - cooling of molten particles striking the substrate, Cooling stress - cooling of the system (coefficient of thermal expansion).
Considerable efforts have been made over the recent years to understand and predict the residual stress. In most cases, it can be assumed that stress in the throughthickness direction are negligible and that the stresses are the same in all directions within the plane of the coating. However establishing the stress state is generally more complex for (thin) films deposited by atomistic processes, since sprayed coatings are considerably thicker and variations in stress level with depth are often significant. Many recent studies have been focused on measurement of 10
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 residual stresses and modeling of their development during spraying. However, very few studies present reliable correlations established among process conditions, measured stress levels, and indicators of coating performance. To get more fundamental understanding of TS coatings residual stress, more investigations at different scales must be performed. According to [1], the methods of measuring residual stresses, most commonly used in industry are: b. Hole drilling (30%), X -ray diffraction (26%), Neutron diffraction (19%), Layer removal or curvature (16%), Other -including magnetic, ultrasonic, Raman (9%) Adhesion
Adhesion is the tendency of certain dissimilar molecules to cling together. Mechanisms of adhesion of thermally sprayed coating to the substrate involve: Mechanical interlocking - during deposition the sprayed material flows around the roughness peaks and into the valleys where it is constrained on cooling, Physical bonding - Van der Waals forces and hydrogen bridge bonding,, Chemical bonding - ionic, atomic or metallic bonding.
Standard adhesion evaluation tests are performed in tension (pull) test according to [3]. However, it is very difficult to determine whether the failure is adhesive, i.e. occurs at the interface between coating and substrate, or cohesive occurs through the coating. Thus many efforts have been made recently in order to develop measurement methods and to perform fundamental studies of adhesion. This will lead to more efficient control of the spraying process and quality evaluation of the obtained coating.
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Chapter 2
MOTIVATION STATE OF THE ART

1. Motivation The purpose of this work was to produce a thermally sprayed coating substrate system suitable for scientific investigations of adhesion and residual stress. Three requirements had to be fulfilled: deposition of a continous film, smooth (without scale roughness and voids) interface between coating and substrate, 2. simple interface chemistry.
State of the art Fundamental study of adhesion and residual stress of thermal spray coatings
will provide new tools for coating development, optimization and control. A lot of efforts have been made in this direction, however interpretation of the results often encountered difficulties due to numerous parameters influencing the measurements. Thus an idea has arisen of using a very simple coatingsubstrate system, which would make interpretation easier. The postulated requirements are presented below. 2.1. Deposition of a continuous film
Deposition of a continuous film was consider important because most of normalized and recently developed testing techniques of both residual stresses and adhesion are based on continues coatings. The most common of them are described below. However, first splat of TS coating is considered the most contributing to the adhesion to the substrate. Thus knowledge on both residual stresses and adhesion of single splats is recently an intensively investigated subject. Recent evaluation of residual stresses within single splats is presented at the end of this part.
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Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2.1.1. Residual stresses
Residual stresses can be evaluated by: Hole drilling method [1], which is a widely used technique because of several advantages; the test is simple, cheap, quick and versatile. The technique is applied to a wide range of materials. Moreover equipment can be laboratory-based or portable. The test involves drilling of a small hole through investigated material and evaluation of stresses by measurement of the locally relieved surface strains. The calculation of residual stress is standardized [4] and requires Finite Element Analyses. Commonly strains are measured using a special strain gauge rosette. Close to the hole, the strain relief is nearly complete but in case of deeper holes the technique becomes limited in strain sensitivity because of uncertainties related to the dimensions of the hole i.e. its concentricity, depth, profile and diameter. Moreover values obtained by gauge rosette are influenced by surface roughness, flatness, and specimen preparation. Hole drilling test can be done in incremental steps, which improves the versatility of the technique and enables measurement of stress profiles and gradients. X-ray diffraction method [1], which is commonly used to measure internal stresses due to elastic deformations within a polycrystalline material. The value is calculated based on comparison between the spacing of the lattice planes in stressed and relaxed material. The same spacing will occur in any similarly oriented plane, with respect to the applied stress. The test is relatively straightforward and equipment commonly available. The specimen is irradiated with high energy X-rays that penetrate the surface. The crystal planes diffract X-rays in accordance with Bragg's law. A detector, which moves around the specimen locates X-rays in respect to their diffraction angle and records their intensity. Stresses within the material are evaluated based on the location of the peaks. neutron diffraction [1] is based on the same principle as X-ray diffraction: stresses are calculated based on comparison between the spacing of the lattice planes in stressed and relaxed material. Neutron diffraction is advantageous when high penetration depth is required. It is possible to evaluate stresses from around 0.2 [mm] down to bulk measurements of up 13
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 to 100 [mm] in aluminium or 25 [mm] in steel. Moreover with high spatial resolution, neutron diffraction can provide complete three-dimensional strain maps of investigated material. There are two considerable disadvantages of neutron diffraction in comparison to different X-rays techniques: i) relatively high cost, ii) much lower availability. curvature and layer removal techniques are generally quick and require just simple calculation. However, a test can be performed only in simple testpiece geometries. In case of bulk material, the layers removal technique is applied. In the case of coatings curvature of the substrate is measured: i) before and after deposition obtained value is a result for the whole coating, ii) after successive deposition of each layer[5] allow obtaining variation of stresses with depth of the coating is obtained. The curvature of can be measured by many methods, such as: optical microscopy, laser scanning, strain gauges, or profilometry. A test is usually performed on narrow strips in order to avoid multiaxial curvature and mechanical instability. (for more details see Chapter 3: Topography and bending curvature by profilometry). 2.1.2. Adhesion
Adhesion testing techniques are based on evaluation of the amount of energy which is necessary to induce delamination of the coating. The type of delamination is selected according to ductility/brittleness of the coating-substrate system. Adhesion tests are normalized [3, 6-12]. Drory listed commonly used adhesion testing techniques, involving induced delamination [2] (see Table 2.1). Two relatively novel (developed in 1996), techniques were of interest in this work: Interfacial indentation applicable for ductile coating - ductile substrate system (for more details see Chapter 4: Interfacial indentation), Rockwell indentation applicable for brittle coating ductile substrate system (for more details see Chapter 4: Rockwell indentation).
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Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2.1.3. Investigation within single splats
Only few quantitative investigations have been done for single splats. For instance, Matejicek [13] investigated residual stresses in isolated splats deposited on stainless steel substrates using X-ray microdiffraction. Two types of spraying techniques and feedstock were used: i) plasma sprayed molybdenum, ii) cold sprayed copper. The results were discussed with respect to the influence of selected spraying parameters, contribution of quenching and thermal stress component and splat formation. The measured stresses ranged from 50 to 1050 [MPa]. These studies provide quantitative understanding of the residual stress states at the splat level. However they also indicate large-scale local heterogeneities that can exist within the complex microstructure of a thermally sprayed coating. Simpler coatingsubstrate system i.e. not affected by unknown surface chemistry of steel, may help understanding change in residual stress with respect only to spraying parameters only.
Table 2.1: Selected adhesion measurement techniques, T denotes tensile stress and C compressive stress [2].
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Table 2.1: Selected adhesion measurement techniques [2] - cont.
2.2.
Simple chemistry interface without scale roughness
The claim for smooth substrate surface combined with simple interface chemistry should allow two important studies: i) the influence of physical and chemical bonding on adhesion, ii) the influence of sinusoidal interface between coating and substrate on the results of interfacial indentation test. The search for a suitable coatingsubstrate system is mainly based on recent investigations on the formation of single splats on different materials in different spraying conditions and by different techniques. Results are listed further in this chapter.
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Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 3. Material system 3.1. Substrate 3.1.1. Steel
The steel substrate was considered as the most common material for thermal spray. However, its surface chemistry is not well known. Recent works [14-15] revealed complex phenomena on smooth stainless steel surface as a result of spraying NiCr alloy particles by plasma spray technique. They investigated how interface chemistry and splat morphology depend on pre-treatment of substrate surface. In the first step, they formed surface oxides (or hydroxides) and/or induced some modification in surface topology of different samples. In the next step they sprayed NiCr splats and studied their surface with reference to the unsprayed specimens, after the same pre-treatments. As a result of deposition, a diversity of splats ranging from disc-shaped to very fragmented were produced (see Figure 2.1). Description of their diameters, average population and particular characteristics for each sample is given in Table 2.2. The observation of splats microstructure and their interface with the substrate at a micro and nanoscale revealed the occurrence of many forms of oxides, voids, and also jetting of the steel within NiCr. Figures 2.2 and 2.3 present cross-sections of splats which solidified in different morphologies: round-shaped and splashed. Round shaped splats (see Figure 2.3) showed: 1 uniform, columnar grains, 2 coincident grain boundaries across the splat-substrate interface, 3,4 voids, 5 phase identified as NiO (by TEM). Cross section of splashed splat done across the central void (see Figure 2.2) showed: 1 regions being presumably a mixture of oxide and NiCr particles, 2 shape indicating that the molten metal had been pushed upwards from the substrate. From [14-15] it can be concluded that steel substrate can be not satisfactory material for fundamental study of adhesion and residual stresses because of very sensitive to pre-treatment surface chemistry.
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Figure 2.1: SEM images of typical splats: (A) disc splat showing a distinct rim and voids at the centre; (B) disc splat with a central void and a distinct rim; (C) flower-shaped splat;(D) fragmented splat; and (E) very fragmented splat [14].
Figure 2.2: FIB cross-sections of a splashed finger across the central void of the NiCr splat [14].
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Figure 2.3: FIB cross-section of a disc-shaped NiCr splat on steel substate (insert shows location of cross-section): [14]
Table 2.2: Description of the different types of splat found on each specimen, their diameter, average population and particular characteristic. All samples were polished to the nanoscale. Sample SS_P were sprayed just after polishing. Samples SS_B and SS_BT were placed into boiling distilled water for 30 min. SS_PT and SS_BT were thermally treated: subsequently heated at 350 for 90 min in air C at atmospheric pressure. [14]
3.1.2.
Aluminium
Aluminium alloy was considered as common substrate for thermal spray. The big advantage of this material is its passive surface due to chemically inert layer of 19
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 Al2O3. Recent works [16] revealed occurrence of plastic deformation at the interface as a result of high-velocity air fuel spraying NiCr alloy (see Figure 2.5). This makes that the claim for smooth interface between the substrate and coating is not satisfied.
Figure 2.5: Secondary electron image of the aluminum substrate sample with a low density of sprayed NiCr particles [16].
3.1.3.
Silicon
Silicon substrate is not used in industry. However, it seemed to be a good choice from chemistry point of view. Its surface chemistry is well known, i.e. it contains a silicon oxide layer, a few nanometers thick. Additionally mechanical properties of this material are well studied. The silicon single crystal coated with passive aluminium oxide coating is well known in electronic industry. During the last few years aluminium oxide films have been widely used in microelectronic devices, optoelectronics, sensors, antireflection coatings and surface passivation of solar cells [17]. Regarding its usefulness as an alternative gate insulator, aluminium oxide has many favorable properties [18]. Deposition of aluminium oxide on silicon wafer was successfully performed by chemical vapor deposition (CVD) [19-20], MOCVD, atomic layer deposition (ALD), spray pyrolysis [21], thermal evaporation, sputtering, pulse laser deposition [22], solgel technique [23-24]. Although aluminium oxide is also commonly sprayed by thermal spray technique, silicon wafer has not been so far used as a substrate. A deposition trial 20
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 has been already carried out for a similar system, i.e. Al2O3-Al composite cold sprayed on silicon single crystal [25]. The results indicated that a cold spray of hard coating on soft aluminium can be successfully performed (see Figure 2.5). Cratering of the substrate surface affects the integrity of coating/substrate. However, deposition of both pure aluminium oxide and aluminium was not successful. Spraying of pure aluminium oxide caused crater formation in silicon substrate, which is typical of cold spray. In this technique hard, not molten particles are deposited with the highest among TS technologies, kinetic energy, which is spent for flattening and adhesion to the substrate. Therefore a conclusion has been drawn that such coating-substrate system might be successfully obtained by another technique, e.g. Vacuum Plasma Spray, where the particles are molten and require much lower deposition speed. In the case of pure soft metal coating such as aluminium on hard substrate, it is very difficult to obtain proper adhesion due to lack of crater formation. Therefore, a only the composite coating might be successful. 1.1. Coating
As was described in first chapter, thermal spray process is controlled and optimized experimentally. The selection of feedstock material has been restricted to previous, successful experience achieved in EMPA (Swiss Federal Laboratory for Material Testing and Research). This experience was related to aluminium oxide coatings, with spraying parameters established for steel and aluminium alloy. However, the coatings were deposited on rough substrates. A very important advantage of spraying aluminium oxide is its thermodynamic stability. Also spraying parameters for Ni-Cr (80-20) alloy have been established for many substrates, in both scientific and industrial applications.
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Figure 2.5: Fractured cross-section images (SEM) of AlAl 2O3 composite coatings using agglomerated Al2O3 powders: (a) 10:1 wt%, (b) 1:1 wt% and (c) higher magnification (1:1 wt%) [25].
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Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2. Thermal treatment Many independent investigations in recent years have shown that the splat morphology can be significantly modified from the undesired splashed morphology to a more round-shaped morphology with limited or no splashing, by just heating the substrate during spraying up to certain point, called transition temperature, Ts. [2629]. Shape of the splat is important because it implicates microstructure, porosity and properties of deposited coating. Transition temperatures range are relatively low substrate temperature (for most materials 100400 [ C]) and are irrespective of the particle melting temperature. Transition occurs over a narrow temperature regime [26,29]. As reviewed in [30], Ts is affected by: Thermal conductivity of the substrate. Fukumoto et. al. [21] found Ts of nickel splats for variety of materials which include stainless steels, mild steels, copper, aluminium, glass, alumina etc. Ts were plotted against thermal conductivity of each substrate. The results indicate that a higher thermal conductivity substrate leads to an increased Ts. It was suggested [21] that greater interaction of the splat with the substrate results in a higher probability of splashing (see Figure 2.6). Surface condition The influence of substrate surface conditions, such as adsorption or condensation of gases, and its effects on the transition temperature has been investigated with limited attention. However, this may be a significant factor controlling the splat morphology. Some recent experiments [30] indicate that, adsorbed gases are an important factor responsible for droplet splashing and poor adhesion at low deposition temperature (see Figure 2.7). The significance of this study is that its applicability for all droplet and substrate materials combinations. Type of deposit particles In the case of alumina, which mainly was of interest in this work, it was found that splat morphology changes from highly fragmented to diskshaped at Ts equals to 100 [ [30]. C]
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Figure2.6: Relation between thermal conductivity of substrate and transition temperature [32].
Figure 2.7: Morphology of ZrO2 splats made on mild steel substrate in 250 Torr low pressure chamber with induction plasma (a) polished substrate at room temperature; (b) polished substrate, preheated to remove the condensation and adsorption and then cooled down in vacuum (5 Torr) for 17 h to room temperature.[32]
3.
TS techniques Several techniques of thermal spray have been developed. Their
characteristics are described below [33]: 3.1. High Velocity Oxy-Feul (HVOF)
HVOF technique (see Figure 2.8a) is a variant of combustion TS which is a relatively low-temperature 2,000-3,160 [ C] process, with the following characteristics: 24
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 - special torch/nozzle design allows exit gas velocity of up to 4000 [m/s], - feedstock powder is fed axially to the hot zone, - momentum transfer to the particles accelerates them up to about 500 [m/s], - high velocity impact compacts the coating to near-zero porosity, high adhesion and wear resistance. These positive characteristics of HVOF can be utilized as long as the particles are largely molten despite the short residence in the relatively low temperature hot zone. The HVOF process is therefore limited to cermets (such as WC/Co), whereas pure ceramic material is difficult to melt and deposit through HVOF. 3.2. Wire arc spraying
Wire spraying technique (see Figure 2.8b) is suitable for metallic coatings, although cermets may also be deposited. Arc is stricken between two metallic wires or ceramic filled wires. The wires are continuously fed into the hot zone (with velocity about 0.1-1[cm/s]), and melt at ends. Only molten particles are sheared from the two wires ends and accelerated towards substrate by compressed gas or air gun: only molten material leaves the torch. This allows high coating rate, which is about 40 [kg/h], at relatively low cost. Additionally it is possible to achieve a high area coating capability, e.g. for infrastructure bridges (zinc), marine (aluminium), corrosion (chemical industry). However, reactive metals, such as titanium or aluminium must be deposited in an inert gas shroud. 3.3. Plasma Spray (PS)
PS coating (see Figure 2.8c) is considered to have the highest performance and versatility among various TS systems. High DC (up to 200 [A]) high voltage (more than 100 [V]) provides medium-high power (20-100 [kW]) arc and high temperature plasma (more than 10,000 [ C]). Plasma - hot ionized gas - is produced out of the mixture of gases fed into the arc zone, which is typically argon (majority inert gas) and hydrogen (minority reducing gas with high enthalpy and high thermal conductivity). Nitrogen can be used to increase the plasma temperature for higher melting point materials. Helium can be used instead of hydrogen but this happens rarely, due to its high cost. PS usually operates with powder, fed into the plasma hot zone by the powder carrier gas. The powder must have ability to flow carried by the 25
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 gas and thus spherical shapes and uniform sizes of powder particles are preferable. The feedstock particle size depends on melting temperature of the material but is generally in the range of 10-50 [m]. The powder injection ports are usually located outside of the torch, and usually inject the powder radially. This is convenient but creates a complex trajectory of the powder particles through the hot zone wherein some particles may under-heat (i.e. remain solidified) and some overheat (evaporate). Axial injection (see Figure 2c) is ideal but creates technical problems for PS (axial injection is easier to achieve in HVOF). Few companies offer axially injected PS torches, such as UBC spin-off Northwest Mettech (N. Vancouver, BC), and Sulzer Metco in Switzerland. PS typically provides medium velocity of particles: 100-500 [m/s]. The velocity and heat transfer decide about particle melting characteristics. The high temperature of plasma allows spraying of almost any non-decomposing material, especially ceramics. PS variants include (i) inert gas shroud to avoid adverse effects of mixing with air, (ii) radial or axial powder feed, (iii) Vacuum Plasma Spray (VPS), where vacuum in chamber is about 0.1 [atm] or Air (APS), (iv) Very High Power (more than 200 [kW]), which allows high deposition rate i.e. more than 5 [kg/h]. This technique needs extensive cooling, e.g. requires that the process is done under water. Recently, a new technology of Liquid PS has been developed, wherein liquid carrying fine (less than [1m]) solid particles is injected into plasma plume. This opens up avenues for nano-coatings. A large number of process variables controls PS process. Among them best studied are the effects of: substrate preparation (sandblast) and temperature (100-300 [ C]), powder and gas characteristics (Ar/He/H2/N2), torch-substrate distance (typically 15-50 [cm]), voltage/current of arc (typically up to 200 [V] / up to 200 [A]), nozzle characteristics: may be shaped into supersonic Laval nozzle resembling rocket nozzle, particle velocity (typically 100-500 [m/s]).
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Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 3.4. Cold spray
Cold spray (see Figure 2.8d) is a novel thermal process, which emerged after 2000. This technique doesnt use plasma heating of the powder passing through the nozzle. Instead, the powder particles are accelerated to very high velocity (more than 1 [km/s]) by fast flowing gas, which is typically nitrogen, heated to a relatively low temperature of 300-500 [ C]. The cold particles impinge on a substrate and generate local heating sufficient for their amalgamation through spot-welding and thus coating build-up. This is why the method is sometimes described as kinetic compaction instead of spraying. In fact, as contact pressures of more than 30 [GPa] exceeds yield strength of particle materials up to a factor of 1000 times, extensive plastic deformation without any melting is sufficient to produce dense coatings. The best results of cold spray are achieved for relatively low-yield-strength metals such as aluminium, copper, or nickel. However, many other metals were coldsprayed, e.g. steel, titanium, tantalum, cobalt etc. Some successful depositions have been carried out with ceramics. The relatively low overall temperature of the process assures little oxidation of the metallic particles, which is very important for reactive metals such as aluminium or titanium, and in oxidation-sensitive applications such as electronics.
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Figure 2.8: Thermal spray techniques; Ref: K.E. Schneider, V. Belashchenko, M. Dratwinski, St. Siegmann, A. Zagorski; Thermal Spraying for Power Generation Components, Wiley-VCH
4.
Summary The presented state-of-the-art allows better understanding of the possibilities
and shortcomings of different materials systems as well as spraying techniques suitable for fundamental study of adhesion and residual stress. Selection of particular coatingsubstrate system will be presented in Chapter 3, in relation to the applicability to particular measurement method. 28
Chapter 3
MATERIALS EXPERIMENTAL PROCEDURE

3. Coating substrate system Materials from different groups were investigated in order to conclude how formation of thermal spray coating depends on mechanical, thermal and chemical properties of selected materials systems Coatings were thermally sprayed on a smooth (without scale roughness) substrates. Five types of coating-substrate systems were selected (see Table 3.1). System type a. ceramic-metalloid b. ceramic-metal ceramic-ceramic metal-metal metal-ceramic Coating Al2O3 1. Al2O3 2. Al2O3 Al2O3 1. NiCr (80-20) 2. NiCr (80-20) NiCr 80-20 Substrate Si(001) 1. AlMgSi0.5 2. St37-2 Sapphire 1. AlMgSi0.5 2. St37-2 Sapphire
c. d.
e.
Table 3.1: Coating-substrate systems selected for VPS experiments.
Detailed reasons of selection of each coating-substrate system are described below: a. Thermally sprayed aluminium oxide on a silicon (001) wafer has been selected as a novel fundamental approach of studying adhesion of VPS coatings. Such investigation requires the simplest possible coating-substrate system, which was expected in this case because of two reasons: i) well known mechanical and chemical properties of silicon, ii) experience in spraying high quality Al2O3 coatings with good adhesion to either ceramic or 29
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 metallic materials [34]. Moreover, Al2O3-Al composite powders were already successfully sprayed on silicon wafers [25]. b. VPS Al2O 3 coatings on polished metallic substrates: aluminium alloy (AlMgSi0.5) and steel (St 37-2), were of interest due to their close to industrial application as wear and corrosion resistant barriers. Successful deposition on flat substrate has been expected because of two reasons: i) presence of natural Al2O3 passive layer on Al alloy which is fully compatible with the deposited particles ii) high ductility of Al alloy, which should compensate stresses generated due to the impact of particles and their fast solidification. However, both systems present constraints for fundamental study of adhesion of VPS coatings due to their complex phase diagrams. Moreover, surface chemistry of the steel substrate is not known. c. VPS Al2O3 on a sapphire has been selected also as a novel fundamental approach of studying adhesion of VPS coatings. A very simple coating - substrate system was anticipated because of three reasons: i) well known mechanical and chemical properties of sapphire, ii) experience in spraying Al2O 3 coatings with good adhesion to ceramic materials, iii) chemical identity of the coating and substrate. d. Both VPS NiCr (80-20) on a flat steel (St 37-2) and aluminium alloy (AlMgSi0.5) substrate have been of interest as examples of two ductile materials system and due to potential industrial applications. Successful deposition on flat substrate has been expected, especially in the case of steel, because of similarity of thermal properties of substrate and coating. e. VPS NiCr (80-20) on the sapphire substrate has been selected in order to investigate the adhesion between a ductile coating and a brittle substrate. Tables 2-8 present comparison of basic properties for each selected coatingsubstrate systems, important for the successful VPS deposition. Values taken from literature have a qualitative meaning only and give an idea what the deposition may result in. If the coating is successfully sprayed, the mechanical properties, important for the particular system and scale of investigation, should be experimentally measured because of: i) size effect [35], ii) dependence on processing method.
30
VPS alumina on silicon (001) Nomenclature GENERAL Formula Density Melting point Boiling point STRUCTURE -rhombohedral Crystal structure diamond cubic (<1000 [ C]), -cubic (>1000 [ C]) THERMODYNAMIC PROPERTIES Enthalpy of formation Heat of fusion Heat of vaporization MECHANICAL PROPERTIES Elastic modulus Fracture toughness Hardness Thermal conductivity Coef. of thermal expansion E KIC GPa MPam0.5 kgfmm-2 WK1m1 106/C 185 0.91 Knoop: 1150 149 (25[ C]) 2.6 (25[ C]) 103 3-5
o fH 298
Units
Substrate
Coating
Si Tm Tb gcm-3 C C 2.33 1414 3265
Al2O3 3.95-4.1 2072 2977
kJmol-1 kJmol-1 kJmol-1
0 50.21 359
1675.7 -
Vickers: 1256 4-3.5 (25-600[ C]) 5.6-7.0 (100300[ C])
Table 3.2: Comparison of selected properties of Al 2O3 and Si.
31
Most of data for Al2O3 and Si from Wikipedia, KIC for Si http://design.caltech.edu/Research/MEMS/siliconprop.html KIC, for Al2O3 http://www.accuratus.com/alumox.html H, , k, E for Al2O 3 Yamasaki R., Physical Characteristics of Alumina Coating Using Atmospheric Plasma Spraying and Low Pressure Plasma Spraying (VPS), 2004 H for Si http://www.ioffe.rssi.ru/SVA/NSM/Semicond/Si/mechanic.html
VPS alumina on aluminium alloy (AlMgSi0.5)

Nomenclature GENERAL Formula Density Melting point Boiling point STRUCTURE faceCrystal structure centered cubic THERMODYNAMIC PROPERTIES Enthalpy of formation Heat of fusion Heat of vaporization MECHANICAL PROPERTIES Elastic modulus Fracture E KIC GPa MPam0.5 69 14-28* 117.212** 3-5
o fH 298
Units
Substrate
Coating
AlMgSi0.5 Tm Tb gcm-3 C C 2.7 615-654 2518.85*
Al2O3 3.95-4.1 2072 2977
-rhombohedral (<1000 [ C]), -cubic (>1000 [ C])
10.79* 293.4*
1675.7 -
32
toughness Vickers hardness Thermal conductivity Coef. of thermal expansion H k kgfmm-2 WK1m1 106/C 107 200 (25[ C)] 25.6 (25[ C]) 43368** 4-3.5 (25-600[ C]) 5.6-7.0 (100300[ C])
Table 3.3: Comparison of selected properties of Al 2O3 and Al alloy (AlMg0.5Si).
Tm, k, for AlMg0.5Si http://asm.matweb.com/search/SpecificMaterial.asp?bassnum=MA6063T832 **E, H for Al2O 3 on AlMgSi0.5 - experimental values, measured by indentation method: Indenter: Diamond Pyramid 136, Load: 0.98 [kgf], Loading/Unloading speed: 0.1 [mm/min]
VPS alumina on steel (St 37-2) Nomenclature GENERAL Formula Density Melting point Boiling point STRUCTURE -rhombohedral Crystal structure *** (<1000 [ C]), -cubic (>1000 [ C]) THERMODYNAMIC PROPERTIES Tm Tb gcm-3 C C St 37-2 7.72-8.0* 13701510 2500 Al2O3 3.95-4.1 2072 2977 Units Substrate Coating
33
Enthalpy of formation Heat of fusion Heat of vaporization MECHANICAL PROPERTIES Elastic modulus Fracture toughness Vickers hardness Thermal conductivity Coef. of thermal expansion E KIC H k GPa MPam0.5 kgfmm-2 WK1m1 106/C 190-210* 50** 213-800* 19.9-48.3 (25[ C])* 9.4-15.1 (25[ C])* 103 3-5 1256 4-3.5 (25-600[ C]) 5.6-7.0 (100300[ C])
o fH 298
0 -
1675.7 -
Table 3.4: Comparison of selected properties of Al 2O3 and steel (st37-2).
* general properties of tool steel from http://www.efunda.com/Materials/alloys/alloy_home/steels_properties.cfm **for steel 4340 (datafrom Wikipedia) Tm for steel http://education.jlab.org/qa/meltingpoint_01.html Tb for steel http://www.sapiensman.com/conversion_tables/specific_weights.htm ***Iron-carbon phase diagram http://en.wikipedia.org/wiki/Steel
VPS alumina on sapphire
Nomenclature
Units GENERAL
Substrate
Coating
Formula Density Melting point Boiling point

Tm Tb gcm-3 C C
Al2O3 3.98 2030 2977
Al2O3 3.95-4.1 2072 2977
34
STRUCTURE Hexagonal -rhombohedral (<1000 [ C]), -cubic (>1000 [ C])
Crystal structure
THERMODYNAMIC PROPERTIES
system, rhomboidal class 3m
Enthalpy of formation Heat of fusion Heat of vaporization

MECHANICAL PROPERTIES
o fH 298
1675.7 -
1675.7 -
Elastic modulus
GPa
345 2.38 (direction
103
Fracture toughness
KIC
MPam0.5
[0001]) 4.54 (direction[1120]) Knoop: 1835 parallel to C-
3-5
Hardness
kgfmm
-2
axis, 2243 perpendicular to C-axis 23.1 parallel to
Vickers: 1256
Thermal conductivity
optical axis, 25.2 k WK m

1 1
perpendicular to optical axis (73[ C])
4-3.5 (25-600[ C])
Coef. of thermal
106/C
6.66 parallel to optical axis, 5
5.6-7.0 (100300[ C]) 35
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 expansion
perpendicular to optical axis (100[ C])
Table 3.5: Comparison of selected properties of Al 2O3 and sapphire.
KIC for sapphire from http://www.ceramics.nist.gov/srd/summary/ftgsaph.htm Crystal structure E, H, k, , Tm for sapphire from http://www.mt-berlin.com/frames_cryst/descriptions/sapphire.htm
VPS NiCr(80-20) on aluminium alloy (AlMg0.5Si) Nomenclature GENERAL Formula Density Melting point Boiling point STRUCTURE Crystal structure THERMODYNAMIC PROPERTIES Enthalpy of formation Heat of fusion Heat of vaporization MECHANICAL PROPERTIES Elastic modulus Fracture toughness E KIC GPa MPam0.5 117.212 14-28* 220 65-150
o fH 298
Units
Substrate
Coating
AlMgSi0.5 Tm Tb gcm-3 C C 2.7 615-654 2518.85*
Ni-Cr 80-20 7.75-8.65 1400-1700 >2000
face-centered cubic
10.79* 293.4*
36
Vickers hardness Thermal conductivity (25[ C]) Coef. of thermal expansion (25[ C])
Table. 3.6. Comparison of selected properties of NiCr 80-20 and Al alloy (AlMg0.5Si).
kgfmm-2
43368
1018
WK1m1
200
8-17
106/C
25.6
9-16
*Ni-Cr phase diagram http://images.google.pl/imgres?imgurl=http://www.msm.cam.ac.uk/UTC/thermocoupl e/images/Chromel2.jpg&imgrefurl=http://www.msm.cam.ac.uk/UTC/thermocouple/pa ges/DriftInTypeKBareWiresThermocouples.html&usg=__41sH8dZY5Phtj0RtywftJQS_bw=&h=384&w=517&sz=30&hl=pl&start=6&um=1&itbs=1&tbnid=AeywW8jaA5 d7M:&tbnh=97&tbnw=131&prev=/images%3Fq%3DNiCr%2B%2Bphase%2Bdiagram% 26um%3D1%26hl%3Dpl%26client%3Dfirefoxa%26hs%3DAI9%26rls%3Dorg.mozilla:pl:official%26tbs%3Disch:1 *data for NiCr from http://www.nickel-alloys.net/nickel_chrome_alloys.html H for Ni-Cr alloy Sampath R., A structural investigation of a plasma sprayed Ni-Cr based alloy coating, 1992
VPS NiCr(80-20) on steel (St 37-2) Nomenclature GENERAL Formula Density Melting point Boiling point STRUCTURE Crystal structure *** * Tm Tb gcm-3 C C St 37-2 7.72-8.0* 1370-1510 2500 Ni-Cr 80-20 7.75-8.65 1400-1700 >2000 Units Substrate Coating
37
THERMODYNAMIC PROPERTIES Enthalpy of formation Heat of fusion Heat of vaporization MECHANICAL PROPERTIES Elastic modulus Fracture toughness Vickers hardness Thermal conductivity (25[ C]) Coef. of thermal expansion (25[ C])
Table. 3.7. Comparison of selected properties of NiCr 80-20 and Al alloy (AlMg0.5Si).
o fH 298
0 -
E KIC H
GPa MPam0.5 kgfmm-2
190-210* 50** 213-800*
220 65-150 1018
WK1m1
19.9-48.3 *
8-17
106/C
9.4-15.1 *
9-16
VPS NiCr(80-20) on sapphire Nomenclature GENERAL Formula Density Melting point Boiling point STRUCTURE Crystal structure Hexagonal system, * Tm Tb gcm-3 C C Al2O3 3.98 2030 2977 Ni-Cr 80-20 7.75-8.65 1400-1700 >2000 Units Substrate Coating
38
rhomboidal class 3m THERMODYNAMIC PROPERTIES Enthalpy of formation Heat of fusion Heat of vaporization MECHANICAL PROPERTIES Elastic modulus E GPa 345 2.38 (direction Fracture toughness KIC MPam0.5 [0001]) 4.54 (direction[1120]) Knoop: 1835 parallel to CMohs hardness H kgfmm
-2 o fH 298
1675.7 -
220
65-150
axis, 2243 perpendicular to C-axis 23.1 parallel to optical axis,
1018
Thermal conductivity
WK1m1
25.2 perpendicular to optical axis (73[ C]) 6.66 parallel to optical axis,
8-17 (25[ C])
Coef. of thermal expansion
106/C
5 perpendicular to optical axis (100[ C])
9-16 (25[ C])
Table.3. 8. Comparison of selected properties of NiCr 80-20 and Al alloy (AlMg0.5Si).
39
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2. Experimental procedure 2.1. Thermal spray process
Vacuum Plasma Spray (VPS) has been chosen as a deposition technique because of the highest performance and versatility among various TS systems, which were described in Chapter 2. The coatings were obtained in a VPS unit using a Medicoat 50 [kW] with powder feeder (F-4 & V21 nozzle), moved by an industrial robot. Surfaces of metallic substrates were mechanically polished to the roughness Ra=1 [m]. Roughness of silicon and sapphire wafers was of a few nm, thus polishing was not necessary. Dimensions of substrates used in this work are presented in Figure 3.1.
Figure 3.1: Scheme of substrates used in this work: A) silicon wafer, B) sapphire wafer C) polished metals (Ra=1[m]): aluminium alloy (AlSi0.5Mg) and steel (St 37-2).
Prior to spraying, the samples were washed with ethanol in order to remove any remaining dust or grease from the surface. The material to be deposited was injected in a powder form using argon as carrier gas. Careful control of the substrate temperature while deposition was necessary to optimize adhesion of the coating. Optimal temperature depends on the type of the coating substrate system. Ceramic coatings are generally brittle. Their fracture strain is below 0.1%. The strain due to the rapid solidification is relaxed in multiple vertical micro-cracks within the single splat. Thus, in this case, substrate must be kept at low temperature during spraying 40
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 in order to avoid failure as a result of the cooling stresses. On the other hand, metallic coatings are generally ductile, relax the solidification strain through plastic deformation and rarely crack. In this case preheating of the substrate over a transition temperature, Ts before spraying increases the adhesion, which has been clearly indicated by all the experimental studies [32]. Such treatment reduces the surface tension of the coating below the surface tension of the substrate which allows particles to wet the substrate and results in disk-shaped, well adhering splats. On the other hand, when the substrate temperature is kept below Ts, extensively fingered splats are obtained, easily detaching from the surface. The transition temperature depends on the substrate-coating system and is generally low compared to the melting temperatures of both. The main spraying parameters were the same as in previous successful VPS deposition processes used for industrial applications (see Table 3.9). Spraying parameters constant for each deposition are listed below: Ar Plasma = 40 [sl/min] H2 Plasma= 6 [sl/min] Vacuum= 100 [mbar] = 10[kPa], which is in range of low vacuum (3 -100 [kPa]) 2.2. Investigation methods
In this work attention was focused mostly on a VPS Al2O 3 coating on silicon wafer, which is a novel system, promising for fundamental study of adhesion. For other samples the analyses were performed if first observation after the VPS process indicated successful deposition. Characterization of the obtained coatings comprised: i) morphology and chemical composition by SEM-EDX analysis, ii) crystalline structure by XRD analysis in either conventional Bragg-Brentano geometry in the case of thick layers or grazing incidence X-ray and neutron diffraction (GID) in the case of thin layers, iii) topography of the surface and residual stress expressed as bending curvature, by profilometry. Additionally basic study of adhesion between the deposited material and the substrate was done by: i) in-situ SEM scratch test, ii) interfacial indentation, iii) Rockwell indentation.
41
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 Spray.distance,mm Spray.velocity,mm/ Current intensity,A
s Number of
NiCr(80-20) /AlMg0.5Si, St37-2, sapphire Al2O3/AlMg0.5Si, St37-2, sapphire 750 275 300 28 Cooling 750 275 300 10 Without cooling, preheating 350 C
passages
Coating/ Substrate
Remarks
Al2O3/Si
900
325
150
20
Cooling and 1 break between pass. Cooling and 1 break between pass.
Al2O3/Si
750
275
150
40
Al2O3/Si
750
275
150
Al2O3/Si
750
275
150
40
10 break between pass.
Al2O3/Si
750
275
300
30
without cooling
Al2O3/Si
750
275
300
without cooling
Al2O3/Si
750
275
300
14
without cooling
Table 9: The main spraying parameters.
42
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2.2.1. Morphology and chemical composition by SEM-EDX analysis
a. SEM technique Scanning Electron Microscopy (SEM) is nowadays one of the most popular microscopy techniques for materials imaging. It is mainly due to multiple types of signal emitted from the sample while scanning, which, by use of suitable detector, allows different types of analysis, such as high resolution investigation of morphology delivered by secondary electron (SE) signal as well as chemical composition delivered by, used in this work, X-ray or an Auger electron signal. SEM imaging requires just small preparation investment, and allows obtaining: magnification ranges 10x-106x and high depth of focus. Basic principles and possibilities of SEM imaging described by many authors e.g. in [36]. Image creation in SEM: imaging uses electron wave as a analysed signal instead of optical wave. Electron wave has shorter length and because of it image resolution can be higher. The wave is released and focused onto sample by electron beam emitting system consisting of a cathode, the Wehnelt Cylinder (Grid Cap) and an anode. Electrons are created by heating a tungsten hairpin cathode at 2600-2900 [K]. They are accelerated between the cathode and the anode in the optic axis. The Wehnelt Cylinder, which works as s lens, focuses the electrons emitted from the cathode into a small beam diameter, the crossover. Next the condenser lenses within the microscope column, make the crossover smaller, approaching at minimum electron beam diameter of 4 [nm] on the sample surface. Obtained electron beam (primary electrons (PE)) is deflected by Scanning coils so that it scans on the sample surface. (See Figure 3.2.) On the sample surface primary electrons interact with the material and creates multiple type of signal: secondary electron (SE), Auger electron, back scattered electron (BSE) and X-rays. Each type of signal is analyzed by an appropriate detector.
43
Figure 3.2: Scheme of image creation in SEM [36].
Interaction of electrons with material: primary electrons (PE) penetrate into the sample where they are elastically and inelastically scattered. Elastic scattering means that PE come back again to the surface, and inelastic scattering means that PE lose their total energy and stay stuck in the material. The region where the interaction between the PE and the material occurs is called interaction volume or electron diffusion cloud. Each type of analysed signal comes a from different volume. Auger, SE and BSE interaction volume have different possibility to approach the surface again. X-rays interaction volume depends on the necessary primary energy for the production of appropriate X-ray. Accordingly the local resolution is different for each type of signal since the information comes from different volumes. (See Figure 3.3.) The secondary electron (SE) is created by inelastic scattering (from depth of 550 [nm]). Released free SE are accelerated towards a detector, what is due to a current between the sample and the detector.
44
Figure 3.3: Interaction volume for different signal emitted in SEM.
Characteristics
of
electron
beam:
The
brightness
and
beam
diameter/crossover are two important parameters describing the characteristics of the electron beam. The brightness, b, which is an intrinsic property of the electron gun, is defined as the ratio of the current density in the crossover and the solid angle of the beam. The brightness is not influenced by the system of lenses and thus does not change along the optical axis. At a given constant brightness, the diameter of second condenser lens is proportional to the probe current, I (hence signal strength). High resolution imaging very small probe diameter is required and thus probe current must decrease strongly. Therefore the gun brightness is often the resolution limiting factor while using thermionic electron guns. For high resolution microscopy, field emission guns, which exhibit much higher brightness values, are suitable. 45
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 The beam diameter/crossover is controlled by condenser lenses. Weak condenser lens strength allows larger probe diameter, thus short acquisition time, however, leads to a high probe current, thus not very high imaging resolution. Weak condenser lens strengths are useful for analyse, which require strong signal (EDX/WDX and EBSD), even at the cost of the highest possible resolution. For high resolution imaging strong condenser lens strength is necessary, thus small probe size. The small current requires, however, long image acquisition times due to a high signal-to-noise ratio. Resolution: the resolution of a SEM is determined by the diameter of the area from which the analysed signal is emitted. In the case of SE electrons which are directly emitted from the primary electron beam, this area corresponds directly to the diameter of the primary beam. The resolution of a microscope is determined by the probe size which still allows recording of noise-free images. According to the Rayleigh resolution criterion, perception of two features as separated requires an intensity difference of at least 25%. This definition is based on knowledge that the human eye can distinguish a feature from the background if the difference between the feature and the background is 5 times larger than the amplitude of the random noise. b. EDX technique Energy Dispersive X-ray Spectroscopy (EDX) is an imaging technique, which allows detection and mapping of elements on the analysed surface. The principle of EDX analysis is as follows: In result of interaction of PE with the sample an electron with sufficient energy removes an electron from the K shell. Electron of the L-shell fills immediately the empty space. This electron jump is accompanied with release of the energy, which is emitted as characteristic of each element X-rays or Auger electrons. Maps of elements are possible due to the scanning of the surface, when the energy distribution of the X-rays can be determined at each point. The X-rays of a characteristic energy are coded as colour images, which intensity represents the distribution of the elements on the surface, but just qualitatively. EDX analysis detects elements from depth of 0.2-2[m].
46
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 c. SEM-EDX investigations
In this work EDX map acquisition was chosen as the best method for quick and reliable recognition whether deposition of a continuous film was successful. Silicon peak was present on each EDX diagram. However, it was not sure whether the coating was discontinuous or the Al2O3 film was thinner than the resolution of the in depth EDX analysis. Additionally, EDX maps allowed recognition of shape of Al2O3 islands. SEM analysis, on the other hand, was done in order to obtain high resolution information on their morphology. EDX maps were acquired by following set up of SEM: Working distance (WD): 24-26[mm], Beam current: 70-75[A], Accelerating Voltage: 15[kV], Spot size: 10[nm], Dead time (DT): 25-30%, Magnification: 200-3000x.
EDX map analysis: recognition of EDX maps was easier using image arithmetics in Matlab. Maps of silicon, oxygen and aluminum were simply added and the outcoming image was analysed (see Figure 3.4). EDX map is an RGB image, which in Matlab is represented as 3D matrix. First two dimensions of this matrix are the same as image size whereas the third one is always three and indicates color for each pixel. Each pixel is represented by three numbers, varying in 256 steps from 0 to 1. First indicate intensity of red (denoted as (100)), second green(denoted as (010)) and third blue (denoted as (001)), thus, taking into account just first letters, the name RGB. 0 means a shortage and 1 maximum of color intensity. Sum of RGB images in Matlab means sum of 3D matrixes. Exemplary sum of red and green pixel in the same location in the image gives yellow pixel.
47
Figure 3.4: Scheme showing the manner of EDX map processing done in Matlab. The target is an easier image recognition.
2.2.2.
Crystal structure by XRD analysis
X-ray crystallography is a method of determining the arrangement of atoms within a crystal, in which a beam of X-rays strikes a crystal and diffracts into many specific directions. The crystal structure is determined based on spacing between the planes in the atomic lattice, d, calculated from Braggs law:
n = 2d sin
(3.1)
where n is an integer, is the wavelength of incident wave, and is the angle between the incident ray and the scattering planes. Diffractometers can be operated both in transmission and in reflection configurations. The reflection one is more common. The powder sample is placed in a small disc-like container and its surface is carefully flattened. The disc is put on one axis of the diffractometer and tilted by an angle of incidence, , while a detector (scintillation counter) rotates around it on an arm at twice this angle. This configuration is known under the name Bragg-Brentano (see Figure 3.5). The geometrical principles of a Bragg-Brentano parafocusing are as follows: X-rays diverge from source. The "reflected" X-rays from the samples on the focusing circle are directed to their respective places back on the circle. The spots labeled G1, G2, G3 are the respective reflections of d-spacings d1, d2, d3. The Bragg-Brentano geometry allows for a constant distance between the sample and the detector. It essentially requires that distance from the source to the sample and the sample to the detector be equal (i.e., R1 = R2) and that the sample is kept on the tangent of the focusing circle. In order to keep the detector distance constant the sample must rotate at 1/2 the angular velocity of the detector. As the angle of incidence, , changes, the detector must move 2. This is called 2:1 motion.
48
Figure 3.5: Scheme of BraggBrentano geometry [7].
Grazing incidence X-ray and neutron diffraction, typically from a crystalline structure (abbreviation GIXD or GID), uses small incident angles for the incoming Xray or neutron beam, so that diffraction can be made surface sensitive. It is used to study surfaces and layers because wave penetration is limited. Distances are in the order of nanometres. Below (typically 80%) of the critical angle of the surface material studied an evanescent wave is established for a short distance and is exponentially damped. Therefore Bragg reflections are only coming from the surface structure. An advantage of GIXD is that the electric field at the critical angle is amplified locally by a factor of four, therefore the GIXD signal is stronger. The diffraction geometries with grazing incidence are presented in Figure 3.6.
49
Figure 3.6: Diffraction geometries with grazing incidence and/or exit. (a) coplanar extremely asymmetric diffraction, (b) grazing-incidence (surface), (c) non-coplanar asymmetric diffraction [37].
2.2.3.
Topography and bending curvature by profilometry
Non-contact profilometry techniques based on reflectometric measurements were used in topography and residual stress investigations. Localization of surface points is determined by triangulation principle: A laser source is focused onto the surface being scanned and its reflection is imaged onto a positionsensitive detector (PSD). Whenever there are small differences in the surface topography, a displacement on the image may be measured on the PSD. This value depends only on the angle between the illumination and detection by optical system. In case of application to diffuse objects, the resolution of the technique is limited by the speckle patterns on the image plane [Dorsch 1994]. The technique may be applied, with good resolution in micro scale, to reflective objects only. As has been already mentioned a simple profilometry measurement allows evaluation of residual stress within a coating by means of the model developed by Stoney [38] and improved by Clyne [39], which is described below: Force and moment balance: within two plates bonded together with a misfit strain in the x-direction, such as would arise during a change in temperature 50
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 ( = T), appears stress, x(y), which leads to curvature, (see Figure 3.7). Both x(y) and can be evaluated from simple beam bending theory. In first step, the misfit strain is removed by the application of two equal and opposite forces (-P and P). When the two plates are joined, an unbalanced moment, M, appears which generates curvature, , of the composite plate. The moment is given by:
M = P ( h s + hc ) 2
(3.2)
where hc and hs are the thicknesses of coating and substrate respectively. The curvature of a beam, , is equal to the through-thickness gradient of strain, and can be expressed as:
(3.3) where is the beam stiffness. Curvature arising from the imposition of a uniform misfit strain, , was
developed from stiffness of composite beam by Clyne in 1996. A general expression is given by
= =
1 r
6 E c E s ( hc + hs ) hc hs E c h + 4 E c E s h hs + 6 E c E s hc2 h s2 + 4 E c E s hc h 3 + E s2 hs4 s
2 4 c 3 c
(3.4)
where E is the Youngs modulus and the subscripts c and s refer to deposit (coating) and substrate respectively. It is important to notice that, for a given coating/substrate thickness ratio (hc/hs), the curvature is proportional to the coating thickness, hc and inversely proportional to the substrate thickness, hs. Therefore in practical terms, relatively thin substrates are essential for accurate measurement. Eqn.(3.3) assumes: i) no stress gradient through thickness of the coating, ii) that the system remains elastic while the curvature is adopted. Biaxial stress and bifurcation: assuming an equal biaxial (in x and z direction) stress state, isotropic in-plane stiffness, and negligible through-thickness stress (y = 0) a conclusion can be drawn that there is a Poisson strain in the x-direction. The relation between stress and strain in the x-direction can be expressed by the modified form of Youngs modulus, E, given by:
X E = = E' X 1
(3.6)
51
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 Consideration that the possibility of multi-directional curvatures leading to mechanical instability leads to conclusion that there will be little or no danger of a bifurcation instability if a long (L~100[mm]) and fairly narrow (b/L<~0.2) strip sample is used. Such dimensions are convenient, because they suit well the accurate measurement of curvature along the length of the strip. Effect of coating thickness and use of the Stoney equation: when the coating is much thinner than the substrate (h << H) i.e. ratio of the thickness of the coating to that of the substrate, hc/hs, is less than about 5%, the misfit strain can be converted directly to a deposit stress, c (= Ec ). Like that the equation Eqn.(3.4) reduces to the Stoney equation (1909):
c,Stoney =
Es 'hs2
6hc
(3.7)
which is commonly used to relate stress to curvature for thin coatings. Eqn. (3.7) is approximately correct, although the details are dependent on the Youngs modulus and on the absolute thickness of the substrate. In the case when the condition hc << hs cannot be applied, stresses and stress gradients are often significant in both constituents. Clyne (1992) developed the formula, which is readily applicable for the simple misfit strain case outlined above, and is given by:
Clyne =
E c ' hs E s ' + E c ' ( hc ) hc E c '+ hs E s '
(3.8)
2.2.4.
Adhesion between the coating and substrate
a. In - situ SEM scratch test Scratch technique: by this method both scratch resistance as well as adhesion of the coating can be measured. Principles of scratch technique are described by [40]: A loaded stylus is drawn across the film surface. There is obviously a simple relationship between the applied load, of which the intensity can be controlled easily in the balance system carrying the stylus, and the shearing force eventually causing detachment of the coating. A critical quantity is the radius at the tip of the tool, and it must be measured with the same accuracy as width of the contact area generated during a scratching procedure. 52
Figure 3.7: Schematic depiction of the generation of curvature in a flat bi-material plate, as a result of the imposition of a uniform, linear misfit strain, . The distributions of stress and strain shown can be calculated, using Eqns.(3.7) or (3.8).
It is recommended [40] that the information obtained directly from the test be supplemented by additional data, such as result of surface profilometers or SEM, which provide insight into the details of the scratch topography. Under such provision, even the adhesion values in a multilayer system can be estimated. It can be seen what type of film failure occurs in those systems when they are subjected to scratch loading. A great advantage of in situ SEM scratch test, which was done, is receiving an information on exact topography of scratching area. Additionally a movie of the whole test can be recorded.
53
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 Procedure of scratch test: in order to check if single splats of Al2O3 were well adherent to the silicon wafer in-situ SEM scratch test was performed. The test had a qualitative target. Five splats were scratched by conical 90 indenter with a load of 40 [g]. The tip scratched through the splat either above silicon surface, or 200 [nm] in depth of the silicon surface. Movies taken during each test are attached in Appendix. b. Interfacial indentation Principle of interfacial indentation test: interfacial indentation method was developed by D.Chicot and J. Lesage in 1996. In their work [41], it was proposed to evaluate adhesion of ductile coating on ductile substrate by means of an apparent interfacial toughness, KIC. The model provides a relation between the applied load, P, and the length of the crack, a, created at the interface between the coating and the substrate (see Figure 3.8). Plotting P against a in bilogarithmic coordinates results in linear relation, which may be expressed by:
a = P
(3.9)
where the exponent n is a function of the coating thickness. In next step residual stresses due to solidification of the coating are relaxed by an appropriate treatment, usually annealing. Now plotting P against a result in the new straight line, which corresponds to different thicknesses and intersects at the same point with previous plot. This point indicates the half diagonal of the indent, ac and critical load, Pc for which indentation stops causing crack between the coating and substrate. The critical load is representative of adhesion of the coating, thus the apparent interfacial toughness, KIC should vary in the same way. KIC was determined by transposition of the principle of indentation tests used to determine toughness of brittle materials, and is given by:
K IC = 0.015 PC
3 aC/ 2
E H i
1/ 2
(3.10)
where (Pc, ac) is a critical point, Ei apparent elastic modulus, and Hi, apparent hardness. The interfacial indentation is influenced by hardnesses and elastic properties of both the substrate and the coating. The (E/H)i , which depends on these properties, is given the following relation: 54
(E H )
1/ 2 i
(E H )
1/ 2 S 1/ 2
H 1+ S HC
(E H )
1/ 2 C 1/ 2
H 1+ C HS
(3.11)
Figure 3.8: Scheme of interfacial indentation test.[42.]
Procedure: the test was performed on mechanically polished cross-section of VPS Al2O3 on aluminium alloy (AlMgSi0.5) substrate. The interface was indented using Vickers pyramid microindenter with increasing loads: 500 [N], 1000[N], 2000[N], 3000[N], 5000[N], 10000[N]. c. Rockwell indentation Principle of Rockwell indentation test: The method was developed by Drory in 1996 [2]: The work aimed development of an indentation test of adhesion for a brittle coating on a relatively ductile substrate. Plastic deformation of the substrate is encouraged in this test. The measurement involves loading by the diamond brale indenter (See Figure 3.9) but under much greater loads than in the case of the Vickers indentation tests. The Rockwell test applies a 100 [N] preload, followed by the major load (ca. 600-1500 [N]), while the typical loading in microhardness test ranges 10 to 200 [N]. The load is applied continuously through a damping mechanism until a single value, determined by the use of hanging weight system, is achieved. The preload is manually released. delamination. The loading is defined by the standard Rockwell Hardness Tester (ASTM 1994). Relatively gross deformation of the substrate causes film
55
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 Rockwell indentation delivers useful information on adhesion through the measurement the interface toughness, KIC. This method has many advantages: i) low cost, ii) current widespread use in metallurgical laboratories.
Figure 3.9: Schematic of the brale indentation test [2].
The investigation of adhesion requires consideration of following issues: a. Surface strains due to conical indentation of an elastic-plastic substrate [2]: The elastic energy stored within the coating arises from two sources: initial residual stress and additional stress induced it the film in the vicinity of the indentation. Model developed by Drory restricts attention to residual stresses which are uniform through the thickness of the film and equibiaxial such that the in-plane stress components are xx=yy=0. Displacement and strains: the substrate half-space is modelled as a finite strain deformation theory solid characterized by a Ramberg-Osgood true-stresslogarithmic-strain curve in uniaxial tension which is given by:
3 Y 1/ N ( ) 7 ES Y
ES
(3.12)
where the substrate is described by its Young's modulus, Es, Poisson's ratio, v s, tensile yield stress, y, and strain hardening exponent, N. The model assumes frictionless indenter surface. After further considerations described by Drory [2], surface strains are divided into the radial, r, and circumferential, . 56
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 Distribution of stresses and elastic energy in film: let 0 and 0 be the uniform, equibiaxial residual stress and strain in the coating prior to indentation which are related by:
1 0 E
0 =
(3.13)
The radial and circumferential stresses in the coating are given by:
r = =
E ( r + ) 1 2 E ( + r ) 1 2
(3.14) (3.15)
Energy release for interfacial delamination: the indenter creates a free edge in the coating at the radius, r = a (see Figure 3.10). From this edge, where the highest induced stresses are located, an interfacial crack between the film and the substrate may be propagated outward radially. It will stop at the point where the energy release rate, G, available to drive the crack drops below the interface toughness. Other phenomena, including buckling, cracking and break-up of the film at some distance behind the interface crack accompany the interfacial delamination. Three models of the delamination process (see Figure 3.11) are listed below including quantitative methods on how these accompanying phenomena influence the energy release rate.
Figure 3.10: Axisymmetric geometry of indentation experiment for mechanics analysis [2].
57
Figure 3.11: Models for interface delamination: (a) small annular plate of film remains with the most of films breaking up as the crack advances; (b) a substantial annular portion of the film remains without buckling as the crack advances; and (c) addition of buckling to (b) [2].
In the case of delamination accompanied by break-up of the detached coating such that a very narrow annular plate of coating is left behind the advancing interface crack front, the energy release rate, G, is given by:
G=
(1 2 )t r ( R) 2 2E
(3.16)
where t is film thickness and R is a radius of circular interface crack. In the case of delamination taking place with an unbuckled annular plate of film remaining intact behind the advancing interface crack front, the radial stress component at the outer edge of the annular plate is given by
r (R ) =
E [1 ( Ri / R) 2 ] [(1 ) + (1 + )(Ri / R) 2 ]
(3.17)
where Ri, is the inner radius, determined, assuming the film does not buckle.
58
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 In the case when the residual stress in the film is compressive, the stresses r and in the annular plate of film left behind the delamination crack tip will also be compressive. In consequence, the plate may buckle, which results in reduction of the constraint analysed above. The distribution of r in the unbuckled plate of film is given by:
r Ri R Ri
r0 ( r ) = r ( R )
(3.17)
Toughness of hard coating ductile substrate interface: the apparent interface toughness is evaluated by:
K IC =
EG 1 2
(3.18)
Procedure: the test was performed for VPS Al2O3 on aluminium alloy (AlMgSi).5) substrate using parameters: indentation speed: 0.5 [mm/min], Indenter 120 diamond.
59
Chapter 4
RESULTS DISCUSSION
4. Al 2O3 on Si wafer 1.1. SEM-EDX analysis 1.1.1. Deposition of Al2O3 in one passage
In the ideal case, single splat deposited on the flat surface has a round shape. Such morphology is considered [32] to increase both adhesion between the coating and the substrate, as well as the density and homogeneity of the coating. In the case of spraying Al2O3 on Si wafer some single splats were observed near the edge of the silicon wafer. Their almost round shape with some thin fingers seemed to be good enough for successful deposition of a continuous film after further spraying passages (see Figure 4.1). In the middle of the sample splats were already accumulated on the surface (see Figure 4.2). Some worrying effects of the deposition were also noticed: i) many of the agglomerated splats seemed not to adhere well to the silicon wafer (see Figure 4.3B), ii) some defects occurred in the silicon substrate (see Figure 4.3A,C).
Figure 4.1: Morphology of the Al 2O3 single splat deposited on the Si (001) wafer by VPS. Images were taken near the edge. of the sample.
60
Figure 4.2: Morphology of accumulated splats of VPS Al 2O3 on Si (001) wafer after one passage: A) top view on irregular-shaped islands of Al 2O3, B) side view during scratch test revealed very rough surface of the accumulated splats.
61
Figure 4.3: SEM SE images of Si (001) wafer after one passage of Al2O3 deposition by VPS: A) failure of silicon wafer near the edge of the sample, B) badly adhering splat, C) failure of silicon wafer and morphology of single splat of Al 2O3.
62
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 1.1.2. Deposition of Al2O3 in multiple passages
Silicon wafers seem not to allow Vacuum Plasma Spraying of continuous Al2O3 films under whatever conditions. The best coverage of silicon surface was obtained after deposition in 20 passages with a 10-minute break between the consecutive passages (see Figure 4.4). However, any general conclusion cannot be drawn because of lacking statistical data. Single EDX map was obtained in the middle of the sample, which do not allow any quantitatively analysis. However, a map of this type is helpful in the evaluation of coating continuity. Most of the EDX maps taken after next trials of coating deposition are similar: irregular-shaped islands of aluminium and oxygen among regions of pure silicon (see Figure 4.4A,B and Figure 4.5). Only the sample sprayed with higher energy plasma is an exception: irregular-shaped islands are composed of aluminium, oxygen and silicon, whereas lower regions are composed just of silicon and aluminium (see Figure 4.4C). The presence of aluminium, oxygen and silicon islands might be explained as local melting of silicon and its diffusion into Al2O3 islands or deposition of Al2O3 thinner than depth resolution of EDX analysis. But the lack of oxygen in valleys of the analyzed surface seems to be very improbable because of very high formation enthalpy of Al2O3. However, a reduction of Al2O3 was already observed in vacuum and H2 plasma condition [43]. On the other hand oxygen gives a weak EDX signal and therefore might be not detected in valleys of the analysed surface. The interface between silicon an alumina was suspected as the origin of any physical or chemical changes. Therefore samples sprayed with lower energy plasma which did not show unexpected composition of elements were fractured and the EDX maps of the interface were collected. The results for both 1 passage and 40 passages of Al2O3 VPS on cooled substrate (see Figure 4.6) were similar to the EDX map from the top of sample sprayed with higher energy plasma (900 [V]) (see Figure 4.4C).
Unfortunately the resolution of EDX analysis is low and does not allow for any certain conclusions about chemical reaction in this system. Anyway, explanation of the observed phenomena required XRD analysis.
63
Figure 4.4: EDX images of Si (001)surface after multiple passages of Al2O3 deposition by VPS : A) 40 passages sprayed with a 10 break between the consecutive passages and without cooling, B) 40 passages sprayed with a 1 break between the consecutive passages and with cooling of the substrate, C) 20 passages sprayed with higher energy plasma (900[A] instead of 750[A]), with a 1 break between the consecutive passages and with cooling of the substrate.
64
Figure 4.5: SE images of Si (001)surface after 40 passages of Al 2O3 deposition by VPS with a 1 break between the consecutive passages and cooling of the substrate at different magnifications.
65
Figure 4.6: Cross-section of Si (001)wafer after Al2O3 deposition by VPS: A) 1 passage B) 40 passages with a 1 break between the consecutive passages and cooling of the substrate.
1.2.
SEM In-situ scratch test
In result of scratching above the surface of silicon occurred only a plastic deformation till the surface of the splat was perfectly flat. Since the indenter had approached inhomogeneity the splat cracked and detached from the surface (see Figure 4.7A). In case of scratching below the surface of silicon all splats cracked and detached from silicon wafer immediately after being approached by the indenter (see Figure 4.7B). Detachment of silicon was not observed in result of any test.
66
Figure 5.7: SEM SE images taken after in-situ SEM scratch test done by conical 90 indenter with a load of 40 g. The tip scratched through the splat: A) above silicon surface B) 200 [nm] in depth of silicon surface.
67
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 1.3. XRD analysis
In order to better understand phenomena caused by spraying of Al2O3 on silicon substrate, the crystal structure of the initial powder and the surface after deposition were analysed. Conventional X-ray diffraction analysis of the Al2O3 powder (see Figure 5.8) indicated rhombohedral structure R-3c, named -Al2O3 and commonly corundum. The powder was contaminated by diaoyudaoite (NaAl11O17), which is formed as byproduct in the Bayer process. According to specification given by the manufacturer, the purity was 99.5%.
Figure 5.8: Diffraction pattern obtained for the Al 2O3 powder used in VPS process.
The analysis of glancing incidence X-ray diffraction (GID) from both samples, one after 20 passages with higher energy plasma and one after 40 passages with cooling of the substrate revealed almost the same crystal structure in near surface region (see Figure 5.9): i) rhombohedral (R-3c) -Al2O3 the same as of the initial powder, ii) cubic (Fd3m) -Al2O3, which is favoured in lower temperature, iii) cubic (Fd3m) silicon. Two peaks in each diffraction pattern, located between 51-55 on the 2 theta axis, were not identified. Most of Al2O3 particles were molten while spraying 68
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 thus it was concluded that cooling speed varied for different particles; some solidified in form whereas some in form. The diffraction pattern obtained from the surface of silicon wafer disclosed the biggest peak intensity at 2 theta of 56 whereas in the reference pattern the location of the biggest peak was at 28 which indicates a , texture effect and might be caused by melting of silicon due to the energy transferred from plasma sprayed Al2O3. Analyzed diffraction patterns differed in three issues: i) peak intensity of Al2O3 and cubic Si increase in the case of spraying by higher plasma energy, which, is in agreement with previous EDX results, ii) location of two unidentified peaks were shifted towards higher 2 theta position, which indicates decreased spacing between the planes in the atomic lattice thus change into more dense structure.
Figure 9: GID pattern of silicon surface after Al2O3 deposition by VPS for 2 samples: one after 40 passages with a 1 break between the consecutive passages and cooling of the substrate and the other after 20 passages with higher energy plasma (900[A] instead of 750[A] ).
69
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 1.4. Topography
The 2D information gained from SEM-EDX maps was complemented by profilometry, done in two perpendicular directions: profile A-A and B-B (see Figure 4.10).
Figure 4.10: Design of sample investigated by profilometry.
Profile A-A should allow estimation of height of the Al2O3 deposit by measurement of the difference between the initial level of silicon surface covered during spraying by a holder and the average level of Al2O3 islands. In fact, samples after 1 and 5 passages of Al2O3 (see Figure 4.11A,B) revealed positive average height of deposited Al2O3. However, some valleys in Si wafer, previously observed by SEM were also present. Surprising profiles were obtained for samples after multiple passages (see Figure 4.11): instead of increased thickness, substrate removal took place, which brought about crater formation. Craters depth varied significantly with the changes in spraying parameters. It seems that increasing number of spraying passages and decreasing temperature of the substrate favoured erosion effect. However such conclusion cannot be certain. The VPS process depends on too many variable and incontrollable parameters which results in different coating thickness in each spraying even though the controllable parameters and number of spraying passages remain the same. Thus, due to erosion effects, craters depth will also vary in each deposition trial.
70
71
Figure 4.11: Topography of VPS Al 2O3 on silicon wafer measured in profile A-A (see Figure 4.10).
Profile B-B should allow estimation of residual stresses caused by spraying, on the basis of Clyne formula (see Chapter 3: Topography and bending curvature by profilometry). Unfortunately calculation of precise values was impossible because the mathematical model required height and Youngs modulus of the coating, which could not be measured in the case of discontinuity of the Al2O3 deposits. However, according to Clyne model residual stress is proportional to curvature, and thus comparison between B-B profiles obtained for the coatings deposited at different parameters gives already an idea about the induced stress (see Figure 4.12). The biggest compressive residual stress within Al2O3 occurred after just one deposition 72
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 passage. Stress induced in samples after multiple passages was similar. The height from minimum to maximum on the profile B-B indicate height from the uncovered Si region to the top of Al2O3 island (see Figure 4.4 and 4.12). Thus a conclusion can be drawn that 20 passages by higher energy plasma and 40 passages deposition result in similar thickness of deposit. The effect of lower residual stress by deposition in multiple passages might be explained as stronger relaxation of stress due to material removal, visible in profile A-A, than stress generation due to next deposition passages.
Figure 4.12: Curvatures measured on VPS Al2O3 on silicon wafer in deposition: A) 1 passage B) 40 passages C) 20passages.
profile B-B as a result of
73
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 1.5. Mechanism of crater formation
Two possible failure mechanisms of the VPS Al2O 3 and silicon wafer are envisaged: i) erosion due to impact of alumina particles, ii) corrosion due to physical or chemical process at the alumina - silicon interface, which might involve melting/evaporation of Si under vacuum/plasma conditions and chemical reaction between the sprayed particles and the substrate. 1.5.1. Erosion There are strong arguments for erosion mechanism of crater formation. First of all single crystal of silicon is very brittle; its fracture toughness is about 0.91 [MPam0.5]. And, as was observed (see Figure 4.3BC), after of just one spraying passage some defects appeared on the silicon surface. Most of particles were believed to be molten but some which were not might induce defects especially taken into account the fact that hardness of alumina particles (about 1175 [Kg/mm2]) [44] is much higher than hardness of SiO2 (about 600 [Kg/mm2]) [44], which is commonly used in sandblasting. Moreover, the impact energy of molten particles on the substrate surface, is partially used for flattening of splats, partially is dissipated as heat and partially for stress generation in the silicon substrate. According to compressive model applied by Armster [45] the hummer pressure (pc1v p, where c1 is sound velocity in liquid, vp the particle velocity at impact and p the density of the impacting liquid) of molten particles is about 7 [GPa], whereas compressive strength of silicon is about 120 [MPa] [46] means that failure due to impact of molten particles is possible. It was also checked in microscale at the cross-sectioned sample whether any cracks were present underneath the adhered particles. Actually, no cracks were detected. However, next passages might cause propagation of cracks originating from the observed defects, bringing about material removal and crater formation. It seems that erosion mechanism was more complicated, because spraying in the same time caused also covering great part of silicon surface with strongly resistant to erosion alumina. Thus in result of deposition some Al2O3 particles would erode the surface and some would be retained on it. Erosive process was favoured in the case of deposition in multiple passages (see Figure 4.11), what might be explained by Griffith's theory [47]. According to it crack propagation in brittle material occurs after overcoming surface energy barrier which in the case of multiple spraying passages is more probable, because some already existing defects might be enlarged as well as 74
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 new defects might be formed. Moreover, failure in single crystal can hardly be stopped because dislocation motion doesnt meet many barriers. Therefore crater formation would be more favourable than deposition. 1.5.2. Corrosion It can be discussed whether thermodynamics permits any chemical/physical processes at the alumina/silicon interface in the vacuum/plasma conditions, e.g.: reduction of Al2O3 to lower oxides, chemical reaction between Al2O3 and Si (possible only in a double oxides environment), evaporation/melting of Si.
a) Reduction of Al2O3 Reduction of Al2O3 is eased and possible at 4000 [K] in either non-reducing or reducing plasma environment [43]. Reduction to volatile aluminium oxides or metallic aluminium may explain losses of feedstock material while VPS process. In this case environment was reducing, due to addition of H2 to argon plasma. According to [43] in this condition Al2O3 is reduced to Al2O: Al2O3 Al2O+2O Al2O is unstable above 4300 [K] (see Figure 4.13) and decomposes to metallic aluminium: Al2O 2Al+O Thus conclusion that while VPS process even very stable alumina may be active chemically.
75
Figure 4.13: Free energy of formation per atom of oxygen vs temperature for various compounds [43].
b) Chemical reaction between Al2O3 and Si Reaction between Al2O3 and Si requires to form a double oxides environment. Standard free enthalpy was calculated using data from thermodynamic tables in 298 [K] and in the highest tabulated temperature 2000 [K]. (see Table 4.2). Standard free enthalpy is negative and increases with increasing temperature for all listed reactions. Thus reaction in the each case is possible but its probability decreases with increasing temperature. Assuming that alumina was melted (TmAl2O3 = 2303[K]) temperature at the interface is higher than 2000 [K], thus standard free enthalpy 76
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 while deposition is higher than calculated value. Moreover vacuum in the chamber (decreased oxygen pressure) decreased probability of the reaction. XRD analysis which has not indicated occurrence of any listed in Table 4.2 compounds confirmed that reaction between Al2O3 and Si in this conditions is improbable. Product Reaction
o r G 298K o r G 2000K
[kcalmol1
[kcalmol1
Al2O3SiO2 andaluisite Al2O3SiO2 sillimanite Al2O3SiO2 kyanite Al2O32SiO2 aluminium disilicate 3Al2O 32SiO2 mullite
Al2O3+Si+O 2Al2O3SiO 2
-206.574
-129.803
Al2O3+Si+O2 Al2O3SiO2
-206.075
-129.945
Al2O3+Si+O2 Al2O3SiO2
-206.444
-126.372
Al2O3+2Si+2O2 Al2O32SiO2
-341.682
-171.06
3Al2O3+2Si+2O23Al2O32SiO2
-396.023
-257.713
Table 4.2: Chemical equilibrium constants calculated for reaction of Al2O3 and Si.
c) Evaporation/melting of Si Assuming that in contact with molten alumina the substrate temperature locally increased, both physical processes i.e. melting and boiling of Si are possible (see Table 4.3) and can account for the phenomenon of considerable material removal. Process Melting: Si(s)Si(liq) Boiling: Si(liq)Si(g) Boiling: Si(liq)Si2(g) Boiling: Si(liq)Si3(g) Temperature [K] 1685 2333 2253 1935
Table 4.3:Phase transformation temperatures for Si.
77
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2. Al2O3 on metallic substrate Alumina on aluminium alloy substrate was successfully deposited by the VPS process. The coating was smooth and homogenous in macro scale (see Figure 4.13). On the other hand, for steel substrates the result was not satisfactory: the coating was optically rough and non-homogenous, moreover it exfoliated just after spraying. Therefore further work was done with the coating sprayed on aluminium alloy substrate only.
Al2O3 coating on polished steel (St37-2)
Al2O3 coating on polished Al alloy (AlMgSi0.5)
Figure 4.13: VPS Al2O3 coating on different metal substrates.
2.1.
SEM-EDX analysis
According to the EDX analysis, thickness of the deposited coating was about 100 [m]. Only two regions were distinguished: one composed of aluminium and oxygen (orange in Figure 4.14), which indicated Al2O3 and the other composed mostly of Al (green on Figure 4.14) which indicated aluminium substrate. BSE images of coatings cross-section revealed occurrence of two phases within the aluminium oxide coating, which according to EDX analysis in points: 1 is composed of aluminium and oxygen, and in 2 is composed of aluminium oxygen and sodium (see Figure 4.15). However, occurrence of sodium was not detected on the EDX map covering a larger area of cross-section (see Figure 4.14). The EDX and XRD analyses from the top surface of the coating did not show any sodium containing phase, although diaoyudaoite (NaAl11O17) was present in the starting powder. Thus two conclusions can be drawn: i) amount of sodium within the coating is very small below resolution of analysis in larger volume, ii) sodium is a component of an amorphous phase. 78
Figure 4.14: EDX map on the cross-section of Al2O3 coating sprayed on aluminium alloy.
Coatings microstructure (see Figure 4.16) was typical for the thermal spray processes i.e. it contained splats composed of different phases, voids and inhomogeneities. Some cracks occurred within and between splats, which was due to stress relaxation in brittle ceramic material. In microscale, the mechanical anchoring effect cannot be neglected (see Figure 4.16B), because of two reasons: i) substrate was polished to Ra=1 [m], ii) plastic deformation might occur as a result of VPS process and induce higher roughness at the interface. However, in macroscale the assumption of smooth interface can be done, since the ratio of coating thickness (~100 [m]) to the interfacial roughness (~few [m]) is high.
79
Figure 4.15: BSE of cross-section of Al 2O3 coating sprayed on the aluminium alloy with EDX analysis in points: 1 and 2.
80
Figure 16: Microstructure of the Al2O3 coating sprayed on the aluminium alloy: A) top view, B) crosssection.
81
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2.2. XRD analysis
The analysis of powder used in VPS has been presented on page 70. Conventional X-ray diffraction analysis of Al2O3 coating deposited on aluminium alloy (see Figure 4.17) revealed: i) rhombohedral structure R-3c, i.e. Al2O3 or corundum - the same as that in the initial powder, ii) cubic (Fd3m) -Al2O3, which is favoured in lower temperature iii) cubic close packed (Fm-3m) aluminium, which is a weak signal from substrate. Lifted baseline between 20 and 40 two theta position indicated amorphous phase within the coating. Aluminium substrate favoured deposition of -Al2O3 while -Al2O3 was the major phase on the silicon substrate. This effect may be explained basing on [48], where Al2O3 was solidified form vapour phase at different cooling rates, than structure was investigated: -Al2O3, stable at lower temperature, was crystallized into fine crystalline structure at higher cooling rates, on the contrary -Al2O, stable at higher temperature crystallized into larger crystals at lower cooling rates. Both substrates: aluminium alloy and silicon wafer, were cooled during deposition. Thermal conductivity of aluminium is bigger than that of silicon (see Chapter 3), which means faster cooling of coating sprayed on aluminium alloy. Heat exchange between silicon wafer and the cooling system placed underneath was lower and crystallization of -Al2O was favoured.
Figure 4.17: Diffraction pattern obtained for Al 2O3 sprayed on aluminium alloy (AlMgSi0.5).
82
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 2.3. Topography
Profilometry allowed evaluation of residual stress within the coating using models developed by Clyne (see Chapter 3: Topography and bending curvature by profilometry). The result obtained by Stony is approximately correct only when the ratio of the thickness of the coating to that of the substrate is less than about 5%, which is not valid in this case. The values measured before VPS were subtracted from those measured after VPS The resulting profile was linear least square fitted to a bow (see Figure 4.18). Thus curvature was evaluated. Material parameters used in calculation are tabulated in Table 3.3. Substrate and coating thicknesses were 3000 [m] and 100[ m], respectively. Residual stresses were compressive. Evaluation done by Clyne model gave 209 [MPa], which is relatively low in comparison with common range measured for VPS Al 2O3: 200-600 [MPa]. It is important to emphasize that Clyne model assumes that the stresses are the same in all directions within the plane of the coating. In the present case variations in stress level with depth were neglected.
Figure 4.18: Curvature obtained by profilometry before and after VPS.
2.4.
Interfacial indentation
Sound interface between the alumina coating and aluminium alloy substrate should allow reliable measurement of adhesion using the interfacial indentation 83
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 method (See Chapter 3: Interfacial indentation). However, this test is designed to evaluate adhesion of a brittle film to a brittle substrate and turned out unsuitable for the investigated system. Due to the difference in plasticity between the hard coating and the soft substrate, the indenter slipped upon loading toward the aluminium alloy and caused its plastic deformation instead of the expected loading and crack propagation at the interface. 2.5. Rockwell indentation
Rockwell indentation allowed evaluation of the adhesion between hard alumina coating and ductile aluminium alloy substrate. The results were calculated using the model developed by Drory (see Chapter 3: Rockwell Indentation). Material parameters used in calculation are listed in Table 3.3. Substrate and coating thicknesses were 3000 [m] and 100[m], respectively. Residual stress was calculated by the curvature method. Values of the delamination radius, D/d, were
measured by profilometry. The film thickness was measured in the scanning electron microscope. The displacements were obtained by linear extrapolation, as required, the
results for function, Fr, in [2], which arguments for the aluminum alloy substrate were y/Es = 0.003 and N = 0.17. Results (see Table 4.4) indicate high interfacial toughness. Adhesion of the Al2O3 coating to the polished aluminium alloy substrate is high. D d Ratio of delamination, D/d 2.26 2.33 KIC [MPa m0.5] 6.67 5.42
Sample Al2O3/Al alloy 1 Al2O3/Al alloy 2
[mm] [mm] 3.42 4.06 1.51 1.74
Table 4.4: Results of Rockwell indentation.
3.
Al 2O3 on sapphire 3.1. SEM-EDX analysis
First trial of deposition gave promising results. Some of alumina particles adhered to the surface (see Figure 4.19B), however did not form a continuous coating. The shape of splats near the zone covered by holder (see Figure 4.20A) 84
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 indicated that splashing occurred during deposition (see Figure 4.20B), which means that transition temperature of the sapphire substrate was not exceeded. A different thermal condition of the substrate may solve the problem of splats shape and lead to a continuous coating. Sapphire is one of the most tough and hard material and these properties explain two important observations: defects were not observed on the surface of sapphire substrate as a result of impingment with aluminium oxide particles. quenching stress was relaxed through cracking but as opposed to alumina-silicon system, in the deposited islands and not in the substrate. (see Figure 4.19B)
Figure 4.19: Topography of the sapphire surface sprayed with alumina: A) in the middle of the sample B) zoom on evidence of cracking.
85
Figure 4.20: Topography of the sapphire surface sprayed with alumina: A) near the zone covered by holder B) zoom on splashed splats.
4.
NiCr(80-20) on metal substrate The coating was successfully deposited but its adhesion to the substrate was
bad. It seems that high thermal conductivity of Ni-Cr caused fast solidification of deposited particles and high ductility of Ni-Cr facilitated anchoring of the splats and resulted in strong cohesive forces. Good adhesion to the substrate was, however, not possible because of a too high spraying temperature (~480[ C]), by which the substrate was too close to its melting point (660[ C]) and yielded thermally. Thus it seems that further works on this system require lower temperature of VPS process.
86
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 NiCr(80-20) on steel (St37-2): the deposition seemed to be successful. However, after cutting and mechanical polishing, a thin band of material was removed from, as appeared brittle, interface. Thus further investigation including interfacial indentation was useless. 5. NiCr(80-20) on sapphire Coating was formed but it did not adhere to the substrate. It seems that high thermal conductivity of Ni-Cr caused fast solidification of the deposited particles and high ductility of Ni-Cr enabled anchoring of the splats, which resulted in strong cohesive forces. Adhesion to the sapphire substrate was not achieved probably because of big difference between the elastic properties of sapphire and Ni-Cr and difference in coefficients of thermal expansion, which led to high cooling stresses.
87
Chapter 5
SUMMARY
The investigations carried out in this work were focused on using the VPS technique to develop a series of coating/substrate systems for fundamental studies of adhesion by interfacial indentation method and the results can be summarized as follows: 1. VPS aluminium oxide on silicon (001) Spraying of a continuous coating was not feasible, mainly due to mismatch of mechanical parameters, especially elastic modulus. Both materials are rigid and even small mismatch of elastic properties in addition to stresses generated during rapid solidification do not allow deposition of continuous film on smooth surface and result merely in the formation of aluminium oxide islands. Numerous craters were observed on substrate surface after deposition of Al2O3 in multiple passages. As revealed by SEM analysis, defects were present in silicon already after one spraying passage. Next deposition passages might cause propagation of the earlier initiated cracks and consequently silicon spalling. On the other hand silicon losses might be related to melting and evaporation. The desired simple coating/substrate system for adhesion studies by interfacial indentation method was not achieved. Both EDX and XRD analysis indicated the occurrence of some unidentified phases. It seems that the vacuum/plasma conditions used for the deposition of alumina on silicon substrate favoured some physical and chemical processes, which are not sufficiently known. 2. VPS aluminium oxide on aluminium alloy (AlMgSi0.5) Successful spraying of thick (~100 [m]) coating on flat (Ra=1[m]) surface was achieved. In microscale mechanical anchoring effect cannot been neglected.
88
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 Evaluation done by curvature method and Rockwell indentation revealed good mechanical properties of the coating: low residual stresses and high adhesion. Shortcomings for the fundamental studies of adhesion are the following: i) inhomogeneous structure of the coating, i.e. presence of both and alumina, ii) occurrence of voids and cracks within the coating and at the interface with the substrate. 3. VPS aluminium oxide on sapphire First deposition trial gave promising results: alumina particles adhered to the surface, although, as indicated by splashed single splats, the deposition parameters were not optimum. In further work, thermal treatment should be modified. Substrate preheating slightly over the transition temperature should allow deposition of the desired
round-shaped splats , which lead to a continuous coating. 4. VPS aluminium oxide on steel The results were not satisfactory. Deposition parameters allowed obtaining a continuous coating, which however did not show good adhesion to the flat (Ra=1m) steel substrate. This was probably due to mismatch of the elastic properties and resulting residual stresses. 5. VPS NiCr on steel Successful spraying of thick (~100 [m]) coating on flat (Ra=1 [m]) surface was achieved. This system seems to be good enough for the adhesion studies using the interfacial indentation method. In the past, measurements of interfacial toughness were made for this system but with a rough interface. It would be interesting to compare values obtained for the rough and flat interface. It will be necessary, however, to develop another method of sample preparation, since parts of brittle interface were removed during mechanical polishing. 6. VPS NiCr on aluminium alloy (AlMgSi0.5) Deposition did not give good results: substrate temperature, which was appropriate for the deposition of a continuous coating, was too close to the melting temperature of the substrate and caused its deformation.
89
Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 7. The behaviour of VPS NiCr coating on sapphire was similar to VPS
alumina on steel: the coating was formed but mismatch of elastic properties did not allow its good adhesion to the flat substrate.
90
Literature
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Vacuum Plasma Sprayed (VPS) Coating Substrate System for Fundamental Study of Adhesion 2010 [27] M. Vardelle, A. Vardelle, A.C. Leger, P. Fauchais and D. Gobin, J.Thermal Spray Technol., 4, 1995, p. 50 [28] T.H. Turner and N.F. Budgen, Metal Spraying, Charles Griffin, London, p. 1926 [29] M. Fukumoto, S. Katoh, I. Okane, Proceedings of the Integrated Thermal Spray Conference, Kobe, Japan, May 1995, Japan High Temperature Society, 1995, p. 353 [30] X. Jiang, S. Sampath and J. Matejicek, Mater. Sci. Eng,. A 272, 1999, p. 189 [31] M. Fukumoto, Y. Huang and M. Ohwatari, Thermal Spray, Meeting the Challenge of the 21st century, 1998, p. 401 [32] S. Sampath and X. Jiang, Materials Science and Engineering, A304306, 2001 pp. 144150 [33] T. Troczyski, Thick Film lecture given in the AGH, 2009 [34] Herbert Herman, Christopher C. Berndt and Hougong Wang In: John B. Wachtman and Richard A. Haber (Ed.), Ceramic Films and Coatings, Noyes Publications, 1993, pp. 139-143 [35] J. W. Hutchinson and A. G. Evans, Acta mater., 48, 2000, pp. 125-135 [36] J. Michler, X. Maeder and C. Niederberger, Materials Characterization in the Scanning Electron Microscope, Gladent training course, 2009 [37] http://sergey.gmca.aps.anl.gov/gid_sl.html, 05-2010 [38] G.G. Stoney, Proc. Roy. Soc., A82, 1909, pp.172-175 [39] T. W. Clyne in: PJ Withers (Ed.), Encyclopaedia of Materials: Science and Technology: Elasticity and Residual Stresses, Elsevier, 2001 [40] U. Zroll in: A. A. Tracton, Coatings Technology Handbook: Adhesion Testing, 2005, pp. 6.7-8 [41] D. Chicot, P. Dmarcaux, and J. Lesage, Thin Solid Fihns, 283, 1996, pp. 151157 [42] G. Marot, Ph. Dmarcaux, J. Lesage, M. Hadad, St. Siegmann and M.H. Staia, Surface & Coatings Technology, 202, 2008, pp. 44114416 [43] R.M. Young, Plasma Chemistry & Plasma Processing, 5, 1985 [44] http://www.accuratus.com/alumox.html, 05-2010 [45] S.Q. Armster, J.-P. Delplanque, M. Rein, and E.J. Lavernia, Int. Mater. Rev., 7(6), 2002, pp. 265-301 [46] www.matweb.com, 05-2010 [47] A.A. Griffith, Philosophical Transactions of the Royal Society of London, A 221, 1921, pp. 163198 [48] Lyubochho, Journal of Engineering Phyiscs & Thermophysics, 73(3), 2000, pp.580-584
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Vacuum Plasma Sprayed (VPS) Coating - Substrate System For Fundamental Study of Adhesion

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AGH UNIVERSITY OF SCIENCE AND TECHNOLOGY IN CRACOW FACULTY OF MATERIAL SCIENCE AND CERAMIC

MOTIVATION STATE OF THE ART

Table 2.1: Selected adhesion measurement techniques [2] - cont.

Simple chemistry interface without scale roughness

TS techniques Several techniques of thermal spray have been developed. Their

Summary The presented state-of-the-art allows better understanding of the possibilities

MATERIALS EXPERIMENTAL PROCEDURE

Table 3.1: Coating-substrate systems selected for VPS experiments.

Si Tm Tb gcm-3 C C 2.33 1414 3265

Al2O3 3.95-4.1 2072 2977

kJmol-1 kJmol-1 kJmol-1

Vickers: 1256 4-3.5 (25-600[ C]) 5.6-7.0 (100300[ C])

Table 3.2: Comparison of selected properties of Al 2O3 and Si.

VPS alumina on aluminium alloy (AlMgSi0.5)

AlMgSi0.5 Tm Tb gcm-3 C C 2.7 615-654 2518.85*

Al2O3 3.95-4.1 2072 2977

-rhombohedral (<1000 [ C]), -cubic (>1000 [ C])

kJmol-1 kJmol-1 kJmol-1

Table 3.3: Comparison of selected properties of Al 2O3 and Al alloy (AlMg0.5Si).

kJmol-1 kJmol-1 kJmol-1

Table 3.4: Comparison of selected properties of Al 2O3 and steel (st37-2).

VPS alumina on sapphire

Formula Density Melting point Boiling point

Al2O3 3.98 2030 2977

Al2O3 3.95-4.1 2072 2977

system, rhomboidal class 3m

Enthalpy of formation Heat of fusion Heat of vaporization

kJmol-1 kJmol-1 kJmol-1

345 2.38 (direction

[0001]) 4.54 (direction[1120]) Knoop: 1835 parallel to C-

axis, 2243 perpendicular to C-axis 23.1 parallel to

optical axis, 25.2 k WK m

perpendicular to optical axis (73[ C])

4-3.5 (25-600[ C])

6.66 parallel to optical axis, 5

5.6-7.0 (100300[ C]) 35

AlMgSi0.5 Tm Tb gcm-3 C C 2.7 615-654 2518.85*

Ni-Cr 80-20 7.75-8.65 1400-1700 >2000

kJmol-1 kJmol-1 kJmol-1

kJmol-1 kJmol-1 kJmol-1

GPa MPam0.5 kgfmm-2

190-210* 50** 213-800*

220 65-150 1018

kJmol-1 kJmol-1 kJmol-1

axis, 2243 perpendicular to C-axis 23.1 parallel to optical axis,

8-17 (25[ C])

Coef. of thermal expansion

5 perpendicular to optical axis (100[ C])

9-16 (25[ C])

Table.3. 8. Comparison of selected properties of NiCr 80-20 and Al alloy (AlMg0.5Si).

10 break between pass.

Table 9: The main spraying parameters.

Figure 3.2: Scheme of image creation in SEM [36].

Figure 3.3: Interaction volume for different signal emitted in SEM.

Crystal structure by XRD analysis

Figure 3.5: Scheme of BraggBrentano geometry [7].

Topography and bending curvature by profilometry

E c ' hs E s ' + E c ' ( hc ) hc E c '+ hs E s '

Adhesion between the coating and substrate

Figure 3.8: Scheme of interfacial indentation test.[42.]

Figure 3.9: Schematic of the brale indentation test [2].

SEM In-situ scratch test