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1. The Pourbaix diagram of manganese is given below. Mark each zone with Corrosion,
Passivation, or Immunity.
Corrosion
Passivation
Corrosion
Passivation
Passivation
Corrosion
Passivation
Passivation
Immune
3. Search on internet (Google, Pubmed and Web of Science are recommended) and find
the pH values of the following organs of the body:
a. Stomach
b. Lung
c. Liver
d. Small intestine
17
4. Search on internet (Google, Pubmed and Web of Science are recommended) for the
electrode potential of Co or Co-base alloys in sea water. Use this electrode potential
as the first approximation to predict the corrosion potential of Co in the body, based
on the Pourbaix diagram of Co below. Analyze what could happen if a cobalt
prosthesis is exposed to the above three micro anatomic environments in Exercise 1,
and cite the reference properly.
Answer
In sea water, Ecorr of Co-Cr alloy is -0.25V (SCE) = -0.008V (SHE).
Ref:http://www.google.com.au/url?sa=t&rct=j&q=&esrc=s&frm=1&source=web&c
d=1&ved=0CB0QFjAA&url=http%3A%2F%2Fstellite.co.uk%2FPortals%2F0%2FS
tellite%25206%2520Final.pdf&ei=c6cJVLenOM-
zuAS4kID4CA&usg=AFQjCNFDqzcIxDd16MXzqTARtYsVwI3eHw&bvm=bv.74
649129,d.dGc
When pH = 3.5, or 7.4, Co2+ ion is stable, and thus corrosion is possible.
When pH = 9.0, Co3O4 is stable and thus passivity is possible.
5. Read the corrosion potential of magnesium on Figure 2.5. The Pourbaix diagram of
magnesium is given below. Analyze the corrosion tendency of this metal in normal
body fluid.
18
Answer
The corrosion potential of magnesium in sea water is about -1.6.
When pH = 3.5, or 7.4, Mg2+ ion is stable, and thus corrosion is possible.
When pH = 9.0, Mg(OH)2 is stable and thus passivity is possible.
6. Compare the relative location of the following pairs of metals in the emf series and
in the galvanic series for seawater.
(a) Zinc and chromium (use 316 stainless steels for chromium in the galvanic series
for seawater)
(b) Platinum and titanium
(c) Nickel and silver
(d) Titanium and aluminium (use aluminium alloys for aluminium in the galvanic
series for seawater)
What does the relative position of these various pairs of metals tell you about the
use of the emf series to predict possible galvanic corrosion in seawater?
Answer
(a) Zinc (-0.762) and Cr (-0.744), the two are close in emf series.
Zinc (-1.0) and Cr (-0.1), the two are distant in the galvanic series.
(b) Pt (+1.18) and Ti (-1.630), the two are distant in emf series.
Pt (+0.2) and Ti (0.0), the two are close in the galvanic series.
(c) Ti (-1.630) and Al (-1.662), the two are very close in emf series.
Ti (0.0) and Al (-0.3), the two are distant the galvanic series.
Hence, the emf series cannot be used reliably to predict the corrosion tendencies of
coupled metals in other than standardized environments, such as sea water.
19
7. Avoid surface damage of metallic implants is strongly advised to orthopedists in
surgical operations. Explain the reason behind this clinical good practice.
Answer
The corrosion resistance of metallic implants are achieved by passivation. That is, a
thin oxide layer forms on the surface, which can protect the metal from anodic
dissolution. Hence, surface perfection is important.
8. What long-term toxic effects could be caused by the release of nickel and chromium
ions?
Answer
Metal allergy and cancer.
9. Although magnesium is a macro-element in the body, what disease could be
introduced by a long-term over-dose of magnesium in the body?
Answer
There is a risk of renal dysfunction with an overdose of magnesium
10. Search on internet and identify at least two trace elements that are not included in
Table 2.4. Describe their biological roles in maintaining health, and their toxicity if
over dosed.
No standard answer. It is entirely for students to find out.
20
Chapter 3
1. In Table 3.1, the yield strength is Not Applicable (N.A.) for ceramics and skin.
Explain the reasons.
Answer
Yield point is when deformation transits from elastic to plastic.
Ceramics are highly brittle such that they virtually show no plastic deformation
before fracture.
Skin, on the other extreme end, is highly elastic, virtually elastic all the way until
rupture with little plastic deformation.
Answer
(a) 420 MPa
(b) 460 MPa
(c) 3.2%
21
Courtesy of CRC Press/Taylor & Francis Group
(a)
Normal bone Osteoporosis
(b)
Figure 2.1
(a) Iron-deficiency anemia; (b) boron-deficiency osteoporosis; (Continued)
002x001a.eps 002x001b.eps
Courtesy of CRC Press/Taylor & Francis Group
(c) (d)
002x001c.eps
Courtesy of CRC Press/Taylor & Francis Group
1.8
Ti
Coefficient of fibroblastic outgrowth
1.6 Capsule
104
Ag 102
0.8 Pt
Bi Vital
Ag
0.6
Fe Co 100 V Au
0.4 Ni
Sr Cu Al Mo
0.2 Mg V, Cu, Zn 10–1
Cd, Hg Toxic Mo? Fe
0 Co
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 Biocompatibility
Relative growth rate of L929 cells
(a) (b)
Figure 2.2
(a) Cytotoxicity of some pure metals. (b) The relationship between polarization resistance and biocompatibility of
pure metals, cobalt–chromium alloy, and stainless steels.
002x002.eps
Courtesy of CRC Press/Taylor & Francis Group
Earth
Mining
(casting)
Billets (or called ingots)
Thermomechanical processing
Figure 2.3
Processing of metals.
002x003.eps
Courtesy of CRC Press/Taylor & Francis Group
Magnesium Copper
2+ 2+
2+
2+ 2+ 2+
2+ 2+
2+
2+ 2+ 2+
2+ 2+ Water
2+
Figure 2.4
Electrical double layer (EDL) around metals in pure water, showing that an electrode potential exits across the
metal/solution interface.
002x004.eps
Courtesy of CRC Press/Taylor & Francis Group
Active Magnesium
Zinc
Berylium
Aluminum alloys
Cadmium
Mild steel, cast iron
Low alloy steel
Austenitic Ni cast iron
Aluminum bronze
Naval brass, yellow brass, red brass
Tin
Copper
Pd-Sn solder (50/50)
Admiralty brass, aluminum brass
Manganese bronze
Silicon bronze
Tin bronzes
Stainless steel Types 410, 416
Nickel silver
90-10 Cu-Ni
80-20 Cu-Ni
Stainless steel Type 430
Lead
70-30 Cu-Ni
Ni-Al bronze
Ni-Cr alloy 600
Silver braze alloys
Nickel
Silver
Stainless steel Type 304
Ni-Cu alloys 400, K-500 (Monel)
Stainless steel Type 316
Alloy 20
Ni-Fe-Cr alloy 825
Ni-Cr-Mo-Cu-Si alloy B
Titanium
Ni-Cr-Mo alloy C
Platinum
Graphite
Noble
0.5 0.0 –.0.5 –1.0 –1.5
E in V vs. SCE
Figure 2.5
The galvanic series in seawater. (Redrawn from LaQue, F.L.: Marine Corrosion, Chapter 6. 1975. Copyright Wiley-
VCH Verlag GmbH & Co. KGaA, New York. Reproduced with permission.)
002x005.eps
Courtesy of CRC Press/Taylor & Francis Group
1.6
Oxygen
1.2
0.8
(b)
0.4
Eh/V
Water
0
–0.4
(a)
–0.8 Hydrogen
–1.2
–2 0 4 8 12 16
pH
Figure 2.6
Pourbaix diagram of water.
Two lines:
Below line (a)—water is unstable and must decompose to H2
Above line (a)—water is stable and any H2 present is oxidized to H+ or H2O
Above line (b)—water is unstable and must oxidize to give O2
Below line (b)—water is stable and any dissolved O2 is reduced to H2O
Three regions:
Upper: H2O electrolyzed anodically to O2
Lower: H2O electrolyzed cathodically to H2
Middle: H2O stable and will not decompose
002x006.eps
Courtesy of CRC Press/Taylor & Francis Group
2.0
(Corrosion)
1.5
b (Passivity) 2.3
1.0 CuO
Cu+2 –2
E in V vs. SHE
Passivation
CuO2
Corrosion
0.5 (Corrosion)
Cu2O Corrosion
0.0 a
Cu
–0.5 0.0
(Immunity)
–1.0
Cu stable
–1.5 (immunity)
0 4 8 12 16 –1.6
0 7 14
pH pH
(a) (b)
Figure 2.7
Pourbaix diagram of copper. (a) The Pourbaix diagram of copper superimposed by diagram for water. (b) Three
regions: corrosion, passivation, and immunity. (From the WikimediaCommons, http://commons.wikimedia.org/.)
In regions where
• Cu2+ or CuO22− ion is stable, corrosion is possible
• Copper oxide Cu2O or copper hydroxide Cu (OH)2 is stable, passivity is possible
• Cu is stable, thermodynamically immune to corrosion
002x007a.eps 002x007b.eps
Courtesy of CRC Press/Taylor & Francis Group
2.0 2.0
AgO
1.5 1.5 Fe+3
(Passivity)
b b
1.0 (Corrosion) 1.0
(corrosion)
Ag+
E in V vs. SHE
E in V vs. SHE
0.5 (Corrosion) 0.5
AgO– Fe2O3
0.0 a
Ag
(Passivity)
0.0 a Fe+2
(Immunity)
Fe3O4
–0.5 –0.5
–1.0 –1.0 Fe
(Immunity) HFeO2– (corrosion)
–1.5 –1.5
0 4 8 12 16 0 4 8 12 16
(a) pH (b) pH
2.0 2.0
(Corrosion)
b
1.5
b (Passivity)
1.0
1.0 +2
CuO
E in V vs. SHE
E in V vs. SHE
Cu
CuO–2
0.5 (Corrosion) 2
a Ti
+3
(Passivity) Cu2O
0.0
TiO2 0.0 a
Cu
–1.0 –0.5
Ti+2
(Immunity)
(Corrosion)
Ti2O3 –1.0
–2.0 Ti (immunity) TiO –1.5
0 4 8 12 16 0 4 8 12 16
(c) pH (d) pH
Figure 2.8
Pourbaix diagrams of silver (Ag), iron (Fe), titanium (Ti), and copper (Cu). (a) E corr = −0.12 V (SCE) = 0.122 V
(SHE). When pH = 3.5, 7.4 or 9.0, Ag is stable. Immunity is possible. (b) Ecorr = −0.466 V (SCE) = −0.224 V (SHE)
[7], when pH = 3.5 or 7.4, Fe+2 is stable, Corrosion is possible; when pH = 9.0, Fe2O3 is stable, Passivity is possible.
(c) Ecorr = 0 V (SCE) = 0.242 V (SHE), when pH = 3.5, 7.4 or 9.0, TiO2 is stable, Passivity is possible. (d) Ecorr =
−0.3 V (SCE) = −0.058 V (SHE), when pH = 3.5 or 7.4, Cu is stable, Immunity is possible. When pH = 9.0, Cu2O
is stable, Passivity is possible.
002x008a.eps
Last Lecture
• A biomaterial is a biocompatible material, which
is used to replace or assist part of an organ or its
tissue, while in intimate contact with living tissue.
Question 1
Part I
Biomaterials Science
Chapter 2
Toxicity and Corrosion of
Materials
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Recommend Reading
Introduction to Corrosion Science, by E
Chapter 2 of
McCafferty. Springer (Excellent Book)
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Element O C H N Ca P K S Na Cl Mg Trace
Elements
Wt.% 65 18.5 9.5 3.3 1.5 1.0 0.4 0.3 0.2 0.2 0.1 <0.01%
At.% 26 10 62 1.5 0.5
Question 2
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Erin Brockovich
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Biocompatibility of
Trace Elements
• Most trace elements can be tolerated
by the body in minute amounts, but
cannot be tolerated in large amounts in
the body, although they are essentials in
cell function (e.g. Fe) and vitamin B12 (e.g.
Co), for instance.
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Metallic Structure-Properties
• Metallic valency gives following properties
Conductive (thermally and electrically)
Ductile (non-brittle, safe to be used in
structure)
Strong (good combination of strength and
ductility)
Corrosion
Considerations in Designing
Metallic Implants
• Primarily
Priority choices of elements are those
either native in the body (such as Fe, Ti
and Cr) or inert (such as Au).
Design corrosion resistant alloys.
• Secondarily
Other desired properties.
Questions 3&4
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Ores
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Processing of Metals
Earth
Mining
Ores: oxides, sulfides, silicates
Extractive Metallurgy Pure metals
(Casting)
During use
Corrosion
Thermomechanical Processing
Electrode Potential E
• The difference in electric potentials across
a metal/solution interface is commonly
referred to as an electrode potential.
• Theoretically, the electrode potential can
be measured as voltage and used to
indicate the tendency of electrons to flow
away, i.e. the tendency of the metal to be
ionised.
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
http://en.wikipedia.org/wiki/Table_of_standard_electrode_potentials
http://www.engr.ku.edu/~rhale/ae510/corrosion/sld021.htm
http://www.csupomona.edu/~seskandari/physiology/physiological
_calculators/nernst_potential.html
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
corrosion tendency
Increasing
corrosion tendency
Decreasing
Electromotive Force Series
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Question 5
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Galvanic Corrosion
• When two dissimilar metals are immersed in
an electrolyte and electrically connected, one
metal corrodes preferentially to another, a
process called Galvanic corrosion. In
Galvanic corrosion, the anodic metal will
have a higher corrosion rate in the couple
than in the freely corroding (uncoupled)
condition. Galvanic corrosion is usually not a
desired occurrence. It can be minimized by a
number of methods
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Pourbaix Diagrams
–Corrosion Phase Diagrams
Two lines:
Below line {a} – water is unstable and must decompose to H2
Above line {a} – water is stable and any H2 present is oxidised to H+ or H2O
Above line {b} – water is unstable and must oxidize to give O2
Below line {b} – water is stable and any dissolved O2 is reduced to H2O
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Oxygen
Water
Hydrogen (Immunity)
Pourbaix diagram is similar to phase diagram. A phase diagram tells you the gas,
liquid, solid state of materials when (T, P and X) change. A Pourbaix diagram tells
you the ionic state of the material when (Voltage and pH) vary.
Part I BIOMATERIALS
Chap 2 Toxicity & Corrosion
Minimisation of Corrosion
1. Use appropriate metals (native or inert
elements of the body).
2. Design alloys to minimise corrosion.
Mechanical Properties