Use of Titanium and its Alloys in Sea-Water Service

C.P. De 1

403 Ganesh Raheja Township, Bombay 400 097, India

CONTENTS

Page

ABSTRACT 62
1. I N T R O D U C T I O N 62
1.1 Materials 62
1.2 Objectives 62
2. PROPERTIES 63
2.1 General 63
2.2 Physical Properties 63
2.3 Alloys of Titanium 64
3. CORROSION RESISTANCE OF Ti AND ITS ALLOYS 65
3.1 General 65
3.2 Corrosion Resistance of Titanium in Sea-Water 68
3.3 Corrosion Problems of Titanium and Preventive Measures 71
4. APPLICATIONS OF TITANIUM AND ITS ALLOYS IN
SEA-WATER SERVICE 76
4.1 B a c k g r o u n d 76
4.2 Condenser and Heat Exchangers 77
4.3 Miscellaneous Application of Titanium and its
Alloys in an Allied Environment 87
5. WORLD PRODUCTION OF TITANIUM 91
6. TITANIUM INDUSTRY IN INDIA 92
6.1 Raw Materials 92
6.2 Sponge-Ingot Metal Products 92
7. MAIN CONCLUSIONS 93
REFERENCES 93

1
Former Director of the Naval Chemical and Metallurgical Laboratory in Bombay, India

61
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

ABSTRACT application of this material was initially in the field of

military aircraft and missiles, the United States
Technologies for application of titanium metal in a sea- Government supported research and development pro-
water environment have made remarkable progress in grammes which transformed the metal from a laboratory
the last four decades. This is due to intensive research curiosity into a useful structural material. Thus the story
and developmental work in the laboratory and field as of titanium became an intriguing one, replete with the
well as to long-term service trials, which have generated boom and burst cyclic fluctuations associated with a
an exhaustive corrosion d a t a b a n k that has created material tied largely to aerospace/military applications.
enough confidence to permit users to switch over to a When demand for titanium in the aerospace
new construction material. industry stagnated, J.B. Cotton / l / recommended as
Titanium and its alloys are being increasingly early as in 1972 that due to its outstanding corrosion
used in power generation as well as a host of marine- resistance behaviour titanium be extensively applied to
based industries and operations due to their unique non-aviational fields like ocean environment, power
corrosion resistance in a chloride environment. This stations as well as chemical industries. Unfortunately,
paper represents an overview of the corrosion resistant in the absence of exhaustive corrosion data at that time,
properties of titanium in a sea-water environment and there was reluctance on the part of the users lo switch
their industrial applications particularly in power over to this new construction material. However,
generation, desalination plants, offshore oil exploration, titanium sponge production increased in 1988 by 25% in
production and refinery operations as well as in a large the USA and 64% in J a p a n over that in 1987 due to
number of ship-based installations. diversification in application / 2 / .

Energy and materials will be of major concern to

mankind during the next century. Energy efficient 1.2 Objective and Scope
materials like titanium will, therefore receive greater
attention. Development of a cheaper extraction process
The following aspects of titanium and its alloys will
for commercial use will play a key role in making
be covered in this review with its sea-water applications
titanium one of the future materials of the twenty-first
in view:
century.

1. INTRODUCTION (a) Physical, chemical and metallurgical properties of

titanium and its alloys
1.1 Background (b) Annual production
(c) Corrosion behaviour in sea-water and allied
In the 1950's, a wonder metal called titanium burst environments
upon the industrial scene due to its high strength to (d) Applications in a sea-water environment
weight ratio which made it a good replacement for the (e) State of the titanium industry and use of titanium in
then-existing light alloys in the production of air frame India
and gas turbine engine components. Since the primary (f) Conclusions

62
C.P. De High Temperature Materials and Processes

2. PROPERTIES (Argon) 3 d 2 4 s 2 The outermost shell of the electrons, 3

d 2 4 s 2 , govern chiefly the chemical properties. Titanium
2.1 General
belongs to the "transition elements" because the inner 3
Titanium Is a metal element of Group IVB with d 2 sub shell is partially filled and since it is quite near
atomic weight 47.90 and atomic number 22. It is the the surface, both the s and d electrons are involved in
ninth most abundant element in the earth's crust, and bonding which shows variable valency. It exhibits 3
the fourth most abundant structural element produced valencies in compounds of the type TiO, Ti203 and 1102·
sifter iron, aluminium and magnesium. Its elemental The +4 oxidation state is the most stable as in dioxide
abundance is about live times less than iron and 100 TiC>2· a white pigment used in paint, and tetrachloride
times greater than copper, although for structural T i C l 4 , a liquid used for production of titanium metal
applications titanium's annual use is about 2000 times either by reduction with Mg (Kroll process) or Na (Hunter
less than iron (tonnage). Titanium is, however, ranked process).
15th (Table 1) in terms of sales volume with a total sale In the EMF series, titanium is classified as an active
of 1 billion dollars compared to 200 billion dollars for metal
iron and steel.

The electron configuration of titanium atom in the Tl++ + 2 e —> Eq = -1.63 V (1)

ground state is 1 s 2 2 s 2 2 p 6 3 s 2 3 p 6 3 d 2 4 s 2 or
TKD2 + 4H+ + 4 e — > Τ Ι + 2Η2θ E o = -0.86V (2)
TABLE 1
Sales volume of metals
However, it behaves as a passive metal due to the
presence of a highly protective oxide film.
IRON AND STEEL 200
The nature, composition and thickness of the
GOLD 26
protective surface oxide film depend upon environmen-
ALUMINIUM 20
tal conditions. This film is less than 10 nm thick: hence,
COPPER 17
it is invisible to the eye and is a highly effective barrier.
LEAD 4
Furthermore, T1O2 film is an η-type semiconductor
NICKEL 4
and therefore possesses electronic conductivity. Hence
SILVER 4
as a cathode it permits reduction of ion in an aqueous
TIN 4
electrolyte. On the other hand, this passive oxide film
ZINC 4
has a very high resistance to anodic flow or dissolution.
URANIUM 2
MOLYBDENUM 1.6
2.2 Physical Properties /3,4/
PLATINUM 1.2
COBALT 1
Titanium is a low density metal (4.54 compared to
MANGANESE 1
7.85 of steel) which can be highly strengthened by
TITANIUM 1
alloying and work hardening. It is non-magnetic and
MAGNESIUM 0.7
has fairly good heat transfer properties compared to

63
Vol. 11, Νos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

stainless steel, though less than that of copper (Table 2). 2.3 Alloys of Titanium
Its thermal expansion coefficient is lower than that of
steels and less than half that of aluminium (Table 2). Ti Pure titanium h a s two allotropic forms, the low
(m.pt. 1668°C) and its alloys have a higher melting point temperature, hexagonal close packed (hep) a phase and
than that of steels, but maximum useful temperature for the high temperature body-centered cubic (bcc) β phase
structural applications generally range from 800°F to with a transition temperature of 882°C.
1000°F (427°C to 538°C) as the metal absorbs gaseous Nearly all alloying elements stabilise one or the
impurities like oxygen and nitrogen from the air and other phase and have been classified as α-stabilisers or
becomes brittle. ß-stabilisers. The ß-stabilisers have been further sub-
divided into β isomorphous elements, where there is
complete solubility above the β transus temperature and
β eutectoid elements which have an eutectoid reaction at
TABLE 2 critical combination of temperature and composition.
Physical properties of titanium metal Al, Ga, In, Pb, Zr, Hf and Sn are soluble in the α
phase, β stabilising elements are normally the transition
Atomic number 22
elements V, Mo, Nb and Ta which are β isomorphous
Atomic weight 47.90
whereas all other transition elements are eutectoid
Isotopes, stable 46, 47, 48, 49, 50
forming elements.
Isotopes, unstable 45, 51
Impurities like C, Ν. Ο and Η behave as interstitial
Melting point (°C) 1668 ± 5
solutes in the a phase and act a s solid solution
Boiling point (°C) 3260
strengtheners a n d have significant effects on the
Density (gms/c.cm 3 ) 4.51
nucleation of the α phase.
Hardness (Moh's scale) 2.8
The type and concentration of alloying elements
Abundance In lithosphere 0.44
affect the equilibrium constitution of the titanium alloys
Oxidation states +2, +3, +4
by preferentially stabilising one or the other of the two
Thermal conductivity (w/mk) 21.6
allotropic forms. Alloying also affects the kinetics of
Tensile strengths MPa (min) 345
decomposition of the elevated temperature β phase. The
Young's modulus of elasticity GPa 102
resulting micro-structure has a strong effect on proper-
Coefficient of thermal expansion
ties. Thus alloying also affects the properties of titanium
(ΙΟ-βΚ 1 ) 9
alloys by influencing the evolution of the micro-
Allotropic transformation 882.5
structure.
Latent heat of fusion (KJ/Kg) 440
Extensive research has been done on the develop-
Latent heat of vaporisation (MJ/Kg) 9.83
ment of "tailor made" commercial titanium alloys.
Latent heat of transition 91.8
Amongst the h u n d r e d s of alloys formulated and
Entropy at 25°C (J/mol) 30.3
developed, about 30 commercial and semicommerclal
Electrical resistivity at 20°C (ηΩ) 420
grades of titanium and its alloys (Table 3) have been
Magnetic susceptibility (mks) 180x10®
introduced into use.

64
CP. De High Temperature Materials and Processes

Choice of specific titanium and Its alloys depend increases. However, drifting the potential in a noble

upon application. Corrosion resistant applications direction by impressed current or alloying with elements

normally utilize low strength "unalloyed" titanium mill like Pd can overcome this limitation to corrosion

products fabricated Into heat exchangers, condenser resistance. The alloying elements Co, Ni, Mo and W shift

tubes, tanks, reactor vessels for power generation the potential to the positive region and increase the

plants, desalination plants or chemical industry etc. In temperature of passivation /29/. In the active state, Ni

contrast, aerospace applications utilise high strength and Co Increase the corrosion rate whereas W and Mo

titanium alloys in a very selective manner depending on have no effect. Best results are obtained by combined

factors such as thermal environment, loading parameter, alloying with Ni and Mo.

product forms, fabrication characteristics and inspec- Titanium is immune to corrosion in all naturally
tion/or reliability requirements. occurring environments including sea-water and most

H-6A1-4V alloy (ASTM grade 5) is the most widely industrial waste water stream. It does not corrode in air,

used titanium alloy, accounting for 45% of production. even if polluted or moist with ocean spray - two critical

Unalloyed grades, popularly known as commercially requirements from which the majority of corrosion

pure C.P. titanium (ASTM grades 1, 2, 3, 4 and 7) used resistant alloys based on copper or stainless steel

mostly for corrosion resistant applications, comprise suffer. It does not corrode in soil and even in deep salt

about 30% of production and all other alloys combined

constitute the remaining 25%.

C.P.T1 (ASTM grades 1, 2, 3, 4 and 7) and the 2 near a

alloys (ASTM grade 12 and ASTM grade 9) as well as the -
α-β alloy ASTM grade 5 CT1-6A1-4V) are the 8 alloys of
primary concern for corrosion resistant applications
CTables 3,4).

3. CORROSION RESISTANCE OF Ti AND

ITS ALLOYS

3.1 General

The Pourbaix diagram for titanium-water system

(potentlal-pH) shows the thermodynamic passive region
(Fig. 1). From the Pourbaix diagram, it can be seen that
Ti and its alloys are safe for use in mildly reducing to
highly oxidising environments in which protective Ti02
and H2O3 form spontaneously and remain stable. On pH
the other hand, an uninhibited strongly reducing acid
Fig. 1 Pourbaix Diagram - Theoretical Domains
environment (like strong inorganic and organic acids) of Corrosion, Immunity and Passivation
of Titanium at 25UC (assuming passivation
may attack titanium, especially when temperature by anhydrous Ti0 2 )

65
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

TABLE 3

S u m m a r y of c o m m e r c i a l a n d s e m i c o m m e r c i a l g r a d e s

a n d a l l o y s of t i t a n i u m

0.2 p.c. Nominal

Tensile Yield Composition
Designation strength strength Impurity Limits
(Min) (Min) N C Η Fe Ο Al Sn Zr Mo Other
(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13)

UNALLOYED G R A D E S

ASTM G r a d e 1 240 170 0.03 0.10 0.015 0.30 0.18

AS'IM G r a d e 2 340 280 0.03 0.10 0.015 0.30 0.25

ASTM G r a d e 3 450 380 0.05 0.10 0.015 0.30 0.35

ASTM G r a d e 4 550 480 0.05 0.10 0.015 0.50 0.40

ASTM G r a d e 7 340 280 0.03 0.10 0.015 0.03 0.25

ALPHA AND NEAR ALPHA ALLOYS:

Tl G r a d e 12 480 380 0.03 0.10 0.015 0.30 0.25 0.3 0.8

(Mo) (Ni)
Ti-5Al-2.5Sn 790 760 0 . 0 5 0.08 0.20 0.50 0.20 5.0 2.5
(Al) (Sn)
Ti-5Al-2.5Sn 690 620 0.07 0.08 0 . 0 1 2 5 0.25 0.12 5.0 2.5
(EU) (Al) (Sn)
T1-6A1 - . 2 S n - 4 Z r
-2Mo 900 830 0.05 0.05 0 . 0 1 2 5 0.12 0.15 2 4 2
(Al) (Sn) (Zr

Τ1-8Α1-1ΜΟ
-IV 900 830 0 . 0 5 0.03 0.015 0.30 0.03 8 1 1
(Al) (MO (V)

T1-6A1 - 2 N b
-lTa-0.8Mn 790 690 0.02 0 . 0 3 0 . 0 1 2 5 0.12 0.10 6 1
(Al) (Mo)
T1-2.5A1-1 l S n
-5Zn- lMo 1000 400 0.04 0.04 0.008 0.12 0.17 2 . 2 5 11.0
(Al) (Sn)
5(Zr) 1 (Mo)

T1-5A1 - 5 S n -

2Zr-2Mo 900 830 0.03 0.05 0 . 0 1 2 5 0.15 0.18 5. 5. 2 . 2 . 0.2 Se

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CP. De High Temperature Materials and Processes

TABLE 4

List of Titanium and its alloys used in corrosion

resistant applications.

0.2 p.c. Nominal

Tensile Yield Composition
Designation strength strength Impurity Limits
(Mpa)
(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13)
Ν C Η Fe Ο Al Sn Zr Mo Others

ALPHA-BETA
ALLOYS:

*Ti-6Al-4V 900 830 0.05 0.10 0.0125 0.30 0.30 6.0 - - - 4.0(V)
(b)
*Ti-6Al-4V 830 760 0.05 0.08 0.0125 0.25 0.13 6.0 - - 4.0fV)
(ELI) (b)
*Ti-6Al-6V
2Sn(b) 1030 970 0.04 0.05 0.015 1.0 0.20 6.0 2.0 - 0.75 6.0(V)
*Ti-8Mn(b) 860 760 0.05 0.08 0.015 0.50 0.20 - - - - 8.0(Mn)
*Ti-7Al-4Mo
(b) 1030 970 0.05 0.10 0.013 0.30 0.20 7.0 - - 4.0 -

*Ti-6Al-2Sn
-4Zr-6Mo(b) 1170 1100 0.04 0.04 0.0125 0.15 0.15 6.0 2.0 4.0 6.0 -

*Ti-5Al-2Sn
2Zr-4Mo-4Cr
a) (c) 1125 1025 0.04 0.05 0.0125 0.30 0.13 5.0 2.0 2.0 4.0 4.0(Cr)
*Ti-6Al-2Sn
2Zr-2Cr
(a) (b) 1030 970 0.03 0.05 0.0125 0.25 0.14 5.7 2.0 2.0 2.0 2.0(Cr)
*Ti-3Al-2.5V
(d) 620 520 0.015 0.05 0.015 0.30 0.12 3.0 - - - 2.5 (V)

BETA ALLOYS:

*Ti- 13V-1 lCr

-3A1 (c) 1170 1100 0.05 0.05 0.025 0.35 0.17 3.0 - - - 11 (Cr)
*Ti-8Mo-8v 11(V)
-2Fe-3Al
(a) (c) 1170 1100 0.05 0.05 0.015 2.5 0.17 - - - 8.0 8.0(V)
•T1-3A1-8V-
6Cr-4Mo-4Zr
(a) (b) 900 830 0.05 0.05 0.020 0.25 0.12 - - 4.0 4.0 6.0(Cr)
8.0(V)
*Ti-l 1.5Mo-
6Zr-4.5Sn
(b) 690 620 0.05 0.10 0.020 0.35 0.18 - 4.5 6.0 11.5 -

a) Semi-commercial alloys
b) Mechanical properties given for annealed condition may be solution treated and aged to
increase strength
c) Mechanical properties given for solution treated and aged condition, normally not used in
annealed condition. Properties may be sensitive to section size and processes
d) Primarily a tubing alloy, may be cold drawn to increase strength

67
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

mine environments, where nuclear waste might be zinc in sea-water both in temperate as well as tropical
buried. conditions (Table 6) show the superiority of titanium as
Thirty percent of titanium consumption is in a construction material for sea-water applications.
corrosion resistant applications. The metal is resistant Pitting and crevice corrosion, which occur with 18:8
to corrosion attack in oxidising, neutral and inhibited series of stainless steels, are totally absent in titanium
reducing acid as well as oxidising environments like in ambient sea-water.
nitric acid, FeCl3 and C u C l 2 solutions and wet chloride
gas. TABLE 6
Reducing acids like HC 1 and H2SO4 are inhibited Comparative values of corrosion rates oflitanium and
with oxidising inhibitors, whereas organic acids require other metals in sea water
only a small amount of water to inhibit corrosion.

3.2 Corrosion Resistance of Titanium in Sea- Metal/Alloy Ocean Depth Corrosion Rate
Water/5-9/

(Mil/Yr)
"Π and its alloys exhibit negligible corrosion rate in Unalloyed TI Shallow 0.00003 (a)
sea-water a n d all neutral waters and stream to a Low Carbon Steel Shallow 7.37 (b)
temperature as high as 260°C (Table 5). Contaminants Copper Shallow 1.13 (b)
s u c h as iron a n d m a n g a n e s e oxides, sulphides, Zinc Shallow 1.64 (b)
sulphates and carbonates present as contaminants do 18:8 Stainless Steel Shallow Pitting (b)
(16 SWG) Crevice Corrosion
not affect passivity. The comparative behaviour of
Naval Brass Shallow 0.76 (b)
ferrous material as well as other corrosion resistant
metal/alloys like copper, naval brass, aluminium and
Note: L (a) / 5 /
2 (b) Based on 2 years immersion at Bombay / 8 /
TABLE 5
Low carbon sleel and copper suffered both
Corrosion rates of titanium in sea water general corrosion and pitting

Deepest pit 115.0 mil (Mild steel) and 59.0

mil (Copper)
Alloy Ocean Depth Corrosion Rate
Naval brass and zinc suffered general
corrosion
(Metres) (Mil/Yr.)
Unlike stainless steels, even if marine deposits are
Unalloyed Titanium Shallow 0.00003
present and biofouling occurs, titanium tubing exposed
Unalloyed Titanium 720-2070 <0.1
for 16 years to polluted and sulphide containing sea-
Unalloyed Titanium 2-2070 Nil
water present in harbours and estuaries showed no
Unalloyed Titanium 1720 0.0015
evidence of corrosion / 5 / .
Ti - 6A1 - 4V 2-2070 <0.01
Exposure of titanium to a marine atmosphere / 1 0 / ,
Tt - 6A1 - 4V 1720 0.0003
splash zone / l l , 12/, tidal zone and soils / 1 2 / also do not
Ti - 6A1 - 4V 1720 <0.04
cause corrosion. The excellent corrosion resistance of

68
C.P. De High Temperature Materials and Processes

titanium to erosion even at high velocities in the most other structural metals / l l / .

presence of suspended impurities make titanium more The above data on corrosion behaviour of titanium

suitable than the existing condenser tube alloys In sea - in a stagnant as well as moving sea-water environment

water environment. In a high velocity sand-laden sea- including polluted waters in harbours containing sus-

water test (8.2 m/s), titanium performed 100 times better pended impurities have made titanium the most appro-

than 18 Cr-8 Ni stainless steels, monel or 70:30 priate and technically suitable material for the following

cupronickel. Resistance to cavitation is also better than sea-water applications (Table 7,8):

TABLE 7

Summary of applications of tubular heat exchangers in

sea water applications

Power Technology Cost

& Efficiency

Condensers - Thinner Wall Tubes

Ancillary Coolers Nuclear - Advanced geometry Tubes

and fossil
Dump Condensers fuel fired power Helically roped
plant Low Finned
Refurbishment - Bi Metal Finned

- Higher Flow Rates

- Thermal Design Codes

- Efficient Shell Side Design

Desalination Plant Reliability

- Brine Heaters - Product Quality

- Heat Recovery - As Welded Tubes

- Heat Rejection - Annealed welded Tubes

- Brine Lines - Non-destructive Testing

Hydrocarbons

- On-Shore Steam & - System Reliability

Overheads Condenser - Refurbishment of existing systems
- On-Shore Product Coolers - Modular Designs
- Off-Shore Product Coolers - Titanium Tube Plates
- Glycol Coolers - Titanium Headers and Shells
- Gas Gathering - Welded Tube Plate
- LNG Finned Coolers Joints
- Hydraulic Expansion
Marine - Tube Plate CoaUngs
- Cathodic Protection
- Condensers & Coolers - Anti-vibration Damping

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Vol. I I , Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

TABLE 8
Other applications for titanium tubuläre in sea water

APPLICATIONS: APPLICABLE TECHNOLOGY:

INJECTION SYSTEMS: TUBES:
hypochlorite commercially pure
water alloy
PIPE WORK: SEAMLESS & WELDED PIPE:
fire mains commercially pure
hydraulic alloy
pipe fittings
RISERS: EXTRUDED & FORGED HOLLOWS & RINGS
production commercially pure
- kill tubes alloy
choke tubes
stress joints
connections
WELLHEADS: BIMETALLIC:
pipe work FORMING
hollow forgings superplastic
PIPELINES explosives
DATA LOGGING SYSTEMS JOINING:
- ΤI G, Μ I G, Plasma welding
TETHERING SYSTEMS E.B. welding
SUB-SEA MODULES Friction welding
Explosion bonding
SONDES Diffusion bonding
- Ni - Ti Alloys
SUBMERSIBLES

(a) Nuclear power stations (g) Shipbuilding and oceanographic equipment

(b) Fossil fuel power plants (h) Deep submersibles and nuclear submarines
(c) Desalination plants (i) Surgical implants
(d) Petroleum refining and petrochemical industries (j) Steam turbine blades
(e) Offshore oil exploration (k) Rotors for superconducting generators clue to the
additional benefit of cryogenic properlies
(1) Ocean Thermal Energy Conversion Scheme (OTEC)

70
C.P. De High Temperature Materials and Processes

3.3 Corrosion Problems of Titanium and Preventive

Measures

UJ

Titanium with a stable passivity over a wide range <j

CO
of temperature potential and chloride environments,
v>
>
however, suffers from pitting, crevice corrosion, hydro-
σ>
c
gen absorption, stress corrosion cracking, corrosion

fatigue as well as from general corrosion whenever the 5_

k_

oxide film is breached or removed. Ο

General corrosion: Titanium corrodes very rapidly in an C

«

acid/fluoride environment. It is also attacked by boiling Ο

CL

HCl or H2SO4 at a concentration above 1 p.c. and at Ο

Ο
room temperature above 10 wt% acid concentration.
Titanium is also attacked by hot caustic solutions, 50 100 150 200 250
Ο-
Temperature (°C)
phosphoric acid solutions (above 25 wt.p.c. concen-
Effect of Temperature on Critical Potential
tration), boiling A I C I 3 (concentration above 10 wt%), for Pitting of Titanium in 0.53 Ν NaCl and
l.ON NaBr
dry chlorine gas, anhydrous ammonia and dry hydrogen
- hydrogen sulphide mixture above 150°C. /13/.

Pitting corrosion: Posey and Bohlman found critical

potentials for pitting greatly affected by temperature
/l,14,15/. Critical potentials for pitting titanium in 0.53
Ν NaCl (3%) and 1 Ν NaBr solutions in an autoclave up
to 250°C along with effect of pH between 1 to 7 were
studied In an autoclave in 0.53 Ν NaCl solution at
200°C. Results are shown in Figs. 2 and 3.

Titanium is resistant to a sea-water environment

up to a temperature of 130°C (Fig. 4) /16/. However, at
ο »H
high NaCl concentration and low pH brines, pitting and = υ

crevice corrosion can occur even at 80°C (Fig. 4). In £ </>

&
ο Sσ»
desalination plants, pitting is associated with formation ο C

of salt plugs and stagnation of brine underneath, which ύ Ξ.

leads to a localised attack by local cell formation. Such
an attack is accelerated by galvanic coupling between
titanium and monel.

This type of attack can be controlled by using

Fig. 3 Effect of pH on Critical Potential
titanium tube sheets, an improved welding technique for Pitting in 0.53 Ν NaCl at 200°C

71
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

Concentration of NaCl

Fig. 4 Immunity of Titanium from Pitting in NaCl Media

and alloying with cathodic elements like Pd, namely, ΤΪ- the crevice, alloy composition, metal surface condition
0.13%Pd alloy. and metal potential.
Crevices can be created from adhering deposits or
Crevice corrosion: As temperature increases, titanium scales (i.e., salt deposits), metal to metal joint like poor
and its alloys become susceptible to crevice corrosion in joint design or tube to tube sheet joints or gasket to
chloride or other halide environments, though under metal flange and other seal joints.
more severe conditions than stainless steel /17/. Schutz
has made a critical preview of the relative influences of Crevice corrosion mechanism: Dissolved oxygen
six primary factors responsible for crevice corrosion of present in the crevice is consumed faster than its
titanium alloys /18/. These often interacting factors diffusion and replacement from the bulk solution resul-

include temperature, solution chemistiy/pH. nature of ting in a potential difference between the crevice (active)

72
C.P. De High Temperature Materials and Processes

and the open exposed surface. Chloride ion from the

bulk migrate into the positively charged crevice where

titanium is corroding. Titanium chloride thus produced

Sr
X
is readily hydrolysed producing more acid. pH inside the

crevice has been measured to be as low as 0-1. The ο

following reactions have been suggested /18/: σ
25
c
β>
υ
c 20
2 Ή + O2 + 2 Η2θ —> 2 TiC>2 + 4 Η (3) ο
υ
c 15
ο
2 Ti + 5 HCl + Η 2 0 — > T i C l 3 + T i O C l 2 + 7Η (4)
3 10
Ο
(Λ
5
TiOCl2 + 2 TiCl3 + 4 Η 2 0 —> Τ10 2 + Τί 2 θ3 +8 HCl (5)

Temperature: Minimum threshold temperatures for

40 80 120 160 200
crevice corrosion are approximately 70°C, regardless of

pH or solution composition (Fig. 5). Solution temperature, eC

Fig. 5 Diagram ofTitanium Resistance in NH 4 C1
and NaCl Solutions.
Alloy composition: Critical pH values for crevice
corrosion in chloride, bromide, iodide, fluoride and
corrosion of commercial Ti and its alloys in hot NaCl
sulphate solutions varying in intensity upon the anionic
brines at 90°C are shown in Table 9.
species. Crevice attack is enhanced as halide concen-

tration is increased with maximum attack in 1 -2 Μ range

Effects of pH and temperature on different grades of
unless solutions are aerated. Pure sulphate solution
titanium are shown in Fig. 6/18/.
seems to be somewhat benign with higher temperature

Solution chemistry: Titanium is susceptible to crevice (> 82°C) and concentration (> 1%) thresholds. Cathodic

12

No corrosion

Grade
8

I
CL

0
30 94 149 205 261
Temperature (°C)

Fig. 6 pH/Temperature Effect on Different Grades of Ή in NaCl Based Brine

73
Vol. 11, Nos. 1-4, 1993 Use of Titanium and Us Alloys in Sea-Water Service

TABLE 9 generally exhibit a layer of titanium hydride precipitates,

Critical pH values for crevice corrosion of titanium which are produced by cathodic hydrogen reduction
alloys in hot (> 90°C) NaCl brines within the crevices (Eqs. 3,4).

Dimension of crevice: Initiation of crevice corrosion in

Alloy Maximum pH at which titanium alloys requires an extremely tight joint (less
Attack Occurs
than 1.5 χ 10"^ cm) and reasonably deep crevice (more
Tl - 6A1 - 4V 10 to 10.5
than 1 cm). Gaskets based on fluorocarbons like Teflon
C. P.TI 9.5 to 10
and certain types of sealants when used against a metal
«1
V Ή -550 3
Pi surface promote more crevice attack. Rubber, asbestos,
ao Grade 12 Ti 2.5
S PVC. epoxy, nylon and silicon rubber gasket - metal
« Tl - 6A1 - 2 Sn - 4Zr - 6M0 2
rt crevices exhibit reduced susceptibility to crevice attack.
Β
υ Tl - 3A1 - 8V - 6Cr - 4Zr - 4 Mo 1
α Titanium metal to metal crevices are generally less
Grades 7 / 1 1 Titanium 0.7 - 0.8
susceptible to attack than gasket to metal crevices.
Tl - 15Mo - 5Zr <1
Alloying elements like Pt, Pd, Ru, Ir which promote
passivation enhance crevice corrosion resistance.

depolarisers such as dissolved oxidising species and H +

Strategies for prevention: Proper alloy selection,
ions stimulate both initiation and propagation.
precious metal surface treatments, metallic/metallic
Cationic oxidising species which accelerate attack
oxide coatings, thermal oxidation, noble alloy contact
and oxidising anionic species which inhibit attack are
and surface pickling are recommended to reduce crevice
listed in Table 1 0 / 1 8 / .
corrosion. For long term service reliability a fully

Microstructure of crevice corrosion pits: The micro- resistant alloy is preferable. Localised surface treat-

s t r u c t u r e of sectioned and polished crevice pits ment is more practical for thicker sections (>20 mm).

TABLE 10 Hydrogen uptake: The surface oxide film of titanium is a

Dissolved oxidising species which may accelerate or highly effective barrier to hydrogen penetration. Traces
inhibit crevice corrosion of titanium in hot halide of moisture or oxygen in a hydrogen gas containing
solutions environment very effectively maintain the protective
oxide film. However, the simultaneous existence of the
ACCELERATE ATTACK INHIBIT ATTACK
following conditions could lead to hydrogen uptake and
Fe+++, Cu++, N1++, oci^ ciajcicf24
embrittlement in aqueous media:
Ti+<4>, Ce+<4>, Sn+(4) -(2) -(2)
NQ2, C r 2 0 / \ Mo 4
VC>2. Te+4, +6
, Se +4 , 46
Mn-2 SaQj-2,
(a) generation of nascent (atomic) hydrogen on a
Pt+2, +4
, Pd+2, Ru +3 , VO4.VO2. ICb,
titanium surface either from a galvanic couple,
Ir+3, Rh +3 , Au +2 WO,
impressed cathodic current or corrosion of
P2, C l 2
titanium (Figs. 7, 8).

74
CP. De High Temperature Materials and Processes

Natural sea water

120 — flowing rate ·· 2 m / s Ρ
Ε
Q.
Q.
3 months
C
Ο
80
ο
<0
-Q
Ο

& 40
ο
k-
•σ

I ι 1 1 1
-0.6 - 0 . 8 -1.0

Potential ( V vs.S.C.E)
Fig. 7 Relationship Between Hydrogen Pickup in Titanium Tube and Cathodic Potential

(b) metal temperature above 80°C, where the diffusion

rate of hydrogen into α-titanium is significant.

εΩ- (c) solution pH less than 3 or more than 12.
Ο.

C
Ο Hydrogen embrlttlement can be avoided by (a) coupling

titanium to a metal like steel, aluminium, zinc, copper

ο alloys or (b) use of an insulating joint or (c) controlled
«Λ
-Ο
σ cathodic protection /30/.
c
<υ
σ>
2 Stress corrosion cracking: Titanium does not suffer
"Ο
stress crack in environments that cause cracking in
I
other metal alloys (e.g., boiling M g C l 2 . NaOH, sulphides,

etc.). However, some of the alloys are prone to hot salt

corrosion cracking, observed under laboratory

-0.6 - 0 . 7 - 0 . 8 - 0 . 9 -1.0 conditions /31/. Ti stress cracks in methanol containing
Potential ( Vvs.S.C.E.)
acid chloride or acid sulphates, red fuming nitric acid,
Fig. 8 Relationship Between Hydrogen Absorption
nitrogen tetroxide and trlcholorethylene.
of Titanium and Applied Potential in Sea
Water at 25°C (test lime 3 months) and at
Susceptibility to sea-water cracking, determined by
100°C (test time 2 months).

75
Vol. I I , Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

a Kscc/Kic relationship, has shown that the likelihood of 100

s.c.c. depends on the alloy composition, namely, C.P.
Ti - 6 A I - 4 V (Air, s t e a m ,
titanium with an oxygen content below 0.15% as well as a> 80 N a C l solution)
"Ο
alloys with an aluminium content up to 3 p.c. and 3

strength below 600 MPa are practically nonsusceptible Q- 60

E ^ίΐΐΤίπιτττπιτΓη Air
ο
to s.c.c. in sea-water. An adverse effect is produced by «η 13 Cr steel
</>
V) JC
alloying with aluminium above 6% and tin, chromium as a>
40 - ItK
well as gaseous impurities oxygen and hydrogen /17/. <Λ
Ο
Isomorphous ß-stabilisers like molybdenum, "θ 20 N a C l solution
Ο ^ m u m D
vanadium, niobium and tantalum have beneficial effect.
13 Cr steel
External parameters like solution concentration, pH, 0 1 1 1
temperature, loading condition, shape of the specimen
10 10 ,ο7 ,ο9
also have an effect. Critical strain rate for low cycle
Cycles to failure
fatigue life has also been established in a sea-water
Fig. 9 Fatigue Properties for Blading Materials
environment /17/. Surface finish has also been found to

affect the susceptibility to s.c.c. Resistance to fatigue resistance of the alloys to fatigue failure.

failure can be improved by hydraulic shot blasting,

tumbling, etc. Low antifriction properties: The natural low anti-friction

properties of titanium alloys can be improved by (a) hard

Corrosion fatigue: Full probability fatigue curves of facing by plating with Cr or Mo, (b) thermal oxidation of

titanium alloys have been studied in sea-water and air at friction surface or (c) detonation plating with metal

room temperature up to physical endurance limits with oxides and carbides. Among them, thermal oxidation is

10% accuracy, raising the reference load from 10^ to 10^ the most efficient and simple method for commercial
cycle /17/. It has been shown that titanium alloys retain application /17/. Coatings based on carbides and
their endurance limit until the first crack initiated by metalloids have a better load bearing capacity and wear
sea-water action at multicycle loading (above 107 resistance but their application in sea-water is limited
cycles) appears /17/. The high level of endurance of due to insufficient corrosion resistance. These coatings
titanium alloys compared to 13 Cr steel (blading are only good for a noncorrosive media.
material) is shown in Fig. 9 /4/.

4. APPLICATIONS OF TITANIUM AND ITS ALLOYS IN

Surface finishing: One of the main factors ensuring a SEA WATER SERVICE
high level of endurance in titanium alloys is surface
finish, which is achieved by plastic surface deformation 4.1 Background

(PSD) In areas subject to cyclic loading. Spinning with a

ball or roller, hydraulic shot blasting, shot peening, At the Second International Conference on
tumbling and needle gun treatment methods are Titanium Science and Technology, Joseph J.B. Cotton
employed. PSD further increases the higher natural /I/ recommended extensive use of titanium in non-

76
C.P. De lligh Τemperalure Materials and Processes

aviational fields like ocean environment and chemical TABLE 11

process Industries owing to its outstanding corrosion Failure rate of condenser tube materials in sea water
resistance behaviour. Hie absence of exhaustive quanti-
F.R = a x 1 0 0 / b x c x 10"4
tative corrosion data at that time was responsible for
a = Number of leakage tubes
reluctance on the part of users to switch over to a new
b = Total number of tubes
construction material.
c = Duration of trial in hours
However, the situation h a s since remarkably
improved due to the wealth of corrosion data generated TUBE MATERIAL FAILURE RATE
and confidence established in the metal's greater
Aluminium brass 0.05 - 0.1
reliability In the system accompanied by cost benefit in
(Pitting and erosion)
the long run. Hie wide range of titanium application and
Titanium No leakage
its alloys is evident from the list in Tables 7 and 8 / 3 1 / .
High Cr Mo Stainless Steel No statistical survey
Listed below are a few of them, which will be highlighted
available. Results of
in this review:
trials currently In
progress In Europe to be
(a) Tubular Heat Exchangers in Power and Desalina-
published In a few years
tion Plants
(b) Oil Exploration and Production
- Injection systems (F.R.) in sea-water leakage trials and physical properties
- Pipework is given in Tables 11 and 12. Corrosion resistance of
- Risers condenser tube materials and their relative cost are
- Wellheads shown In Tables 13-15.
(c) Sea Water Pipelines Titanium h a s the advantage of a low specific
(d) Tethering Systems gravity, a low thermal expansion coefficient and superior
(e) Data Logging Systems corrosion resistance to both cupro nickels as well as
(f) Sub-Sea Modules stainless steels. Copper alloys show excellent thermal
(g) Sondes conductivity, while stainless steel has the advantage of
(h) Submersibles high tensile strength, fatigue strength and Young's
modulus with the disadvantage of low thermal con-
4.2 Condenser and Heat Exchangers ductivity. Copper alloys suffer from pitting, stress
corrosion cracking, impingement attack as well a s

Condenser and heat exchanger tubes currently cavitation. High Cr-Mo stainless steel is stiff against

used in power stations are either made of (a) copper cavitation but occasional pitting and crevice corrosion

based alloys like aluminium brass and cupro nickels have been reported.

90:10 and 70:30 fortified with iron or (b) high chrome -

molybdenum steels like A1-6X, MONIT and SEA CURE, Cost: On the basis of relative cost per unit length for 25.4
or (c) C.P. Titanium. A comparison of their Failure Rate mm, OD condenser tubes, aluminium b r a s s is the

77
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service
TABLE 12

Physical properties of condenser tube materials

MATERIALS
- Ti A l brass Al-6x SEA-CURE
(MONIT)
PROPERTIES

Tensile strength 345 392 500 650

MPa

Yield strength 280 196 210 550

MPs

Elongation 25 60 40 25
%

Fatigue strength 232 225 377

MPa

Specific gravity 4.51 8.4 8.2 7.9

Thermal conductivity 17 99 13 22
w/mk

Co-efficient of linear
expansion 9 18.5 17 17
10-6 K -i

TABLE 13

Corrosion Resistance of Condenser Tube Materials (1 - Lowest : 6- Highest)/4/

CORROSION TYPE
Stainless steel 90-10 Ti Grade 11
(304) Cr-Ni
MATERIAL

General Corrosion 5 4 6

Erosion-Corrosion 6 4 6

Pitting (Flowing) 4 6 6

Pitting (Stagnant) 1 5 6

Impact of Bubble 6 3 6
fTube interior)

Impact of Steam 6 3 6
(Tube interior)

Stress Corrosion 5 6 6

Corrosion by Chloride 1 6 6

Corrosion by NH 3 6 4 6

Corrosion (Average) 4.4 4.5 6

78
C.P. De High Temperature Materials and Processes

TABLE 14
Comparison of cost of condensers in different materials
(1988)

Single Pass Condenser Double Pass Container

Item/Thickness 90-10 SS-304 Titanium 90-10 SS-304 Ti

Cu-Ni Cu-Ni
mm 1.24 0.7112 0.5 1.24 0.7112 0.5
Relative Capital 1.41 1.247 1.364 1.443 1.243 1.394
Cost of Condenser
Delta P. across 3.22 3.54 3.26 4.73 5.15 4.79
Condenser MWC
C.W. Pump Power in KW 678.5 746.0 686.90 815.45 887.86 825.8
for Condenser Pressure
drop
Differential C w Pump +40.0 +107,-5 +48.4 +48.3 +120.7 +58.62
in (kW)
Relative Total 1.45 1.34 1.425 1.489 1.344 1.445
Devaluated cost

Note: 1) Aluminium brass of 1.0mm is taken as 1.0

2) Reference p. 31, 32 (1988) Report of the Sub-Committee or Techno-Economic study of
condenser system with use of Titanium Tubes, June.

TABLE 15
Capital cost - A case for Ή condenser tube

Al -brass Cupro-nlckel Titanium

(Welded)

Amount of tube 330,000 m 360,000 m 300,000 m

(metres)
Capital Cost 133.3 185.3 195.9
(Rs in lakhs)
Discounted Replacement 58.4 89.9
(8 th & 16th years)
(Rs in lakhs)
Outages (20 yrs) 332.0 332.0

Total (Rs in lakhs) 523.4 607.4 195.9

79
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

cheapest while cupro nickel and stainless steel tubes sea-water or river water with a high salinity due to the

are almost the same in price. Ti tubes, however, instability of the protective oxide film in the presence of

becomes cheaper when the thickness is reduced to 0.5 velocity, pollutants, suspended solids, etc.

and still lower at 0.3 mm (Fig. 10). 18:8 suffer severely from pitting and crevice

A similar comparison on the long term economic corrosion in the tropics /3/ due to the settlement of

advantage of titanium shows that based on a service life fouling organisms.

of 40 years titanium tube (0.7 mm) is only one-fourth as

expensive as cupro nickels (1.6 mm) or A l - brass (1.6 Tube thickness: In power and desalination plants, 0.5

mm) under sea-water conditions. By using 0.3 or 0.5 mm mm and 0.6 mm thick tubes are specified whereas 0.7

thick titanium tubes, the cost advantage is enhanced mm tube was previously more common. In new plants

since zero leakage condenser efficiency can be achieved which have freedom of design, 0.3 and 0.4 mm thick tubes

with titanium tubes. are projected for desalination plants. Nuclear power

Susana R. de Sanchez /20/ has made a detailed plants, however, continue with the present stipulated

survey of various copper based alloys in heat exchangers thickness of 0.6 and 0.7 mm on safety grounds.

at the thermal power stations based on the Atlantic Titanium has an additional advantage in nuclear

coast. Most of the copper based alloys, including cupro power plants. Due to higher capacity on the order of

nickels, aluminium brass. Admiralty brass, aluminium 1000 MW resulting from an absence of leakage, there is

bronze, suffered corrosive attack in power stations using less shutdown and also an increase in the maintenance

period by longer intervals.

1.5 Early trials: In October 1974, 500 aluminium brass

tubes were replaced in the main condensers of a large

1.4
steam turbine vessel (164, 578 DW, 16 knots) in Japan.
1.3
After operation of 4,702 hrs. (8 months) in the Persian

Gulf and African coast, two tubes were removed for

8 1.2
υ detailed examination. Both the internal and external
I I .1 surfaces were found to be completely free of corrosion

/21.33/.
1 1.0
QL
Cupro- nickel
Power plants /22/: In the U.K. alone, titanium tube
1.9
Aluminium installations exceed 26,000 MW and Ihe total for the

1.8 brass non-Communist world is over 100,000 MW. As early as

J L March 1984, Japan achieved 21.0% of total power
0.20 . 3 0.5 0.7 0.9 I.I 1.3 generating capacity of 18,000 MW using nuclear power.

Wall thickness, m m There were 34 nuclear power stations including those

under construction in Japan. Among them 7 PWR and 10

Fig. 10 Relative Costs Per Unit Length for 25.4 mm
BWR plants are being fitted with all titanium conden-
OD Condenser Tube

80
CP. De High Temperature Materials and Processes

sers. Capacity of the nuclear power plants using trials are expected to be published within a few years.

titanium tubes was planned for 60 p.c. of the total In view Titanium has an erosion resistance due to steam

of their greater reliability, ease of maintenance and droplets, which is much higher than that of copper

lower dependence on Imported petroleum as fuel. Thick- alloys and almost equal to stainless steel.

ness of the tubes varied between 0.5 mm and 0.7 mm.

In the USA by 1988, 28 nuclear power plants were Hydrogen absorption: Hydrogen absorption by titanium

fitted with all titanium condensers using 0.7112 mm (22 heat exchangers was experienced with titanium tubing

BWG) thick tubes. In France, EDF has adopted fully when used with copper alloy tube plate or when

titanium tube condensers at 6 PWR units of 900 MW and excessive cathodic protection was applied to the tube

5 of 1300 MW. Total length of titanium tubing (0.5 to 0.6 ends. This is, however, unnecessary for titanium tubes.

mm) for each unit is about 826 km. A tube plate or water box when used with titanium tubes

Sweden has 12 units at 4 nuclear power plants all can be protected against galvanic corrosion by the

using Ti tubed condensers. Titanium condensers are application of coating. Critical potential for hydrogen

also in operation in England, Belgium, Finland, absorption by titanium in flowing sea-water has been

Germany, India, Philippines, Korea and Taiwan observed to be -0.75 V (S.C.E.) (Fig. 9).

Sea water leakage trial of condenser tubes: Based on the Tube vibration: Greater susceptibility to vibration of

report of condenser tube leakage in Sweden and Finland titanium tubes having a smaller wall thickness (0.3 to 0.7
/5/, the failure rate (F.R.) after 10,000 hrs of operation mm) compared to A l - brass (1.25 mm) has been
lies between 0.005 to 0.1 for aluminium brass tubes, controlled by reducing the tube support spacing as
mostly due to pitting and erosion, whereas F.R. for indicated below:
titanium tubes is zero, showing zero leakage. The zero

leakage for titanium tubes has also been reported from Material Wall thickness Support spacing
(mm) (Ratio)
the USA France, England and Japan

Al-brass 1.25
axl00_ Titanium 0.7 0.86
F.R
( b x c x 10-4)
0.6 0.83
a = No. of leakage in tubes 0.5 0.80
b total number of tubes used 0.4 0.76
c = time of operation in hours 0.3 0.71

There is no statistical survey of stainless steel Use of thin wall titanium tube: In Japan and France, the

condenser tube though a total of 7300 km of A1-6X has wall thickness of titanium tubes has been reduced in

been used in the USA since 1973. There are, however, stages of 0.5 mm, 0.4 mm and 0.3 mm, thus improving the

some cases of crevice corrosion experienced in Europe. heat transfer efficiency as well as economy, in view of

Large scale evaluation of stainless steel tubes is, absolute freedom of titanium tubes to corrosion in sea-

however, in progress in Europe and results on evaluation water cooling system.

81
Vol. I I , Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

A fifteen year trial with 0.3 mm titanium tubes / 2 4 / : A ment at the edge protruding from the tube sheet. The
fifteen year trial with 0.3 mm titanium tubes was carried reduction of heat transfer coefficient even after 15 years
out in a MHl-WH Radial Flow type sea-water cooling service was negligible. The suitability of 0.3 mm thin
condenser of 156 MW output at the Monato Power titanium tubing for sea water cooling was established by
Station in Japan. Essential details are given below: the trial. Fatigue testing h a s also concluded the
reliability of 0.3 mm tube in service.
(a) Ti tubes - steam welded (25.40 χ 0.3 t χ 8,657 L in
mm) Biofouling in temperature and tropical waters: In
(b) Tubes fixed to Müntz metal tube sheet by 5 roller- coastal power stations situated at northern latitudes
expander like Sweden, U.K., U.S.A. and Japan, where the intensity
(c) Condenser capacity 10,620 m^ sea water cooling of fouling is low and only seasonal, biofouling in
(d) Tube supporting plate span 970 mm each titanium tube was prevented by intermittently flown
(e) Test period of 15 years: September 1965 to sponge balls or treatment with low dosage chlorine
November 1980 (106,452 cumulative hours) In tropical countries, there are two operating
(f) Sea-water flow rate 2.25 m/sec. nuclear power stations Tarapur Atomic Power Station
Back washing of tube twice a week (TAPS) and Madras Atomic Power Station (MAPS). The
(g) Sea-water t e m p e r a t u r e : 28°C (summer), 8°C intensity and nature of fouling is more severe - occurring
(winter) all year round and also at specific sites. Mussel shell
and jelly fish impingement have been a matter of great
Results of withdrawn tube: concern to MAPS. Strategies for control of biofouling
have made considerable progress using chlorination as
(a) Appearance - A ring of blackish-brown scale 60-80 well as other mechanical contrivances /25-27/.
mm near the tube supporting plate (exterior side)
only consisting of the elements Fe. Ο, C and ferrous Fabrication of titanium structures: Fabrication of
oxides by ΕΡΜΑ analysis. No changes on the titanium is comparable with that of stainless steel in
remaining area method, degrees of difficulty and cost. Commercial grade
(b) NDT - No defects in the base metal or weld could be titanium can be bent 105° without cracking and a radius
detected either by ultrasonic or eddy current test of 2-2.5 times the sheet thickness. The bend radius of
methods. the alloys is as high as five times the sheet thickness. A
(c) Mechanical testing - No change in mechanical loss of 15-25° in the included bend angle is normal due
properties like U.T.S., yield strength, elongation, to springback action at room temperature. Heat is
flattening, expanding. required to form most titanium metal parts.

(d) Heat transfer - Reduction of heat transfer was 5.5%

compared to new tube due to deposition of scales of Welding requires a protected atmosphere: Parts and
Fe, Μη. filler wire are degreased with acetone a n d not
Conclusion: There was no deterioration of material even trichloroethylene. The pieces to be welded are clamped
after 15 years of service including hydrogen embrittle- and not tacked unless the tacks are shielded with inert

82
C.P. De High Temperature Materials and Processes

gas. Coated electrodes are excluded and higher purity Titanium tube sheet: Production of a solid titanium tube
metal is preferred as a filler. Titanium cannot be fusion sheet of one piece, 30 mm thick. 4000 to 4500 mm wide
welded to other metals due formation of brittle inter- and 5000 to 7000 mm long has been possible through
metallic phases in the weld zone. Ti sheet, however, can the use of large steel plate mill.
be explosively bonded to a steel plate for cladding. Welding operation and quality control: To achieve a
satisfactory weld joint, the following precautions are
Fabrication of titanium condensers / 3 3 , 3 4 / : Initially, rigidly observed:
copper alloy-based condenser tubing was replaced with
titanium tubes, retaining the existing naval brass tube (a) Welding environment: Wind, dust, moisture and
plates. This lead to the excessive corrosion of tube plate vapour are kept under control, using, if necessary,
unless a rubberised protective coating was applied as an airconditioned environment at the welding site.
well as difficulty in achieving air tightness. The problem (b) Surface preparation: Sound edge preparation of the
was mitigated by fabrication of all-titanium condensers tube end and tube holes and cleaning the surface
after overcoming the following constraints: with solvent (acetone) is done before despatch from
the factory to the site. At the site, the tube ends and
(a) Titanium tubing used for condensers and heat tube holes should be cleaned again to meet daily
exchangers has very thin walls (0.5 mm and 0.7 mm) requirements.
compared to massive tube plate giving rise to (c) Welding operation: TIG arc welding is restricted to
incompatible heat input requirements as well as 90 tubes per welder per day. It takes 45 days to
achieving a leakage-free joint. complete a 600 MW fossil fuel power plant. Welding
(b) Titanium has a strong affinity for the atmospheric is done with automatic welding machines.
gases, oxygen and nitrogen, at high temperatures
resulting in hardening and embrittlement. This was Inspection of weld zone: A preliminary evaluation is
achieved by inert gas shielding of the welded as well made with a liquid penetrant test, a vacuum leak test,
as heat affected zones (HAZ) or vacuum welding. and water tightness is tested by filling with water and
applying hydraulic pressure. In addition, ultrasonic
Precautions during fabrication of titanium tubing: Flaw methods to detect weld imperfections such as
on the surface of titanium tubes should be avoided to Insufficient weld penetration, defective butt weld as well
prevent deposition of iron rust as well a s rolled-in as rolling streak flaws. Eddy current methods detect
materials and fine scratches. Rolling technology has localised fluctuation In the width and height of the weld.
been improved in order to prevent these problems. In the eddy current method, the frequency is raised from
Control of material, shape of roller, stability of arc 8 KHz to 130 KHz to increase the ratio of detective
during welding, high frequency welding power have led to signals to noise (S/N ratio) and has resulted in accurate
production of good quality seam welded thin-walled detection of micro defects to achieve service life of 100
titanium tube even at the tube-forming speed of 200 years.
meters/hour.

Desalination plant: Titanium heat exchangers were used

83
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

in t h e following s e c t i o n s of a multistage flash (CMFS) Hydrogen absorption: Titanium m a y a b s o r b hydrogen if

desalination plant / 2 8 / : it is excessively cathodically polarised in sea-water. The
(a) Brine heaters, critical potential for hydrogen absorption by titanium in
(b) Heat recovery, sea-water is -0.75 V (SCE) at 25°C a n d -0.65 V (SCE) at
(c) Heat rejection, 100°C (Fig. 8).
(d) Brine lines. Galvanic corrosion of copper alloys by titanium: Copper
Early trials: T i t a n i u m t u b e s were first u s e d in t h e alloys s u c h a s a l u m i n i u m bronze when used a s a t u b e
desalination plant installed in the Virgin Islands, USA in sheet a n d a water box with titanium tubing is protected
1 9 6 5 with n o corrosion d a m a g e . E x p e r i e n c e s with against galvanic corrosion either by pure iron for lower
t i t a n i u m t u b i n g in desalination p l a n t s in Libya (Azura), temperature or Fe - 9% Ni / 3 5 / for higher temperature a s
in t h e B a h a m a s (Nassau) a n d in New York have also galvanic anodes.
d e m o n s t r a t e d no corrosion p r o b l e m s d u r i n g operation S a t o a n d h i s c o w o r k e r s / 2 8 / have carried o u t
periods varying from 3 to 10 years. e x h a u s t i v e work on hydrogen a b s o r p t i o n in t i t a n i u m
The p e r c e n t f a i l u r e s a n d r e p l a c e m e n t of h e a t t u b e s u s e d in t h e b r i n e h e a t e r a n d h e a t recovery
e x c h a n g e r t u b e s in desalination p l a n t s worldwide, a r e sections a n d have come to the following conclusions:
given in Table 16, which is b a s e d on 1981 d a t a . No
failure w a s reported in titanium t u b e s after 72 m o n t h s of (a) Hydrogen a b s o r p t i o n o c c u r r e d only at t e m p e r a -
operation, while copper alloys showed a relatively higher t u r e s above 100°C in solutions with 0.01-1 Μ Fe
rate, p a r t i c u l a r l y in the b r i n e - h e a t i n g a n d the h e a t - (OH)2 precipitates.
rejecting sections. Types of corrosion encountered were (b) Hydrogen a b s o r p t i o n w a s accelerated by coupling
mainly pitting, erosion-corrosion a n d s u l p h i d e a t t a c k . with steel, iron contamination on titanium a n d by
The wall thickness of titanium tubes was 0.7 m m and 1.2 roller expansion.
m m for copper alloy tubes. (c) Hydrogen a b s o r p t i o n can be prevented by acid
pickling of titanium.
Corrosion resistance of t i t a n i u m tubes: Crevice (d) Ti-0.15 Pd alloy t u b e w a s more susceptible t h a n
corrosion a n d hydrogen absorption are considered to be C.P. Ti.
t h e m a i n likely corrosion problems of t i t a n i u m t u b e s . (e) R e s u l t s s u g g e s t e d t h e possibility of hydrogen
The critical conditions for o c c u r r e n c e of crevice evolution a n d absorption by Schikorr reaction:
corrosion in t i t a n i u m in 6% NaCl solutions simulating
the concentrated brine are shown in Fig. 11. The d a t a 3 Fe (OH)2 = F e 3 0 4 + H2 + 2 H 2 0 (6)
s h o w s t h a t t i t a n i u m t u b e s a n d tube sheet a n d / o r water
boxes m a d e of copper alloy are i m m u n e to corrosion (f) The problem can be controlled by avoiding ferrous
even at 120°C. Crevice corrosion is, however, likely with corrosion p r o d u c t s coming from steel components
Ti t u b e / T l t u b e sheet or of Ti t u b e / s e a l a n t / T i tube sheet in plants a s well a s preventing iron contamination
at the interfaces. However, t h e crevice corrosion during fabrication a n d pickling of titanium tube.
problem h a s been solved by seal-welding or PdO/TiC>2
coating / 3 5 / . Use of t i t a n i u m in MSF d e s a l i n a t i o n p l a n t s : MSF

84
C.P. De High Temperature Materials and Processes

TABLE 16

Percent failures and replacements in desalination plant

PLANT SECTION

Alloy Recovery Reject Brine Average Service

Heater Time, Months

Aluminium Brass 1.66 7.94 18.60 68

90-10 Cu/Ni 0.40 2.95 3.41 34

(Alloy 706)

70-30 Cu/Ni 0.00 2.36 11.28 39

(Alloy 715)

70-30 Cu/Ni+

(2% Mn + 2% Fe 0.02 0.03 1.33 91

(Alloy 715
modified)

Titanium 0.00 0.00 0.00 72

No crevice corrosion of
Ti /Cu alloyjsiven a t j 2 0 t £ J _ _
120
Crevice corrosion of
„o 100 Ti/Ti
Q.
immune
ε<υ 80 Crevice corrosion of
Ti/sealant/Ti
60 u i m u m ι
'
,
Immune
j L
0 4 6 θ 10

pH
Fig. 11 Immunity/Crevice Corrosion Region of Titanium Having Various Types of Crevice in 6%
N a C l Solution

desalination plants provide large markets for titanium. at Al-Jobail and contain over 2500 Ions of titanium. In

These have been Installed in Japan, Peru and Indonesia. 1984, the total weight of titanium used worldwide was

The above plants are, however, small compared to those over 6000 tons for desalination plants /22/.

in the Middle East. The largest plant is in Saudi Arabia Nine thousand two hundred km of titanium tubes (0.6

85
Vol. 11, Nos. 1-4. 1993 Use of Titanium and its Alloys in Sea-Water Service

mm and 0.7 mm) fabricated in J a p a n have been installed Offshore oil industry / 3 2 / : The excellent corrosion
in the Middle East as follows: resistance of titanium to sea-water and also to sulphide-
bearing crude and pollutants like H2S has been
Location Capacity exploited for cooling gas/oil products in the offshore oil
industry. Ti heat exchangers are also used in oifshore
Al-Jobail Phase I 23.000 T / d x 6
refineries as well as onshore where the quality of cooling
Phase II 23.600 T/d χ 40
water is poor.
Yambui No. 1 22.730 T / d x 5
Hypochlorite dosing and water injection piping
Al-Khobar 23,000 T / d x 10
systems, fire mains and hydraulic lines used in the
production platforms are increasingly being made of C.P.
General: Titanium is an improved alternate material to
Titanium and its alloys.
cupro-nickels in sea-water piping systems and heat
Ti-6A1-4V extruded hollows and sections are used
exchangers on board sea-going ships and offshore
for encapsulating oil well data logging systems. They are
platforms. Pipings can be designed with very thin wall
also used for underwater instrumentation packages and
sections and reduced sizes resulting in more efficient
will also provide technology for potential use as kill and
and cost effective material utilisation. The reduction in
choke tubes and other high pressure critically stressed
system weight and increase in space is a great advan-
tubuläre within drilling or production riser systems,
tage in the design of naval ships and submarines as well
their associated well heads and undersea distribution
as deep submersibles where space is at a premium. A
network.
number of such applications have been listed in Table 8.
S u c c e s s f u l application of titanium demands
Risers: Complete titanium systems for production risers
attention to (a) minimum flow velocity to control bio-
systems will become economical with the progress of
fouling, (b) prevention of galvanic action at Ti/Cu alloy
deep water exploration and exploited when costly
interface and (c) procedure for field welding technique.
recurring corrosion protection measures associated
Ti-3A1-2.5V (grade 9) promises to be a very attrac-
with ferrous systems are replaced or substituted. The
tive candidate material for advanced piping application
lower dynamic modulus of titanium alloys (105 to 116
/37/.
GPa at 20°C) is an additional benefit in terms of
flexibility for stress joints.
Titanium tubes with fins: Titanium tubes with fins have
In oil and gas refinery applications, titanium is
been developed with a heat transfer coefficient twice
suitable in environments of H2S. SO2, CO2, NH3, steam
that of smooth tubes / 3 8 / . Such tubes are planned for
and cooling water. It is used in heat exchangers, con-
future use as follows:
densers for fractional condensation of crude hydro-
carbons, propane and desulphurisation products using
(a) Heat exchanger and cooling equipment of geother-
sea-water or brackish water for cooling.
mal power stations
(b) LNG and oil refining
High strength titanium alloy for sea-water systems / 2 3 / :
(c) RAD waste evaporation
The strength of titanium alloy is to be increased to the

86
C.P. De High Temperature Materials and Processes

level of stainless steels and nickel alloys in the region of Deep sea submersibles: Deep sea submersibles are

700-1000 MPa to serve as an alternate material to required because they fill the following needs:

nickel-based alloys. Alloys of competitive strength with (a) Deep sea exploration of mineral resources

good wet fracture toughness are available. Substitutes (b) Scientific research in the field of oceanography and

Include T1-6A1-4V, Ti-4Al-3Mo-IV and T i - 6 A l - 2 N b - l T a - geophysics

O.8M0. (c) Rescue of conventional and nuclear submarines in

distress

Sizes of titanium tubing: Seamless tubes varying from 6

to 60 mm in diameter are made in strengths of up to 860 Ti alloys are used in deep diving vessels for structures,

MPa. Seamless extruded pipe is available up to 170 mm pipework and the buoyancy sphere. The submersible is

diameter In Ti-6A1-4V, with an annealed tensile strength designed to be compact, lightweight and fabricated at a

over 900 MPa. This weldable grade is available up to high strength to weight ratio with an exceptionally good

1000 mm dia, as fabricated pipework for diverse, sea- resistance to sea-water corrosion. It is unrivalled in

water applications currently in use or likely to be used in depths greater than 2000 meters as is evident from a

the future. comparative evaluation of Ti-6A1-4V-ELI with the

previously used HY-100 steels (Table 18). Alvin, the first

such vessel consructed with Hy-100 and A l alloy and

4.3 Miscellaneous Application of Titanium and its
launched in 1965 was recently renovated with titanium.
Alloys in an Allied Environment

Due to continuous efforts made in the last four Naval ships and submarines: In view of its non-

decades after titanium was first commercially produced, magnetic properties, a variety of indispensable engi-

applications of titanium and its alloys have been deve- neering components in fibre glass minesweepers, which

loped in a large number of fields as seen in Table 17. are currently made of steel, can be replaced by titanium.

Some of the applications involving sea-water and Other uses include hydrofoil struts due to cavitation

chloride environments are highlighted below: resistance, propeller shafts, sea-water trunking for fire

fighting vessels as well as mast top radar components to

Marine propeller shaft: In a certain class of high reduce weight and stability with improved corrosion

resistance. In the USSR, nuclear submarines have been

performance ships, when aluminium alloys are used as
fabricated with titanium in view of superior corrosion
the hull material and copper alloys for the marine
resistance and minimum hull weight for maximum
propeller T1-6A1-4V appears to be a promising material
buoyancy, thus increasing the underwater speed, maxi-
for the propeller shaft due to its high strength and good
mum buckling strength to hydrostatic pressure with en-
corrosion resistance to sea-water.
hanced operational depth and non-magnetic property.

Tanker purger system: Fans in the tanks' purger

systems are preferred to be fabricated with titanium Prosthatic devices /35,36/: Body fluids are chloride

because low density has the added advantage in the brines with pH values ranging from 7.4 to acidic range

prevailing marine atmosphere. and contain a variety of organic acids. Due to its unique

87
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

TABLE 17
Fields of Application of Titanium and its Alloy / 4 /

L AEROSPACE
Compressor discs and blades, fan discs and blades, casings, after burner cowlings, flange
rings, spacers, bolts, hydraulic tubing, hot air ducts, rotor hubs for helicopters.
Fittings, bolts, landing gear beams, wing boxes, fuselage frames, flap tracks, slat tracks, brake
assemblies, fuselage panels, engine support mountings, undercarriage components. Inlet guide
valves, wing pivot lugs, keels, fire bulkheads, fairings, hydraulic tubing, de-icing ducts, SPF parts.
Rocket engine casings, fuel tanks.

2 CHEMICAL PROCESSING INDUSTRY

Storage tanks, agitators, pumps, columns, frames, screens, fabric mixers, valves, pressurised
reactors, filters, piping and tubing, heat exchangers, electrodes, and anode baskets for metal
electrolytes (Cu, Ni, Co, Zn), electrodes for chloride-alkali electrolysis, tanks for sodium chlorate
and calcium chloride

a ENERGY PRODUCTION AND STORAGE

Condensors, cooling systems, piping and tubing, steam turbine blades, retaining rings for
generators, rotor slot wedges, evaporators, condensers, tubes, heat exchangers, cooling system,
tubing etc.

4 COOLING UNITS
Plate and tube type heat exchangers.

5 OCEAN ENGINEERING
Heat exchangers, condensers, piping and tubing, propellers, propeller shafts, rudder shafts,
data logging equipment, gyro-compasses, pumps, life boat parts, mast top radar components,
mine sweepers, racing yacht equipment, cathodic protection anodes, hydrofoil struts, foils, deep-
sea pressure hulls, submarines (USSR), submarine ball valves (USA), vapour heaters, deep drilling
riser pipes, flexible risers, drilling steels, Christmas trees, desulphurisers, catalytic crackers,
sea-water trunking for naval ships, sour water strippers, regenerators.

β FLUE GAS DESULPHURISATION

Linings for lime/limestone scrubbers.

88
C.P. De High Temperature Materials and Processes

TABLE 17 (continued)

7. MEDICAL ENGINEERING
Hip joint, endoprosthesis, knee joint prosthesis, bone plates, screws and nails for use in bone
fractures, pacemaker housings, heart valves, instruments dentures, hearing aids, high speed
centrifugal separation for blood.

a DEEP DRILLING
Drill pipes, riser pipes, production tubulars, casing liners, stress joints, instrument cases,
wire probes.

9 AUTO ΜΑΤΙ VE INDUSTRY

Connecting rods and screws, valve springs, valve retainers, crankshafts, camshafts, drive
shafts, torsion bars, suspension assemblies, coil springs, pedals, bolts and socket Joints, gears,
gear synchromeshes.

10. MACHINE BUILDING

Flexible tube connections, protective tubing instrumentation and equipment.

11. FOOD INDUSTRY

Tanks, (diaries, beverage industry), heat exchangers, packaging machinery compartments.

12. PAPER INDUSTRY

Bleaching towers, pumps, piping and tubing.

13. JEWELLERY INDUSTRY

Jewellery, clocks and watches.

14. OPTICAL INDUSTRY

Spectacle frames, camera shutters.

15. FINE ART

Sculptures, fountain, basin, ornaments, door plates.

16. SPORTS EQUIPMENT

Bicycle frames, tennis rackets, shafts and heads for golf clubs, mountain climbers equipment
(Ice crews, hooks), bob components horse shoes, fencing blades.

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Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

TABLE 17 (continued)

17. CONSTRUCTION INDUSTRY

Facing and roofing, concrete reinforcement, monument refurbishment (ACROPOLIS), Ti
anodes for cathodic protection of steel in concrete.

18. PERSONAL SECURITY AND SAFETY

Armour (Cars, trucks, helicopters, fighter aircraft), helmets, bullet proof vests, protective
gloves.

19. TRANSPORT
Driven wheelsets for highspeed trains, wheel tyres.

20. PRINTING PRESSES AND LOOMS

Fast moving parts with anti-wear protective coatings (e.g. high speed line printer).

21. NUCLEAR WASTE DISPOSAL

Plate and shell fabrication.

22. MEMORY ALLOYS

Springs, flanges, made of Ni Ti alloys.

23. SUPERCONDUCTORS
Wire rod of Nb Ti alloys for the manufacture of powerful electro magnets (used at about
absolute zero), rotors for super conductive generators.

24. HYDROGEN STORAGE AND HANDLING

Ti Fe and Ti Mn granules.

25. MISCELLANEOUS
Fan blades, cutting implements, scissors, knife, pliers, musical instruments, bells, pens,
name plates, telephone relay mechanism, ocean lines breathing apparatus, pollution control
equipments, titanium-lines large vessels for salt-bath nitride treatment of steel products, ultra
centrifuge rotors.

90
C P. De High Temperature Materials and Processes

TABLE 18
Advantage of Ή - 6A1 - 4 V ELI Alloy as a Pressure Hull Material for Deep Sea Submersible Operating
at or more than 6,000m Depth / 2 3 /

Personal pressure Hull

Material 0.2% Y.S. Density Strength
(kgf/mm 2 ) (g/cm 3 ) to weight Thick- Wt Buo- Wt Sub
ratio ness yancy In mersible
water
(mm) (ton) (ton) (ton) (ton)

T1-6A1-4 V ELI > 81 4.42 18.3 68.0 4.66 5.28 -0.62

Fe-10Nl-8Co > 120 7.85 15.3 48.5 5.82 4.98 0.34
Difference - -1.17 0.30 -1.46 -2.79

corrosion resistance in a chloride environment, titanium 5. WORLD PRODUCTION OF TITANIUM / 2 , 4 /

is used extensively in prosthatic devices such a s heart
Titanium was discovered a s a metal in 1791 by
valve components and load bearing hip joint replace-
Gregor. The metal was first isolated in a pure state in
ments. Titanium is totally inert and biocompatible with
1910. A n o t h e r 4 0 y e a r s e l a p s e d before it was
h u m a n tissues. Allergic reactions occasionally reported
commercially produced by Kroll's process by reduction
with previously u s e d s t a i n l e s s steel i m p l a n t s are
of titanium chloride with magnesium (1948).
completely absent with titanium devices.
Titanium is the ninth most a b u n d a n t element in the
e a r t h ' s c r u s t and occurs primarily a s the minerals,
Ocean thermal energy conversion scheme (OTEC) / 2 2 / :
ilmenite (FeTK>3) and rutile (Ήθ2), in black sands.
Another possible major use of titanium tubing would be
World o u t p u t of titanium sponge in 1985 w a s
the ocean thermal energy scheme which makes use of
approximately 90,000 tons / 2 / . The two major Western
temperature gradients in the sea to generate energy.
producers, J a p a n and the USA, contributed to the world
Should titanium eventually be selected as the heat
output of titanium 21,897 tons and 21,100 tons, respec-
exchanger material - it h a s performed excellently in
tively, and the USSR's contribution was approximately
tests to date - very large quantities of the tube would be
equal to that of the former two combined. The produc-
required.
tion of titanium in 1985 fell about 8%, chiefly due to
Container for radioactive waste: Titanium is considered reduction in aerospace applications.
to be a suitable candidate material for fabrication of With t h e economic recovery of the developed
containers to store radioactive wastes for a long period countries and diversification in application of titanium,
of time, u p to 1000 years. the downward trend has been reversed. Demand for the

91
Vol. 11, Nos. 1-4, 1993 Use of Titanium and its Alloys in Sea-Water Service

metal has steadily Improved due to an increase in (a) Rutile 15,071 M.T.
commercial aircraft, (b) chemical processing industries Leucoxene 313 M.T.

and (c) ocean engineering applications. Sy. rutile 7,670 M.T.

A low cost high purity electrolytic process for

It is estimated that about 20,000 TPY of TiC>2 pig-
production of titanium has been announced by an
ments and 16,000 tons of synthetic rutile are produced in
Italian firm (Electrochemie Mario Girattl, Turin) which is
likely to widen the range of applications. India. In addition, the country imports about 25,000 TPY

The forecast for 1989 is both continuing increase in of TiC>2 pigment. A major portion of the pigment

production tonnage and price. In 1988, the price of produced/imported is used by the paint industiy.

sponge increased from $4.00 to $4.75. The present world

production and capacity (1988) is given below:
6.2 Sponge-Ingot Metal Products

Production (T/y) Capacity (T/y)

1987 1988 1988 The Defence Metallurgical Research Laboratory
(DMRL) is setting up a 1000 TPY titanium sponge plant
USA 18,000 23,000 28,000 which will u s e Kroll processing technology and
Japan 10,000 16,500 34,000 indigenously-developed know how generated through
UK 2,000 2,000 5,000 initiatives taken by DAE & DRDO. The sponge produced
China 2,000 2,000 3,000 at the demonstration plant has been supplied to various
USSR N/A N/A 60,000 users for evaluation.
Mishra Dhatu Nigam (MIDHAN1), with facilities for
The estimated world titanium sponge production in 1990
melting of the sponge as well as forgings and production
is expected to be 138,000 tons / 4 / .
of wire and sheet products, melted about 120 tons of C.P.
grade Ti sponge and 25 Τ alloy ingots during 1989-90
6. TITANIUM INDUSTRY IN INDIA / 3 8 / using imported sponge.
Vikram Sarabhai Space Centre (VSSC) is engaged
6.1 Raw Materials in development and production of titanium equipments
like high pressure gas bottles, liquid propellant tanks for
Though India is endowed with extensive reserves of launch vehicles and satellite control system propellant
titanium minerals mainly in the form of beach sand in tanks. VSSC h a s solved the technology problems
Kerala and in Orissa, the titanium metal industry is still associated with forging, ring rolling, heat treatment and
in the development stage compared to that of Western electron beam welding. A hemisphere weighing 150 kg
countries. The production of titanium mineral by Indian has been die forged.
Rare Earths (IRE) is given below Bharat Heavy Electricals Ltd. (BHEL) has supplied
titanium tube condensers for 2 χ 500 MW Trombay
Mineral Production (1989-90)
thermal station. Bombay and 2 χ 210 MW for Madras
Ilmenite 2,49,461 M.T. Power Station. BARC h a s installed titanium tube

92
C.P. De High Temperature Materials and Processes

condensers in a 100 MW research reactor DHRUVA with the last 2-3 decades, confidence to change over to the
satisfactory performance results. new metal has been created.
Titanium is currently used in India to the extent of The present disadvantages of higher cost have been
200-300 TPY / 4 / . Titanium is an excellent substitute for neutralised by longer life and greater service reliability
nickel (which is not available in the country) and of titanium structures In a sea-water environment. Deve-
stainless steel for low temperature and corrosion resis- lopment of a cheaper extraction process for commercial
tant applications. The growing foreign exchange prob- use will give a further boost to consumption of titanium
lem and the likely requirement for increased corrosion in the coming decades.
resistant materials promise a great f u t u r e for the
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