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Biocompatibility testing and marketing authorisation of degradable magnesium implants 351

dyes: one passes through the intact cell membrane, whereas the other does not) or viable cell counting. However, there are little data available on the genotoxicity and hemocompatibility of magnesium (Di Virgilio, Reigosa, and de Mele, 2011; Gu,

Zhen, Cheng, Zhong, and Xi, 2009). Besides the in vitro data, animal experiments

have been performed that focus on in vivo degradation and the local effects after implantation. Witte et al. (2007) also tested sensitisation using the MagnussoneKligman test (GMPT) according to 10993-10 for comparison of the various magnesium alloys. One publication focuses on the fate of hydroxide gas developed during the degradation of magnesium (Bartsch, Willbold, Yarmolenko, and Witte, 2012).

Some scientists try to explain the effects of magnesium and alloying components on the cellular level to reveal the mechanisms, unknown dangers, and potential markers for the biocompatibility of magnesium implants (Feyerabend et al., 2010; Purnama,

Mantovani, and Couet, 2013). In recent years, it has become increasingly apparent

that in vitro corrosion of magnesium alloys is highly variable depending on the solution used in the test set-up. Ions such as chloride, biological buffers, proteins, and amino acids and temperature can inﬂuence in vitro degradation (reviewed in Xin et al.

(2011)). In a new approach using artiﬁcial neural networks, the inﬂuence of the CO

content is highlighted (Willumeit, Feyerabend, and Huber, 2013). Dynamic conditions involving sheer stress, continuous mass transport, and the exchange of ﬂuids also have an impact on degradation (Levesque, Hermawan, Dube, and Mantovani, 2008).

To compare the results of the in vitro data in the future, it would be worthwhile to develop a standardised procedure for measuring in vitro degradation with a deﬁned corrosion (or extraction) medium, temperature, and speciﬁc atmospheric conditions (CO

2,O2,N2

) in addition to reference materials. In would also be helpful to establish adeﬁnition of the different phases of degradation to facilitate compatibility of the re- sults of the toxicity tests of degradation intermediates. However, despite the many efforts to ﬁnd a predictable model for an in vitro/in vivo correlation, it seems that we will continue to depend on animal experiments for infor mation about the time course and intermediates of degradation.

References

Adams, C. P., & Brandnter, V. V. (2006). Estimating the cost of new drug development: is it

really 802 million dollars? Health Affairs (Millwood), 2, 420e428. ANSI/AAMI HE 74. Human factors design process for medical devices. ASTM F3036-13. Standard guide for testing absorbable stents biological evaluation. ASTM F2502-11. Standard speciﬁcation and test methods for absorbable plates and screws for

internal ﬁxation implants. Bartsch, I., Willbold, E., Yarmolenko, S., & Witte, F. (2012). In vivo ﬂuorescence imaging of

apoptosis during foreign body response. Biomaterials, 33, 6926e6932. Blind, K. (2004). The economics of standards. Theory, evidence, policy. Cheltenham: Edward

Elgar. Bobe, K., Willbold, E., Morgenthal, I., Andersen, O., Studnitzky, T., Nellesen, J., et al. (2013).

In vitro and in vivo evaluation of biodegradable, open-porous scaffolds made of sintered

magnesium W4 short ﬁbres. Acta Biomaterialia, 10, 8611e8623.

352 Surface Modiﬁcation of Magnesium and its Alloys for Biomedical Applications

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Di Virgilio, A. L., Reigosa, M., & de Mele, M. F. L. (2011). Biocompatibility of magnesium

particles evaluated by in vitro cytotoxicity and genotoxicity assays. Journal of Biomedical Materials Research Part B, 99B, 111e119.

DiMasi, J. A., Hansen, R. W., & Grabowski, H. G. (2003). The price of innovation: new esti-

mates of drug development costs. Journal of Health Economics, 2, 151e185.

Feyerabend, F., Dr€ucker, H., Laipple, D., Vogt, C., Stekker, M., Hort, N., et al. (2012). Ion

release from magnesium materials in physiological solutions under different oxygen tensions. Journal of Materials Science: Materials in Medicine, 23,9e24.

Feyerabend, F., Fischer, J., Holtz, J., Witte, F., Willumeit, R., Dr€ucker, H., et al. (2010).

Evaluation of short-term effects of rare earth and other elements used in magnesium alloys on primary cells and cell lines. Acta Biomaterialia, 6, 1834e1842.

Fischer, J., Prosenc, M. H., Wolff, M., Hort, N., Willumeit, R., & Feyerabend, F. (2010).

Interference of magnesium corrosion with tetrazolium-based cytotoxicity assays. Acta Biomaterialia, 6, 1813e1823.

GHTF/SG1/N044:2008. (2008). Role of standards in the assessment of medical devices. Global

Harmonization Task Force. Study Group 1.

Gu, X., Zheng, Y., Cheng, Y., Zhong, S., & Xi, T. (2009). In vitro corrosion and biocompati-

bility of binary magnesium alloys. Biomaterials, 30, 484e498.

Hoffheinz, S., & Dimitroff, N. (1928). Experimentelle Studie€uber die resorption parental

zugef€uhrten metallischen Magnesiums. Deutsche Zeitschrift fuer Chirurgie, 208, 346e353. IEC 62366. Medical devices e Application of usability engineering to medical devices. ISO 10993. Biological evaluation of medical devices. ISO 11135. Sterilization of health care products e Ethylene oxide. ISO 13022. Medical products containing viable human cells e Application of risk management

and requirements for processing practices. ISO 14630. Non-active surgical implants e General requirements. ISO 14971. Medical devices e Application of risk management to medical devices. ISO 22442 series. Medical devices utilizing animal tissues and their derivatives. ISO 25539-2. Cardiovascular implants e Endovascular devices e Part 2: Vascular stents. ISO Central Secretariat. (2007). Joining in e Participating in international standardization,

ISBN 978-92-67-10453-9. http://www.din.de/sixcms_upload/media/2896/joining_in_

2007.pdf.

ISO/CD 18362. Processing of cell-based health care products. ISO/IEC 17025. General requirements for the competence of testing and calibration laboratories. ISO/IEC Guide 2. Standardization and related activities e General vocabulary. ISO/TR 37137. Biological evaluation of medical devices e Guidance for absorbable implants. ISO/TS 17137. Cardiovascular implants and extracorporal systems e Cardiovascular absorbable

implants.

Kaplan, A. V., Baim, D. S., Smith, J. J., Feigal, D. A., Simons, M., Jefferys, D., et al. (2004).

Medical device developmentefrom prototype to regulatory approval. Circulation, 109, 3068e3072.

Levesque, J., Hermawan, H., Dube, D., & Mantovani, D. (2008). Design of a pseudo-

physiological test bench speciﬁc to the development of biodegradable metallic biomaterials. Acta Biomaterialia, 4, 284e295.

Purnama, A., Mantovani, D., & Couet, J. (2013). Caveolin: a possible biomarker of degradable

metallic materials toxicity in vascular cells. Acta Biomaterialia, 10, 8754e8760.

Vert, M., Doi, Y., Hellwich, K.-H., Hess, M., Hodge, P., Kubisa, P., et al. (2012). Terminology

for biorelated polymers and applications (IUPAC Recommendations 2012). Pure and Applied Chemistry, 84(2), 377e410.

Biocompatibility testing and marketing authorisation of degradable magnesium implants 353

Williams, D. F. (1987). Deﬁnitions in biomaterials. Amsterdam: Elsevier. Williams, D. F. (2008). On the mechanisms of biocompatibility. Biomaterials, 29, 2941e2953. Willumeit, R., Feyerabend, F., & Huber, N. (2013). Magnesium degradation as determined by

artiﬁcial neural networks. Acta Biomaterialia, 10, 8722e8729.

Willumeit, R., Fischer, J., Feyerabend, F., Hort, N., Bismayer, U., Heidrich, S., et al. (2011).

Chemical surface alteration of biodegradable magnesium exposed to corrosion media. Acta Biomaterialia, 7, 2704e2715.

Witte, F. (2010). The history of biodegradable magnesium implants: a review. Acta

Biomaterialia, 6, 1680e1692.

Witte, F., Abeln, I., Switzer, E., Kaese, V., Meyer-Lindenberg, A., & Windhagen, H. (2007).

Evaluation of the skin sensitizing potential of biodegradable magnesium alloys. Journal of Biomedical Materials Research Part A, 1041e1047.

Witte, F., Fischer, J., Nellesen, J., Crostack, H. A., Kaese, V., Pisch, A., et al. (2006). In vitro and

in vivo corrosion measurements of magnesium alloys. Biomaterials, 7, 1013e1018.

Xin, Y., Hu, T., & Chu, P. K. (2011). In vitro studies of biomedical magnesium alloys in a

simulated physiological environment: a review. Acta Biomaterialia, 7, 1452e1459.

Index

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Note: Page numbers followed by “f” and “t” indicate ﬁgures and tables, respectively.

Acid treatment, 238–239 Advanced therapy medicinal products

(ATMPs), 332–333, 333f–334f Alkaline heat treatment (AHT), 33–35, 34f, 237 Alumina

biocompatibility and biodegradability of,

234t

-containing coatings, on biodegradable Mg-based metals, 235

Aluminium

inﬂuence on stress corrosion cracking,

188–189, 189f

pharmacophysiology of, 144

American Society for Testing and Materials

(ASTM International), 336

Amino acids

effect on magnesium corrosion

performance, 210–214

coated magnesium performance,

211–214, 212f–213f

uncoated magnesium performance,

210–211, 210t, 211f–212f

-induced corrosion, buffer and atmosphere effect on, 219–226, 219f–224f, 226f

physiological gap, bridging, 206–207

role in biocorrosion, 206–209 Anisotropy, of magnesium, 312 Anodization, 298–299

biodegradable magnesium alloys, 93–94.

See also Biodegradable magnesium alloys

electrochemical surface modiﬁcation, 55–56 Antibacterial effect, 276 Anticorrosive behavior, 270–271, 272t–273t

Bare-metal stents, 159 Bias sputtering, 95–96

Bioabsorbable behavior, of magnesium

alloys, 123–178

ex vivo test on bovine udder via

microdialysis, 129–130, 130f general considerations for, 124–125 in vivo biocompatibility of magnesium

alloys, 140–150

energy dispersive X-ray analysis, 149 ﬂorescent microscopy, 149 general considerations for, 140

142f–143f

histology, pharmacophysiology, 144–147, 145t–146t scanning electron microscopy, 149

in vivo biodegradation of magnesium

energy dispersive X-ray analysis, 139,

general considerations for, 130–137,

scanning electron microscopy, 138–139,

volumetry, 137, 138f–139f weight loss, determination of, 137–138

mechanical and corrosion properties,

chemical analysis, 150, 153t histomorphometry, 149–150, 151t–152t,

m-computed tomography, 149–150

Bioactive glass coatings, 46–48, 47f Biocompatibility, 29–30, 38–40, 140–142,

antibacterial effect, 276 assessment in vivo, 276–277 cellular, 271–274 hemocompatibility, 274–276, 275t

147–150

alloys, 130–140

140f

131f, 133t, 134f–136f

140f

125–127, 126t, 127f

153f

271–277. See also Biocompatibility

of surface modiﬁed magnesium-

based metals

–142,

356 Index

Biocompatibility of surface modiﬁed

magnesium-based metals, 231–260,

233t. See also Biocompatibility alumina, 235 calcium phosphates, 232 factors inﬂuencing, 242f, 246–249

composition, 246–247 morphology, 246–247 physicochemical properties, 246–247 surface modiﬁcation layer, degradation

resistance of, 247

surface-modiﬁed magnesium-based

metals, average degradation rate of,

247–249 future trends of, 249–250 in vitro results, 236–242

inorganic coating, 236–240, 236f, 237t organic coating, 240–242, 241f–242f

in vivo ﬁndings, 243–246

inorganic coating, 243–245

organic coating, 245–246 magnesium ﬂuoride, 234 magnesium phosphate, 232 magnesium silicate, 232–234 organic materials, 235–236 titania, 235

Biodegradable biomaterials, revolutionizing,

3–28

Biodegradable magnesium alloys

alloy elements for, 233t biocompatibility and biodegradability of

coating materials on, 234t

surface design of. See Biodegradable

magnesium alloys, surface design of

Biodegradable magnesium alloys, surface

design of, 89–120 aims of, 99–100, 100f future trends of, 114 issues associated with, 98–99, 98f–99f research examples, 102–113

Ca-P based coatings, 105–107, 105f,

107f

composite

coatings, 111–113, 112f–113f ion implantation, 109–111, 110f–111f microarc oxidation coatings, 102–104,

103f

physical vapor deposition coatings,

108–109

polymer-based coatings, 107–108

surface modiﬁcation in traditional

biometals, role of, 98 strategies in, 100–102 surface modiﬁcation techniques, 89–97

chemical conversion coatings, 92–94 electrochemical deposition, 90–92 physical vapor deposition, 94–97

Biodegradation, in vivo. See Bioabsorbable

behavior, of magnesium alloys

Biofunctionality, 140–142 Biomimetic coating, 208–209, 211f,

216–218, 216f

Biomimetic treatment, 236f, 237t

inorganic coatings on biodegradable

magnesium alloy, 238

Biomolecules, coating with, 50–52, 51f Bis-[triethoxysilyl] ethane (BTSE), 48–50 Blood vessels, testing of magnesium alloy

in, 159–161 coronary angiography, 161 coronary stents, 159 intravascular ultrasound, 161 magnesium stents, 159–160, 160f optical coherence tomography, 161

Bone, testing of magnesium alloy in or on,

150–159 metallic implants, suitability of magnesium

for, 155–158, 157t, 158f metallic nonresorbable implants, 150–155,

154t resorbable polymer-based implants, 155, 156t three -and four-point bending tests, 158–159

Bovine serum albumin (BSA), 207–208 Bovine udder ex vivo test on, via

microdialysis, 129–130, 130f

Buffer effect on amino acids/protein-

induced corrosion, 219–226,

219f–224f,

226f

Buffering agents, constituents and

concentrations of, 129t

Calcium, pharmacophysiology of, 144–147 Calcium phosphates

biocompatibility and biodegradability of,

234t

-containing coatings, on biodegradable

Mg-based metals, 232 glass ceramic coating, 44–46

Index 357

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Ca-P based coatings, 105–107, 105f, 107f Cathodic electrodeposition, 239 Cathodic plasma electrolytic deposition, 56–57 Cellular biocompatibility, 271–274 Cerium-based conversion coatings, 38–39 Characterization, of modiﬁed magnesium

and magnesium alloys, 263–282 future trends of, 277 mechanical properties, 264t methods, 266–277

anticorrosive behavior, 270–271,

272t–273t

biocompatibility, 271–277 mechanical properties, 269–270 surface characteristics, 266–268

Chemical conversion coatings, 38–44, 92–94

anodization, 93–94 general aspects of, 92–93 microarc oxidation, 93–94, 93f

Chemical passivation, 35 Chemical surface modiﬁcations, 35–55

chemical conversion coatings, 38–44 chemical passivation, 35 coating with biomolecules, 50–52, 51f polymer coatings, 52–55, 54f reaction with ionic liquids, 35–36 self-assembled monolayers, 36–38, 37f silane coatings, 48–50, 49f sol-gel coatings, 44–48

Chemical vapor deposition (CVD), 94–95 Coatings

biomimetic, 208–209, 211f, 216–218, 216f with biomolecules, 50–52, 51f Ca-P based, 105–107, 105f, 107f cerium-based conversion, 38–39 chemical conversion, 38–44, 92– composite,

111–113, 112f–113f, 242, 242f

for corrosion control, 297–301 ﬂuoride conversion, 41–44, 42f inorganic. See Inorganic coating nicotinic acid-based conversion, 38–39 organic, 240–241, 241f, 245–246 phosphate conversion, 39–40 phytic acid-based conversion, 40–41, 41f polymer, 52–55, 54f polymer-based, 107–108 silane, 48–50, 49f sol-gel, 44–48 titanate-based conversion, 38–39

Co-Cr alloy, mechanical properties, 264t Cold spray deposition, 69–72, 71f Composite coating, 242, 242f

biodegradable magnesium alloys, 111–113,

112f–113f Constant load testing (CLT), 190 Coronary angiography, 161 Coronary stents, 159 Corrosion failure mechanism, on coated

Mg-based materials, 101–102, 101f Cumulative fatigue damage (CFD),

284–286, 289, 303

Degradable biomaterials, 29–30, 48–50, 52–53 Degradable implant, life cycle of, 311–312

Degradable magnesium implants,

biocompatibility testing and

marketing authorization of, 331–354

biological safety evaluation, 340–346, 341f classiﬁcation, 332–333 general principles of, 346 ISO 10993, 347, 348f nonstandardized in vitro and in vivo

techniques, 350–351

speciﬁc considerations for, 348–350 standards for, 347 testing according to international standards,

335–340

standards,

development of, 337–338 standards, kinds of, 336–337, 337f using standards, 339–340

Degradation-related mechanical properties,

316–318 environmentally assisted cracking, 317 fatigue strength, 318 material requirements, 316 strength retention, 317 wear resistance, 318

Diamond-like carbon (DLC), 102, 267–268 Dicalcium phosphate dihydrate (DCPD), 43 Drug-eluting stents (DES), 159 Ductility, 315 Dynamic interface, 98–99, 98f, 114

Electrochemical deposition, 90–92 Electrochemical impedance spectroscopy

(EIS), 5–6, 14f

358 Index

Electrochemical surface modiﬁcation, 55–59

anodizing and microarc oxidation, 55–56 cathodic plasma electrolytic deposition,

56–57 electrodeposition. See Electrodeposition(ED) electrophoretic deposition. See

Electrophoretic deposition (EPD)

Electrodeposition (ED), 43, 57–58, 90–91,

90f

Electroless deposition, 91–92, 91f–92f Electron cyclotron resonance (ECR), 97 Electrophoretic deposition (EPD), 43, 58–59 Energy-assisted deposition, 95–96 Energy dispersive X-ray analysis (EDX)

in vivo biocompatibility of magnesium

alloys, 149 in vivo biodegradation of magnesium

alloys, 139, 140f

Environmentally assisted cracking, 317 Equal-channel angular pressing (ECAP),

295–297

European Committee for Electrotechnical

Standardization (CENELEC), 336

European Committee for Standardization

(CEN), 336

European Medicines Agency (EMA), 332 European Telecommunications Standards

Institute (ETSI), 336

Evaporation, 94

Fatigue

behavior of magnesium alloys, 284–289,

285f, 287f crack growth rate and stress level,

relationships between, 287–288, 288f strength, 318 surface treatments, effect of, 290–303

coatings, 297–301 future trends of, 303–304 ion implantation, 301–303 mechanical treatments, 290–297

testing under cyclic stress, 323–324

Fatigue crack propagation (FCP), 287–289,

303

Fe tolerance limit, 6 Fetal bovine serum (FBS), 207 Florescent microscopy, 149 Fluoride conversion coatings, 41–44, 42f

Food and Drug Administration (FDA), 332 Four-point bending tests, 158–159 Fractography, 193 Fracture mechanics-based approach, for

stress corrosion cracking, 195–198, 195f

–197f

Galvanic

corrosion, 17, 180–182 impurities, 181, 181f secondary phases, 181–182, 182f typical morphology of, 18f

Global Harmonization Task Force (GHTF),

332

Haematoxylin staining, 148 Hardness, 316 Hemocompatibility, 274–276, 275t Hexagonal close-packed (HCP) system, 187 High-purity (HP) Mg, 4–5

corrosion of, 5f, 7f–8f

Histology, 147–150 Histomorphometry, 149–150 Human serum albumin (HAS), 207–208 Hydrogen-assisted stress corrosion cracking

(HASCC), 187, 192–193 Hydrogen embrittlement (HE), 187 Hydrogen evolution method, 5–6, 12–13

cathodic, 11 and corrosion behavior, 12–13, 12f

Hydrothermal treatment, 50, 72, 268

effect on corrosion behavior, 32–33, 33f

Hydroxyapatite (HA) coating, 44–46,

58–59, 101, 124 Hypermagnesemia, 131 Hypomagnesemia, 131 HZG (Helmhotz Zentrum Geesthacht) Mg

ingot, 6, 8f

Implantation-related mechanical properties,

313–316

ductility, 315 hardness, 316 material requirements, 313–315 stiffness, 315 strength, 315 toughness, 316

Index 359

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Inorganic coating, 236–240, 236f, 237t

acid treatment, 238–239 alkaline treatment, 237 biomimetic treatment, 238 cathodic electrodeposition, 239 in vivo ﬁndings, 243–245 microarc oxidation treatment, 239–240 plasma enhanced chemical vapor

deposition, 240

plasma immersion ion implantation and

deposition, 240

Intergranular stress corrosion cracking

(IGSCC), 185–187

International Electrotechnical Commission

(IEC), 336

International Medical Device Regulators

Forum (IMDRF), 332

International Organization for

Standardization (ISO) necessary modiﬁcations, 349 project deliverables, stages of, 338t standard development process, 339f ISO 10993, 344, 345t, 347, 348f

International Telecommunication Union

(ITU), 336

Intravascular ultrasound (IVUS), 161 In vitro corrosion, 9, 11–13

comparison with in vivo, 16

In vitro testing, 320–324

biocompatibility, 140–150

chemical analysis, 150, 153t energy dispersive X-ray analysis, 149 ﬂorescent microscopy, 149 general considerations for, 140–142,

142f–143f

histology, 147–150 histomorphometry, 149–150, 151t–152t,

153f

m-computed tomography, 149–150 pharmacophysiology, 144–147,

145t–146t

scanning electron microscopy, 149

degraded samples

with load, 322 without load, 321–322

after plastic deformation, 323 fatigue testing under cyclic stress, 323–324 mechanical tests without medium, 320–321 nonstandardized, 350–351

In vivo corrosion, 9, 11–13

comparison with in vitro, 16

In vivo testing, 324–327

animal models, suitability of, 324–325 biodegradation, 130–140

energy

dispersive X-ray analysis, 139,

140f

general considerations for, 130–137,

131f, 133t, 134f–136f

m-computed tomography, 135f–136f,

137, 138f–139f

scanning electron microscopy, 138–139,

140f volumetry, 137, 138f–139f weight loss, determination of, 137–138

degraded samples, 325 future trends of, 327 implants using functional animal models,

326–327

nonstandardized, 350–351 residual volumes, extrapolation of

mechanical properties from, 325–326

Ion assisted deposition (IAD), 95–96 Ion beam assisted deposition (IBAD), 95–96 Ion concentrations, 128t Ionic liquids (ILs), reaction with chemical

surface modiﬁcations, 35–36

Ion implantation, 96–97, 96f

biodegradable magnesium alloys, 109–111,

110f–111f

effect on fatigue, 301–303

Ion plating, 61, 95–96

plasma-based, 95–96, 95f Ion vapor deposition (IVD), 95–96 Iron

inﬂuence on stress corrosion cracking,

189–190

mechanical properties, 264t

Joule heating, 56–57

Kirschner wire (K-wire), 316

Laser-assisted coloring/darkening, 69 Laser-assisted surface patterning, 69 Laser composite surfacing, 68

360 Index

Laser shock peening (LSP), 68–69,

292–293, 293f

advantages and drawbacks of, 294t Laser surface alloying (LSA), 67–68 Laser surface cladding (LSC), 68 Laser surface melting (LSM), 65–67, 66f Laser surface modiﬁcation, 65–69 Lithium, pharmacophysiology of, 147 Localized/pitting corrosion, 182–183, 183f Low-purity Mg, 5

corrosion of, 5f

Magnesium alloys. See also individual

entries

corrosion of, 4–9

as implant material, 179–180

under severe conditions, testing of,

314t

stress corrosion cracking. See Stress

corrosion cracking (SCC)

Magnesium chloride (MgCl

), 131–132

Magnesium corrosion, 3

corrosion behavior, 12f

ﬁshing-line specimens, 13

in vitro and in vivo comparison, 16

measurement of, 11–16

mechanism, 17

plug-in specimens, 13, 14f Magnesium ﬂuoride

biocompatibility and biodegradability of,

234t

-containing coatings, on biodegradable Mg-based metals, 234

Magnesium implants, biomedical

applications of, 311, 320f

Magnesium metabolism, 131f Magnesium metallurgy, 3

typical mounted specimen, 15f

Magnesium oxide (MgO), 30, 57–58,

131–132

Magnesium phosphate

biocompatibility and biodegradability of,

234t

-containing coatings, on biodegradable Mg-based metals, 232

Magnesium silicate

biocompatibility and biodegradability of,

234t

-containing coatings, on biodegradable Mg-based metals, 232–234

Magnesium stents, 159–160, 160f Magnesium, surface modiﬁcation of, 29–88

alkaline heat treatment, 33–35, 34f chemical surface modiﬁcations, 35–55.

See also Chemical surface modiﬁcations

electrochemical surface modiﬁcation,

55–59. See also Electrochemical surface modiﬁcation

hydrothermal treatment, 32–33, 33f laser surface modiﬁcation, 65–69

alloying, 67–68 cladding, 68 composite surfacing, 68 laser-assisted coloring/darkening and

surface patterning, 69

melting, 65–67, 66f shock peening, 68–69

plasma surface modiﬁcation, 59–64.