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Biomaterial – TMT 614419

Jurusan Teknik Metalurgi


Fakultas Teknik Universitas Sultan Ageng Tirtayasa

(1)Schedule
Semester Ganjil 2014/1015, 10:50〜12:30
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. Lütjering 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.
4
Grading System

 Exam 1 (UTS) = 40%


 Exam 2 (UAS) = 40%
 Homework = 20%

 Attendance (*) = 80%

5
1. Introduction: contents

1.1 Biological environment


1.2 What is biomaterials?
1.3 Classification
1.4 Focus in this class
1.5 History of implant materials
1.6 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

7
Biological and mechanical conditions
Table 1-1

(Biological performance of materials, (1999), p.18) 8


Human blood
Table 1-2

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

9
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.


(中野貴由:医療用金属材料概論, (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. Material properties
b. Design of the implants
c. Biocompatibility of the materials
d. Technique used by the surgeon
e. Health and condition of the patient
f. 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.
Spinal Fixation Stent

I.L
Heart valve
Sekrup plat tulang

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 18th–19th Various metal device to fix bone fracture: wire
century 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 didn’t 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

Number of elderly population in Indonesia Much more medical


in 2050 estimated 57.6 million. devices required
Source : Kompas.com – June 2, 2009 37
Artificial joints and stents

Figure 1-5 Total expenditure of artificial joints


and coronary stents. 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

biocompatible metals
Platinum and gold:
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 Corrosion Strength Impact Wear Plasticity Machinability Cost
resistance resistanace resistance
Stainless steel SUS316L △ ○ ◎ △ ◎ ◎ ◎
Co-Cr alloy Cast ○ ○ ○ ○ × × ○
Wrought ○ ◎ ◎ ○ ○ ○ △
Ti&Ti alloy C.P.Ti ◎ △ ◎ △ ○ ○ △
Ti-6Al-4V ◎ ◎ ◎ △ ○ △ ×
Ceramics Al2O3 ◎ △ × ◎ × × ×

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 Intertstitial Subtitution

Subtitution Frenkel 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 Bone fixation wire
Excellent ductility 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
Type 316L
g+M ● g+a

10
(M)
g+M+a

a+M
M+a (a)
0
0 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%)
(Md30:Temperatur 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 Cr
Figure 2-4 Phase diagram of Co-Cr binary.
71
Effect of elements on phase stability
Fe Mn Ni
100
Solubility in FCC Co
C (mol %)
80

FCC (g) Stabilized HCP (e) Stabilized


60
High SFE Low SFE

40 Cr
V

Mo W
Ti 20
Zr
C Ta Nb Si

-200 -100 0 +100


Change in Ms temperature per 1mass% / K
Figure 2-5 Effect of elements on g/e phase stability in Co-based alloys.

(縦軸は添加元素の固溶限を示し、横軸は添加元素1%あたりのMsの変
化する温度を示す。0からマイナスの温度が高いほどfcc結晶を安定化す
る効果を有する。逆に、ゼロからプラスに温度が高くなるほどhcp結晶
が安定化する。)
(C.T. Sims et al.: Superalloys II, (1987), 141.) 72
Co-Cr alloys registered in ASTM for surgical implants
Exhibit excellent Sliding parts
wear resistance 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研究内容
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研究内容
of precipitates
M: Co, Cr, Mo X: C or N
s-phase h-phase
M23X6 M7X3
Co(CrMo) M6X-M12X

Co Cr Mo C or N

Intermetallics 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 p h s
0.12C ○ × × ◎
0.15C ◎ ○ ○ ○ Fig. 2-7 XRD patterns of precipitates
0.25C ◎ × ○ ×
electrolytically extracted from as-cast
alloys. (S. Mineta et al., Metall. Mater.
0.35C ◎ × ○ ×
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
c-phase:
Intermetallic compound
with a-Mn structure
Co
Mo or Cr
0.25C1Si (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
1Si0Mn0.175N
Phase
Alloys Blocky
p M2X type
dense
1Si0Mn0.175N ◎ -
0Si1Mn0.175N 〇 ◎ p- phase
1Si1Mn0.175N ◎ -
0Si0Mn0.175N 〇 ◎
◎ Major precipitate
0Si1Mn0.175N
M2X type
Lamellar
Metallic cellular
elements
C or N M2X type

82
Precipitates in Co-Cr-Mo alloys
σ-phase η-phase p-phase
c-phase M23X6 M7X3 M2X
Co(CrMo) M6X-M12X M2T3X

5 mm

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


Phase Alloys (heat treat. cond.) Co Cr Mo C N Si Mn
16.1 67.4 10. 5.6 N.D. N.D. 0.1
M23X6 type 1Si1Mn0.175N (1448 K, 0 ks)
8
34.4 38.1 21. 2.7 0.7 1.3 1.1
p-phase 1Si1Mn0.175N (1548 K, 0 ks)
7
32.5 21.6 38. 2.3 1.0 4.0 -
h-phase 1Si0Mn0.175N (1523 K, 1.8 ks)
6
47.3 33.4 17. N.D. - 1.8 -83
Microstructural control in biomedical Co-Cr-Mo alloys

Elements Matrix
Metallic fcc
C, N
elements hcp
Reaction・Interaction
Corrosion resistance
Workability
Mechanical properties

Precipitates
Carbide
Intermetallics
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 Applied to the medical
those of stainless steels and Co-Cr alloys. 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 For parts that experience
living remodeling bone without any soft long-term contact with bone
tissue component between implant and
bone on the optical microscopic level 85
Contents

(1) Allotropic transformation


(2) Metastable phase
(3) Reactivity
(4) Reaction with oxygen
(5) Classification of titanium materials
(6) 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 Tβ 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
酸素(O2) 窒素(N2) 炭素(C) 親和力 溶解度 類似元素
チタン :2TiO :2TiN :TiC 大 大 Zr
鉄 :2FeO :2Fe4N :Fe3C 小 中 Ni, Cr
アルミニウム :(2/3)Al2O3 :2AlN :(1/3)Al4C3 大 小 Mg, Si

高親和力
高溶解度

95
Stability of passive film on Ti

Table 2-9 Regeneration time of passive film.

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

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 High corrosion Biocompatible


variety of microstructure resistance

High solubility of Titanium Strong bonding Difficult to react


other elements (very reactive) with oxygen with biomolecules

Reduction of rutile (TiO2) or


ilmenite (FeTiO3) is difficult.

Expensive
Difficult to purify 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 single phase microstructure
b type 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.

5µm

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% ) To tal
Te nsileS treng th
N o. T ype M aterials Elongation
Al V Nb Ta Mo Zr Fe H O N C O thers Ti (MP a)
(% )
CP T i,Gr .1E L I - - - - - - < 0.10 < 0.0125 < 0.10 < 0.012 < 0.03 - B al. > 200 > 30
CP T i,Gr .1 - - - - - - < 0.20 < 0.0125 < 0.18 < 0.03 < 0.10 - B al. > 240 > 24
CP T i,Gr .2 - - - - - - < 0.30 < 0.0125 < 0.25 < 0.03 < 0.10 - B al. > 345 > 20
JIS T 7401- 1 a CP T i,Gr .3 - - - - - - < 0.30 < 0.0125 < 0.35 < 0.05 < 0.10 - B al. > 450 > 18
CP T i,Gr .4A - - - - - - < 0.50 < 0.0125 < 0.40 < 0.05 < 0.10 - B al. > 550 > 15
> 680 > 10
C P T i,Gr .4B - - - - - - < 0.50 < 0.0125 < 0.40 < 0.05 < 0.10 - B al.
(CW ) (CW )
> 860 > 10
JIS T 7401- 2 a+ b T i-6Al- 4V 5.5- 6.75 3.5- 4.5 - - - - < 0.30 < 0.015 < 0.20 < 0.05 < 0.08 - B al.
(bar) (bar)
> 860 > 12
JIS T 7401- 3 a+ b T i-6Al- 2N b- 1T a 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.
(bar) (bar)
Pd > 860 > 12
JIS T 7401- 4 a+ b T i-1 5Z r-4 Nb -4T a - - 3.5- 4.5 3.5- 4.5 - 14.5-15 .5 < 0.25 < 0.0125 < 0.20 < 0.05 < 0.05 B al.
< 0.25 (bar) (bar)
> 900 > 10
JIS T 7401- 5 a+ b T i-6Al- 7N b 5.5- 6.5 - 6.5- 7.5 < 0.50 - - < 0.25 < 0.009 < 0.20 < 0.05 < 0.08 - B al.
(bar) (bar)
> 940 > 12
JIS T 7401- 6 b T i-1 5Mo-5Z r-3Al 2.5- 3.5 - - - 14.0-16 .0 4.5- 5.5 < 0.35 < 0.02 < 0.20 < 0.05 < 0.05 - B al.
(bar) (bar)
CP T i,Gr ade 1 - - - - - - < 0.20 < 0.015 < 0.18 < 0.03 < 0.08 - B al. > 240 > 24
CP T i,Gr ade 2 - - - - - - < 0.30 < 0.015 < 0.25 < 0.03 < 0.08 - B al. > 345 > 20
AS T M F 67 a
CP T i,Gr ade 3 - - - - - - < 0.30 < 0.015 < 0.35 < 0.05 < 0.08 - B al. > 450 > 18
CP T i,Gr ade 4 - - - - - - < 0.50 < 0.015 < 0.40 < 0.05 < 0.08 - B al. > 550 > 15
> 860 > 10
AS T M F 136
a+ b 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. (bar< (bar<
(Wr oug ht)
0.187in.) 0.187in.)
AS T M F 1108
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. > 860 >8
(Cast)
> 900 > 10
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.
(bar,w ire) (bar,w ire)
AS T M F 1472 Y > 930 > 10
a+ b T i-6Al- 4V 5.5- 6.75 3.5- 4.5 - - - - < 0.30 < 0.015 < 0.20 < 0.05 < 0.08 B al.
(Wr oug ht) < 0.005 (Ba r<2 in.) (Ba r<2 in.)
> 860 >8
(aged ) (aged )
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. > 550 > 15
(solution (solution
treated) treated
AS T M F 1813 b T i-1 2Mo-6Z r-2F e - - - - 10.0-13 .0 5.0- 7.0 1.5- 2.5 < 0.020 0.008-0 .28 < 0.05 < 0.05 - B al. > 931.5 > 12
14.00- > 690 > 20
AS T M F 2066 b T i-1 5Mo - - - - - < 0.10 < 0.015 < 0.20 < 0.05 < 0.10 - B al.
16.00 (bar,w ire) (bar,w ire)
> 621 > 15
(anne aled) (anne aled)
2.00- Y > 862 > 10
AS T M F 2146 a+ b T i-3Al-2.5V 2.50-3 .50 - - - - < 0.30 < 0.015 < 0.12 < 0.020 < 0.050 B al.
3.00 < 0.005 (cold w orked (cold w orked
and stress- and stress-
relieved) relieved)

(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 Gr.4

Oxygen content Increase


Iron content Increase
Strength Increase
Ductility 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 (V→other b stabilized elements)
1980 Ti-5Al-2.5Fe
1985 Ti-6Al-7Nb
1995 Ti-5Al-3Mo-4Zr
Al-free (Al→other 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


(Young’s modulus)

111
Effect of elastic modulus
Load
荷重
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
Bone
骨:20GPa main cause of implant loosening and stress
shielding of bone.

316Lステンレス鋼:200GPa
SUS316L : 200 GPa
Co-Cr合金(鋳造):200GPa
Co-Cr-Mo alloy : 200 GPa
Co-Cr合金(鍛造):200GPa
CP Ti, Ti-6Al-4V
純Ti:100GPa : 100-110 GPa
b type Ti alloys
Ti-6Al-4V合金:100GPa : 80 GPa

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. Brånemark
(ルンド大学, スウェーデン)
1952年:
チタンと骨が結合することを発見
オッセオインテグレーション:
骨組織とチタンが光学顕微鏡レベルで
直接密着し、持続した結合状態を呈し、
インプラント体に加わった力が骨組織
に直接伝達される

長期間にわたり骨組織との接触が
想定される部位へのチタン応用に関
する学術的根拠が与えられる
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 a+b type Ti-15Zr-4Nb-4Ta-0.2Pd-0.2O-0.05N
Neurotoxicity of Al b type Ti-29Nb-13Ta-4.6Zr
Low cost
Fe and O are main impurity elements in a+b type Ti-Fe-O-N alloys
sponge Ti produced by the Kroll process
Lowering in elastic modulus
Mismatch between the elastic loosening and b type Ti alloys in Ti-Nb
moduli of the implant and bone stress shielding and Ti-Mo systems
Shape memory effect/superelasticity
NiTi exhibits a shape memory Dental archwire Ti-Nb and Ti-Mo systems
effect and superelasticity Vascular stent with b/a” transformation
Surface modification
Improving tissue compatibility with Morphology
Surface
maintaining microstructure of titanium Phase/composition
Fabrication of porous body
Low elastic modulus 118
Applied to scaffold for bone regeneration and tissue engineering
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
Ta:高耐食性、弾性率は185 GPa程度、展延性に富み
高比重(>19),高融点(約3300 K)で

1990年代半ばから生体用の電極やメッシュとしてとして使用
1990年代後半からはポーラスTaが人工股関節のカップ部,人工膝関節
の大腿骨側,脛骨側部に利用

ポーラスTa:CVD/CVI法で網目状ガラス質炭素表面に形成
オッセオインテグレーションを有するとされる

Zirconium
Zr:Tiと同族元素、不動態皮膜に起因する優れた耐食性、低磁化率
オッセオインテグレーションの機能は有していない
表面硬化処理を施したZr-2.5Nb合金が人工股関節骨頭などへ応用

120
Future trend in fabricating metallic biomaterials

New generation
Low cost metallic biomaterials

121