15446183.ppt

General University
Hospital in Prague
Metals and
Dental Alloys
Assoc. Prof. M.D. Ivan Malbohan, Ph.D.
M.D. Lenka Fialová , Ph.D.
Medical Chemistry and Biochemistry
1st year – Winter term - Dentistry
First Faculty of Medicine Institute of Medical Biochemistry and Laboratory Diagnostics
© Institute of Medical Biochemistry and Laboratory Diagnostics of the General University Hospital in Prague
and of The First Faculty of Medicine of Charles University - 2005-2019

Stomatological materials
 Metallic
 Dental metals and alloys
 Dental amalgams
 Nonmetallic
 Dental plasters
 Dental cements
Dental porcellains (silicates)
 Dental resins
 Impression materials
 Modell materials
 Modelling materials
 Grinding and polishing tools and means
2018/2019 2
Metals and Dental Alloys

Introduction
 Metals belong to the oldest dental materials.
 Pure metallic elements are not frequently used in stomatology.
 As main materials are the pure metals used only for special
purposes (titanium – implants), because the properties of the
elementary metal are usually not suitable for the needs of
clinical practice.
 Sometimes the pure gold, which is relatively soft, is used for
preparation of high quality, but very expensive inlays.
2018/2019 3

Requirements for the metallic
material
 For preparation of artificial denture, fix or
removable, a material with higher durability, is
needed, having also appropriate hardness, stiffness
and toughness, but also the plasticity and malleability.
 Very important is also the resistance of the material
to corrosion and to wear and tear.
 The colour of the material is important esthetically .
 In contrast the good thermal and electric
conductivity means in artificial denture rather a
disadvantage.
2018/2019 4

Requirements for the metallic
material
All this requirements are best fulfilled by
SPECIALLY PREPARED STOMATOLOGICAL ALLOYS
2018/2019 5

Metallic bond
 Metallic bond is a specific type of chemical bond,
formed between the atoms of metals .
 Atoms of metals tend to form a stable configuration
and throw away the weakly bonded electrons and
transform to cations.
 The valence electrons are delocalized over the entire
crystal. In fact, metal atoms in a crystal can be
imagined as an array of positive ions immersed in a sea
of delocalized valence electrons.
2018/2019 6

Crystallography of metals
 Cations of metals immersed in a „ sea of valence electrons“, are
organized in a crystal lattice.
 Most of dental metals crystalize in following unit cells:
 Body centred cubic (Cr, Mo, W)
 Particles are placed in the corners and in the middle of a unit
cell
 Face centred cubic (Au, Ag, Pt, Pd, Ir, Cu, Co, Ni, Fe)
 Particles are placed in corners and in the middle of walls of
the unit cell
 Hexagonal close packed (less frequent - Os, Ru, Zn, Ti)
2018/2019 7

Crystallographic properties of dental
metals
 By crystallographic methods, with the use of microscope, we
follow on the fracture or on the cut the lattice parameters and
the types of crystallic lattices and mainly the disturbances of
crystalline lattice.
 The arrangement of a crystalline lattice is not completely
regular in real metals.
 According to the size and shape of the crystallographic
anomalies of atomic arrangement we recognize different lattice
irregularities.
Crystal lattice irregularities
 Dot
 Linear
 Planar
 Volume
2018/2019 8

metals
 Dot – missing particle or an extra particle
 vacancy
 an interstitial atom
 a small substitutional atom
 a big substitutional atom
 Linear (dislocations)
 falling out of a part of the edge, elimination of the whole line
 sliding of atoms out of the regular positions in the crystalline
lattice
 Planar
 Originate e.g. by removing of a part of the plane of atoms or by
its addition to the structure
 Volume
 The volume disturbances are the fissures and precipitates
(islets of different crystalline structure), present in a crystal.
2018/2019 9

metals
 Amount and character of the crystal lattice
disorders have an influence on the mechanical
properties of metals and particularly of their
alloys.
Presence of these disturbances enables the
plastic deformation of the metal.
 Deformation means a change of the form of the lattice
which results in a change without formation of fissures.
 Plastic deformation is a change of the shape, which
remains conserved after elimination of the cause of
deformation.
2018/2019 10

Crystallization process
 Crystallization starts during the transition
from liquid to solid state.
Solid state of
a metal
Liquid state of
a metal
Crystallization
2018/2019 11

 Mechanism of crystallization starts by the origin of
stable crystal seeds (nuclei). Nuclei are tiny volumes
of a new phase in the liquid phase to which another
atoms attach.
 Crystallization nuclei possess the crystal structure
and are oriented any direction.
 Crystallization nuclei of solid phase originate:
 spontaneously directly in the liquid phase – homogenous
nucleation
 on present nuclei of foreign phase – heterogenous nucleation
2018/2019 12

 On the crystallization nuclei progressively attach
another atoms and a homogenous crystal originates.
During the growth the crystal is limited by the
adjacent growing crystals, and therefore the shape
of the crystal is uneven. Crystals with uneven shape
are labelled as grains.
 Inside of grains are the particles arranged regularly,
but the reciprocal positon of grains is random and
irregular.
 On the border of grains the impurities may place and
they may be the point, where the corrosion starts.
2018/2019 13

Number of grains affects properties of the
metal.
 Better mechanical quality have small-grained
metals. This structure is correlated with the
highest number of nuclei. The number of grains
higher than 500 on mm2 and size of grains 30 m
and less is required.
Finer structure may be achieved by:
 Faster cooling down
 Introducing of foreign fine particles into the liquid
alloy as heterogeneous nuclei
2018/2019 14

 During fast cooling down more nuclei are formed. The result is
a fine-grain structure having better mechanical quality.
 During slower cooling down coarse-grained structure originates.
Fast cooling Slower cooling
Fine grain structure
BETTER MECHANIC
QUALITY
(superior stregth)
Coarse-
grained
structure
2018/2019 15

 If the cooling down of the alloy is too fast,
the grain grows faster in one direction -
primary branch, from which perpendicularly
protrude shorter secondary branches.
Herringbone-like branched structure is
formed – dendrites.
 Dendrites possess different composition
than other parts of the alloy and show a non-
homogeneity of the material.
 Dendritic structure may weaken the
mechanical and corrosion resistance of the
alloy.
Primary branch
Secondary branch
2018/2019 16

Endogenous crystallization
 The germ crystals arise uniformly in the whole cast
 Suitable for the dental alloys – fine-grain, homogenous cast
 Au-Pt alloys
Exogenous crystallization
 The germ crystals form only on the surface of the cast
2018/2019 17

 Crystallization is always accompanied by the
contraction, which is most expressed in the
centre of the cast, where the solidification
takes place at last. The result of contraction
are the contraction defects.
 Au alloys – contraction 1,4 %
 Common metal alloys 2,3 – 2,7 %
2018/2019 18

Alloys
 Alloy is a mixture of a metal with other
metals or other elements or compounds,
usually in a form of solid solution.
 Suitable combination of metals allows the
achievement of required quality.
 As the alloying elements we call the elements
which even in very small amount significantly
improve the characteristic of the alloy.
2018/2019 19

Alloys of metals mutually soluble in
fluid and solid state
 When the elements contained in the alloy are
completely mutually soluble and retain this quality
even during solidification, a solid solution results.
Characteristic
 Only one phase exist
 Not only atoms of the fundamental metal, but also the atoms of
the additive element are present in the crystal lattice .
 Base is the atom lattice of the basic component, with the atoms
of the admixed element inside. Depending on position of admixed
atoms we differentiate two basic types of mixed crystals.
2018/2019 20

Alloys of metals mutually soluble in
fluid and solid state
 Substitutional alloys
 The size of atoms metals forming the alloy must not differ
more than 15 %.
 Atoms of the base metal are in his crystal lattice randomly
substituted by the atoms of additive metal.
Example: Binary systems Au-Pt, Au-Ag
Used in dentistry
 Interstitial alloys
 Combination of atoms several fold differing in the size
 The additive element (e.g. N, C) is placed into the crystal
lattice of the base metal (large atoms)
2018/2019 21

Properties of dental alloys
Dental metal (alloy) is characterized by
following properties:
 mechanical
 physical
 chemical
 biological
2018/2019 22

Mechanical properties of dental alloys
 Modulus of elasticity
(transient deformation)
 Yield strength
(permanent deformation)
 Tensile strength
(„breaking point“ of the
material)
 Hardness
Traction test
2018/2019 23

Modulus of elasticity – transient
deformation
 It is a measure of the bending resistance of an
alloy
Higher modulus of elasticity  lower bending during
mechanical load
 It is important in alloys used in porcelain fused to
metal (PFM) systems.
Higher modulus of elasticity  lower susceptibility
to splitting of the ceramics
2018/2019 24

Yield strength - permanent deformation
 Quotes the force which causes a permanent
deformation of the material (usually 0,1 % or 0,2 %).
Higher yield strength  higher resistance to stress
Low value of yield strength  easy deformation of
the material
 Evaluation of the alloys according to the yield strength.
2018/2019 25

Firmness of the material
Firmness in traction
 Is characterized as maximal traction, which
material endures without breaking
Firmness in pressure
 Is characterized by a pressure, which the
material endures without a damage
2018/2019 26

Hardness
 Indicates the ability of an alloy to resist the local
stress during the bite
 Requirements
 Hardness of prosthetic alloys should not exceed the
hardness of the enamel and should be between
125 kg/mm2  340 kg/mm2 (=hardness of the enamel)
Sufficient resistance of
the material against
mastication load
Must not damage the teeth
in opposite jaw
x
2018/2019 27

 Testing of hardness
 Hardness according to Vickers
 Impression of qadrilateral diamond pyramid
in the studied material
 Hardness according to Brinell
 Impression of steel ball in the studied
material
2018/2019 28

 Very hard materials are usually quite fragile and may
break or chip off by impact or by higher strain on the
prostheses. For that reasons the too hard materials
are unsuitable for the use in stomatology.
 Hard metals - Ni, Fe, Cr, Co
2018/2019 29

Physical properties of dental alloys
 Melting and boiling point
 All metals with the exception of mercury and gallium
are solid at normal room temperature.
 Temperature necessary for the change from the solid
state of the metal to the liquid state is called the
melting point.
 The values of the melting point differ substantially in
individual metals and alloys.
High melting point Very low melting point
Ir, Pt, Pd Ga, In, Sn
2018/2019 30

Physical properties of dental alloys
 Density
 The ratio of mass and volume (g/cm3)
 The highest density have the gold alloys containing also
platinum and iridium and a bit lower the gold alloys with the
reduced content of gold.
 The lightest is the titanium and its alloys.
 The use of alloys of higher density is better for casting.
 The density has an influence on the final weight of the whole
construction. The heaviest pieces of work are from platinum
and gold alloys.
 The density has also an influence on the costs of the used
material.
2018/2019 31

Chemical properties of dental alloys
Important chemical properties
 Corrosion
 Surface passivity of the alloy
2018/2019 32

Corrosion
 Corrosion is a progressive erosion of the material by
chemical or physically-chemical reactions with the
surrounding environment.
 During corrosion in the oral cavity the release of
ions or of ion complexes from dental alloys occurs.
 A manifestation of corrosion may be the change of colour.
Alloys with high content of Au and Pt are stable.
Alloys based on common metals containing Cr form on the
surface a corrosion resistant layer of chromic oxide -
passivation effect.
2018/2019 33

Passivation
 Passivation is a process forming a protective layer
on the surface of an metal preventing corrosion.
 The protecting layer, called passivation layer, is
formed mainly by oxides. The passivation layer
prevents the release of ions of elements present
in the alloy to the oral cavity.
2018/2019 34

Galvanic currents
 May arise at close contact of two different
metals in a wet environment of the oral cavity
(saliva).
 Galvanic currents come in existence on a base of
different electrode potentials of individual
metals and alloys and are quoted in A.
 Pathologic value  5 A.
2018/2019 35

Biological properties of dental alloys
 Besides of above mentioned properties is necessary in
stomatological alloys study their relation to living
tissues.
 The cytotoxicity of alloys has to be tested usually on
tissue cultures of fibroblasts.
 The direct contact is also tested to determine if the
elution of the parts of alloy arises. Also the change of
the color of the material during the contact with
living tissues must be monitored.
2018/2019 36

Toxicity
Allergic reactions
Mutagenity and cancerogenity
2018/2019 37

Toxicity
 General toxicity of ISO dental alloys was not
observed.
 Local toxicity – is usually of small importance.
2018/2019 38

Allergic reaction
Metallic alloys represent an foreign material in
the organism. They may therefore induce allergic
reactions in patients, but also in dental technicians.
 Local manifestations
 In the oral cavity (i.e. tongue coating or edema, small
blisters, red colour of oral cavity, pain)
 General manifestations
 Fatigue, cephalea (headache)
 Nausea (feeling on vomiting)
2018/2019 39

 Very frequent allergens are nickel,
cobalt and chromium.
 Manifestation of allergy may be so
called metallic spots.
2018/2019 40

Biologic properties of dental alloys
Mutagenity and cancerogenity of alloys
 Mutagenic and cancerogenic effect
 Berylium and cadmium !!!
 No more used in dental materials
 Mutagenic effect
 Some nickel compounds are carcinogenic
 Nickel is not a mutagen
 Chromium(VI) is toxic and mutagenic
 In stomatology chromium(III) is used
2018/2019 41

Technology of dental alloys processing
The lost wax technique of casting
 In our country it is a most frequently used
technique for casting of metallic dental prostheses
(inlays, crowns, bridges).
 The wax model equipped with an inflow system is
immersed into the investment material. When the
investment material sets hard the wax is burned out and
into the obtained mold the liquid alloy is poured, usually
with the help of centrifugal force.
2018/2019 42

Technology of dental alloys processing
Procedure:
 Preparation of the tooth (or teeth) to
receive restoration (grinding)
 Making an impression of prepared tooth
 Making of gypsum replica which is an exact
model of the dental arch, from which
individual pars (die(s)) representing the
prepared tooth (teeth) are sectioned
 Making a wax pattern representing the lost
tooth structure.
Office
Laboratory
2018/2019 43

Technology of dental alloy processing
 Procedure:
Fixation of the wax
modelu in space
Layer of ceramic
paper
Investment
material
Base
Metal cylinder
(ring)
Wax
model
Base
Metal cylinder
(ring)
Wax
model
Pouring of the investment
material
Layer of ceramic
paper
Investment
material
Metal cylinder
(ring)
After elimination of the wax
by burning off in a furnace
we obtain a mold
Sprue
The mold
after burnig
out the wax
2018/2019 44

Technology of dental alloy processing
Procedure:
The released cast is cleaned,
the sprue is removed from
the cast, the cast is finished
and polished and than
cemented on the prepared
tooth or teeth
Breaking of the mold
Investment
material
Metal cylinder
(ring)
Forcing of the molten alloy
into the mold usually with the
use of centrifugally force.
This is necessary to achieve
perfect cast of the crown or
bridge.
Investment
material
2018/2019 45

Classification of dental alloys
Dental alloys are divided in three main groups:
 Alloys with high content of noble metals –
high noble alloys
 Alloys with lower content of noble metals –
noble alloys
 Alloys of base metals – base metal alloys
The composition of the alloys must correspond to the relevant ISO
(International Standardization Organization ) standards.
2018/2019 46

 Ag
Representative parts of noble metal
alloys
strength
hardness
Corrosion
resistance
Cu Pt Pd Zn Ag

Fragility of
the alloy
Antioxidant

Strength
Hardness
Fine-grain

Corrosion
resistance
Fine-grain

Harder
than
gold
Au
soft
2018/2019 47

Alloys with high content of noble metals
 Noble metals ≥ 60 %
 Au ≥ 40 %
 Types of „high-noble alloys“
 Au-Ag-Pt
 Au-Cu-Ag-Pd-I
 Au-Cu-Ag-Pd-II
2018/2019 48

Alloys with high content of noble metals
Au; 78 Au; 76
Au; 56
Ag; 11,5
Ag; 10
Ag; 25
Cu; 10,5
Cu; 11,8
Pt; 9,9
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Au-Ag-Pt Au-Cu-Pd-I Au-Cu-Pd-II
Zn
Pt
Pd
Cu
Ag
Au
Yellow Yellow
Yellow
Au-Cu-Ag-Pd-I Au-Cu-Ag-Pd-II
2018/2019 49

Alloys with lower content of noble metals
 Noble metals ≥ 25 %
 Au content is not specified
 Types of „ lower content noble alloys“
 Au-Cu-Ag-Pd-III
 Au-Ag-Pd-In
 Pd-Cu-Ga
 Ag-Pd
2018/2019 50

 If the gold content is under 45 % the risk of
discolouring a corrosion increases. The gold is
usually replaced by palladium.
 The alloys with lower content of noble metals
are adequately strong and hard.
2018/2019 51

Au; 40
Au; 20
Ag; 47
Ag; 38,7
Ag; 70
Cu; 7,5
Cu; 10
Pd; 21
Pd; 77
Pd; 25
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Au-Cu-Ag-Pd-III Au-Ag-Pd-In Pd-Cu-Ga Ag-Pd
Zn
Pd
Cu
Ag
Au
Yellow Light
Yellow
White
Hardest
White
Palladium content higher than 10 % gives to the alloy white color.
2018/2019 52

Gold dental alloys
Gold (Au) is the most stable metal, no oxidation
occurs, no change in the oral cavity.
 Pure gold
 For the softness and malleability the pure gold is
used only exceptionally (inlays, galvanoforms)
 Alloys
2018/2019 53

Gold dental alloys
Proportional content of gold in an alloy, or the purity, is
expressed with the carates or in percents or in
thousandths.
Carate (c) represents 1/24 of the whole. 24 carates
responds to the pure gold.
Examples Carates Percents Thousandths
Pure gold 24/24 100 1000
Alloy 18 C 18/24 75 750
2018/2019 54

Gold dental alloys
 Traditional classification recognizes gold
alloys according to hardness.
 4 types of gold alloys are recognized:
 I. soft
 II. medium
 III. hard
 IV. extra hard
2018/2019 55

Composition of gold alloys
0%
20%
40%
60%
80%
100%
I. měkká II.
střední
III. tvrdá IV. velmi
tvrdá
Pt/Pd
Cu
Ag
Au
Strength
Hardness
Ductility
Corrosion
resistance
Cu
Increases
Decreasees
Increases
2018/2019 56

Examples of alloys with high gold
content
Au 22 CAR Au 18 CAR Pt
Low strength alloy Very high strength alloy
Au; 91,5
Au; 74,5
Ag; 4
Ag; 8,5
Cu; 4,5
Cu; 11
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Au 22 kar Au 18 kar Pt
Pt
Pd
Cu
Ag
Au
2018/2019 57

Examples of alloys with lower gold
content
Aurosa® Aurix®L
Very high strength alloys
Au; 20
Au; 65
Ag; 45
Ag; 20
Cu; 15
Cu; 9,6
Pd; 20
Pd; 3
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Aurosa® Aurix®L
Zn
Pt
Pd
Cu
Ag
Au
Gold and platinum metals 25 – 75 %.
2018/2019 58

Base metal alloys
 The main disadvantage of gold and platinum is very
high price. That is why the base metal alloys are used.
 Chromium – hardness, corrosion resistance
 Cobalt - firmness and hardness, corrosion resistance
 Nickel - ductility, malleability, firmness decrease, allergies
 Molybdenum – hardness
 Lower density compared with gold alloys.
2018/2019 59

Base metal alloys
Cobalt-chromium alloys
Co 53 - 67 %
Cr 25 - 32 %
Sometimes C is added to increase firmness.
Examples of composition
 Co-Cr-Mo-Si-Mn
 Co-Cr-Mo-W-Si
 Co-Cr-Mo-Ti
Cr a Mo increase hardness
Cobalt alloys are usually stronger and harder nickel alloys.
Very hard
2018/2019 60

Base metal alloys
Nickel-chromium alloys
Ni 60 – 80 %
Cr 10 - 27 %
Examples of composition
 Ni-Cr-Mo-Si
 Ni-Cu-Mo
Higher nickel content increases toxicity (ALLERGIES !!)
Very high melting point (1400 – 1600 °C) – difficult casting
2018/2019 61

Pure titanium
from the point of view of mechanical properties
titanium is the best dental metal
 Very resistant to corrosion
 A passivation layer on the surface is formed very rapidly
and after scratching is very fast restored.
 Biocompatible, light.
 The alloys are very expensive.
Titanium and its alloys
2018/2019 62

 Composition:
 Cu-Al-Ni-Fe-Zn-Mn; Ag-Sn
 Many patients do not tolerate Al bronzes.
 Contraindication: gastric and duodenal ulcers.
No ISO standards !!
Aluminium bronzes
Nice colour
• Very low corrosion resistance
• Unpleasant metallic taste
(high amount of released ions)
• Allergic reactions
x


2018/2019 63

Alloys for PFM (porcelain fused to
metal) restorations
 PFM restorations use the benefits of both
materials.
METAL CONSTRUCTION
Mechanic resistance
X
Low esthetics of alloys
FIRED CERAMIC LAYER
Convenient esthetic and
biological properties
X
Fragility
+
2018/2019 64

PFM alloys
 Melting point must be over 1000 °C, because firing
of ceramic material takes place at 900 °C.
 Harmonizing of thermal expandability of metal and
ceramic is necessary to prevent separation of both
materials during firing.
2018/2019 65

PFM alloys
 Materials used in Czech republic
 Palladium base: Safibond: Au-Ag-Pd-Sn-In-Ga-
Zn-Ru
 Base metals:
 Oralium Ceramic ( cobalt and chromium)
 Wiron 99 (chromium and nickel)
2018/2019 66

Materials for dental implants
 Metallic
 At present almost exclusively the materials on base titanium
are used. They possess of high strength and resistance to
corrosion. Both it is virtue of their very tight hexagonal
crystal lattice.
 Excellent biocompatibility is a result of the very stabile layer
of oxides on the surface of the metal (passivation layer).
 Strength property of titanium is outstanding. (It is also used
for the rotaries of the highest-ratings ultracentrifuges !!).
Special, more strength alloys also exist, but they are very
expensive.
2018/2019 67

Materials for dental implants
 Ceramic
 Ceramic materials are fully oxidized, and therefore
chemically very stable.
 Solely ceramic implants may be used, or the ceramic
materials may be used for coating of metallic materials.
 So called bioactive ceramic materials, which react with the
bone and merge together are introduced now. They contain
oxyapatite a fluoroapatite [Ca10(PO4)6)O,F2], -wollastonite
(SiO2-CaO) in MgO-CaO-SiO2 glass matrix.
 Further advantage is low thermal and electrical conductivity
and similar elasticity as the bone.
 In the literature they are usually labeled as CPC (calcium
phosphate ceramics).
2018/2019 68

Stomatological solders
 Solders are special alloys, serving for joining of metallic
parts together.
 Soldering is a process, when the metals are joined together
at lower temperature (to 425 °C), when higher temperature
is used it is technically brazing.
 The stomatological prosthetics the term soldering is used
even when higher temperatures are used.
 During soldering different soldering pastes are used, which
clear the surface of the alloy from oxides, which would
impede the correct joining of the soldered parts. The
mechanical cleaning must of course precede.
2018/2019 69

 The solder must have the melting point lower than the joined
material. This means also the different composition, which
increases the risk of corrosion in oral cavity. It follows, that
mainly the solders on the base of gold or silver are used, to
which tin is added (tin lowers the melting point).
 Solders on the base of gold are used mainly for joining of
casts of fix and removable prostheses.
 Solders on the base of silver are used mainly in orthodontic
applications, which stay in the oral cavity for limited time,
because silver shows higher corrosion.
2018/2019 70

 Due to very high toxicity of cadmium the earlier
very common CADMIUM solders are now prohibited.
The most dangerous are the cadmium vapors, which
are formed during soldering and may cause chronic
intoxication in dental laboratory technicians.
(cancerogenicity !!)
2018/2019 71

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