Titanium and its

alloys

Introduction
Titanium

appears on the periodic table as element

22, a fourth-row transition metal with an atomic
weight of 47.88.
An

extremely reactive metal, titanium forms

tenacious oxide layer that
contributes to
electrochemical passivity.

a
its

Titanium is the ninth most abundant element and is

plentiful in the Earth's crust.

Not

found in its free, pure metal form in nature but as

oxides, i.e., ilmenite (FeTiO3) and rutile (TiO2)
( J Prosthod 1999;8:40-43 )
2

Ilminite ( FeTiO3 )

Lutile (TiO2 )

( J Prosthod 1999;8:40-4 )
4

History
The

element was discovered by Wilheim Gregor, a

clergyman, who found the metal in a "black
magnetic sand" in Cornwall in 1791.
Three

years later, Klaproth found a rutile that

was the oxide of a new metal he named
titanium, after the Greek Titans. He recognized
that this metal was identical to the material
Gregor had discovered
( J Prosthod 1999;8:40-43 )

Extraction of titanium
Titanium

ore rutile (TiO2) is converted into

titanium sponge by KROLLS PROCESS :
1)

Passing Cl2 gas through charge the ore,

resulting in colourless. titanium tetrachloride TiCl4.
2)

TiCl4 is purified by fractional distillation.

3)

The liquid form of TiCl4 is reacted with either Mg

or Na under an inert (Ar)atmosphere to obtain
titanium sponge while Mg or Na is recycled.

Krolls

process :

Tio2 + 2 cl2 + c = Ticl4 + co2

2Mg (l) + TiCl4(l) = 2MgCl2 (l) + Ti (s)
7

Advantages

Classification of titanium alloys

ASTM

International (the American Society

for Testing and Materials) recognizes 4
grades of commercially pure titanium, or Ti,
and 3 titanium
alloys (Ti-6Al-4V, Ti-6Al-4V Extra Low
Interstitial [low components] and Ti-Al-Nb).

Physical properties
It

rapidly form a
tenacious oxide that
responsible for the metal's biocompatibility.

is

At

temperatures up to 882C, pure titanium

exists as
a
hexagonal close-packed atomic
structure (alpha phase).
Above

that temperature, the structure is bodycentered cubic (beta phase).

The

metal melts at 1,665C.

( J Prosthod 1999;8:40-43 )

10

Advantage of oxide
layer
The

metal oxidizes almost instantaneously in air to

form a tenacious and stable oxide layer
approximately 10 nanometers thick.
This

oxide layer provides a highly biocompatible

surface and a corrosion resistance similar to that of
noble metals.
In

addition, the oxide layer allows for bonding of

fused porcelains, adhesive polymers or in the case
of endosseous implants, plasma-sprayed or surfacenucleated apatite coatings.
11

( J Prosthod 1999;8:40-43 )

12

Mechanical properties
The

characteristic trend of increasing strength

with relatively constant modulus continues when
comparing cp titanium with titanium alloys.
The

elastic modulus of the alloys is slightly

higher (113 MPa compared with 104 MPa of cp
grade IV titanium), but the yield strength
increases over 60% to 795 MPa for ELI (Extra Low
Interstitial) alloys and 860 MPa for Ti-6Al-4V alloys.
Typically, fatigue strength limits are less than
50% of the ultimate tensile stress.

13

Compared

with Co-Cr-Mo alloys, titanium alloy is

almost twice as strong and has half the elastic
modulus.
Compared

with 316L stainless steel, the Ti-6Al-4V

alloy is roughly equal in strength, but again, it has
half the modulus.
Strength is beneficial because materials better resist
occlusal forces without fracture or failure.

Lower

modulus is desirable because the implant

biomaterial better transmits forces to the bone.
14

Titanium

grade 1 has the highest purity, lowest

strength, and best room-temperature ductility of the
four ASTM titanium unalloyed grades.
Grade 2 titanium is the main cp Ti used for
industrial
dental
implant
applications.
The
guaranteed minimum yield strength of 275 MPa for
grade 2 is comparable to those of annealed
austenitic stainless steels.

15

Titanium

grade 3 has 0.30 maximum iron content,

which is lower than grade 4 (0.50 maximum).
Grade 4 has the highest strength of the unalloyed
ASTM grades.

Grade 5, an ASTM titanium alloy (Ti-6Al-4V), is the

most widely used titanium alloy in medical implants
but not common in dental implants. The alloy is
most commonly used in the annealed state.

16

Density

4.5g/cm
(considerably less than gold or Ni-Cr or Co-C r alloys)
Because

of the light weight of the titanium and its

strength-to-weight ratio, high ductility, and low
thermal
conductivity
would
permit
design
modifications in Ti restorations and removable
prostheses, resulting in more functional and
comfortable use.

17

Corrosive behaviour
Titanium

is corrosive under mechanical stress ,

oxygen deficit, or at a low ph level.
Flouride

reveals a high affinity to titanium, &

Flouride ions can destabilize the oxide layer.
The

self formed protective oxide film on titanium

can be affected by excessive use of the commonest
preventive
agents
in
dentistry,
prophylactic
polishing and topical fluoride applications.
( JIPS 2005 vol.5 issue 3 )
18

Cp titanium
Commercially

pure Ti is available in four grades,

which vary according to the oxygen (0.18 to 0.40 wt
%) and iron (0.20 to 0.50 wt%) content.
These

apparently slight concentration differences

have a substantial effect on the physical and
mechanical properties.
At

room temperature, c.p. Ti has an HCP crystal

lattice, which is denoted as the alpha () phase. On
heating, an allotropic phase transformation occurs. At
883 C, a body-centered cubic (BCC) phase, which is
denoted as the beta () phase, forms.
19

20

Ti-6Al-4V
Several

alloys of titanium are used in dentistry. Of

these alloys, Ti 6Al-4V is the most widely used.
At

room temperature, Ti-6Al-4V is a two-phase +

alloy.
At approximately 975C, an allotropic phase
transformation takes place, transforming the
microstructure to a single phase BCC -alloy.

21

Composed

of 90% Ti , 6% Al , 4% V .

Aluminium

decreases specific weight and improves

elastic modulus
Vanadium

decreases thermal conductivity and

increases hardness.

22

The

alloys most commonly used for dental

implants are of the alpha-beta variety.
Of

these, the most common contains 6%

aluminum and 4% vanadium (Ti-6Al-4V).
After

heat treatment these alloys possess many

favorable physical and mechanical properties
that make them excellent implant materials.

23

24

Phase transformation
Allotropic
transformation

882.3
C
Alpha phase
HCP structure

phase
BCC structure

25

Titanium

alloys of interest to dentistry exist in

three forms: alpha, beta, and alpha-beta.
These types originate when pure titanium is
heated, mixed with elements such as aluminum
and vanadium in certain concentrations, and
then cooled.

This

treatment produces true solid solutions.

These

added elements are

phase-condition stabilizers.

said

to

act

as

26

Aluminum

has been
condition stabilizer.

called

an

alpha-phase

Aluminum

also serves to increase the strength and

decrease the weight of the alloy.
Vanadium

has been called a beta-phase stabilizer.

As

aluminum or vanadium is added to Ti the

temperature
at which
the
alpha- to-beta
transformation occurs changes to a range of
temperatures.
27

They

are light, strong, and highly resistant to

fatigue and corrosion.
Although they are stiffer than bone, their
modulus of elasticity (stiffness) is closer to bone
than any other important implant metal; the only
exception is pure Ti.

This

property leads to a more even distribution

of stress at the critical bone-implant interface
because the bone and implant will flex in a
more similar fashion.
28

Titanium castability
The

two most important factors in casting

titanium-based materials are its high melting point
(= 1700 C for c.p. Ti) and chemical reactivity.
Because of the high melting point, special
melting procedures, cooling cycles, mold material,
and
casting equipment
to
prevent
metal
contamination are required.

Titanium readily reacts with gaseous elements

such as hydrogen, oxygen,
and
nitrogen,
particularly at high temperatures (>600C).

29

As

a result, any manipulation of titanium at

elevated temperatures must be performed in a wellcontrolled vacuum.
Without a
well-controlled
vacuum, titanium surfaces will be contaminated
with case, an oxygen enriched and hardened
surface layer, which can be as thick as 100 m.
Because

of the high affinity titanium has for

hydrogen,
oxygen, and
nitrogen,
standard
crucibles and investment materials cannot be
used.

30

Investment

materials must have oxides that are

more stable than the very stable titanium oxide,
and must also be able to withstand a temperature
sufficient to melt titanium.. If this is not the case,
oxygen is likely to diffuse into the molten metal.
Investment

materials
such phosphate-bonded
silica and phosphate investment materials with
added trace elements achieve this goal.
It has been shown that with magnesium oxidebased investments, internal porosity results.

31

Advanced

casting techniques, which combine

centrifugal,
vacuum,
pressure, and
gravity
casting, new investment materials, and advanced
melting techniques (e.g., electric arc melting)
have been developed.
By alloying titanium, the melting temperature
can be lowered to the same temperature as that
of nickel-chromium and cobalt-chromium alloys.
For example, the Ti-Pd and Ti-Cu alloys have
melting points of 1350 C.

32

Uses
Today,

The

Titanium And Titanium Alloys Are Used For :

Fabrication of Prosthetic Joints,

Surgical

Splints,

Stents

And Fasteners,

Dental

Implants,

Dental

Crowns And Partial Denture Frameworks

33

Artificial

hip joints,

Artificial

knee joints,

Bone

plates,

Screws
Cardiac
Pace

for fracture fixation,

valve prostheses,

- makers, and artificial hearts.

34

Bone

conduction hearing aids are anchored with

titanium connected to the middle ear.
Shoulder

and elbow joint implants.

In

general stronger beta alloys are used in low

modulus applications.
And

alpha-beta alloys are used in high modulus

applications ( bone plate )

35

Ti-6Al-4V

( eli ) - alpha beta alloy orthopedic

surgery.
Ti-5Al-2.5Fe
Ti-6Al-7Nb

- used for heart pacemaker electrodes

- copings

Ti-13Nb-13Zr

orthopedic implants

Ti-15Mo-3Nb

- orthopedic implants

36

Ti-6Al-4V

has long been a main medical titanium

alloy. However, for permanent implant applications
the alloy has a possible toxic effect resulting from
released vanadium and aluminum.
For

this reason, vanadium- and aluminum-free alloys

have been introduced for implant applications, based
on the Ti-6Al-4V implants.
These

new alloys include Ti-6Al-7Nb (ASTM F1295),

Ti-13Nb-13Zr (ASTM F1713), and Ti-12Mo-6Zr (ASTM
F1813).
37

The

main physical properties of titanium responsible

for the biocompatibility are:

low level of electronic conductivity,

high corrosion resistance,

thermodynamic state at physiological pH values,

low ion-formation tendency in aqueous environments,

an iso-electric point of the oxide of 56.

38

Applications in
dentistry
Titanium

and its alloys are also used for dentistry

devices such as :
Implants
Crowns

, bridges,

Overdentures
Dental

, and

implant prosthesis components (screw and

abutment).

39

Dental implants
There

are three types of dental implant:

Osseo

integrated ,

Mini

-implant for orthodontic anchorage,

and

zygomatic.

Each

group needs different mechanical properties

and must be made of cp Ti or a titanium alloy.

( JOM March 2008 )

40

Osseo integrated
implant
The

osseointegration of dental implants was

initially defined by Branemark et al. as a direct
bone-to-implant contact and later on defined on a
more functional basis as a direct bone-to-implant
contact under load.
In

the past, osseointegrated endosseous dental

implants have been made in a variety of shapes,
including hollow baskets, blades, tripods, needles,
disks, truncated cones, cylinders, and screws.
( JOM March 2008 )
41

Currently

the most commonly used dental implant

has a screw shape and is made of cp Ti or Ti-6Al-4V
The

dental implants are available with diameters

from 3.3 mm to 6.0 mm and lengths from 6 mm to
16 mm.

42

Long

term placement of implant revealed higher

levels of the component elements ( especially
vanadium ) can be detected in tissues locally and
systemically.
Therefore

vanadium and aluminium free alloys

have been developed.

43

44

45

Orthodontic miniimplant
Another

dentistry implant is a temporary

orthodontic mini-implant used generally to secure
anchorage in contemporary orthodontic treatments.
This implant has a small diameter (1.2 mm to 2.0
mm) and the orthodontic load can deform the miniimplant.

the

orthodontic implants are made with Ti-6Al-4V

instead of cp Ti due to the alloys superior strength

(JOM March 2008 )

46

47

Zygomatic fixture
The

third dentistry implant group is the zygomatic

implants, which are made of cp Ti.
The

zygomatic implant developed by Branemark as

been used as posterior anchorage for implant
supported prostheses in patients with atrophic maxillae.
The

zygomatic implant has a diameter equal to 45

mm and 3053 mm length.
It penetrates the maxilla at the second premolar
region as close to the alveolar crest as possible

(JOM March 2008 )

48

49

Titanium in complete
denture

Complete denture with titanium framework

( Journal of Oral Rehabilitation 27; 131 135 )

50

Titanium in RPD

(J PROSTHET DENT 1995;73:4-7 )

51

Titanium in maxillofacial
prosthetics

Cranial prosthesis with titanium mesh

52

53

54

Titanium ceramic
Biological

advantages
of
comparing it to metal coping are :

titanium

1)

good biocompatability due to formation

of oxide layer.
2) low specific weight.
3)low corrosion activity.
4) low thermal conductivity
5)forms a bacteriostatic gel in combination
with gingival fluid.
( quint int.2007 )

55

Fabrication of a titanium dental

coping using powder metallurgy

Int J Prosthodont 2004;17:1116

56

Titanium

powder was pressed at 300 to 900 MPa,

milled to the right shape, and sintered at 1,200C for
a 2-hour holding time.
The copings were silvery bright in appearance and
showed sharp edges.

The titanium in the sintered copings was ductile,

dense (97% to 99%+), and free from open porosity
after sintering.

( Int J Prosthodont 2004;17:1116 )

57

( Int J Prosthodont 2004;17:1116 )

58

IMPROVING THE TITANIUM

CERAMIC BOND
Firing

porcelain in a reduced argon atmosphere

significantly improved titanium-ceramic bonding for
machined and as-cast titanium.
The

sputter-coated gold layer on titanium provided

improved titanium-ceramic bonding only when combined
with firing porcelain in reduced argon atmosphere.
When

porcelain was fired in vacuum in the presence of

the gold layer, the titanium-ceramic bonding was
weakened in as-cast titanium and was not affected in
machined titanium.
(J Prosthet Dent 2003;90:10-17.)
59

Sputter

coating and electroplating

chromium forms protective oxides .

coating

of

Surface

treatment using either airborne-particle

abrasion or bonding agent alone enhanced the bond
strength of cast commercially pure titanium to lowfusing
porcelain.
The combination of airborne-particle abrasion and
bonding agent provided the greatest improvement in
titanium-ceramic bond strength.

(J Prosthet Dent 2005;94:350-6.)

60

According

to study conducted on various titanium

alloys by Koichi Akagi, and Yosbizo Okamoto,
10Ti-Ir

is considered to sufficiently fulfill the

conditions of a titanium metal/ceramic alloy that
can be cast in the ordinary atmosphere using a
high frequency centrifugal casting machine and a
ceramic crucible.

( J PROSTHET DENT 1992;68:462-7 )

61

Cytotoxicity of
titanium
According

to Li etal elemental
metal
powders of Ti and Nb showed substantial
cytotoxicity, but the bulk Ti and Nb
showed biocompatibility.

( J Dent Res 89(5):493-497, 2010 )

62

Thank you
63