Metals and alloys

in dental medicine
©Department of Medical and Clinical Biochemistry
UPJŠ in Košice, Faculty of Medicine
Metals and alloys in dental medicine
Contents

• General characteristics
• Crystal formation, crystal structure
• Metallic bond
• Cooling curves
• Phase diagram, eutecticum
• Properties of pure metal
• Classification and properties of dental alloys
Metals and alloys
Metals and alloys

• The oldest material used in prosthetics

• Etruscan dentures, implant of a Gallic
warrior
• Widely used for its strength, hardness,
durability
• Necessary to combine them in the
form of an alloy
Metals and alloys
Properties
• Metals in general: hard and shiny (except mercury) - the characteristic
properties of metals disappear in the gaseous state
‒ crystalline structure
‒ opaque
‒ good conductors of heat and electricity (electrical conductivity decreases with
increasing temperature)
• Shaping:
‒ casting (heating until it becomes molten)
‒ cold working (mechanical shaping at relatively low temperatures)
‒ amalgamation (some alloys mixed with Hg to form plastic mass)
Metals and alloys
Properties

• Halves: properties between metals and nonmetals

‒ retain the properties of metals such as strength and luster, but are brittle
and not malleable
‒ low electrical conductivity (increases with increasing temperature)
• Using in dentristry:
‒ crowns
‒ filling material (amalgam)
‒ construction for instruments
‒ wires for orthodontics...
Metals and alloys
Classification
Accordin to:
- weight: hard – Pt, Au, W, Rh, Pd, Pb, Ag, Ni, Cu
light – Al, Mg, Be, Li, Na, K, Ti, Si
- melting point: low-melting – e.g. Sn, Bi, Cd, Pb, Zn, Mg, Al
medium-melting – e.g. Ag, Au, Cu, Be, Ni, Co, Fe
high-melting – e.g. Mo, W
- reactivity: noble – e.g. Ag, Au, Pt, Pd, Rh
base
- their appearance: white (Zn, Sb, Pb and their alloys)
black (Fe and its alloys)
coloured (Cu and its alloys)
Metals and alloys
Crystal structure
Crystal formation
cooling of the melt leads to solidification
‒ solidification - the transformation of the liquid phase into a solid
‒ crystallization - the event when the substance solidifies as a crystalline substance

− creation of crystal nuclei oriented in each direction

− crystal growth, depletion of the liquid phase
− formation of grains of metals
Metals and alloys
Crystal structure
The shape of grains:

- globular

- polyhedral

- dendritic

- lamelar
Metals and alloys face-centered cubic
Crystal structure FCC
Au, Ag, Pt, Pd, Ir, Cu, α-Co, Ni, γ-Fe,
Crystal types
Al, Th, Rh, Pb
body-centered cubic
BCC
Li, Na, K, α-Cr, Mo, W, V, Ta, α-Fe, δ-Cr

hexagonal closed-packed
HCP
Zn, Cd, Ti, Os, Ru, Tl, Zr, Be, Mg, Hf,
Cr, Co

rhomboedric
Hg, Sb, Bi
Metals and alloys
Crystal structure
Characteristic of crystals
- coordination number - the number of its nearest neighbours
8 12 12

BCC FCC HCP

- atomic packing factor, APF
the fraction of volume in a crystal structure occupied by atoms
FCC 0.74 f=Vn/V * 100
BCC 0.68 Vn – the volume of n atoms in the crystal unit cell,
HCP 0.74 V – the volume of the crystal unit cell
Metals and alloys
Crystal structure
rapid cooling slow cooling
Crystal formation

Rate of cooling

more nuclei fewer nuclei

smaller grains larger grains

desirable to have 500 grains / mm2

Metals and alloys
Metalic bond – Metallic bonding

− electrons of metals released easily

− can move freely within positively charged ions
− the electrons said to be delocalized
− electrostatic attractive forces between the delocalized electrons
− accounts for many physical characteristics of metals, such as strength, malleability,
ductility, conduction of heat and electricity, and luster
Metals and alloys
Types of minerals
Type Mineral
Carbonates CaCO3 (calcite), MgCO3 (magnesite), CaCO3.MgCO3 (dolomite),
PbCO3 (cerussite), ZnCO3 (smithsonite)
Halides CaF2 (fluorite), NaCl (halite), KCl (sylvite), Na3AlF6 (cryolite)

Oxides Al2O3 (corundum), Al2O3.2H2O (bauxite), Fe2O3 (hematite), Fe3O4

(magnetite), Cu2O (cuprite), ZnO (zincite)
Sulfides Ag2S (argentite), Cu2S (chalcocite), FeS2 (pyrite), HgS (cinnabar),
PbS (galena), ZnS (sphalerite)
Sulfates BaSO4 (barite), CaSO4 (anhydrite), PbSO4 (anglesite)
Silicates Be3Al2Si6O18 (beryl), AnAlSi3O8 (albite)
Phosphates Ca5(PO4)3OH (hydropxyapatite)
Hydroxides Al(OH)3 (gibbsite), Mg(OH)2 (brucite), Mg3(Si4O10)(OH)2 (talc)
Metals and alloys
Methods of preparation
reduction of oxides:
the most important method for the preparation of metals from minerals - the possibility of
reducing by electronegativity

if the electronegativity > than Zn (1.6) – reduction at high temperature by hydrogen

other reductants: C, Al, Mg

reduction of carbonates: ZnCO3 → ZnO + CO2

reduction of sulfides:
heating at the air, the sulfide converted to oxide, then reduction by carbon
2ZnS + 3O2 → 2ZnO + 2SO2 subsequently ZnO + C → Zn + CO

heating of the sulfide by powdered iron

HgS + Fe → FeS + Hg
Metals and alloys
Methods of preparation
reduction of halides
less important
by the action of low electronegative metals, such as Na, K, Ca
method of thermal decomposition of halides
great importance
run on incandescent tungsten wire
ZrI4 → Zr + 2I2
electrolysis of melted halides
usually in a mixture with compounds that lower the melting point and increase the
conductivity
electrolysis of water solutions of salts
in technical practice for the preparation of metals in a pure state
Metals and alloys
Phase diagrams
Phase
the structure or form of the substance with certain characteristics

in alloys
the areas with the same chemical composition but different state
or vice versa

− the number of phases affects the strength, corrosion resistance, biocompatibility

Pure metal vs. an alloy

2 metals – binary alloy, 3 metals – ternary alloy ....
Metals and alloys
Cooling curves

molten state

crystallization

solid state

pure metal
Metals and alloys a binary alloy of metals A and B
Cooling curves TmA greater than TmB
the first material to crystallize
rich in the metal A (higher Tm)
molten state the last material to crystallize rich in the
metal B (lower Tm)

crystallization
the higher melting metal concentrated
close to the nucleus
the lower melting metal close to
solid state
the grain boundaries
cored structure
an alloy such coring may influence corrosion
resistance
Metals and alloys
Cooling curves
Phase diagram formation

molten state

crystallization

solid state

an alloy
Metals and alloys
Phase diagram

liquidus

solidus

the composition of the resulting

crystals different from the composition
of the starting melt
Metals and alloys
Phase diagram
Types of alloys:
1. alloys with component metals soluble in each other in liquid and solid state:
Au-Ag, Au-Pt

- only 1 phase in this system, formation of mixtured crystals

- such crystals can be substitutional or interstitial

Metals and alloys
Phase diagram
Types of alloys:
1. alloys with component metals soluble in each other in liquid and solid state:
Au-Ag, Au-Pt
substitutional solid solutions
− atoms of solute can substitute the atoms of solvent in crystal lattice
− atoms of solvent and solute with similar atomic size (difference no more than 15%),
similar electro- chemical properties, electron configuration (ratio of valence e-)
− principal importance in dentistry
Metals and alloys
Phase diagram
Types of alloys:
1. alloys with component metals soluble in each other in liquid and solid state:
Au-Ag, Au-Pt
interstitial solid solutions
− the solute atom small enough to fit at interstitial sites between the solvent atom
− limited number of solute atoms, solute atoms with very low atomic radius (e.g. C, B, N)
Metals and alloys
Phase diagram
Types of alloys:
1. alloys with component metals soluble in each other in liquid and solid state:
a diagram of typical representative of this type of alloys: Au-Ag

a diagram of Ag – Au system
Metals and alloys
Phase diagram
Types of alloys:
1. alloys with component metals soluble in each other in liquid and solid state:

a diagram of Ag – Au system
Metals and alloys
Phase diagram
Types of alloys:
1. alloys with component metals soluble in each other in liquid and solid state:

degree of coring – heat treatment

Metals and alloys
Phase diagram
Types of alloys:
1. alloys with component metals soluble in each other in liquid
and solid state:
Au-Ag, Au-Pt

2. alloys with component metals soluble in each other in liquid

and partially in solid state: Au-Cu

3. alloys with component metals soluble in each other in liquid

and insoluble in solid state (eutectic): Bi-Cd
Metals and alloys
Phase diagram
Eutectic system:

- a homogeneous mixture of substances that melts or solidifies at a single temperature

that is lower than the melting point of either of the constituent

- the eutectic temperature the lowest possible melting temperature over all of the
mixing ratios for the involved component species

- the coordinates defining a eutectic point on a phase diagram are:

the eutectic percentage ratio (on the atomic/molecular ratio axis of the diagram)
and the eutectic temperature (on the temperature axis of the diagram)
Metals and alloys
Phase diagram
Eutectic phase diagram

liquidus line: points A, C, E solidus line: A, B, C, D, E eutectic point: C

- the addition of one metal to another always lowers the melting temperature
- the lowest melting temperature corresponds to an alloy with a composition at the eutectic
point
- alloys with a eutectic composition melt and solidify at a single temperature - like pure metals
Metals and alloys
Phase diagram
Eutectic phase diagram
alloys with component metals soluble in each other in liquid and insoluble in solid
state (eutectic): Bi-Cd

a diagram of Cd – Bi system
Metals and alloys
Noble metals
Noble metals
Definition

• The noble metal is a metallic element that resists oxidation or

corrosion even at high temperatures
Noble metals
Properties
Noble metals selected for alloys
Noble metals
Au – properties
Gold
Melting point [°C] 1064,43
Boiling point [°C] 2808
density/ at the melting point [g cm-3] 19,32/ 17,31
Hardness according to Mohs 2,5
Hardness according to Vickers/Brinell [MPa] 216/ 2450
Modulus of elasticity in shear/ tension [GPa] 27/ 78

- in nature in rocks, rivers

- isolation: panning for gold
amalgamation – Au is dissolved in Hg, then Hg is distilled by cyanide
4Au + 8KCN + O2 + 2H2O → 4K[Au(CN)2] + 4KOH
2[Au(CN)2]- + Zn → [Zn(CN)2]2- + 2Au
Noble metals
Au – properties
Gold
− yellow, lustrous, air-stable and soft metal
− chemically extremely stable element
− insoluble in common acids or bases, with the exception of royal jelly the reaction
of gold with royal jelly produces gold chloride AuCl3, with an excess
of HCl tetrachlorogoldic acid
− well soluble in selenic acid to form gold selenate Au2(SeO4)3:
Au + 3HCl + HNO3 → AuCl3 + NO + 2H2O
Au + 4HCl + HNO3 → H[AuCl4] + NO + 2H2O
2Au + 6H2SeO4 → Au2(SeO4)3 + 3H2SeO3 + 3H2O
Noble metals
Au – properties
Gold
− willingly reacts directly with halogens to form halides
− reacts even more willingly with solutions of halogens in their oxygen-free acids
− well soluble in an aqueous solution of chlorine:
2Au + 3Cl2 + 2H2O → 2H[AuCl3(OH)]
− in the presence of atmospheric oxygen, well soluble in dilute solutions of alkali
metal cyanides, in thiosulfates and thiourea
Compounds
− forms numerous complex compounds, mainly with a complex anion, compounds
with a complex cation rarely occur
Noble metals
Pt – properties
Platinum
Melting point [°C] 1772
Boiling point [°C] 3827
density/ at the melting point [g cm-3] 21,45/ 19,77
Hardness according to Mohs 3,5
Hardness according to Vickers/Brinell [MPa] 549/ 392
Modulus of elasticity in shear/ tension [GPa] 61/ 168
− grey-white, shiny, hard, ductile, malleable metal
− increases hardness and strength, absorbs oxygen during melting
− for a similar coefficient of thermal expansion suitable for combination with ceramics
− usable in the form of cast iron, foil or thin wire present
− in nature usually pure, accompanied Ir, Os, Pd, Au, Ag, Cu, Pb a Fe
Noble metals
Rh – properties
Rhodium
Melting point [°C] 1966
Boiling point [°C] 3695
density/ at the melting point [g cm-3] 12,41/ 10,7
Hardness according to Mohs 6
Hardness according to Vickers/Brinell [MPa] 1246/ 1100
Modulus of elasticity in shear/ tension [GPa] 150/ 275
− white, ductile, soft metal
− pure rhodium extremely resistant to all acids
− softens the grain
− with platinum used in thermocouples of ceramic furnaces
− in nature the only stable isotope 103Rh, 23 artificially prepared radioisotopes
Noble metals
Pd – properties
Palladium
Melting point [°C] 1554
Boiling point [°C] 2940
density/ at the melting point [g cm-3] 12,02/ 10,38
Hardness according to Mohs 4,8
Hardness according to Vickers/Brinell [MPa] 461/ 37,3
Modulus of elasticity in shear/ tension [GPa] 44/ 121

− shiny, white, hard, malleable, malleable, silver-like metal

− with a content above 10%, the white color of the alloys
− high ability to absorb gases, catalyst for many hydrogenation reactions
− increases resistance to corrosion
− it can replace platinum in alloys
Metals
Properties
• Properties of non-noble metals selected for noble metal alloys
− 47Ag - soft, malleable, ductile, conductive, increases the hardness of
gold alloys. oxidizes during melting, danger of gas porosity, reacts
with S, P, Cl
− 28Ni- hard, increases the strength and hardness of gold alloys in a
small amount
− 29Cu - malleable, ductile, conductive, forms solid solutions with Au
and Pd, lowers the melting temperature of palladium alloys, increases
hardness and strength in alloys
− 30Zn - brittle, easily oxidizes (in 1-2% it is added as an antioxidant), in
large quantities increases the brittleness of the alloy, reduces the
viscosity of the melt
Metals
Ag – properties
Silver
Melting point [°C] 961,9
Boiling point [°C] 2162
density/ at the melting point [g cm-3] 10,49/ 9,32
Hardness according to Mohs 2,5
Hardness according to Vickers/Brinell [MPa] 251/ 24,5
Modulus of elasticity in shear/ tension [GPa] 30/ 83

− white, soft, highly ductile, shiny, malleable and conductive metal

− increases the hardness of gold alloys
− metal with the highest electrical and thermal conductivity (of all metals)
− forms many coordination compounds
− natural silver is a mixture of two stable isotopes: 107Ag and 109Ag, artificially
prepared additional 31 radioactive silver nuclides
Metals
Ni – properties
Nickel
Melting point [°C] 1453
Boiling point [°C] 2913
density/ at the melting point [g cm-3] 8,91/ 7,81
Hardness according to Mohs 4
Hardness according to Vickers/Brinell [MPa] 638/ 700
Modulus of elasticity in shear/ tension [GPa] 76/ 200

− silver-white, shiny, malleable and ductile metal with ferromagnetic properties

− soluble in dilute acids to form hydrogen and the nickel salt of the acid
− in a small amount it increases the hardness and strength of alloys
− present in nature as a pure metal and in ores, often accompanied by cobalt
− natural nickel with a mixture of 5 stable isotopes, the most represented isotope
58Ni, artificially prepared additional 18 radioactive silver nuclides
Metals
Zn – properties
Zinc Melting point [°C] 419,6
Boiling point [°C] 907
density/ at the melting point [g cm-3] 7,14/ 6,57
Hardness according to Mohs 2,5
Hardness according to Vickers/Brinell [MPa] 300 / 412
Modulus of elasticity in shear/ tension [GPa] 43/ 108

- blue-white shiny metal, very ductile at higher temperatures, but brittle

- increases the brittleness of alloys
- oxidizes easily, added as an antioxidant, is covered with a layer of oxides
- part of some types of amalgams, up to 1% content
- natural zinc with a mixture of 5 stable isotopes, the highest proportion
isotope 64Zn
Metals Ti

Properties
• Properties of general metals selected for alloys
Cr
− 27Co - resistant to corrosion, increases the strength, rigidity
and hardness of the alloy
− 24Cr - resistant to corrosion, ensures the hardness of the
alloy Mo
− 28Ni - does not oxidize, reduces strength, increases
malleability and ductility, allergen, carcinogen
− 42Mo - significantly increases hardness Al
− 22Ti - strong, light, easily oxidizes with oxygen, hydrogen,
nitrogen and ensures the homogeneity of the alloy
− 13Al - low density, malleable, ductile, corrosion resistant,
V
increases tensile strength
− 23V - improves mechanical properties of alloys, increases
resistance to wear, in alloys with titanium
Metals
Co – properties
Cobalt
Melting point [°C] 1495
Boiling point [°C] 2927
Density/ at the melting point [g cm-3] 8,8/ 7,75
Hardness according to Mohs 5
Hardness according to Vickers/Brinell [MPa] 1043 / 700
Modulus of elasticity in shear/ tension [GPa] 75/ 209
− shiny, gray, very hard and strong metal with ferromagnetic properties occurs in two
allotropic modifications, hexagonal α-Co stable up to a temperature of 417°C,
above this temperature stable cubic modification β-Co
− they stood in the air and in the water increases rigidity
− hardness and strength of alloys 100% natural isotope 59Co, artificial other 21
unstable isotopes
Metals
Properties

• Properties of non-metals selected for alloys

− 6C - ensures the hardness and strength of the alloy
(around 2%), with a higher content, the alloy
hardens and becomes brittle due to the formation
of carbides

− 14Si - reduction of viscosity during casting,

increases the brittleness of the alloy

− 7N - affects the alloy similarly to carbon, above

0.1% causes brittleness
Thank you for attention