Physical Deposition Methods for Films and Coatings E-Book

Lech Pawlowski

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 803

Veröffentlichungsjahr: 2025

Beschreibung

Comprehensive resource on the subject of deposition techniques for films and coatings and their characterization

Physical Deposition Methods for Films and Coatings presents a pedagogical compilation of current knowledge of dry deposition.

Written by a renowned and awarded academic with more than 40 years of experience in the field, Physical Deposition Methods for Films and Coatings covers topics including:

• The process of making a deposit that appears on the surface, growth of deposits, their post treatments, and characterization methods
• Different physical and chemical deposition techniques including atomistic, chemical vapor, and various thermal spraying methods
• Properties of deposits depending on the material and deposition technique
• Substrate preparation, coating microstructure, and morphology and stability of thin films
• Examples of applications of thin films in optical devices, environmental applications, telecommunications devices, and energy storage devices

Physical Deposition Methods for Films and Coatings is an essential reference on the subject for professionals and researchers in surface treatment and graduate students in related programs of study.

Leseprobe

Table of Contents

Cover

Table of Contents

Title Page

Copyright Page

Dedication Page

Preface

Abbreviations and Symbols

Acronyms

Symbols

Indices

Exponents

Greek Letters

Atomic Shells and Subshells

Introduction

Bibliography

1 Substrate Preparation

1.1 Introduction

1.2 Surfaces of Different Types of Substrates (Metals and Alloys, Ceramics, Polymers)

1.3 Cleaning of Surface

1.4 Patterning of Films and Coatings

1.5 Activation of Substrates Surface

References

2 Films and Coatings Deposition Techniques

2.1 Introduction

2.2 Atomistic Deposition Methods

2.3 Granular Methods of Coatings Deposition

2.4 Bulk Methods of Coatings Deposition

References

3 Nucleation, Growth, and Microstructure of Physical Deposits

3.1 Introduction

3.2 Atomistic Deposition Methods

3.3 Granular Deposits

3.4 Bulk Deposits

References

4 Methods of Films and Coatings Characterization

4.1 Introduction

4.2 Methods of Microstructure Characterization

4.3 Mechanical Properties of Films and Coatings

4.4 Physical Properties of Films and Coatings

4.5 Corrosion Resistance

4.6 Electric and Magnetic Properties of Films and Coatings

4.7 Optical Properties of Films and Coatings

4.8 Characterization of Biomaterials

References

5 Properties of Films and Coatings

5.1 Introduction

5.2 Mechanical Properties

5.3 Electric and Magnetic Properties

5.4 Thermophysical Properties

5.5 Corrosion Resistance

5.6 Optical Properties

5.7 Biomaterials

References

Index

End User License Agreement

List of Tables

Introduction

Table I.1 Physical deposits discussed in this work.

Chapter 1

Table 1.1 Standard free energy of formation of some oxides and nitrides

a

....

Table 1.2 Physicochemical and mechanical properties of some metals and allo...

Table 1.3

Surface energy

of some ceramic materials and glasses [4,14–16].

Table 1.4

Surface tension

of some liquids having temperature of

T

= 293 K....

Table 1.5 Elasticity modulus for some ceramics [4, 20].

Table 1.6 Some properties of frequently used polymers.

Table 1.7 Examples of chemical cleaning.

Table 1.8 Substrates materials etched by different low‐pressure plasmas....

Table 1.9 Industrial lasers used in surface cleaning [15, 45, 46].

Table 1.10 Optical data for selected metals and oxides at the wavelengths a...

Table 1.11 Examples of laser cleaning for different application.

Table 1.12 Wavelengths corresponding to particles having different energies...

Table 1.13 Different masks used in lithographic processes of film patternin...

Table 1.14 Examples of different substrates activated prior to atomistic fi...

Table 1.15 Examples of surface activation prior to atomistic film depositio...

Table 1.16 Principal grit‐blasting parameters.

Table 1.17 Examples of different substrates activated prior to granular coa...

Table 1.18 Typical parameters of surface activation using a water jet.

Chapter 2

Table 2.1 The constants enabling determination of vapor pressure by Eq. (2....

Table 2.2 Experimentally determined

sputtering yield

of some oxides submitt...

Table 2.3 Examples of compounds synthesized by thermal evaporation and sput...

Table 2.4 Most important effects of ions and neutral atoms bombardment at

I

...

Table 2.5 Typical processing parameters used in different pulsed laser depo...

Table 2.6 Main types of chemical reactions in thermal CVD [52, 55, 61–63]....

Table 2.7 Comparison of deposition temperatures of some oxide, nitrides, an...

Table 2.8 Typical parameters of plasma generated in

glow discharge

[17, 18,...

Table 2.9 Examples of films synthesized by thermal LCVD.

Table 2.10 Typical reactions in the photochemical

LCVD

process [64, 78].

Table 2.11 Examples of films synthesized in

MO CVD

processes.

Table 2.12 Description of

ALD

processes applied to obtain metal films.

Table 2.13 Methods of powders manufacturing from different kinds of materia...

Table 2.14 Discussed thermal spraying techniques using solid feedstock.

Table 2.15 Typical chemical composition of solution precursors used to spra...

Table 2.16 Typical chemical composition of aqueous suspensions used to ther...

Table 2.17 Metal, alloys, and composite coatings obtained by laser

cladding

Table 2.18 Alloying parameters of Al substrate with other metals using diff...

Table 2.19 Parameters of deposits obtained by the dispersion of the hard ph...

Table 2.20 Parameters of heat treatment in solid phase with different laser...

Table 2.21 Example of laser glazing treatment of thermally sprayed coatings...

Chapter 3

Table 3.1 Atomistic processes discussed in the chapter and variables determ...

Table 3.2 Typical variables determining the microstructure for frequently u...

Table 3.3 Estimation of critical velocities of some metals and alloys.

Table 3.4 Contact temperatures and solidification times for Ni sprayed onto...

Table 3.5 Crystal grain sizes measured in typical sprayed coatings.

Table 3.6 Heat fluxes generated at thermal spraying deposition and delivere...

Table 3.7 Variables determining the microstructure of bulk deposits.

Table 3.8 Experimental values of surface tension for some liquid metals....

Chapter 4

Table 4.1 Techniques used in characterization of films and coatings

a

.

Table 4.2 Synthesis of the techniques presented in Table 4.1 and discussed ...

Table 4.3 Tests enabling determination of mechanical properties of deposits...

Table 4.4 Examples of thin films thickness measurement techniques.

Table 4.5

Standard reduction potential

of some metals at room temperature a...

Table 4.6 The properties of electromagnetic waves and of associated photons...

Table 4.7 The ions concentrations in

SBF

and in human blood [186–188].

Table 4.8 The animals used in testing different types of medical devices in...

Chapter 5

Table 5.1 Atomistic techniques and parameters of carbon deposits having mic...

Table 5.2 Atomistic techniques and deposition parameters of nitrides films ...

Table 5.3 Atomistic techniques and parameters of carbide deposits whose mic...

Table 5.4 Thermal spraying techniques properties of powders and carbide dep...

Table 5.5 Powders and

APS

coatings properties of oxides whose microhardness...

Table 5.6 Powders and thermally sprayed metal and alloys coatings propertie...

Table 5.7 Powders and some properties of ceramic and composite coatings hav...

Table 5.8 Powders and some properties of alloys coatings obtained using dif...

Table 5.9 Adhesion determined by scratch test of TiN films obtained on stee...

Table 5.10 Examples of adhesion determined by scratch test for atomistic fi...

Table 5.11 Examples of adhesion determined by tensile test for typical gran...

Table 5.12 Modulus of elasticity of typical atomistic films.

Table 5.13 Mechanical properties of carbides containing coatings obtained b...

Table 5.14 Mechanical properties of oxides obtained by thermal spraying.

Table 5.15 Mechanical properties of metals and alloys obtained by thermal s...

Table 5.16 Elastic modulus of composites obtained by thermal spraying.

Table 5.17 Detailed description of some atomistic films applied against adh...

Table 5.18 Atomistic films of compounds against different types of wear.

Table 5.19 Examples of granular coatings applied against adhesive wear.

Table 5.20 Properties of some granular deposits tested against 2‐body and 3...

Table 5.21 Properties of granular coatings tested against erosion wear.

Table 5.22 Examples of granular coatings applied against fretting wear.

Table 5.23 Examples of bulk coatings applied against adhesive wear.

Table 5.24 Examples of bulk coatings applied against wear resulting from

th

...

Table 5.25 Examples of bulk coatings applied against wear resulting from er...

Table 5.26 Examples of bulk coatings applied against wear resulting from fr...

Table 5.27 Mean free path of electrons and different temperatures, resistiv...

Table 5.28 Resistivity of some air plasma sprayed metals [210].

Table 5.29 Examples of dielectric properties of some atomistic films

a

.

Table 5.30 Examples of dielectric properties of some granular coatings

a

.

Table 5.31 Magnetic properties of some atomistic deposits

a.

Table 5.32 Magnetic properties of some granular deposits

a.

Table 5.33 Examples of superconducting films obtained using atomistic metho...

Table 5.34 Examples of films tested for electrons' emission obtained using ...

Table 5.35 Examples of thermophysical properties of some atomistic deposits...

Table 5.36 Thermophysical properties of some thermally sprayed oxide coatin...

Table 5.37 Thermophysical properties of metal and alloys coatings thermally...

Table 5.38 Emissivity of some atomistic and granular films and coatings of ...

Table 5.39 Examples of atomistic films applied against aqueous corrosion te...

Table 5.40 Examples of thermal sprayed coating tested against aqueous corro...

Table 5.41 Examples of coatings obtained using powders feedstock using bulk...

Table 5.42 Examples of materials used as films or coatings against differen...

Table 5.43 Examples of atomistic deposits tested against hot corrosion.

Table 5.44 Examples of thermally sprayed coatings applied against hot corro...

Table 5.45 Examples of bulk deposits tested against hot corrosion.

Table 5.46 Axes of the sphere of color space

L

*

a

*

b

*

[368, 369]....

Table 5.47 Colors and hardness of thin films synthesized using

PVD

[370].

Table 5.48 Examples of functional optical deposits obtained by atomistic te...

Table 5.49 Examples of atomistic films of biomaterials.

Table 5.50 Examples of coatings of biomaterials obtained by thermal sprayin...

List of Illustrations

Introduction

Fig. I.1 Diagram of a typical deposition process.

Fig. I.3 Hydraulic cylinders in coal mines.

Fig. I.4 Cycle of development film or coating.

Chapter 1

Figure 1.1 Forces acting on atoms or molecules on the surface and in the bul...

Figure 1.2 Forces acting on the surface including a corner and a peak.

Figure 1.3 Five‐zones of metallic surface after mechanical or thermomechanic...

Figure 1.4 Mechanism of parabolic growth of oxide film.

Figure 1.5 Metallic bonding showing metal ions and sea of valence electrons....

Figure 1.6 Behavior of liquid droplet on a solid surface: (a) spreading corr...

Figure 1.7 Possible molecular structure of polymers: (a) linear; (b) branche...

Figure 1.8 Typical strain–stress behavior of: (a)

thermosets

; (b) partly cry...

Figure 1.9 Types of plasmas generated by electrical discharges applied for c...

Figure 1.10 Reactor with capacitive coupling having cylindrical electrodes (

Figure 1.11 Sketch of laser ablation.

Figure 1.12 Illustration of empirical Moore's law valid in semiconductor ind...

Figure 1.13 Sketch of patterning of a film with photolithography: (a) applic...

Figure 1.14 Simplified geometry of illumination at lithography.

Figure 1.15 Possible geometries of

PM

and

PR

at following lithographic print...

Figure 1.16 Optical micrographs of laser‐treated surface of aluminum alloy (...

Chapter 2

Figure 2.1 Sketch of vacuum evaporation system by electron bombardment (

EBPV

...

Figure 2.2 Thermionic electrons emission.

Figure 2.3

EB PVD

laboratory installation used in the research center ARCI i...

Figure 2.4 Sketch of

RE

and

ARE

installation with the source heated by

e‐bea

...

Figure 2.5 Sketch of a in a

dc‐diode‐sputtering system

in which ...

Figure 2.6 An elastic collision between a moving projectile and immobile tar...

Figure 2.7 Some effects of an impact of incident ion on target surface.

Figure 2.8 The target of hafnium having diameter of 50 mm used in the labora...

Figure 2.9 The deposition of films by evaporation using

e‐beam

assiste...

Figure 2.10 Sketch of typical pulsed laser deposition (

PLD

) processes.

Figure 2.11 Deposition process using

PLD

installation of the IRCER laborator...

Figure 2.12 Schematic presentation of CVD processes.

Figure 2.13 Sketch of CVD reactors delivered with: (a) liquid precursor; (b)...

Figure 2.14 Industrial thermal CVD installation used for deposition of titan...

Figure 2.15 The

boundary layer

of a gas: (a) geometry in the neighborhood of...

Figure 2.16 Installation PECVD used to obtain diamond‐like carbon films and ...

Figure 2.17 Temperatures of electrons

T

e

and of heavy particles

T

h

in a plas...

Figure 2.18 Different

LCVD

processes: (a) thermal and (b) photochemical.

Figure 2.19 Energy of photons emitted by different industrial laser.

Figure 2.20 SEM micrograph (secondary electrons) of commercial fused and cru...

Figure 2.21 SEM micrograph (secondary electrons) of Cr

2

O

3

+ 5 wt. % SiO

2

pow...

Figure 2.22 SEM micrograph (secondary electrons) of cross‐section of

YBCO

po...

Figure 2.23 SEM micrograph (secondary electrons) of CN

x

powder obtained by r...

Figure 2.24 SEM micrograph (secondary electrons) of the cross‐section of Al

2

Figure 2.25 Commercial powder feeder.

Figure 2.26 The geometry of the pipeline connecting powder feeder with the s...

Figure 2.27 Calculation of injection velocity of HA particles of different s...

Figure 2.28 Sketch of flame spraying of powder (

FS

– powder): 1, working gas...

Figure 2.29 View of a torch fed with powder attached to a robot.

Figure 2.30 Sketch of arc spraying technique: 1, flow of atomizing gas; 2, t...

Figure 2.31 Section of a typical plasma torch: 1, anode – nozzle; 2, cathode...

Figure 2.32 A plasma torch installed on the robot [113]: 1, torch; 2, compre...

Figure 2.33 Calculated profiles of temperatures (in K) and velocities (in m/...

Figure 2.34 Heat transfer phenomena occurring at flight of a particle of low...

Figure 2.35 Sketch of HVOF torch: 1, oxygen inlet; 2, combustion gas inlet; ...

Figure 2.36 Sketch of detonation gun: 1, powder injection; 2, ignition of co...

Figure 2.37 Detonation spray gun used in the institute ARCI in Hyderabad (In...

Figure 2.38 Sketch of cold gas spray method.

Figure 2.39 The nozzle of low‐pressure CGSM installed in laboratory of Facul...

Figure 2.40 Sketch of vacuum plasma spray installation: 1, working gases inl...

Figure 2.41 Small laboratory vacuum plasma spray installation used to spray ...

Figure 2.42 Modern laboratory installation

PS PVD

used in FZ Jülich (Germany...

Figure 2.43 Phases content in an initially solid particle at plasma spray ph...

Figure 2.44 The stabilized and not‐stabilized suspensions including

YSZ

soli...

Figure 2.45 Liquid feedstock pneumatic delivery: (a) sketch of a feeder; (b)...

Figure 2.46 Atomization of zirconia suspension injected radially using pneum...

Figure 2.47 Sketch of spray pyrolysis process.

Figure 2.48 Influence of substrate temperature on the processes occurring at...

Figure 2.49 Phenomena occurring at interaction of suspension with plasma jet...

Figure 2.50 Phenomena occurring at interaction of solution precursor with pl...

Figure 2.51 The transformation inside a droplet of solution precursor of zir...

Figure 2.52 Dilution in coatings obtained using melting: (a), weight of molt...

Figure 2.53 Sketch of

PTA

processes: 1, plasma gas; 2, injection of powder t...

Figure 2.54 Coating deposition by PTA using a torch produced by

Saint Gobain

...

Figure 2.55 The laser‐assisted coatings processes: (a)

cladding

, (b)

alloyin

...

Figure 2.56 Sketch of the one‐step laser deposition,

1SLD

process.

Figure 2.57 Sketch of rapid prototyping.

Figure 2.58 Laboratory installation of rapid prototyping: (a) preparation of...

Figure 2.59 Sketch of the two‐step laser deposition,

2SLD

process.

Figure 2.60 Sketch of a laser engraver: 1, engraving unit; 2, anilox roll; 3...

Chapter 3

Figure 3.1 Types of films growth: (a)

3D

; (b)

2D

; and (c) mixed being partly...

Figure 3.2 Some processes at the beginning of the condensation of a vapor on...

Figure 3.3 SEM micrograph of a ZrO

2

+ 7YSZ deposit obtained by

EB PVD

on the...

Figure 3.4 Structure zone models (

SZM

) for main atomistic

PVD

techniques: (a...

Figure 3.5 Arrhenius plot of the logarithm of growth rate vs. the reciprocal...

Figure 3.6 Generation of non‐destructive and destructive thermal stresses in...

Figure 3.7 Impact of spherical particle Cu particle on Cu substrate.

Figure 3.8

SEM

(secondary electrons) of splat formed using

HA

particles arc ...

Figure 3.9 The estimation of the minimal velocity at impact of liquid partic...

Figure 3.10 An example of interfacial instability inspired by a microscopic ...

Figure 3.11 Mechanism of

mechanical anchorage

of splats on the substrate irr...

Figure 3.12 TEM micrographs of image of the of TiO

2

coatings sprayed using

S

...

Figure 3.13 Optical microscope image of the polished cross–section of an Al

2

Figure 3.14 Optical microscope image of the polished cross‐section of a Cr

2

O

Figure 3.15 Optical microscope image of the polished cross‐section of the co...

Figure 3.16 Composite deposits reinforced with: (a) whiskers; (b) fibers; an...

Figure 3.17 SEM (secondary electrons) image of a fractured cross‐section of ...

Figure 3.18

SEM

(secondary electrons) image of suspension plasma sprayed

HA

...

Figure 3.19

SEM

(secondary electrons) image of

YSZ

coating sprayed using sus...

Figure 3.20 Forces acting on a small particle and moving it: (a) toward subs...

Figure 3.21 Formation of columns from small particles at the substrate's sur...

Figure 3.22

SEM

(secondary electron) image of the polished cross‐section of

Figure 3.23 SEM (secondary electrons) image of the TiO

2

coating's surface ob...

Figure 3.24 The convective movement of the liquid in the melt pool generated...

Figure 3.25 SEM (secondary electrons) image of the cross‐section of an Al + ...

Figure 3.26 The dendrites formed at solidification of metals or alloys: (a) ...

Figure 3.27 Optical microscope image of the polished cross‐section of the In...

Figure 3.28 XRD of

MMC

coating having composition Fe13Cr + 55 wt. % TiC obta...

Figure 3.29 SEM (secondary electron) image of the surface of atmospheric pla...

Chapter 4

Figure 4.1 The beams of species or waves used to excite the tested sample an...

Figure 4.2 The spectrum of X‐rays emitted by a sample bombarded by primary b...

Figure 4.3

EDX

mapping of graded

SPS

coating showing distribution of Si (rep...

Figure 4.4 The spectrum of the energy loss of electrons traversing a sample....

Figure 4.5

EMPA

analysis using

WDX

detector of a line across the

HA

coating ...

Figure 4.6 The peak corresponding to PO

4

3−

vibrations in the Raman spe...

Figure 4.7

XPS

spectra of Ti 2p energy bands corresponding to different stag...

Figure 4.8 Selected area diffraction pattern of one of the Al grains shown i...

Figure 4.9 The

EBSD

pattern of tetragonal ZrO

2

: (a) obtained originally; (b)...

Figure 4.10 SEM micrograph (

BSE

) and

EDS

analyses of a polished cross‐sectio...

Figure 4.11

TEM

image of the Al grains in the Al + SiC composite coating obt...

Figure 4.12

TEM

image showing typical morphology of

8YSZ

coating obtained by...

Figure 4.13 The stress–strain curves obtained by a static tension load tests...

Figure 4.14 Sketch of tensile adhesion test.

Figure 4.15 Principle of the scratch test.

Figure 4.16 Optical microscope view of a scratch in suspension plasma spraye...

Figure 4.17

Vickers test

of thick (a) and thin (b) deposits.

Figure 4.18 Sketch of indentation test showing loading and unloading and res...

Figure 4.19 Diagram of 3‐point (a) and 4‐point (b) bending tests.

Figure 4.20 The sketches of double‐cantilever beam (DCB), (a) and double tor...

Figure 4.21 Sketch of a bloc on cylinder tribometer to determine the coeffic...

Figure 4.22 Wear test using oscillating sphere.

Figure 4.23 Schematic of the tests: (a)

two‐body abrasion

, 1, load; 2 ...

Figure 4.24 Laser flash set‐up used to determine thermal diffusivity.

Figure 4.25 Contact angle between liquid droplet on solid surface.

Figure 4.26 Laboratory electrochemical or

polarization cell

.

Figure 4.27 Curve of anode potential vs. current density in a polarization c...

Figure 4.28 4‐point resistivity probe:

1

, deposit;

2

, substrate;

I

, current;...

Figure 4.29 Geometry of planar resistor deposited onto insulating substrate....

Figure 4.30 Schematic of planar capacitor: 1 – top electrode, 2 – bottom ele...

Figure 4.31

SEM

micrograph (

SE

) of a channel left by an electrical breakdown...

Figure 4.32 The magnetization of

ferromagnetic

or

ferrimagnetic

materials in...

Figure 4.33 The sketch of trajectories of polarized incident light reflected...

Chapter 5

Figure 5.1 Microhardness of carbonic films obtained by atomistic techniques....

Figure 5.2 Microhardness of nitride films obtained by atomistic techniques. ...

Figure 5.3 Microhardness of carbide films obtained by atomistic techniques. ...

Figure 5.4 Two types of composite thin films: (a)

nanocomposites

with nanocr...

Figure 5.5 Microhardness of carbide deposits obtained by thermal spray techn...

Figure 5.6 Microhardness of oxide coatings obtained by APS. The deposition p...

Figure 5.7 Microhardness of metals and alloys coatings obtained by thermal s...

Figure 5.8 Microhardness of ceramic coating and of composite coatings reinfo...

Figure 5.9 Microhardness of coatings of some alloys obtained using

PTA

and l...

Figure 5.10 Multilayers composites with small number (a) and great number (b...

Figure 5.11

Mixed composite

deposited on WC – Co substrate proposed by Fan

e

...

Figure 5.12 3‐body abrasion wear test made following ASTM G65‐00 norm for ai...

Figure 5.13 Effects of 2‐body abrasion on the surface on particulate composi...

Figure 5.14

3‐body abrasion

wear test of alloys and composites coating...

Figure 5.15 Part of a flexographic printing machine [194], 1, anilox roll; 2...

Figure 5.16 Planar resistors with: (a) L‐shape and (b) shape of meander.

Figure 5.17 The surface of air plasma sprayed Cr

2

O

3

coating polished after d...

Figure 5.18 SEM micrograph (secondary electrons) of the surface of suspensio...

Figure 5.19 Thermal conductivity of oxide coatings obtained by plasma sprayi...

Figure 5.20 Alumina sample with deposited planar resistor of NiO+ Fe

3

O

4

and ...

Figure 5.21 Thermal conductivity of Mo and of some Ni alloys coatings obtain...

Figure 5.22 Emissivity of Mo and of NiCr alloy coatings obtained by plasma s...

Figure 5.23 Emissivity of ceramic coatings obtained by plasma in function of...

Figure 5.24 Emissivity at

RT

at different wavelengths of coatings plasma spr...

Figure 5.25 Increase of mass of metal surface per unit area,

w

, in function ...

Figure 5.26 Kinetics of cyclic oxidation of a thermal barrier of the duplex ...

Figure 5.27 Reflection coefficient vs. light wavelength of an amorphous diam...

Figure 5.28 Hip prosthesis with a

femoral stem

coated by plasma spraying wit...

Figure 5.29 SEM (secondary electrons) images of the 3% copper‐doped hydroxya...

Figure 5.30 SEM images (secondary electrons) of bioglass film obtained by

SP

...

Guide

Cover Page

Table of Contents

Title Page

Copyright Page

Dedication Page

Preface

Abbreviations and Symbols

Introduction

Begin Reading

Index

WILEY END USER LICENSE AGREEMENT

Pages

iii

iv

v

xiii

xiv

xv

xvi

xvii

xviii

xix

xx

xxi

xxii

xxiii

xxv

xxvi

xxvii

xxviii

xxix

xxx

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

119

120

121

122

123

124

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

142

143

144

145

146

147

148

149

150

151

152

153

154

155

156

157

158

159

160

161

162

163

164

165

166

167

168

169

170

171

172

173

174

175

176

177

178

179

180

181

182

183

185

186

187

188

189

190

191

192

193

194

195

196

197

198

199

200

201

202

203

204

205

206

207

208

209

210

211

212

213

214

215

216

217

218

219

220

221

222

223

224

225

226

227

228

229

230

231

232

233

234

235

236

237

238

239

240

241

242

243

244

245

246

247

248

249

250

251

252

253

254

255

256

257

258

259

260

261

262

263

264

265

266

267

268

269

270

271

272

273

274

275

276

277

278

279

280

281

282

283

284

285

286

287

288

289

290

291

292

293

294

295

296

297

298

299

300

301

302

303

304

305

306

307

308

309

310

311

312

313

314

315

316

317

318

319

320

321

322

323

324

325

326

327

328

329

330

331

332

333

334

335

336

337

338

339

340

341

342

343

344

345

346

347

348

349

350

351

352

353

354

355

356

357

358

359

360

361

362

363

364

365

366

367

368

369

370

371

372

373

374

375

376

377

378

379

381

382

383

384

385

386

387

388

389

390

391

392

393

394

395

396

397

398

399

Physical Deposition Methods for Films and Coatings

Lech Pawłowski

Faculty of Science and TechnologyInstitute of Research for CeramicsUniversity of LimogesLimogesFrance

This edition first published 2025© 2025 John Wiley & Sons Ltd

All rights reserved, including rights for text and data mining and training of artificial intelligence technologies or similar technologies. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions.

The right of Lech Pawłowski to be identified as the author this work has been asserted in accordance with law.

Registered Office(s)John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USAJohn Wiley & Sons Ltd, New Era House, 8 Oldlands Way, Bognor Regis, West Sussex, PO22 9NQ, UK

For details of our global editorial offices, customer services, and more information about Wiley products visit us at www.wiley.com.

Wiley also publishes its books in a variety of electronic formats and by print‐on‐demand. Some content that appears in standard print versions of this book may not be available in other formats.

Trademarks: Wiley and the Wiley logo are trademarks or registered trademarks of John Wiley & Sons, Inc. and/or its affiliates in the United States and other countries and may not be used without written permission. All other trademarks are the property of their respective owners. John Wiley & Sons, Inc. is not associated with any product or vendor mentioned in this book.

Limit of Liability/Disclaimer of WarrantyWhile the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials or promotional statements for this work. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

Library of Congress Cataloging‐in‐Publication Data applied for

Hardback ISBN 9781119713067

Cover Design: WileyCover Image: SEM image of a cross‐section of Cr3C2 – NiCr coating obtained by APS method© Lech Pawłowski

This volume is dedicated to my wife Muryel and to our daughter Irene with all my gratitude for their support and patience.

Preface

Since the publication by Presse Polytechnique et Universitaire Romandes (PPUR) of the French edition of this book in 2003 under the title Dépôts Physiques, the techniques of physical methods of films and coatings deposition changed considerably. Many new countries started to develop and produce in this field, and the author hopes to reach these new readers. The economic growth of these methods has also resulted in new industrial applications of films and coatings. The new applications came from traditionally innovative fields such as microelectronics but also from the new domain grown rapidly in recent years such as biomaterials. Consequently, the content of the English edition covers these new fields and new applications.

Chapter 1 that describes the preparation of the substrates prior to films and coatings deposition. The chemical and physical properties of zones close to surfaces of substrates made of different types of materials were carefully described. The modern methods of cleaning and activation of surfaces using photons emitted by different types of industrial lasers were added to the methods using electric discharges. Also, methods describing the patterning of films and coating using different lithographic processes were described.

Some new atomistic films deposition techniques such as atomistic layer deposition (ALD) or plasma spray physical vapor deposition (PS PVD) were added to the second chapter. As the granular techniques using liquid feedstock, such as suspension plasma spraying (SPS) or solution precursor plasma spraying (SPPS), were intensively tested in recent years, they are also described in the present edition. An important activity, especially in research and development, concerning additive manufacturing being a part of bulk deposition methods was also considered in the chapter.

Chapter 3 includes the description of new knowledge concerning the simulation of atomistic layers’ growth. Similarly, the phenomena of coating growth at the use of cold‐gas spraying method (CGSM) and the splashing of micro‐ and nano‐sized particles during liquid feedstock thermal spraying resulting in possible generation of columnar microstructure are part of the new knowledge added to this chapter. Finally, the description of bulk coatings’ nucleation includes detailed description of the phenomena taking place at the deposition.

The methods of films and coating characterizations described in Chapter 4 include much more examples visualizing the usefulness of described methods. Some methods such as characterizing of the contact angle of a droplet on a solid surface or in vitro and in vivo testing of biomaterials were added.

Finally, Chapter 5 includes the description of properties of films and coatings obtained with new materials or new methods of deposition. Some new properties such as electron emission or results of biomaterials testing were also considered.

The author hopes that the readers from academia including students and professors as well as engineers and managers from industry will appreciate this edition of book in learning and keeping abreast with the development of films and coatings technologies.

June 2024

Lech PawłowskiProfessor EmeritusUniversity of LimogesFaculty of Science and TechnologyInstitute of Research for Ceramics

Introduction

A generic term “physical deposition methods of films and coatings” is often used but rarely defined in a rigorous way. In this work, this term is related to a deposition process, shown schematically in Fig. I.1.

This process is initiated by a source of the species forming the deposits (atoms, molecules, solid particles, etc.). These species are transported through a passive (vacuum or low pressure, inert gas, etc.) or active (plasma, reactive gas, etc.) medium to a substrate. The term “physical deposition” would relate to physical nature of generation of the constituent species from source. This mechanism of such generation can be:

evaporation of solid sources in thermal evaporation;

ejection of species by energetic ions in sputtering;

laser ablation in the

PLD

technique;

injection of reacting gaseous precursors in

CVD

techniques;

injection of solid (powder particles) or liquid (suspension, solution) feedstock in thermal spraying;

injection of powder particles in bulk methods.

In contrast, the chemical mechanism of generation of the species would be, for example, movement of ions toward an electrode being also a substrate in electrochemical processes. The passive environment does not modify species, unlike the active environment. For example, in a CVD process, a chemical reaction modifies initial chemical composition of the precursor gases. It should be noted that plasma in atomistic deposition processes is an active medium, because it can modify the chemical composition of the species (atoms, ions, molecules) constituting a deposit. This modification can be negligible in the granular‐ and bulk‐coating processes in which the species are much larger (solid particles having more than 1012 atoms [1]), and the interaction time with the medium is short (in the range of milliseconds in thermal spraying) enough to avoid any important modification. Consequently, in these methods, the plasma is rather a passive medium.

The physical deposits described in this book are classified according to the size of the constituent species (see Table I.1) as: (i) atomistic; (ii) granular; and (iii) bulk deposition methods. In the atomistic techniques, atoms, ions, and molecules build up the films. The granular deposition methods use species such as particles typically about ten micrometers in size. These species may be formed by nucleation of liquids being precursors in some methods (e.g. solution thermal spraying). The solid particles are used as species in bulk deposits. However, in bulk deposits the size of particles is generally greater than in granular deposits, and the particles are injected in molten substrate. Some explanation is necessary to make a difference between film and coating. The difference is thickness. A film is up to a few μm thick and a coating has a thickness greater than, say, more than 10 μm. This difference sticks also to the methods of manufacturing. Consequently, the methods with atomic species generate films and those having powder particles species generate coatings. As usual, there are many exceptions. For example, a thin‐film technology of EB PVD enables manufacturing of thermal barriers being more than a few hundreds μm thick, and thermal spraying solution generates frequently a few μm thick film being frequently called coatings.

Fig. I.1 Diagram of a typical deposition process.

Table I.1 Physical deposits discussed in this work.

Source: Bunshah [2]/with permission of Elsevier.

Atomistic

Granular

Bulk

Inert medium

Pulsed laser deposition

Solid feedstock

Flame spraying

Arc melting of substrate

PTA

Evaporation

Arc spraying

Laser melting of substrate (with or without pre‐deposited coating)

Cladding

Reactive medium

Evaporation in reactive atmosphere

APS

Laser surface alloying

Chemical vapor deposition (

CVD

)

HVOF

Hard‐phase dispersion

Atomic layer deposition (

ALD

)

Plasma

Sputtering

Detonation spraying

Ion plating

VPS

Plasma enhanced

CVD

Liquid feedstock

Suspension plasma spraying

Solution precursor plasma spraying

Spray pyrolysis

Fig. I.2 A bracelet watch.

Source: From https://www.dillards.com/p/movado‐bold‐evolution‐gold‐mesh‐strap‐bracelet‐watch/509056845,[5]/Reproduced with permission from Dillard's/last accessed under April 05, 2023.

There are a lot of deposition techniques belonging to the classes defined above, and not all of them are described in this book. A selection had to be made to limit the description to the techniques most representative from a point of view of current or potential industrial applications. There are a number of books where an interested reader can find descriptions of other films and coatings techniques (e.g. [2–4]). The aim of this book is to present deposition techniques from the point of view of a user who is mainly interested in the properties of deposits leading to their practical application thanks to the value added to a product. Such a benefit can be, for example, a color of a watch bracelet.

In this case, it would be important that the film has a desired color and that its roughness is small. Film properties such as the modulus of elasticity or thickness do not play an important role in this application. Moreover, it seems reasonable that an atomistic deposition technique would be recommended to the film manufacturing. The coatings obtained by one granular deposits technique would be too heterogeneous (porosity, contact between the lamellae, etc.) and rough to fulfill the requested role.

Another example would be a deposit on hydraulic cylinders used in coal mines (Fig. I.3). This tool wears out quickly through abrasion and, therefore, the deposit must be well adherent, resistant to abrasive wear, and very thick in order to prolong its life. In this case, bulk deposits are much more advantageous.

Fig. I.3 Hydraulic cylinders in coal mines.

Source: From https://www.laserline.com/de‐int/laser‐cladding/,[6]/Reproduced with permission from Laserline GmbH/last accessed under April 05, 2023.

The deposition techniques presented in this book should make possible to solve most of practical problems that can be solved with help of films and coatings in industry of today.

The book structure is linear and quite similar to a coating manufacturing procedure (see Fig. I.4) and describes:

substrate preparation;

methods of films and coatings deposition;

treatment post‐deposition;

nucleation, growth and microstructure of films and coatings;

methods of films and coatings characterization;

properties of films and coatings.

Thanks to this structure, a reader could easily solve a problem related to a film or coating in service. Such a problem is somehow linked to one of the stages of development cycle. Consequently, all stages should be good enough to propose an appropriate solution. On the other hand, a good knowledge of the procedures included in the development cycle would make it easier to offer a deposit for any industrial need. Developing a repository for an industrial need, however, requires, in addition to knowledge of deposition techniques, a good knowledge of the useful materials that could be applied. Some of the materials are shortly discussed in some chapters of this book can serve as references to initiate a more in‐depth study of specialized works such as, among many others, [7–9].

This book is addressed to the engineers in the films‐ and coatings‐related industries who wish to deepen their knowledge of physical deposition processes and to the researchers starting or developing their activity on this field. The professors teaching the different aspects of surface engineering and their students should find many useful information. For the purpose of this book, the author has used some information contained in his previous book on the field [11] and reviewed the literature from 2000 up to 2024 of the main scientific and technical journals in which appear the papers on physical methods of films and coatings deposition, of the presentations of scientific conferences, and of industrial exhibitions.

Fig. I.4 Cycle of development film or coating.

Source: Pawłowski [7].

Bibliography

1

Pawłowski, L. (1999). Thin films technology vs. thermal spraying: towards peaceful co‐existence.

J. Thermal Spray Technol.

8 (2): 179–180.

2

Bunshah, R.F. (ed.) (1994).

Handbook of Deposition Technologies for Films and Coatings

. Park Ridge, NJ: Noyes Publications.

3

Martin, P.M. (2009).

Handbook of Deposition Technologies for Films and Coatings

. Amsterdam: Elsevier.

4

Pawłowski, L. (2008).

The Science and Engineering of Thermal Spray Coatings

, 2nde. Chichester: Wiley.

5

https://www.dillards.com/p/movado‐bold‐evolution‐gold‐mesh‐strap‐bracelet‐watch/509056845

(accessed 18 March 2020).

6

https://www.laserline.com/de‐int/laser‐cladding/

(accessed 18 March 2020).

7

Pawłowski, L. (1997). Microstructure des dépôts physiques.

Galvano – Organo – Traitement de Surface

97 (678): 633–637.

8

Callister, W.D. Jr. and Rethwisch, D.G. (2018).

Materials Science and Engineering: An Introduction

, 10the. New York: Wiley.

9

Richerson, D.W. and Lee, W.E. (2018).

Modern Ceramic Engineering. Properties, Processing and Use in Design

, 4the. Boca Raton, FL: CRC Press.

10

Inagaki, M. and Kang, F. (2014).

Materials Science and Engineering of Carbon: Fundamentals

, 2nde. Waltham, MA: Butterworth‐Heinemann.

11

Pawłowski, L. (2003).

Dépôts Physiques

. Lausanne, Switzerland: PPUR.

1Substrate Preparation

1.1 Introduction

Deposits must adhere well to the substrates in the chosen places. The adhesion of a deposit is achieved by several physico‐chemical mechanisms in contact between the deposit material and that of the substrate (discussed in detail in Chapter 4). All these mechanisms work, however, under the condition that the surface of this contact is clean. A clean surface can be defined after Mattox [1] as “a surface which contains no significant amount of undesirable material.” The degree of required property varies with the deposition technique.

Consequently, the films obtained with atomistic deposition methods require high level of cleanliness so that the atoms or molecules of a deposit that condense on the surface do not come into contact with a very fine of dust or another contamination of a small dimension. The thick coatings obtained by granular deposition techniques use generally molten particles to build up the deposit, and the required degree of purity is relatively smaller than that required for thin films. However, the adhesion of such coatings to the substrate must be improved by the surface activation. Similarly, the surfaces of the substrates coated by bulk deposition methods are molten to enable coating material particles to be injected what lowers considerably the purity requirement.

The impurities, which can be found on the surfaces of substrates and the methods of their cleaning, depend also on the material. The types of material determine the type bonding and the nature contaminants, which is different for metal and alloys, ceramics, and polymers. Consequently, the typical substrates materials used in different deposition methods are shortly described.

The purity of a surface of a substrate can be achieved by removing the contamination by following methods:

chemical (chemical attack, dissolution of impurities, etc.);

physical which is realized by:

high temperature treatment;

mechanical cleaning

using particles abrasion (grit blasting) or water jet

ultrasonic cleaning

;

photonic cleaning

using laser or by polychromatic

uv

radiation;

plasma cleaning

using arc or ion bombardment.

The films or coatings should be deposited in chosen places on the substrate. The places must be somehow defined. The chapter describes patterning using lithography and direct patterning. The lithography is a classical masking technique, which has been used in semiconductor industry since many decades. It can be applied directly on the substrate if high resolution is desired. Alternatively, this technique can be applied to manufacture the stencil masks which, although less precise, can be used multiple times also in granular deposition methods. The resolution photolithographic masks depend on the illumination sources leading to the photo‐polymerization (uv – radiation, X‐rays, e‐beam, i‐beam, etc.). The direct patterning enables maskless protection of the substrates using different mechanisms such as oxidation of thin metal films or thermal decomposition of polymers [2]. This kind of patterning may be used in technology of atomistic films. Some granular coatings, such as cold‐gas spraying method (CGSM), enable also direct patterning of sprayed coating.

The methods of cleaning methods are often empirical and are a part of a deposition procedure. The surface should be clean to obtain well‐adhering film or coating. However, this condition is necessary but not sufficient to obtain a good adhesion of a deposit. Sometimes the surface has to be activated prior to deposition processes. In particular, the surface activation is essential to obtain adhesion of granular deposits. This results from the fact that one of principal adhesion mechanisms is the mechanical attachment of liquid particles to the top parts of surface irregularities. Consequently, it is necessary to roughen the surface by, e.g. grit‐blasting. On the other hand, a surface of a polymer substrate must be activated in order to apply any deposit. Such activation can be done using plasma by, e.g. corona discharge. Finally, the application of a bond‐coat can also be seen as activation of a substrate.