Biomaterial TMT 614419

Jurusan Teknik Metalurgi

Fakultas Teknik Universitas Sultan Ageng Tirtayasa
(1)Schedule
Semester Ganjil 2014/1015, 10:5012:30
Engineering Faculty Building, Untirta
Lecture Room #2-5
(2)Instructor
Alfirano, ST., MT., PhD.
Physical Metallurgy Lab,
Department of Metallurgy Engineering
Sultan Ageng Tirtayasa University
e-mail: alfirano@ft-untirta.ac.id
1

Contents
1. Define biomaterials
2. Describe biomaterial applications
3. Define and describe biocompatibility
principle
4. Explain factors contribute to the
performance of biomaterials in the
body.
2

Contents
1. Introduction

2. Metallic biomaterials
3. Ceramic biomaterials
4. Surface modification
3

References
Biomaterials:
J. Park and R.S. Lakes, Biomaterials: an introduction, New York, Springer, (2007).
Biomaterials Science, An Introduction to Materials in Medicine, 2nd Ed.
Elsevier, (2004).
Metallic biomaterials:
V.A. Mayer, 2008 annual book of ASTM standards, section thirteen, medical
devices and services, vol.13.01, West Conshohocken, ASTM International, (2008).
M. Niinomi (ed), Metals for biomedical devices, Woodhead, Cambridge, UK, (2010).
Co-Cr alloys:
C.T. Sims, N.S. Stoloff and W.C. Hagel, Superalloys II, Wiley, New York, (1987).
Ti and its alloys:
R. Boyer, G. Welsch and E.W. Collings, Materials properties handbook:
titanium alloys, Materials Park, ASM International, (1994).
D.M. Brunette, P. Tengvall, M. Textor and P. Thomsen, Titanium in medicine:
material science, surface science, engineering, biological responses and medical
applications, Berlin, Springer, (2001).
G. Ltjering and J.C. Williams, Titanium, second edition, Berlin, Springer, (2007).
Ceramic biomaterials:
J.C. Elliott, Structure and chemistry of the apatites and other calcium
orthophosphates, Elsevier, (1994).
L.L. Hench, J.Am.Ceram.Soc., 74 [7] (1991) 1487-1510, 81 [7] (1998) 1705-1728.

Grading System
Exam 1 (UTS)
Exam 2 (UAS)
Homework

= 40%
= 40%
= 20%

Attendance (*)

= 80%

1. Introduction: contents
1.1
1.2
1.3
1.4
1.5
1.6

Biological environment
What is biomaterials?
Classification
Focus in this class
History of implant materials
Background of the research
6

1.1 Biological environment

(i) High demand
Internal in living system: remarkably aggressive
high chemical activity
mechanical stress
reactions with cells
(ii) Invariant conditions
The biological environment displays extraordinary quality of
constancy in both physical conditions and composition.
homeostasis
(iii) Many sets of conditions associated with parts and life process

Biological and mechanical conditions

Table 1-1

(Biological performance of materials, (1999), p.18)

Human blood
Table 1-2

(Biological performance of materials, (1999), p.20)

1.2 What is biomaterials?

Biomaterial is used to make devices to replace a
part or a function of the body in a safe, reliable,
economic, and physiologically acceptable manner.
Definition:
materials of natural or manmade origin that are used to direct,
supplement, or replace the functions of living tissues
a synthetic material used to replace part of a living system or to
function in intimate contact with living tissue

Any nondrug material that can be used to treat, enhance or

replace any tissue, organ, or function in a organism.
a nonviable materials used in a medical device, intended to
interact with biological systems

10

The concept of biocompatibility

Biocompatibility:
Biocompatibility in the ability of a material to
perform with an appropriate host response in a
specific application (William, 1987).
Good biocompatibility is achieved when the
material exists within a living body without
adversely or significantly affecting it or being
affected by it
it..

11

The concept of biocompatibility

Biocompatibility characteristic:
a. Biocompatibility involves the acceptance of an
artificial implant by the surrounding tissues and
by the body as a whole.
b. Biocompatible materials
Do not irritate the surrounding structures
Do not provoke an abnormal inflammatory
response
Do not incite allergic or immunologic reactions
Do not cause cancer
12

The concept of biocompatibility

Biocompatible materials have adequate
mechanical properties.
Biocompatible materials have appropriate optical
properties (eye).
Biocompatible materials have appropriate density.

13

1.3 Classification
Biomaterials are classified as:
Organic if contain carbon

Inorganic if they do not.

More specifically biomaterials fall into one of

three of materials:
Metals (inorganic material)

Ceramics(inorganic material)
Polymers (organic material)
14

1.3 Classification
by structure and chemical bonding
Metals: metallic bonding
Ceramics: ionic and covalent bonding
Polymer : van der Waals and hydrogen bonding
(atoms: covalent bonding)
Table 1-3 Classification of biomaterials by structure and chemical bond.

15

Stress-strain curves

Figure 1-1 Schematic illustration of stress-strain curves of biomaterials.

, (2010), 191

16

Artificial hip joint

backing
ball

cup
stem

Figure 1-2 Medical devices using biomaterials.

17

Applications of biomaterials
Table 1-4

(Cr2O3)

(Biomaterials Science, An Introduction to Materials

in Medicine 2nd Ed. Elsevier, (2004), p.2.)

18

Applications of biomaterials

19

Performance of biomaterials
The success of biomaterials in the body
depends on factors such as:
a.
b.
c.
d.
e.
f.

Material properties
Design of the implants
Biocompatibility of the materials
Technique used by the surgeon
Health and condition of the patient
Patient activities

20

1.4 Focus in this class

Metallic and ceramic biomaterials as implants

Hip Joint

21

Continued
Metallic and ceramic biomaterials as implants.
Akar Gigi

Kawat gigi

Gigi palsu
Penyangga gusi

22

Continued
Metallic and ceramic biomaterials as implants.
Stent
Spinal Fixation

Sekrup plat tulang

Heart valve

I.L

23

Characterictic of biomaterials

Many Materials: A wide range of materials

(metals, ceramics, polymers, and natural materials) is
routinely used and no one researcher will be
comfortable synthesizing and designing with
all these materials.

Thus, specialization is the rule. However, a

board appreciation of the properties and
application of theses materials is a hallmark of
professional in the field.

24

Characterictic of biomaterials
Hard tissue replacement biomaterials: metals,
ceramics, used in orthopedic and dental materials
materials..
Soft tissue replacement biomaterials: polymers,
cardiovascular and general plastic surgery materials.
Some devices involved both soft and hard tissue.
There is need for a general understanding of all
class of materials.

25

Development of biomaterials

It provides a perspective on how different

disciplines work together,
together starting from the

identification of a need for a biomaterial,

biomaterial
materials synthesis,
materials testing,
(ASTM: American Society for Testing Materials)

fabrication,
sterilization and packaging,
device testing,
regulatory
clinical use, and
explant analysis

26

Development of biomaterials

27

Development of biomaterials

28

1.5 History of implant materials

Year

Development

Late 18th19th
century

Various metal device to fix bone fracture: wire

and pins from Fe(Iron), Au (gold), Ag(silver), Pt
(platinum)

1860-1870

Aseptic surgical units

(The use of biomaterials did not become practical
until the advent of an aseptic surgical technique
develop by Dr J. Lister.)

Early 1900

Bone plates were introduced to aid in fixation of

long bone fracture.
However, many of these early plates broke due
unsophisticated mechanical design;
-too thin
-Had stress concentrating corners.
-Corrode rapidly in the body
Introduction of stainless steel and cobalt
chromium alloys

1.5 History of implant materials

Year

Development

1930s

Introduction of stainless steel and cobalt chromium alloys

1938

First total hip replacement prosthesis.

1940s

First used polymethyl methacrylate (PMMA) for corneal

implant and replacement of section of damaged skull bone.
(During World War II shattered perspex in pilots didnt cause
problem.)

1946

First biomechanically designed femoral head replacement

prosthesis: first plastic (PMMA) used in joint replacement.

1950s

First successful blood vessel replacement

1960s

First commercial heart valve replacement

Cemented joint replacement

Recent implant materials

Since the 1930s, the biomaterials that are currently applied
for practical uses have been developed.

Figure 1-3 History of metals, plastics (polymer) and

ceramics for biomedical applications.
(M.Niinomi, Metall.Mater.Trans.A, 33A (2002), 477-487.)

31

Current status
Today, biomaterials represent a significant
portion of the healthcare industry, with an
estimated market size of over $9 billion per
year in the United States.

32

Current status
Cardiovascular area:
approximately 100,00 replacement
heart valves and 300,000 vascular
graft implanted per year in US.

Artificial joints replacements:

Over 500,000 artificial joint
replacements, such as knee or hip,
are implanted yearly in United
States.

33

Future directions
Cardiovascular area:
approximately 100,00 replacement
heart valves and 300,000 vascular
graft implanted per year in US.

Artificial joints replacements:

Over 500,000 artificial joint
replacements, such as knee or hip,
are implanted yearly in United
States.

34

1.6 Background of the research

Super-aged society

Increase in the number of people suffering from

injuries sustained during falls and due to the
deterioration of bodily functions
In order to improve the quality of life (QOL) of the
patients
Further improvements in dental and medical
materials with regard to reconstruction of the
human body
35

Super-aged society

Figure1-4 Change in population ratio of over 65 years old men in each country.
(M.Niinomi, Metall.Mater.Trans.A, 33A (2002), 477-487.)

36

Indonesia
Elderly population in Indonesia 2000 - 2025

Source : BPPN Badan Pusat Statistik (Statistics Center Bureau) Jakarta 2005

Much more medical

devices required
Source : Kompas.com June 2, 2009
37

Number of elderly population in Indonesia

in 2050 estimated 57.6 million.

Artificial joints and stent

Figure 1-5 Total expenditure of artificial joints

and coronary stent.

Figure 1-6 Intravascular stents.

38

2 Metallic biomaterials: contents

2.1 Introduction
2.2 Stainless steels
2.3 Co-Cr alloys
2.4 Titanium and its alloys
2.5 Other metallic biomaterials

40

2.1 Introduction

70% of implants: composed of metallic

biomaterials
In terms of their mechanical properties, their performance
cannot be equaled by ceramic or polymer biomaterials.

Concern: toxicity by ion elution from implants

in human body

41

Biomaterials used in orthopedic field in Japan

Figure 2-1 Mass of biomaterials in orthopedic field in Japan.

(T.Narushima, J.Jpn.Inst. Light Metals, 55 (2005), 561-565.)

42

Classification
Stainless steels
Co-Cr alloys
Titanium and its alloys
Platinum and gold:

biocompatible metals
very expensive

cannot be applied for orthopedics

(Used in dental field)
43

Corrosion resistance and mechanical property

Corrosion resistance: Passive film (< 10 nm)
Stainless steels
Cr2O3 layer
Co-Cr alloys
TiO2 layer

Ti and its alloys

High corrosion resistance

Mechanical properties:
Thermomechanical Co-Cr alloys
treatment
Titanium alloys
Work hardening
Stainless steels
Wide variety of mechanical properties
even in the same chemical composition 44

Properties of metallic biomaterials

Table 2-1 Comparison of metallic biomaterials.
Materials
Stainless steel
Co-Cr alloy
Ti&Ti alloy
Ceramics

SUS316L
Cast
Wrought
C.P.Ti
Ti-6Al-4V
Al2O3

Corrosion
resistance

Strength

Impact
resistanace

Wear
resistance

Plasticity

Machinability

Cost

Table 2-2

(Biomaterials Science, An Introduction to Materials in Medicine 2nd Ed. Elsevier, (2004), p.143.)

45

Mechanical properties of metallic biomaterials registered in ASTM

Working

+
Heat treatment

+
Alloy composition

Wide variety of
mechanical properties

46

Metals used for medical devices

Table 2-3 Metals used for medical devices.

(T. Hanawa, Metals for biomedical devices,

Woodhead, Cambridge, UK, (2010), p.7. )

47

Nature of metals
Figure: The metallic
bond forms when
atoms give up their
valence electrons,
which then form an
electron sea. The
positively charged
atom cores are
bonded by mutual
attraction to the
negatively charged
electrons
48

Structure of metals
Basic atomic architecture is a crystal structure

49

Metals Manufacturing

50

Metals Manufacturing

Molten metal is cooled to form the solid.

The solid metal is then mechanically shaped to

form a particular product.

How these steps are carried out is very important

because heat and plastic deformation can
strongly affect the mechanical properties of a
metal.

51

Metals Manufacturing
What Happens When You Cool a Molten Metal?

52

Formation of Crystal
Contained nucleation starts at edges
(where coolest) and grows inward

In the free state growth

proceeds simultaneously in
all three axes.

53

Formation of Crystal
Nucleation -The first
unit cell solidifies
Growth -New unit
cells attach to
existing unit cells.

Where crystals meet

grain boundaries are
created.

54

Phase
A phaseis a homogeneous
part or aggregation of the
material that differs from
another part due to a
difference in structure,
composition, or both;
The difference in structures
forms an interface between
adjacent or surrounding
phases;
These structural defects affect
mechanical performance.
55

Crystal Defect

56

Crystal Defect

Vacancy

Subtitution

Intertstitial

Frenkel

Subtitution

Schottky
57

Crystal Defect

Edge and Screw Dislocation

58

Crystal Defect

Grain Boundary
59

2.2 Stainless steels

Predominant implant alloy.
In 1926-The first stainless steel (18Cr-8Ni)
was utilized for implant fabrication, which is
stronger and more resistant to corrosion
than the vanadium steel.
In 1943, type 302 stainless steel had been
recommended to U.S Army and navy for
bone fixation.
60

2.2 Stainless steels

Later 18-8sMo stainless steel or known as 316
stainless steel, which contains a small percentage of
molybdenum to improve corrosion in chloride
solution (salt water) was introduced.
In the 1950s 316L stainless steel was developed
by reduction of maximum carbon content from 0.08%
to 0.03% for better corrosion reduction especially to
physiological saline in human body.

61

2.2 Stainless steels

High corrosion resistant steel
with at least 11mass% chromium
Chromium can make protective passive film,
Cr2O3 film, on the surface of stainless steel.
Nickel and molybdenum are added to enhance
corrosion resistance.

62

Chemical composition of stainless steels in ASTM

Low cost
Excellent ductility

Bone fixation wire

Electrode

Table 2-4 Stainless steels registered in ASTM for surgical implants.

All the registered alloys: austenitic stainless steels.

Ni is pointed out to be highly associated with metal allergy and
toxicity when Ni ions elute from implants in the human body.
Ni-free stainless steels: Fe-Cr-Mn-Mo-N system
63

Chemical composition of stainless steels in AISI

64

Types of stainless steel

On the basis of the predominant phase
constitute of the microstructure;
Martensitic
Ferritic
Austenitic
As a biomaterials,
austenitic stainless steel has been used because
the most corrosion resistant
not magnetic
the most ductile

65

Typical biomedical stainless steel

Type 316L: Fe-(17-20)Cr-(12-14)Ni-(2-3)Mo
L: Low carbon content (< 0.03 mass%)
Prevent the formation of Cr23C6 precipitates
Depleted zone (7-8% Cr)

Intragrain (18% Cr)

Cr23C6

66

Schaeffler diagram
NiE (%) = Ni + Co + 0.1Mn + 18N + 30C

30
(g)

20
g+M

10

(M)

g+a

g+M+a

(a)

M+a

a+M

Type 316L

10

20

30

40

CrE (%) = Cr + 1.5Mo + 1.5W + 0.5 Si + 2.3 V + 1.8 Nb +2.3 Al

Figure 2-2 Schaeffler diagram.

67

Ni-free austenitic stainless steels

Stability of the austenitic phase
Addition of Mn and N (austenite phase stabilizers)
N: strengthening and improving corrosion resistance
Mn: increasing N solubility but lowering corrosion
resistance

Corrosion resistance

PRE (Pitting Resistance Equivalent)

= [Cr]+3.3[Mo]+30[N]-[Mn]

Magnetism
Low magnetic susceptibility is preferred
for MRI (Magnetic Resonance Imaging).
Md30() = 413 - 462[C+N] - 9.2[Si] - 8.1[Mn]
- 13.7[Cr] - 9.5[Ni] - 18.5[Mo] (mass%)
Md30Temperatur di mana martensit 50% untuk true starin 30%

68

Ni-free austenitic stainless steels

69

Austenitic stainless steel wire

Figure 2-3 Stimulation electrode made of Fe-22Cr-10Ni-6Mn-2Mo-0.4N alloy.

(T.Narushima et al., Mater.Trans. 46 (2005), 2083-2088)

70

2.3 Co-Cr alloys

plastic deformability
g phase > e phase

g (fcc)

e (hcp)
Co
Figure 2-4 Phase diagram of Co-Cr binary.

Cr
71

Effect of elements on phase stability

Fe Mn Ni

100
80

FCC (g) Stabilized

60

Solubility in FCC Co
C (mol %)
HCP (e) Stabilized
Low SFE

High SFE
V

C
-200

Ta Nb

Zr

-100

Ti

40

Cr

20

Mo W
Si

+100

Change in Ms temperature per 1mass% / K

Figure 2-5 Effect of elements on g/e phase stability in Co-based alloys.

(1Ms
0fcc
hcp
)
(C.T. Sims et al.: Superalloys II, (1987), 141.)

72

Co-Cr alloys registered in ASTM for surgical implants

Exhibit excellent
wear resistance

Sliding parts
in artificial joints

Table 2-5 Co-Cr alloys registered in ASTM for surgical implants.

Ni-free Co-Cr alloys: Co-Cr-Mo system

73

Ni-free Co-Cr-Mo (CCM) alloys

Alloy composition
Co-28Cr-6Mo (mass%, ASTM F75, F1537, F799)
+ C(<0.35)+N(0.25)+Si(<1)+Mn(<1)+..

Wrought Co-Cr-Mo alloy

Improvement of workability without addition of Ni
Suppression of grain boundary precipitation
Stabilization of fcc g phase

Cast Co-Cr-Mo alloy

Precipitates (carbide, nitride and intermetallic compound)
Utilization of minor alloying elements
Heat treatment
74

Precipitates
in Co-Cr-Mo alloys
Co-Cr-Mo (CCM) alloys
Ni-free Co-Cr alloy
Mechanical strength
Corrosion resistance
Wear resistance

Artificial joints
Wrought

Cast

Precipitates in the matrix

Phase Size
Shape Distribution
75

Phase
of precipitates
M: Co, Cr, Mo
s-phase
Co(CrMo)

M23X6

h-phase
M6X-M12X

Co

Intermetallics

Cr

X: C or N
M7X3

Mo

C or N

Carbide, Nitride or Carbonitride

76

Co-28Cr-6Mo-xC alloys: as-cast

(a) 0.12C

(b) 0.15C

(c) 0.25C

(d) 0.35C

Fig. 2-6. Microstructure of as-cast (a) 0.12C, (b)

0.15C, (c) 0.25C and (d) 0.35C alloys.

Alloy

M23C6

0.12C

0.15C

0.25C

0.35C

Fig. 2-7 XRD patterns of precipitates

electrolytically extracted from as-cast
alloys. (S. Mineta et al., Metall. Mater.
Trans. A, 41 (2010), 2129.)
77

p-phase
p-phase: carbide/nitride with b-Mn structure
Ideal composition: M2T3X
M (Co): Low affinity with X
T (Cr,Mo): high affinity with X
X (C,N): octahedral site of T
Co
Mo or Cr
C or N
78

Co-28Cr-6Mo-xC alloys: heat-treated

0.12C

0.15C

0.25C

0.35C

79

Co-28Cr-6Mo-xC-1Si: as-cast

0.25C1Si

c-phase:
Intermetallic compound
with a-Mn structure
Co
Mo or Cr
(possible) C or N

80

c-phase in F75 Co-28Cr-6Mo alloys

Detrimental for toughness
and corrosion resistance
Narrow formation conditions
Si 1 mass%
C 0.15 mass%
formed just below solidus line
dissolved for short period
Si and C contents
Heat treat. temp.

Possible to avoid the

precipitation of c-phase
in Co-Cr-Mo alloys
81

M2X phase in Co-28Cr-6Mo-(0-1)Si

-(0-1)Mn-0.175N alloys
Table 2-6 Phases of precipitates formed in as-cast alloys

Alloys

1Si0Mn0.175N

Phase
p

M2X type

1Si0Mn0.175N

0Si1Mn0.175N

1Si1Mn0.175N

0Si0Mn0.175N
Major precipitate

M2X type
Metallic
elements
C or N

Blocky
dense
p- phase

0Si1Mn0.175N

Lamellar
cellular

M2X type
82

Precipitates in Co-Cr-Mo alloys

-phase
Co(CrMo)

c-phase

-phase
p-phase
M6X-M12X M2T3X

M23X6

M7X3

M2X

5 mm

Table 2-7 Chemical compositions of precipitates (mass%).

Phase
Alloys (heat treat. cond.)
Co
Cr Mo
M23X6 type

1Si1Mn0.175N (1448 K, 0 ks)

p-phase

1Si1Mn0.175N (1548 K, 0 ks)

h-phase

1Si0Mn0.175N (1523 K, 1.8 ks)

16.1 67.4
34.4 38.1

32.5 21.6
47.3 33.4

10.
8
21.
7
38.
6
17.

C
5.6

Si

N.D. N.D.

Mn
0.1

2.7

0.7

1.3

1.1

2.3

1.0

4.0

N.D.

1.8

-83

Microstructural control in biomedical Co-Cr-Mo alloys

Matrix

Elements
Metallic
elements

fcc
hcp

C, N

ReactionInteraction
Corrosion resistance
Workability
Mechanical properties

Precipitates
Intermetallics

Carbide
Nitride

Phase relation

84

2.4 Titanium and its alloys

The mechanical strength, ductility, and wear
resistance of Ti and its alloys are inferior to
those of stainless steels and Co-Cr alloys.

Applied to the medical

and dental implants

Titanium and its alloys

Light weight
Appropriate combination of
strength and ductility
Superelasticity and shape
memory effect
High corrosion resistance
Excellent biocompatibility
Osseointegration
the direct connection from implant to
living remodeling bone without any soft
tissue component between implant and
bone on the optical microscopic level

For parts that experience

long-term contact with bone
85

Contents
(1)
(2)
(3)
(4)
(5)
(6)

Allotropic transformation
Metastable phase
Reactivity
Reaction with oxygen
Classification of titanium materials
Surface reactions of titanium
86

(1) Allotropic transformation

Pure Ti 1155 K

a Ti (hcp) b Ti (bcc)

Temperature at which b single phase is obtained

: b trunsus (Tb)
b trunsus can be controlled by alloying elements.
b trunsus (K) = 1159 +147.7[O] +20.4[Al] +161.8[C] +294.3[N]
-19.8[Fe] -10.3[Mo] -4.1[Zr] -8.4[Nb] -13.1[V]
-30.8[Ni] -23.0[Co] -15.7[Mn] -17.0[Cr] -0.2[Sn]
-8.5[Cu] (mass%)
87

Effect of alloying elements on phase stability

Figure 2-8 Three types of alloying elements in titanium.

(T.Narushima, J.Jpn.Soc. Biomater., 23 (2005), 86-95.)

88

Typical phase diagrams in Ti-X system

Figure 2-9 Phase diagrams of a and b stabilizing elements.

(T.Narushima, J.Jpn.Soc. Biomater., 23 (2005), 86-95.)

89

(2) Metastable phase

When phase transforms to phase,
Metastable phase:
w phase
athermal w
thermal w
a, a martensite
/a transformation
shape memory effect
superelasticity
90

Metastable phases in Ti alloys

Table 2-8 Metastable phases in titanium.

(T.Narushima, J.Jpn.Soc. Biomater., 23 (2005), 86-95.)

91

Metastable phases in Ti-Nb system

Figure 2-10 Metastable phases in Ti-Nb system.

(Materials Properties Handbook, Titanium Alloys, (1994), 57.)

92

(3) Reactivity
Titanium: a very reactive metal
high solubility of other elements
Freedom in alloy designing
Controlling T and microstructure
(can use light elements such as C, N and O)

high chemical affinity with other elements

Strong chemical affinity with oxygen
Stable and protective passive film (TiO2)
Rapid regeneration of passive film

93

Titanium, Iron and Aluminum

94

Types of metals
(O2)

:2TiO
:2FeO
:(2/3)Al2O3

(N2)
:2TiN
:2Fe4N
:2AlN

(C)

:TiC
:Fe3C
:(1/3)Al4C3

Zr
Ni, Cr
Mg, Si

95

Stability of passive film on Ti

Current density

Table 2-9 Regeneration time of passive film.

(Morita et al., J.Jpn.Soc.Biomater., 10 (1992), 1033.)

Time

Figure 2-11 Change in current density on

titanium surface with time in the Hanks
solution.

96

Reactivity of titanium
Provide a lot of titanium alloys with
a wide variety of mechanical properties.

variety of alloying design

variety of microstructure

High corrosion
resistance

Biocompatible

High solubility of
other elements

Strong bonding
with oxygen

Difficult to react
with biomolecules

Titanium
(very reactive)

Reduction of rutile (TiO2) or

ilmenite (FeTiO3) is difficult.

Difficult to purify

Expensive
Special smelting process

Figure 2-12 Relationship between reactivity and properties of titanium materials.

97

(4) Reaction with oxygen

Figure 2-13 Ti-O binary phase diagram.

98

Important reactions
(a) Equilibrium with titanium oxide
2Ti(s) + O2(g) = 2TiO(s)
Equilibrium
(b) Oxygen in titanium stable region

(c) Strict treatment of oxygen in titanium equilibrated with MO

MO(s) = M(mass% in Ti(l)) + O(mass% in Ti(l))
M = Ca
F. Tsukihashi et al., Metall. Mater. Trans., 27B (1996), 967.

99

(5) Classification of titanium materials

a type

a single phase microstructure

Commercially pure (CP) titanium

near a type

a+b type

two phase (a+b) microstructure

Ti-6Al-4V

near b type
b type

b single phase microstructure

Metastable at room temperature
Ti-15Mo-5Zr-3Al

100

Effect of structure on properties

Figure 2-14 The relationship between phase and properties

in titanium materials. (Titanium in medicine, Springer, (2001), p.32. )

101

Characteristics of three types of Ti materials

Table 2-10 Characteristics and examples of three type of
titanium materials for biomedical applications.

5m
Figure 2-15 Microstructure of
a+b type titanium alloy.

102

Phase diagram

Figure 2-16 Three types of titanium materials in phase diagram.

(T.Narushima, J.Jpn.Soc. Biomater., 23 (2005), 86-95.)

103

Ti materials registered in JIS and ASTM

Table 2-11 Titanium materials registered in JIS and ASTM for surgical applications.
C ompo sition(ma ss% )
N o.

JIS T 7401- 1

T ype

M aterials
CP
CP
CP
CP
CP

T i,Gr .E L I
T i,Gr .
T i,Gr .
T i,Gr .
T i,Gr .A

C P T i,Gr .B
JIS T 7401- 2

a+ b

T i-6Al- 4V

JIS T 7401- 3

a+ b

T i-6Al- 2N b- 1T a

Al

Nb

Ta

Mo

Zr

Fe

O thers

Ti

< 0.10
< 0.20
< 0.30
< 0.30
< 0.50

< 0.0125
< 0.0125
< 0.0125
< 0.0125
< 0.0125

< 0.10
< 0.18
< 0.25
< 0.35
< 0.40

< 0.012
< 0.03
< 0.03
< 0.05
< 0.05

< 0.03
< 0.10
< 0.10
< 0.10
< 0.10

B al.
B al.
B al.
B al.
B al.

< 0.50

< 0.0125

< 0.40

< 0.05

< 0.10

B al.

5.5- 6.75

3.5- 4.5

< 0.30

< 0.015

< 0.20

< 0.05

< 0.08

B al.

5.5- 6.5

1.5- 2.5

0.5- 1.5

0.5- 1.0

< 0.25

< 0.0125

< 0.10

< 0.03

< 0.05

B al.
B al.

3.5- 4.5

3.5- 4.5

14.5-15 .5

< 0.25

< 0.0125

< 0.20

< 0.05

< 0.05

Pd
< 0.25

5.5- 6.5

6.5- 7.5

< 0.50

< 0.25

< 0.009

< 0.20

< 0.05

< 0.08

B al.

2.5- 3.5

14.0-16 .0

4.5- 5.5

< 0.35

< 0.02

< 0.20

< 0.05

< 0.05

B al.

< 0.20
< 0.30
< 0.30
< 0.50

< 0.015
< 0.015
< 0.015
< 0.015

< 0.18
< 0.25
< 0.35
< 0.40

< 0.03
< 0.03
< 0.05
< 0.05

< 0.08
< 0.08
< 0.08
< 0.08

B al.
B al.
B al.
B al.

T i-6Al- 4V E L I

5.5- 6.50

3.5- 4.5

< 0.25

< 0.012

< 0.13

< 0.05

< 0.08

B al.

a+ b

T i-6Al- 4V

5.5- 6.75

3.5- 4.5

< 0.30

< 0.015

< 0.20

< 0.05

< 0.10

B al.

AS T M F 1295

a+ b

T i-6Al- 7N b

5.50-6.50

6.50-7.50

< 0.50

< 0.25

< 0.009

< 0.20

< 0.05

< 0.08

B al.

AS T M F 1472
(Wr oug ht)

a+ b

T i-6Al- 4V

5.5- 6.75

3.5- 4.5

< 0.30

< 0.015

< 0.20

< 0.05

< 0.08

Y
< 0.005

B al.

AS T M F 1713

N ear b

T i-1 3N b-1 3Z r

12.5-14 .0

12.5-14 .0

< 0.25

< 0.0120

< 0.15

< 0.05

< 0.08

B al.

AS T M F 1813

T i-1 2Mo-6Z r-2F e

1.5- 2.5

< 0.020

0.008-0 .28

< 0.05

< 0.05

B al.

T i-1 5Mo

10.0-13 .0
14.0016.00

5.0- 7.0

AS T M F 2066

< 0.10

< 0.015

< 0.20

< 0.05

< 0.10

B al.

AS T M F 2146

a+ b

2.50-3 .50

2.003.00

< 0.30

< 0.015

< 0.12

< 0.020

< 0.050

Y
< 0.005

B al.

JIS T 7401- 4

a+ b

T i-1 5Z r-4 Nb -4T a

JIS T 7401- 5

a+ b

T i-6Al- 7N b

JIS T 7401- 6

T i-1 5Mo-5Z r-3Al

AS T M F 67

CP
CP
CP
CP

AS T M F 136
(Wr oug ht)

a+ b

AS T M F 1108
(Cast)

T i,Gr ade
T i,Gr ade
T i,Gr ade
T i,Gr ade

T i-3Al-2.5V

1
2
3
4

> 200
> 240
> 345
> 450
> 550
> 680
(CW )
> 860
(bar)
> 860
(bar)
> 860
(bar)
> 900
(bar)
> 940
(bar)
> 240
> 345
> 450
> 550
> 860
(bar<
0.187in.)

To tal
Elongation
(% )
> 30
> 24
> 20
> 18
> 15
> 10
(CW )
> 10
(bar)
> 12
(bar)
> 12
(bar)
> 10
(bar)
> 12
(bar)
> 24
> 20
> 18
> 15
> 10
(bar<
0.187in.)

> 860

>8

> 900
(bar,w ire)
> 930
(Ba r<2 in.)
> 860
(aged )
> 550
(solution
treated)
> 931.5
> 690
(bar,w ire)
> 621
(anne aled)
> 862
(cold w orked
and stressrelieved)

> 10
(bar,w ire)
> 10
(Ba r<2 in.)
>8
(aged )
> 15
(solution
treated
> 12
> 20
(bar,w ire)
> 15
(anne aled)
> 10
(cold w orked
and stressrelieved)

Te nsileS treng th
(MP a)

(T.Narushima, J.Jpn.Soc. Biomater., 23 (2005), 86-95.)

104

(a) a type
First titanium materials used for biomedical
applications
High ductility, low strength

In CP titanium, strength and ductility are

controlled by oxygen and iron contents

105

CP titanium
Gr.1

Gr.2

Gr.3

Oxygen content
Iron content
Strength
Ductility

Gr.4
Increase
Increase
Increase
Decrease

Applications
Wire, Screw
Dental implant
Miniplate
106

Properties of CP titanium
Table 2-12

Table 2-13

107

(b) a+b type

a type: low strength
Needs of high strength Ti materials for biomedical application
1960s-1970s Strengthening of implants
a+b type titanium alloys
Ti-6Al-4V , Ti-3Al-2.5V (Aerospace materials)
1980s Safety concerns over V and Al
V-free (Vother b stabilized elements)
1980 Ti-5Al-2.5Fe
1985 Ti-6Al-7Nb
1995 Ti-5Al-3Mo-4Zr
Al-free (Alother a stabilized or neutral elements)
1993 Ti-15Zr-4Nb-4Ta-0.2Pd-0.2O-0.05N
Ti-15Sn-5Nb-2Ta-0.2Pd-0.2O
Applications
dental and orthopedic fields
CP Ti and Ti-6Al-4V > 90% of titanium biomaterials
108

Cytotoxicity of vanadium

Figure 2-17 Cytotoxicity of

vanadium.
(Y.Okazaki and E.Gotoh,
Mater.Trans., 43 (2002), 2944.)

109

Biocompatibility and corrosion resistance

in pure metals and alloys

110

(c) b type
Excellent workability
High strength
(through aging treatment)
Low elastic modulus
(Youngs modulus)
111

Effect of elastic modulus

Load

20GPa
Bone

In the 1990s, finite element studies and animal

studies suggested the effectiveness of low
elastic modulus biomaterials in hip prostheses.
The ensuing mismatch between the elastic
moduli of the biomaterials and that of the
surrounding bone has been considered the
main cause of implant loosening and stress
shielding of bone.

316L200GPa
SUS316L
: 200 GPa
Co-Cr200GPa
Co-Cr-Mo alloy
: 200 GPa
Co-Cr200GPa
CP Ti, Ti-6Al-4V
: 100-110 GPa
Ti:100GPa
b type Ti alloys
: 80 GPa
Ti-6Al-4V100GPa

112

Elastic modulus of b-type Ti alloys

Figure 2-18 Elastic modulus of b-type titanium alloys.

(T.Narushima, J.Jpn.Inst. Light Metals, 55 (2005), 561-565.)

113

(6) Surface reactions of titanium

(a)Formation of passive film (TiO2)
High corrosion resistance
(a)Formation of calcium phosphate (apatite)
in biological environment
Osseointegration
(direct bonding between titanium and
bone on an optical microscopic level)

Applied to the parts where

long-term contact with bone
is expected
114

Osseointegration
P.-I. Brnemark
(, )
1952

115

Apatite formation on Ti surface

Figure 2-19 Formation of hydroxyapatite on titanium surface in human body.

116

Apatite formation rate

Figure 2-20 Formation rates of calcium phosphate layer

on titanium surface in the Hanks solution.

117

Hot research topics in titanium and its alloys

Alloy design with biocompatible elements
Cytotoxicity of V
Neurotoxicity of Al

Low cost

a+b type Ti-15Zr-4Nb-4Ta-0.2Pd-0.2O-0.05N

b type Ti-29Nb-13Ta-4.6Zr

Fe and O are main impurity elements in

sponge Ti produced by the Kroll process

a+b type Ti-Fe-O-N alloys

Lowering in elastic modulus

Mismatch between the elastic
moduli of the implant and bone

loosening and
stress shielding

b type Ti alloys in Ti-Nb

and Ti-Mo systems

Shape memory effect/superelasticity

NiTi exhibits a shape memory
effect and superelasticity

Dental archwire
Vascular stent

Surface modification

Improving tissue compatibility with

maintaining microstructure of titanium

Ti-Nb and Ti-Mo systems

with b/a transformation

Surface

Morphology
Phase/composition

Fabrication of porous body

Low elastic modulus

Applied to scaffold for bone regeneration and tissue engineering

118

118

2.5 Other metallic biomaterials

Magnesium alloys
Biodegradable implants eliminate the need for a second operation
to remove the implants.
Mg and its alloys: candidates for biodegradable metallic biomaterials

The corrosion rate of highly pure Mg in the human body is too high and its
mechanical properties are inferior to those of other metallic biomaterials.
Alloying
Surface modification

Bulk metallic glasses

Amorphous alloys usually exhibit a higher tensile strength and
corrosion resistance than crystalline alloys of the same composition.
Ti-based bulk metallic glasses in Ti-Zr-Cu-Pd and Ti-Zr-Cu-Pd-Nb systems

119

Continued
Tantalum
Ta185 GPa
>193300 K
1990
1990Ta

TaCVD/CVI

Zirconium
ZrTi

Zr-2.5Nb

120

Future trend in fabricating metallic biomaterials

Low cost

New generation
metallic biomaterials

121