Bioceramic Coatings for Medical Implants - Robert B. Heimann - E-Book

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Robert B. Heimann

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Beschreibung

Reflecting the progress in recent years, this book provides in-depth information on the preparation, chemistry, and engineering of bioceramic coatings for medical implants. It is authored by two renowned experts with over 30 years of experience in industry and academia, who know the potentials and pitfalls of the techniques concerned.

Following an introduction to the principles of biocompatibility, they present the structures and properties of various bioceramics from alumina to zirconia. The main part of the work focuses on coating technologies, such as chemical vapor deposition, sol-gel deposition and thermal spraying. There then follows a discussion of the major interactions of bioceramics with bone or tissue cells, complemented by an overview of the in-vitro testing methods of the biomineralization properties of bioceramics. The text is rounded off by chapters on the functionalization of bioceramic coatings and a look at future trends.

As a result, the authors bring together all aspects of the latest techniques for designing, depositing, testing, and implementing improved and novel bioceramic coating compositions, providing a full yet concise overview for beginners and professionals.

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Table of Contents

Cover

Related Titles

Title Page

Copyright

Preface

References

Glossary

Chapter 1: Bioceramics – A Historical Perspective

Synopsis

1.1 Alumina

1.2 Zirconia

1.3 Calcium Phosphates

References

Chapter 2: Socio-Economic Aspects and Scope of Bioceramic Materials and Biomedical Implants

Synopsis

2.1 Types of Biomaterial

2.2 The Growing Global and Regional Markets for Biomedical Implants

2.3 Role of Bioceramic Coatings in Arthroplasty

2.4 Ceramic Femoral Ball Heads

References

Chapter 3: Fundamentals of Interaction of Bioceramics and Living Matter

Synopsis

3.1 Principle of Biocompatibility

3.2 Hierarchical Structure of Bone and Teeth

3.3 Bioceramic/Bone Interface

3.4 Basic Aspects of Biomineralisation

3.5 Interaction at a Cellular Level

3.6 Interaction at a Tissue Level

3.7 Advantages of Hydroxyapatite and Bioglass Coatings

3.8 The Promise of Cytokines

References

Chapter 4: Structure and Properties of Bioceramics Used in Orthopaedic and Dental Implants

Synopsis

4.1 Bioinert Ceramics

4.2 Bioactive Ceramics

References

Chapter 5: Technology of Coating Deposition

Synopsis

5.1 Overview

5.2 Non-Thermal Deposition Methods

5.3 Thermal Deposition Methods

5.4 Other Techniques

References

Chapter 6: Deposition, Structure, Properties and Biological Function of Plasma-Sprayed Bioceramic Coatings

Synopsis

6.1 General Requirements and Performance Profile of Plasma-Sprayed Bioceramic Coatings

6.2 Structure and Biomedical Functions of Bioceramic Coatings

6.3 The Role of Bond Coats

References

Chapter 7: Characterisation and Testing of Bioceramic Coatings

Synopsis

7.1 Phase Composition: X-ray Diffraction

7.2 Phase Composition: Vibrational (Infrared and Raman) Spectroscopy

7.3 Phase Composition: Nuclear Magnetic Resonance Spectroscopy

7.4 Phase Composition: Cathodoluminescence

7.5 Adhesion of Coatings to the Substrate

7.6 Residual Coating Stresses

7.7 Fundamentals of Roughness and Porosity

7.8 Microhardness

7.9 Potentiodynamic Polarisation and Electrochemical Impedance Spectroscopy (EIS)

7.10 Biological Performance Testing of Bioceramic Coatings

References

Chapter 8: Future Developments and Outlook

Synopsis

References

Appendix Relevant Scientific Journals/Book Series with Bioceramic Content

Index

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Begin Reading

List of Illustrations

Figure 1.1

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Figure 2.5

Figure 2.6

Figure 2.7

Figure 2.8

Figure 2.9

Figure 2.10

Figure 2.11

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Figure 4.9

Figure 4.10

Figure 4.11

Figure 4.12

Figure 4.13

Figure 4.14

Figure 4.15

Figure 4.16

Figure 4.17

Figure 4.18

Figure 4.19

Figure 4.20

Figure 4.21

Figure 4.22

Figure 4.23

Figure 4.24

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Figure 5.12

Figure 5.13

Figure 5.14

Figure 5.15

Figure 5.16

Figure 5.17

Figure 5.18

Figure 5.19

Figure 5.20

Figure 5.21

Figure 5.22

Figure 5.23

Figure 5.24

Figure 5.25

Figure 5.26

Figure 5.27

Figure 5.28

Figure 5.29

Figure 5.30

Figure 5.31

Figure 5.32

Figure 5.33

Figure 5.34

Figure 5.35

Figure 5.36

Figure 5.37

Figure 5.38

Figure 5.39

Figure 5.40

Figure 5.41

Figure 5.42

Figure 5.43

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Figure 5.46

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Figure 5.48

Figure 5.49

Figure 5.50

Figure 6.1

Figure 6.2

Figure 6.3

Figure 6.4

Figure 6.5

Figure 6.6

Figure 6.7

Figure 6.8

Figure 6.9

Figure 6.10

Figure 6.12

Figure 6.11

Figure 6.13

Figure 6.14

Figure 6.15

Figure 6.16

Figure 6.17

Figure 6.18

Figure 6.20

Figure 6.21

Figure 6.22

Figure 6.23

Figure 6.24

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Figure 7.5

Figure 7.6

Figure 7.7

Figure 7.9

Figure 7.8

Figure 7.10

Figure 7.11

Figure 7.12

Figure 7.13

Figure 7.15

Figure 7.16

Figure 7.17

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List of Tables

Table 2.1

Table 2.2

Table 2.3

Table 2.4

Table 3.1

Table 4.1

Table 4.2

Table 5.1

Table 5.2

Table 5.3

Table 5.4

Table 5.5

Table 5.6

Table 6.1

Table 6.2

Table 6.3

Table 6.4

Table 6.5

Table 6.6

Table 6.7

Table 6.8

Table 6.9

Table 7.1

Table 7.2

Table 7.3

Table 7.4

Table 7.5

Table 7.6

Table 7.7

Table 7.8

Table 7.9

Table 7.10

Table 7.11

Related Titles

Vallet-Regi, M. (ed.)

Bio-Ceramics with Clinical Applications

2014

Print ISBN: 978-1-118-40675-5; also available in electronic formats

 

Taubert, A., Mano, J.F., Rodríguez-Cabello, J.C. (eds.)

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Santin, M., Phillips, G.J. (eds.)

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Jones, J.J. (ed.)

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Robert B. Heimann and Hans D. Lehmann

Bioceramic Coatings for Medical Implants

Trends and Techniques

The Authors

Prof. Dr. Robert B. Heimann

Am Stadtpark 2A

02826 Görlitz

Germany

 

Dipl.-Chem Hans D. Lehmann

Jauernicker Str. 19

02826 Görlitz

Germany

 

Cover

“Künstliches Hüftgelenk 2. Source: Fotolia Cpsdesign 1”

 

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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Preface

This introductory text deals predominately with calcium phosphate-based bioceramic materials that are now ubiquitously used in clinical applications to coat the surfaces of metallic endoprosthetic and dental implants that aim at replacing lost body parts or restoring functions to diseased or damaged tissues of the human body. The authors have written the text from a materials scientist's point of view. Hence, its main subject matter concerns the technology of coating deposition as well as the description of properties of bioceramic coatings including their in vitro alteration and testing in contact with simulated body fluids. We will also provide some salient information on in vivo coating–tissue interactions within the natural environment of the living body. Relevant information gained from experimental animal models will be described, without diving too deeply into the biomedical, physiological and endocrinological background.

Calcium phosphates are harbingers of life. They play a paramount role on Earth as one of the essential basic building blocks of living matter. Hydroxyapatite–collagen composite scaffolds provide the mechanical supporting strength and resilience of the gravity-defying bony skeletons of all vertebrates. The dentine and enamel of teeth are likewise based on these materials. However, natural biological apatite–collagen composites provide not only strength but also flexibility, their porous structure allowing exchange of essential nutrients, and a biologically compatible resorption and precipitation behaviour under appropriate physical and chemical conditions that control the build-up by osteoblasts and resorption by osteoclasts within bony matter. Hence, the calcium-deficient defect hydroxyapatite in bone is a reservoir of phosphorus that can be delivered to the body on demand (Pasteris, Wopenka and Valsami-Jones, 2008).

Nevertheless, if one considers the low abundance of phosphorus in the Earth's crust of slightly less than 0.1 mass%, it is a remarkably odd and puzzling choice of Nature to construct many critical pathways of both plant photosynthesis and animal metabolism around this exceedingly rare element (Westheimer, 1987; Filippelli, 2008). Apart from building up the skeleton of vertebrates, biological phosphate compounds are engaged in fuelling the energetic requirements of the photosynthetic pathway of plants called the Calvin–Benson cycle as well as the intercellular energy transfer within the mitochondria of animals that both rely on adenosine triphosphate (ATP). ATP releases the energy needed to sustain the metabolic processes when reduced to adenosine diphosphate (ADP). Hence, this unique energetic contribution of the phosphate groups is central to the functioning of ATP, arguably the most abundant biological molecule in Nature. Furthermore, deoxyribonucleic acid (DNA) as the carrier of the genetic information code owes its double helical structure to phosphate ester bridges that link the two strands of the helix, and are composed of the four nucleobases, the purine-based adenine and guanine, and the pyrimidine-based thymine and cytosine. Lastly, phospholipid bilayers are the main structural components of all cellular membranes that isolate the cell interior from its surrounding, potentially hostile environment. Most phospholipids contain a glycerol-derived diglyceride, a phosphate group, and a simple organic molecule such as choline, a quaternary 2-hydroxy-N,N,N-trimethylethanammonium salt.

The inorganic calcium phosphate minerals most ubiquitously occurring in Nature belong to the apatite group in its many crystal chemical expressions such as hydroxyapatite, fluorapatite and chlorapatite as well as other calcium orthophosphates such as monetite, brushite and whitlockite. While in the past there has been general agreement that these calcium phosphate-based minerals are the most important reservoirs supplying life on Earth with essential phosphorus, more recently feldspars came into focus as a hidden source of phosphorus. It happens that in feldspars P5+ is able to replace tetrahedrally coordinated Si4+ by coupled substitution with Al3+ to maintain charge balance, that is (London et al., 1990; Manning, 2008). Considering the abundance of feldspars in the Earth's crust, and the easy accessibility for plants and soil biota of their P-containing weathering products, predominately clays, feldspars may indeed be a much more significant source of phosphorus than apatites (Parsons, Lee and Smith, 1998).

Considering the importance of the structure of bone as a biocomposite of Ca-deficient defect hydroxyapatite and triple helical strands of collagen I, it is not surprising that as early as about 40 years ago synthetic hydroxyapatite was suggested as a biocompatible artificial material for incorporation in the human body. Hydroxyapatite was used in the form of densified implants for dental root replacement (Denissen and de Groot, 1979) and as a suitable material for filling bone cavities, for fashioning skeletal prostheses (Hulbert et al., 1970) and for coatings hip endoprosthetic devices (Ducheyne et al., 1980; León and Jansen, 2009). Since then research into the biomedical application of calcium phosphate as osseoconductive coatings has virtually exploded. Many deposition methods were experimentally and some, eventually, clinically evaluated that range from biomimetical processing routes intended to mimic Nature's low temperature, template-mediated biomineralisation pathways (Bryksin et al., 2014) to surface-induced mineralisation (SIM), to electrochemical and electrophoretic deposition, to plasma-assisted metal–organic chemical vapour deposition (PA-MOCVD), to atmospheric plasma spraying (APS) or suspension plasma spraying (SPS) (Campbell, 2003). This treatise will review many of these deposition techniques and will thus provide up-to-date information on the resulting bioceramic coatings, their structure, composition and biomedical functions (see Heness and Ben-Nissan, 2004; Sarkar and Banerjee, 2010; Ducheyne et al., 2011; Heimann, 2012; Dorozhkin, 2012; Zhang, 2013; Surmenev, Surmeneva and Ivanova, 2014). In short, the present book intends to act as a primer to introduce non-specialists to the wide-reaching field of bioceramic coatings that are being designed, developed and tested with the aim to alleviate medical deficiencies and the associated suffering of millions of people afflicted with joint and dental maladies.

During the last several decades, research into bulk bioceramics and bioceramic coatings has emerged as a hot topic among materials scientists. Virtually thousands of papers can now be found in relevant journals (see Appendix) and on the Internet. Attempting to treat this vast field in an encyclopaedic fashion is clearly impossible as each day new contributions are being published with ever-increasing speed and regularity. Hence, trying to keep abreast with these developments is akin to shooting at a very fast moving target. The best that one can do is to provide snapshots of currently available information and attempting to separate the wheat from the chaff whenever possible. To paraphrase the resigning comment by the great German poet Johann Wolfgang von Goethe, uttered in his autobiography ‘Out of my Life: Poetry and Truth’: ‘Such (…) work will never be finished; one has to declare it finished when one has done the utmost in terms of time and circumstances’.

As a parting glance, it should be mentioned that during the preparation of the text, three imaginary readers have intently looked over our shoulder: an interested layperson, a professional working in the area of the subject matter of this treatise, and a diligent student whose interest and knowledge are located somewhere in-between. The layperson may not be conversant with many of the subtleties expounded throughout our text but may be eager to penetrate deeper into the subject of bioceramic coatings. Hence, to somewhat relieve this potential reader from the burden of looking up non-familiar analytical techniques and special scientific terms in other textbooks or encyclopaedias, we have provided in the Chapters 5 and 7 short explanations that precede the more detailed descriptions of coating deposition techniques, and characterisation and testing procedures.

Our second imaginary reader is the professional who may look into specific chapters to extract expert knowledge. He or she will act as a thorough if not harsh critic of our endeavour, and will undoubtedly castigate us for having left out crucial aspects of the subject matter treated in this book. This expert may also criticise us for having used inappropriate terms and faulty connections among materials science and biomedical facts. Alas, we used such possibly scientifically shaky explanations to satisfy the limited level of understanding of imaginary reader #1. The expert may also accuse us of having skimmed over the deep subtleties of the subject, and, in particular, not having given due consideration to those aspects in which he or she has earned scientific standing and international acclaim. However, during the vast progress made in developing increasingly sophisticated techniques to design and engineer bioceramic materials including coatings, many unexplored vestiges and nooks and crannies have been left behind the speedily advancing battle lines that require additional and more detailed studies. Some of the content of this book has been devoted to ‘mopping up’ such neglected research topics. These topics notwithstanding, we are much aware of deficiencies in our approach and hence ask imaginary reader #2 for understanding and kind forgiveness.

Our third imaginary reader is a student who may want to inform himself/herself quickly on the general subject of bioceramic coatings, their preparation technology, materials science, uses, properties, as well as analytical characterisation, and in vitro and in vivo testing. We are hopeful that our treatise will provide the information sought by this student without forcing him/her to delve into the abyss of specialised literature. Hence, imaginary reader #3 may benefit from our concise and condensed approach in as much as it will provide relief from ploughing through piles of original papers scattered over dozens of scientific journals.

The dangers of attempting to satisfy both the curiosity and the need for knowledge of these three imaginary readers are obvious. The only thing we can hope for is, on the one hand, to have avoided to be over the head of the layperson, and on the other hand, to have provided enough scientific ‘meat’, limited as it may be, to earn the approval of the expert and the appreciation of the student as well. Readers trained in the realm of medical and biological sciences will likely appreciate the materials science aspects of bioceramic coatings whereas those educated in materials science may find the biomedical content of the book enlightening and useful. To satisfy both types of our potential audience is intrinsically difficult, and should we have failed here and there in this endeavour, we beg the gentle reader for pardon.

Robert B. HeimannHans D. Lehmann

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Sarkar, R. and Banerjee, G. (2010) Ceramic-based biomedical implants.

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Surmenev, R.A., Surmeneva, M.A., and Ivanova, A.A. (2014) Significance of calcium phosphate coatings for the enhancement of new bone osteogenesis – a review.

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Westheimer, F.H. (1987) Why nature chose phosphates.

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Zhang, S. (ed) (2013)

Hydroxyapatite Coatings for Biomedical Applications

, Advances in Materials Science and Engineering, CRC Press, 469 pp., ISBN: 978-1-4398-8693-9.

Glossary

AAGR

average annual growth rate

AAS

atomic absorption spectroscopy

a.c.

alternating current

ACP

amorphous calcium phosphate

ADP

adenosine diphosphate

AFM

atomic force microscopy

ALP

alkaline phosphatase

ANOVA

analysis of variance

AO

acridine orange

APS

atmospheric plasma spraying

ATP

adenosine triphosphate

A/W

apatite/wollastonite

ATZ

alumina-toughened zirconia

BCA

bone-like carbonated apatite

BCP

biphasic calcium phosphate

bFGF

basic fibroblast growth factor

BIC

countries Brasil, India, China

BIR

bone ingrowth rate

BMD

bone mineral density

BMP

bone morphogenetic protein

BMSC

bone marrow stromal cell

BP

bisphosphonate

BRIC

countries Brasil, Russia, India, China

BSA

bovine serum albumin

BSE

back-scattered electron

BSP

bone sialoprotein

CAGR

compound annual growth rate

calcein-AM

acetoxymethyl-ester of calcein

CaP

calcium phosphate (in a general sense)

Ca-PSZ

calcia-partially stabilised zirconia

CCC

carbon–carbon composite

CCD

charge-coupled device

CCDS

computer-controlled detonation spraying

CCVD

combustion chemical vapour deposition

CDHAp

calcium-deficient hydroxyapatite

CEC

Fédération Européene des Fabricants de Carreaux Ceramiques

Ce-TZP

ceria-stabilised tetragonal zirconia polycrystal

CFD

computational fluid dynamics

CFRP

carbon fibre-reinforced polymer

CGDS

cold gas dynamic spraying

CHAp

carbonated hydroxyapatite

CiA

citric acid

CL

cathodoluminescence

ClAp

chlorapatite

CMP

calcium metaphosphate

CNS Glasses

calciumoxide-sodiumoxide-siliciumdioxide glasses, see also NCS

CNT

carbon nanotubes

CP

cross polarisation (in NMR)

CPM

calcium dihydrogenphosphate monohydrate

CPP

calcium pyrophosphate

CPPD

calcium pyrophosphate dihydrate

cp-titanium

commercially pure titanium

CR

corrosion rate

CRM

confocal Raman microscopy

CTE

coefficient of thermal expansion

CTO

calcium titanate, CaTiO3, perovskite

CVD

chemical vapour deposition

d.c.

direct current

DCPA

dicalcium phosphate anhydrate

DCPD

dicalcium phosphate dihydrate

DDA

degree of deacylation

DFT-LDA

density-functional theory with local-density approximation

DGS

detonation gun spraying

DIPS

diffusion-induced phase separation

DLC

diamond-like carbon

DMEM

Dulbecco's modified eagle's medium

DNA

deoxyribonucleic acid

DOE

design of experiment

DS

detonation spraying

DTA

differential thermal analysis

EBAD

electron beam assisted deposition

EBPVD

electron beam physical vapour deposition

EBSD

electron back-scattered diffraction

ECD

electrochemical deposition

ECF

extracellular fluid

ECM

extracellular matrix

ED

electron diffraction

EDS

energy dispersive spectroscopy

EDTA

ethylenediaminetetraacetic acid (sequestrant)

EDX

energy-dispersive X-ray spectroscopy

EELS

electron energy loss spectroscopy

EIS

electrochemical impedance spectroscopy

ELISA

enzyme-linked immunosorbent assay

EPD

electrophoretic deposition

EPMA

electronic probe microanalysis

EPR

electron paramagnetic resonance (spectroscopy), see also ESR

ESEM

environmental scanning electron microscopy

ESR

electron spin resonance (spectroscopy), see also EPR

EtBr

ethidium bromide

EXAFS

extended X-Ray absorption fine structure

EXSY

exchange spectroscopy (in NMR)

FA-CVD

flame-assisted chemical vapour deposition

FE-SEM

field emission scanning electron microscopy

FFT

fast Fourier transform

FGC

functional gradient composites

FGHA

functionally graded hydroxyapatite

FGM

functionally graded material

FHAp

fluorine-doped hydroxyapatite

FIB

focused ion beam

FTIR

Fourier transform infrared spectroscopy

FTRS

Fourier transform Raman spectroscopy

GD

glow discharge

GN

graphene nanosheet

HA, HAp

hydroxyapatite

HAV

hyaluronic acid visco-supplementation

HBDC

human bone-derived cell

hBMSC

human bone marrow stromal cell

HBSS

Hank's balanced salt solution

HCA

hydroxycarbonate apatite

HCP

heptacalcium phosphate

HDPE

high-density poly(ethylene)

hECF

human extracellular fluid

HEPES

2-(4-(2-

h

ydroxy

e

thyl)-1-

p

iperazinyl)-

e

than

s

ulfonic acid (buffer)

HETCOR

heteronuclear correlation

hICF

human intracellular fluid

hISF

human interstitial fluid

hMSC

human mesenchymal stem cell

HRTEM

high resolution transmission electron microscopy

HSTC

hierarchical-structured titanium coating

hUVEC

human umbilical vein endothelial cell

HVOF

high velocity oxyfuel spraying

HVSFS

high velocity suspension flame spraying

IBAD

ion beam assisted deposition

IBSD

ion beam sputtering deposition

ICP/MS

inductively coupled plasma/mass spectroscopy

ICPS

inductively coupled plasma spraying

IGF

insulin-like growth factor

IPS

induction plasma spraying

IR

infrared (spectroscopy)

ISE

indentation size effect

ISQ

implant stability quotient

KDR

kinase insert domain receptor

LASAT

laser shock adhesion test

LEPS

low-energy plasma spraying

LGN

laser gas nitriding

LPCVD

low pressure chemical vapour deposition

LPPS

low pressure plasma spraying

LRS

laser Raman spectroscopy

MAO

micro-arc oxidation

MAPLE

matrix-assisted pulsed laser evaporation

MAS

magic angle spinning (technique in NMR)

MCSF

macrophage colony-stimulating factor

MEMS

microelectromechanical system

Mg-PSZ

magnesia-partially stabilised zirconia

M(I)PS

micro-plasma spraying

MRI

magnetic resonance imaging

MSC

marrow stem cell

MTT

3-(4,5-di

m

ethyl

t

hiazol-2-yl)-2,5-diphenyl

t

etrazolium bromide (dye)

MWCNT

multi-walled carbon nanotubes

NAD

nicotinamide adenine dinucleotide

NCS

sodiumoxide calciumoxide silicate glasses, see also CNS

NASICON

sodium super ionic conductor (structural family)

NMR

nuclear magnetic resonance (spectroscopy)

NZP

sodium zirconium phosphate

OAp

oxyapatite

OC

osteocalcin

OCP

octacalcium phosphate

OES

optical emission spectroscopy

OHAp

oxyhydroxyapatite

OP

osteopontin

OPG

osteoprotegerin

PA

polyamid

PAA

poly(acrylic acid)

PA-MOCVD

plasma-assisted metal-organic chemical vapour deposition

PBC

periodic bond chain

PBTCA

2-phosphonobutane-1,2,4-tricarboxylic acid (dispersant)

PC

pulsed current

PCA

percentage of coated area

PCL

poly(ε-caprolactone)

PDA

post deposition annealing

PDGF

platelet-derived growth factor

PDOP

poly(dopamine)

PE

poly(ethylene)

PECVD

plasma-enhanced chemical vapour deposition

PEEK

poly(etheretherketone)

PEG

poly(ethyleneglycol)

PEI

poly(ethylene imine)

PEO

plasma electrolytic oxidation

PE-UHMW

poly(ethylene) ultra-high molecular weight

PGA

poly(glutamic acid)

PIXE

particle- or proton-induced X-ray emission

PLA

poly(lactic acid)

PLD

pulsed laser deposition

PLGA

poly(lactic-

co

-glycolic acid)

PMMA

poly(methylmethacrylate)

PSZ

partially-stabilised zirconia

PVD

physical vapour deposition

RANK(L)

receptor activator of nuclear factor kappa (ligand)

REE

rare earth elements

RF, r.f.

radio frequency

RFA

resonance frequency analysis

rhBMP

recombinant human bone morphogenetic protein

RIPS

reaction-induced phase separation

RNA

ribonucleic acid

ROS

reactive oxygen species

r-SBF

revised simulated body fluid (see also: SBF-H,

Table 7.8

)

RT-PCR

reverse transcription polymerase chain reaction

RTQ

removal torque

RUNX

2

runt-related transcription factor 2

SAED

selected area electron diffraction

SAM

self-assembled monolayer

SAXS

small-angle X-ray scattering

SBF

simulated body fluid

SCE

standard calomel electrode

SDE

statistical design of experiments

SEM

scanning electron microscopy

Si-HAp

silicate-doped hydroxyapatite

SIM

surface-induced mineralisation

SIMS

secondary ion mass spectrometry

SOFC

solid oxide fuel cell

SPC

statistical process control

SPM

scanning probe microscopy

SPPS

solution precursor plasma spraying

SPS

suspension plasma spraying

Sr-HAp

strontium-doped hydroxyapatite

SRO

short range order

SS

stainless steel

STEM

scanning transmission electron microscopy

SZS

strontium-zinc-silicium ceramic

TCP

tricalcium phosphate

TCPS

tissue culture-grade polystyrene

TDHP

tetracalcium dihydrogenhexaphosphate

TEM

transmission electron microscopy

TERS

tip-enhanced Raman spectroscopy

TGA

thermogravimetric analysis

TGF

transforming growth factor

THA

total hip arthroplasty

THR

total hip replacement

TiCN

titanium carbonitride

TiN

titanium nitride

TIPS

temperature-induced phase separation

TKA

total knee arthroplasty

TL

thermoluminescence

TLR

toll-like receptor

TMCP

transition metal-substituted calcium phosphate

TNF

tumor necrosis factor

ToF-SIMS

time-of-flight secondary ion mass spectrometry

TRAP

tartrate-resisting acid phosphatase

TRIS

tris(hydroxymethyl)-aminomethan (buffer solution)

TTCP, TetrCP

tetracalcium phosphate

TZP

tetragonal zirconia polycrystal

UHMWPE

ultra-high molecular weight poly(ethylene)

UV

ultraviolet

VCS

vacuum/reduced pressure cold spraying

VEGF

vascular endothelial growth factor

VPS

vacuum plasma spraying

XANES

X-ray absorption near-edge structure

XPS

X-ray photoelectron spectroscopy

XRD

X-ray diffraction

Y-PSZ

yttrium-partially stabilised zirconia

YSZ

yttria-stabilised zirconia

Y-TZP

yttria-stabilised tetragonal zirconia polycrystal

ZA

zoledronic acid

ZTA

zirconia-toughened alumina

μCT

micro computed tomography

1Bioceramics – A Historical Perspective

Synopsis

In this chapter, we will attempt to trace briefly the long and sometimes anfractuous history of important bioceramics including coatings. Emphasis will be put on the bioinert ceramics alumina and zirconia, as well as on bioactive, that is osseoconductive calcium phosphates.

1.1 Alumina

Alum (potassium aluminium sulfate, KAl(SO4)2·12H2O) was already known in antiquity (‘sal sugoterrae’ of Pliny), and widely utilised in dying of wool, as a coagulant to reduce turbidity in water, and as a medicine to remedy various ailments based on its astringent, haemostatic and antibiotic nature. In 1754, the German (al)chemist Andreas Sigismund Marggraf (1709–1782) was first to isolate aluminium oxide (‘Alaunerde’) from alum but was unable to determine its exact composition (Marggraf, 1754, 1761). Between 1808 and 1810, Sir Humphrey Davy tried unsuccessfully to reduce the oxide to metallic aluminium, a feat that was accomplished later by Oerstedt (1825) by heating aluminium chloride with potassium amalgam.

Aluminium oxide (alumina) has also been known since ancient times and several isolated uses have been reported for emery (smirgel), an impure corundum occurring, for example, on the Greek island of Naxos. Gorelick and Gwinnett (1987) have shown that emery was likely employed as an abrasive for drilling of hardstone beads and cylinder seals during ancient Mesopotamian times. In addition, finely ground emery powder was arguably used by the famous Greek sculptor Pheidias as a separation medium to avoid adhesion of heated glass sheets to clay-based moulds. The corrugated glass sheets thus obtained were likely designed to be clothing folds adorning the himation (ancient Greek cloak) of the giant statue of Zeus in his Olympia temple (Heilmeyer, 1981).

The unique mechanical and thermal properties of alumina have spurred its utilisation as high temperature-, wear- and corrosion-resistant ceramics. Besides this, its first application as biomaterial was suggested by Rock (1933) in a Deutsches Reichspatent, followed by a patent issued to Sandhaus (1966) for the use of alumina for dental and jaw implants. However, it was only after the groundbreaking paper by Boutin (1972) that alumina took off on its worldwide triumphal course as a suitable ceramic material for femoral balls of hip endoprostheses.

Figure 1.1 shows the development of bioinert and bioactive ceramics (Rieger, 2001). In 1920, tricalcium phosphate (TCP) was suggested as a bioresorbable ceramic material for filling of bone gaps that, however, was unable to bear extended loads (Heughebaert and Bonel, 1986). Alumina entered the scene around 1930 (Rock, 1933) and was subsequently much improved in terms of its compressive strength and fracture toughness by painstaking engineering of its purity and ever decreasing grain size down to the nano-scale level. This development led to orthopaedic structural ceramic products such as Ceraver-Osteal® (Boutin, 1972), Keramed® (Glien, Kerbe and Langer, 1976), Frialit® (Griss and Heimke, 1981), and finally the family of Biolox® ceramics by Feldmühle, later CeramTec companies (Dörre and Dawihl, 1980, see also Clarke and Willmann, 1994) as well as BIONIT® manufactured by Mathys Orthopädie GmbH (Bettlach, Switzerland). The current high-end product of CeramTec is Biolox® delta, a zirconia-toughened alumina (ZTA) alloy reinforced with chromia as a crack arrester (see Chapter 4.1.1).

Figure 1.1 Application of bioceramics in medical devices: 100 years of history. (Adapted from Rieger (2001), and adjusted to current developments.)

Evaluation of biocompatibility resulted chiefly from clinical experience (Boutin, 1972; Hulbert, Morrison and Klawitter, 1972; Griss et al., 1973; Griss, 1984; Mittelmeier, Heisel and Schmitt, 1987) supported by in vitro cytotoxicity testing (for example Catelas et al., 1998; Nkamgueu et al., 2000, and many other contributors).

1.2 Zirconia

Zirconium dioxide was first extracted from the mineral zircon (zirconium silicate, ZrSiO4) by the German chemist Martin Heinrich Klaproth (1743–1817) in 1787, using the yellowish orange-coloured, transparent gemstone jacinth (hyacinth) from Ceylon as starting material. Zircon has been known to man for a very long time; its name presumably originated from the Arabian word ‘zargun’, meaning ‘gold-coloured’ that etymologically is related to the ancient Persian words ‘zarenu’ (gold) and ‘gauna’ (colour) (Vagkopoulou et al., 2009). In 1824, the Swedish chemist Jöns Jakob Berzelius (1779–1848) was first to isolate metallic zirconium by reduction of K2ZrF6 with potassium.

For the following 150 years, zirconium as well as zirconia were considered mere scientific curiosities without any substantial technological merits apart from limited utilisation of zirconia in heavy-duty bricks for high temperature applications and for special glasses (Morey, 1938) with a high index of refraction. It was only in 1969 that the first scientific study of the outstanding biomedical properties of zirconia emerged (Helmer and Driskell, 1969). Subsequently, it was discovered that alloying zirconia with oxides such as yttria, calcia, magnesia and others was able to stabilise its tetragonal modification thus halting the structurally and mechanically deleterious phase transition from the tetragonal to the monoclinic phase (Garvie and Nicholson, 1972). This discovery allowed using the so-called transformation toughening of zirconia to produce ceramics with unsurpassed crack resistance (‘ceramic steel’) (Garvie, Hannink and Pascoe, 1975). Still later, it was found that even unalloyed microcrystals of zirconia could be stabilised against transformation if the tetragonal high temperature phase has a reduced surface free energy with respect to the monoclinic low temperature structure (Garvie, 1978). These partially stabilised tetragonal zirconia polycrystalline ceramics (TZP) are characterised by a structure of high density, small grain size and high purity that jointly elicit strength and fracture toughness unusually high for a ceramic material. Consequently, such ceramics were employed to fashion femoral ball heads starting by the mid-eighties of the past century (Cales and Stefani, 1995, Figure 1.1) and, later, to make dental parts of all kinds including dental roots, inlays and veneers.

Starting in the 1980s, besides structural and mechanical investigations of zirconia (see, for example Rühle, Claussen and Heuer, 1983), studies on its biocompatibility moved into the limelight as evidenced, for example, by the pioneering work of Garvie et al. (1984), Christel et al. (1989) and Hayashi et al. (1992). Their work triggered a virtual avalanche of research that used increasingly sophisticated evaluation techniques of material properties. In addition, studying the in vitro and in vivo biomedical performance of zirconia in contact with biofluid and tissues established zirconia as a viable bioceramics (for example Piconi and Maccauro, 1999; Piconi et al., 2003; Fini et al., 2000; Clarke et al., 2003; Thamaraiselvi and Rajeswari, 2004; Manicone, Rossi Iommetti and Raffaeli, 2007; Afzal, 2014). Later, several applications emerged as bond coats as well as reinforcing particles for hydroxyapatite coatings for implants.

Today, a large segment of utilisation of zirconia as colour-adapted tooth veneers in dental restoration exists (Cales, 1998). At this point, it is appropriate to mention the ancient French dental doctor Pierre Fauchard (1678–1761) who may be considered the vanguard of modern tooth restoration. He has been credited with recognising the potential of porcelain enamels and initiating research with porcelain to imitate the natural colour of teeth and gingival tissue (Fauchard, 1728).

1.3 Calcium Phosphates

Calcium orthophosphates have been known to be associated with organic tissue, diligently researched and eventually applied for at least 250 years. As early as 1769, the Swedish chemists Johan Gottlieb Gahn and Carl Wilhelm Scheele discovered that TCP, Ca3(PO4)2 could be obtained by burning bone, and they continued to isolate elemental phosphorus by reducing acid-treated bone ash with charcoal, and distilling off the escaping phosphorus vapour in a retort (Threlfall, 1951). In fact, bone ash was the predominant source of phosphorus until the 1840s when mining, first of tropical island deposits formed from bird and bat guano and, later phosphate rock, took over.

The preparation of pure tricalcium orthophosphate by an alternate route was already described 200 years ago in an encyclopaedia as follows:

Phosphate of lime, proper. As this salt constitutes the basis of bones, it is not necessary to prepare it artificially. It may be obtained in a state of purity by the following process: Calcine the bones to whiteness, reduce them to powder, and wash them repeatedly with water, to separate several soluble salts, which are present. Dissolve the whole in muriatic acid, and precipitate by means of ammonia. The precipitate, when well washed and dried, is pure phosphate of lime (Good, Olinthus and Newton, 1813).

A chemistry textbook for students of medicine written in 1819 (Bache, 1819) states:

Phosphate of lime is a white insoluble powder, destitute of taste, and unaltered by exposure to air. It is soluble in hydrochloric (muriatic) and nitric acids, and may be precipitated from solution in them by means of ammonia. When exposed to a very violent heat, it undergoes a kind of fusion, and is converted into white semi-transparent porcelain.

Heated and crushed animal bones were used copiously in making bone China, predominately in Britain, commencing around the mid-eighteenth century (Heimann, 2012; Heimann and Maggetti, 2014). As it turned out, by the end of the eighteenth century much research had been performed on calcium phosphates, which involved the names of many renowned scientists of the time including Klaproth, Proust, Lavoisier, Vauquelin and de Fourcroy. Recently, these research activities were exhaustively summarised by Dorozhkin (2013).

The nineteenth century saw increasingly important research on calcium phosphates, culminating in a series of contributions by Mitscherlich (1844), Berzelius (1845), Fresenius (1867), Warington (1871) and Church (1873). In our context, particular attention has to be paid to Warington's paper that describes the dissolution of bone ash in the presence of carbonated water, an important precondition for the agricultural use of calcium phosphates, and to the contribution by Church who was presumably the first to determine and publish the exact formula of fluorapatite.

The knowledge of the presence of calcium phosphates in bone (De Fourcroy et al., 1788; Parr, 1809; von Bibra, 1844), teeth (Davy, 1814), blood and milk (De Fourcroy, 1804), urine (De Fourcroy et al., 1788) as well as urinary and renal calculi (Colon, 1770; Pemberton, 1814) was solidly established by the early nineteenth century. Additional historic evidence for this has been painstakingly recorded by the prolific chronicler of calcium phosphates, Dorozhkin (2012), quoting no less than 279 references on the history of calcium phosphate research. Among these treasures there appears faint indication that several calcium phosphate phases, important for biomineralisation, were already known, suspected or suggested early on such as amorphous calcium phosphate, ACP (Brande and Taylor, 1863) and octacalcium phosphate, OCP as well as dicalcium phosphate dihydrate, DCPD (brushite) (Warington, 1866).

The discoveries of X-ray radiation by Röntgen (1895) and its application to crystal structure analysis by Bragg father and son (Bragg, 1921) moved research on calcium phosphates from a descriptive to a predictive acquisition of knowledge, and allowed investigating phase transitions in unprecedented detail. Consequently, a series of studies emerged in early 1930 using X-ray diffraction (XRD) as an important and versatile tool to assess the structural chemistry of calcium phosphates in general and hydroxyapatite in particular (Hendricks et al., 1931; Roseberry, Hastings and Morse, 1931; Trömel, 1932; Bredig, 1933; Bredig, Franck and Füldner, 1933). De Jong (1926) was first to identify the structure of the calcium phosphate phase in bone as being akin to geological apatite that has long been known as an important phosphate mineral (Werner, 1788). From their XRD studies Hendricks et al. (1931) concluded that animal bone consisted of carbonate apatite, Ca10[CO3(PO4)6]·H2O, a compound isomorphous with fluorapatite. They also reported the existence of oxyapatite, Ca10O(PO4)6 that could be prepared by heating hydroxyapatite or bone at 900 °C until constant weight had been attained. The latter finding met with disagreement by Bredig et al. (1933) who drafted one of the earliest CaO–P2O5 phase diagrams in the absence of water, and first proposed the existence of ‘mixed’ apatites, that is oxyhydroxyapatites Ca10(PO4)6X2mOn (, F; ). However, they denied the existence of a pure stable oxyapatite structure, because in their opinion the X position could not be left empty. Much later, research refuted this contention (see Chapter 6.2.1.4). Bredig et al. (1933) based their conclusion about the non-existence of pure oxyapatite on experimental evidence and went on to postulate the likewise non-existence of TCP with apatite structure, unlike the existence of an isomorphous relationship between pyromorphite, Pb10(PO4)6Cl2 and Pb3(PO4)2 established by Zambonini and Ferrari (1928). The systematic progress of the knowledge gained on the chemical composition and structure of bone mineral, that is Ca-deficient hydroxyapatite was recently reviewed by Rey et al. (2010). The important, but still not quite resolved, role water assumes in the structure of bone was beautifully highlighted by Pasteris (2012).

Considering the importance of the structure of bone as a biocomposite of Ca-deficient defect hydroxyapatite and triple helical strands of collagen I, it is not surprising that as early as about 40 years ago synthetic hydroxyapatite was suggested as a biocompatible artificial material for incorporation in the human body (Jarcho et al., 1976; Jarcho, 1981). In a next step, hydroxyapatite was introduced as a bioactive, that is osseoconductive coating. Its first application was in plasma-sprayed coatings for dental implants, followed by coatings for the stem of hip endoprostheses to improve implant integration with the surrounding bone (Ducheyne et al., 1980; Figure 1.1). Although the preferred deposition technology was and still is atmospheric plasma spraying (APS, León and Jansen, 2009; Heimann, 2010), other techniques abound including low-pressure (vacuum) plasma spraying (VPS, Gruner, 1986) and most recently high-velocity suspension flame spraying (HVSFS, Bolelli et al., 2010). Chapter 5 of this treatise will exhaustively review many deposition techniques. Hydroxyapatite was also utilised in the form of densified implants for dental root replacement (Denissen and de Groot, 1979), as a suitable material for filling bone cavities, and for fashioning skeletal prostheses (Hulbert et al., 1970; Capello and Bauer, 1994).

In 2003, an up-to-date summary of studies was edited by Epinette and Manley (2003), describing the state-of-the-art of hydroxyapatite coatings in orthopaedics as this stood at the close of 2002. This compilation of results was designed to help to answer the still somewhat hotly debated question of whether the favourable results achieved in the short term with this method of biologic fixation of total joint implants has withstood the test of time. The goal of Epinette and Manley's book was mainly to determine if the use of hydroxyapatite coatings for the fixation of orthopaedic implants to bone has been proven by the survivorship and satisfaction of those patients who had received hip and knee implants.

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