Biomaterials, Artificial Organs and Tissue Engineering

Chapter 2

Metals
Dr E. Jane Minay and Dr Aldo R. Boccaccini Imperial College London

The Periodic Table

H Li Na K Rb Cs Fr Be Mg Ca Sr Ba Ra Sc Y
Rare earth series Actinide series

He B Al Ti Zr Hf V Nb Ta Cr Mo W Mn Tc Re Fe Ru Os Co Rh Ir Ni Pd Pt Cu Ag Au Zn Cd Hg Ga In Tl C Si Ge Sn Pb N P As Sb Bi O S Se Te Po F Cl Br I At Ne Ar Kr Xe Rn

La Ac

Ce Th

Pr Pa

Nd U

Pm Np

Sm Pu

Eu Am

Gd Cm

Tb Bk

Dy Cf

Ho Es

Er Fm

Tm Md

Yb No

Lu Lw

Fig. 2.1 The periodic table showing the metals (yellow), non-metals (red) and intermediate (blue) elements. Metals are good conductors of heat and electricity, opaque to visible light, and have a familiar metallic lustre.

Model 1
e+ + + eee+ e+ + ee+ e+ e- + e+ + e- + e- + + ee + + ee+ + e- e+ - + e e e+ + e+ e-

e+ e- e+ e+

+ e + + e- ee e+ + + + e- + eeee e + + + + + e

e+

Fig. 2.2 One model of a metal, positive ions are surrounded by a sea or cloud of electrons. These free electrons are not bound to any particular metal ion but are free to move around within the structure. It is these free electrons that result in some of the typical properties of a metal including the good conductance of heat and electricity, and the metallic lustre of a polished surface.

Model 2: f.c.c.

A A B A B A C C A A B B C C A A A A

A A A B B B B A B A B A C C C C A A A A B A B A B B C C C C C C A A A A AA

Fig. 2.3 (animated) The face centred cubic (f.c.c.) structure can be considered as a repeating stack of closely packed layers of hard spheres.

Fig. 2.3 shows that the face centred cubic (f.c.c.) structure can be considered as a repeating stack of closely packed layers of hard spheres. Each layer has the highest possible density of spheres, each sphere touching six neighbouring spheres. The first layer can be considered as being in the A position. The next layer sits on top of this layer in the B position. The third layer can sit on the second layer either with each sphere directly above the spheres in the A layer or in the third possible position, C. In the f.c.c. structure the third layer sits in the C position. The overall structure is a sequence of layers stacked in the order ABCABCABC. Each sphere touches 12 others. Aluminium, nickel and iron (at high temperatures) all have this type of structure.

Fig. 2.4 (animated) The face centred cube structure

Fig. 2.4 shows that the face centred cube in this structure can be easily seen if you take two closely packed layers, each containing 6 spheres arranged in a triangle, pointing down in the lower layer and up in the other layer. Place one sphere in the recess of the spheres below the lower layer and another sphere in the recess above the upper layer. Now stack the two structures so the atoms sit in a ABCA sequence. The cube has a sphere centred on each corner and a sphere in the centre of each face.

Model 2: h.c.p.

B B A C

A C B B A

B B A C

A C B B A

B B A C

A C B B A

B B A C

Fig. 2.5 The hexagonal close packed structure also consists of a stack of closely stacked planes, however this time the stacking sequence is ABABAB. Like the f.c.c. structure each sphere is touching 12 others. Zinc, magnesium and titanium (at room temperature) all have this type of structure.

h.c.p.

a
Fig. 2.6 A hexagonal prism can be seen in this structure by taking atoms from
three of the closely packed planes, ABA.

Model 2: b.c.c.

<B> <B> <B> <B>

Fig. 2.7 The bcc structure does not contain closely packed planes. The structure can be contained in a cube with a sphere centred on each corner and a sphere in the centre of the cube. Each sphere is only touching 8 other spheres. Chromium, Iron (at room temperature) and Ti (at high temperature) all have this type of structure.

Microstructure of a steel

50m

Fig. 2.8 Microstructure of an Fe-C alloy observed using an optical microscope. The material has been polished to give a smooth surface and etched using nital to reveal grain and phase boundaries. Light coloured grains are outlined and dark areas consist of a finer structure which is not resolved at this magnification.

Metallic Fracture

5m

10m

Fig. 2.9 Scanning electron microscope image of a metallic fracture surfaces. The top image is of a metal which has fractured along the grain boundaries in a brittle manner. The lower image shows a typical fracture surface of a metal that has failed in a more ductile manner. The large depth of field can be seen in these images.

Precipitation

200nm
Fig. 2.10 Transmission electron microscope image taken through a thin film of metal showing small bright cubic precipitates in a darker matrix.

Effect of grain size

Fig. 2.11 Graph showing the effect of grain size on the yield stress of a commercially pure titanium alloy. YS=231+10.54 d-1/2 where the yield stress is in MPa and the grain size is in mm.

Tensile properties of metals

Tensile Strength Yield Stress Plastic Deformation Non-reversible

Fracture

Recoverable Elastic Strain

Fig. 2.12 Typical stress strain behaviour of a metallic material tested in tension. The metal behaves elastically for the blue portion of the curve, permanent (plastic) deformation (red section) begins at the yield stress of the metal, a maximum stress is reached, the stress then decreases until ultimately the metal fractures.

Mechanical properties of metals

Youngs Modulus (GPa) Steels (General) Stainless Steels Titanium Alloys Platinum 210 190-210 100-115 170

Yield Stress (MPa) 210-1600 200-1650 170-1100 10

Tensile Strength (MPa) 400-1800 400-1800 400-1200 120-240

% elongation 10-40 5-40 10-30 1-40

Fracture Toughness (MPam1/2) 50-90 80 40-70 -

Fig. 2.13 Table of typical properties of some metals and alloys

Fatigue properties of metals

Bending Stress, S, MPa
400

Mild Steel
300 200 100 0

Fatigue Limit Aluminium

105

106

107

108

109

Number of Cycles to Failure, N

Fig. 2.14 The typical way of presenting fatigue data is a graph of the alternating stress against the log of number of cycles to failure. The two types of fatigue behaviour are shown here, the first in green is the behaviour of many non-ferrous alloys such as aluminium. The number of cycles to failure increases as the alternating stress decreases. The second type of behaviour, in red is typical of ferrous alloys and titanium alloys, a fatigue limit is observed. Below this stress the metal has an effectively infinite fatigue life.

The shape memory effect

Heat Cool
Correspondence Variant A Correspondence Variant B Correspondence Variant A

Fig. 2.15

Correspondence Variant A Correspondence Variant B Correspondence Variant A

Figure 2.15 shows a schematic mechanism of the shape memory effect. As the metal is heated and cooled the atomic arrangement changes between one of high symmetry at high temperature (in this schematic a square array) to a lower symmetry arrangement at low temperature (in this case a diamond array). Several variants of the lower symmetry phase will form. The arrangement will change backwards and forwards as the metal is heated and cooled with no overall shape shape being observed. If the metal is deformed whilst it is in its low temperature structure the atoms move in such a way that one variant grows at the expense of the others. If the metal is then heated to return to the higher symmetry structure (the square array) the metal will return to is original shape. This is the shape memory effect.

Crevice Corrosion

Magnification of metal joint and crevice

Cl-

O2
M+

OH-

O2
Na+

e e
Na+ M+ ClNa+ M+

O2
Na+ Cl-

O2 O2
Cl-

OHOHOHClCl-

O2
M+

Na+

O2

e e e
M+

O2 ClOH-

O2
OH-

M+

O2
OH-

O2
OH-

O2 O2
OH-

O2

M+ M+ H+ Cl H+ Cl- H+ M+ M+

Fig. 2.16 The mechanism of crevice corrosion.

Figure 2.16 shows the mechanism of crevice corrosion. A stagnant zone exists in the crevice. Initially corrosion occurs at a uniform rate over the entire surface of the metal. After a short time the oxygen in the crevice is used up. No reduction of oxygen to hydroxyl ions occurs in this area, although the dissolution of metal continues. An excess of positive charge is produced in the solution by the metal ions. This is balanced by the migration of chloride ions into the crevice. The concentration of metal chloride increases within the crevice. The metal ions and chloride ions react with water to form an insoluble metal hydroxide, MOH and a free acid H+Cl-.Both chloride and hydrogen ions accelerate the dissolution rates of most metals and alloys and the process becomes auto catalytic.