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(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
5
1. Introduction: contents
6
1.1 Biological environment
(i) High demand
Internal in living system: remarkably aggressive
high chemical activity
mechanical stress
reactions with cells
(iii) Many sets of conditions associated with parts and life process
7
Biological and mechanical conditions
Table 1-1
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
• 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
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
cup
stem
(Cr2O3)
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
24
Characterictic of biomaterials
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)
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
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
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
41
Biomaterials used in orthopedic field in Japan
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
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
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
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
53
Formation of Crystal
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;
56
Crystal Defect
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
61
2.2 Stainless steels
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.
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
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
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
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
40 Cr
V
Mo W
Ti 20
Zr
C Ta Nb Si
(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.
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
76
Co-28Cr-6Mo-xC alloys: as-cast
(a) 0.12C (b) 0.15C
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.
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
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
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.
87
Effect of alloying elements on phase stability
88
Typical phase diagrams in Ti-X system
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
91
Metastable phases in Ti-Nb system
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
Time
96
Reactivity of titanium
Provide a lot of titanium alloys with
a wide variety of mechanical properties.
Expensive
Difficult to purify Special smelting process
Figure 2-12 Relationship between reactivity and properties of titanium materials. 97
(4) Reaction with oxygen
5µm
102
Phase diagram
104
(a) a type
105
CP titanium
Gr.1 Gr.2 Gr.3 Gr.4
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
109
Biocompatibility and corrosion resistance
in pure metals and alloys
110
(c) b type
Excellent workability
High strength
(through aging treatment)
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
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
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
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