l·
25
The Formability of
Reactive Metals
B.J. SANDERS, PE
CONSULTANT
B.J. Sanders & Associates, Inc.
3359 Clearwood Circle
Alvin, Texas 77511-4573
USA
T: 832-867-2526
E: bjsainc@sbcglobal.net
Co-author
RICHARD C. SUTHERLIN, PE
MANAGER, TECHNICAL SERVICES
A T/ Wah Chang
1600 Old Salem Road NE
Albany, Oregon 97321
USA
T: 541-967-6924
F: 541-924-6892
E: richard.sutherlin@ATlmetals.com
ABSTRACT
Both titanium and zirconium have
been formed, welded and fabricated
into chemical processing vessels
and equipment for over a half a
century. It is well-known that reactive
metals and alloys such as titanium
and zirconium do not have the
CORROSION
PAP E R 1 B
formability of metals like carbon steel
or stainless steel. This paper will
review important metallurgical
characteristics that will affect the
formability of these materials such
as crystal structure, deformation
mechanisms, mechanical properties,
chemistry, microstructure, and
anisotropy. This article will also
explore the types of processes and
equipment that are used for titanium
and zirconium, and discuss what
factors (e.g., cold and hot forming,
forming speed, types of dies,
surface finish, lubrication, and
others) may assist in improved
formability of these materials. Finally,
the article will endeavor to provide
the guidance needed to help insure
the successful forming with these
types of materials.
KEYWORDS
• reactive metals
• titanium
• zirconium
• hexagonal close-packed
• anisotropy
• springback
• chemical processing
SOLUTIONS' CONFERENCE 2009
equipment
• sulfuric acid
• nitric acid
• hydrocloric acid
• acetic acid
• fabrication
INTRODUCTION
Reactive metals such as titanium
and zirconium are used in all types
of equipment and devices for the
chemical , nuclear, aerospace, and
medical industries. This paper will
primarily focus on the uses of these
materials in the chemical processing
industry (CPI). In the CPI, titanium
and zirconium are commonly
fabricated into solid and clad
columns and vesse ls, heat
exchangers , reactors, piping
systems, and support equipment.
Some of the equipment and
components will require that mill
products be bent and formed to
create piping, vessels, cylinders,
trays, heads, or internal
components. When these materials
are formed and fabricated into
chemical equipment there are a
number of factors that must be
- PROCEEOINGS
26 PAPER 18 - THE FORMA 81L1TY OF REACTIVE METALS

taken into consideration to help
insure a successful result. Important
factors to consider when these
reactive metals are formed are the
physical and mechanical properties.
When alloying elements are added
to titanium or zirconium, the
mechanical and physical properties
may change depending on the
particular element added.
Both zirconium and titanium are
anisotropic materials. Anisotropic is
defined as a material exhibiting
different mechanical properties in
different directions. This means that
the transverse and rolling direction
are different in mechanical strength
and ductility. Because of this, the
material will exhibit a greater ductility
in one direction than in the other.
Normally, companies do not
consider the preferential forming of
materials in a specific direction for
chemical processing equipment
since the design properties always
meet the minimum ASTM
mechanical property requirement.
Any concerns with improvement of
formability due to forming direction
could be overcome by other means
such as establishing and following
proper or alternate procedures.
REACTIVE METALS FOR USE
IN CPI APPLICATIONS
Titanium Alloys
Titanium alloys are commonly used
in a large number of chemical
processing applications due to their
good corrosion resistance in
chemical media . The application
areas for titanium consist of
chemical plants, pulp and paper,
petrochemical , waste treatment ,
and metal fin ishing. The titanium
alloys used in chemical processing
industry range from the very low
interstitial unalloyed grades to the
highly alloyed alpha -beta grades.
The lower strength alpha titanium
grades are primarily used for
chemical processing equipment of
all types where some higher
strength alpha-beta titanium alloys,
such as titanium Grade 5 (Ti-6AI-4V)
are used primarily in pump and valve
appl ications. The chemical and
mechanical properties of select
titanium alloys used in the CPI are
shown in Table 1 and Table 2.
For the chemically pure (CP)
titanium alloys, the formability of
these will generally depend on their
mechanical strength since the lower
strength materials will form more
easily than that of the high-strength
alloys. For example, titanium Grade
1 is commonly used in the
production of plate and frame heat
exchanger panels and for explosive
clad plate which require maximum
ductility due to the severe forming
requirements . The higher strength

Table 1. Chemical composition of titanium a//oys,

Titanium Grade Ti-1 Ti-2 Ti-3 Ti-9 Ti-12 Ti-3S
ASTM Designation R50250 R50400 R50550 R56320 R53400 R54250
Nitrogen, max. 0.03 0 .03 0.05 0.03 0.03 0.03
Carbon, max . 0.08 0.08 0.08 0.08 0.08 0.08
Hydrogen, max. 0.015 0.015 0.015 0.015 0.015 0.015
Oxygen, max . 0.18 0.25 0.35 0.15 0.25 0.20-0 .30
Iron, max . 0.2 0.3 0 .3 0.25 0.3 1.2-1.8
Aluminum -- -- -- 2.5-3.5 -- 3.5-4.5
Vanadium -- -- -- 2 .0-3 .0 -- 2.0-3 .0
Nickel -- -- -- -- 0.6-0,9 --
Molybdenum -- -- -- -- 0.2-0.4 --
Table 2. Mechanical properties of titanium a//oys.

Ti-1 "Type" Ti-2 "Type"

Titanium Grade Ti -3 Ti-9 Ti-12 Ti-38
Grades Grades

ASTM Designation R50250 R50400 R50550 R56320 R53400 R54250

Tensile Strength , MPa (ksi) 240(35) 345(50) 450(65) 620(90) 483(70) 895(130)
Yield Strength, MPa (ksi) 138(20) 275(40) 380(55) 483(70) 345(50) 794(115)
Elongation, % 24 20 18 15 18 10
Min. Bend Radius 2T 2.5T 2.5T 3T 2.5T 4.5T
Note: Ti·1 "Type" Grades consist ofTi Grades 11 , 17, and 27. Ti-2 ''Type '' Grades consist of n Grades 7, 16, and 26.

CORROSI O N S OLUTIONS ' CONFE R E N CE 2 00 9 - PRO C EEDING S

 PAPER 1B - THE FORMABILITY OF REACTIVE METALS 27

alloys have the lowest elongation
and require larger bend radii during
forming. In regards to the ASME
Boiler and Pressure Vessel
construction code, solid titanium
vessels can be produced using
alloys Ti-1, Ti-2, Ti-3, Ti-9 , Ti-11,
Ti-12, Ti-17, and Ti-38 (through a
code case).
Zirconium Alloys
Zirconium alloys are also used in a
number of chemical processing
applications due to their excellent
resistance to severe corrosive
media. The application areas for
zirconium consist of chemical and
petrochemical plants because of
zirconium's resistance to organic
acids (acetic, formic), mineral acids
(sulfuric acid, nitric acid,
hydrochloric acid), and other media
such as chloride solutions and urea.
Zirconium alloys used in the
chemical processing industry
consist of the unalloyed Zr 700
grade, the Zr 702 grade, and the Zr
705 grade . The Zr 700 grade is
used primarily for the explosive
welding (cladding) process onto
steel or stainless steel and where
high formability is required. The Zr
702 grade comprises, by far, the
highest quantity of zirconium alloys
used in the CPI. The Zr 705 alloy is
primarily used for fasteners, valves,
and pumps. Although the Zr 705
alloy has a higher strength than that
of the Zr 702 grade, it also has
better bend ductility due to its 2-
phase alloy composition. Table 3
and Table 4 show the chemical and
mechanical properties of common
zirconium alloys.
Effect of Alloying
Both titanium and zirconium have a
strong affinity for oxygen, nitrogen,
and hydrogen. This reactivity leads
to a strengthening effect of the
materials as these interstitial
elements increase . The
commercially pure (CP) titanium
alloys are all alpha grades with
essentially only oxygen added for
strength or alloys with small levels
of Platinum Group Metals (PGM)
elements added for improved
corrosion resistance. The CP alloys
are generally very fabricable. The
alpha-beta titanium alloys, on the
other hand, contain elements
(aluminum) to stabilize and
strengthen the alpha phase and
beta stabilizers (vanadium) to give
solid solution strengthening . These
alloys also have fairly good
fabricability. The more common
titanium and zirconium grades and
their characteristics are shown in
Tables 5 and 6.
Crystal Structure of Titanium
and Zirconium
Both zirconium and titanium are
allotropic. At ambient temperatures,
the chemically pure grades exist as
hexagonal close-packed (HCP)
structures. These commercially pure
(CP) alloys are termed alpha phase
structures. The alpha phase exists
in the CP or pure alloys at
temperatures up to about 885°C
(1625°F) for titanium and about

Table 3. Chemical composition of zirconium alloys.

Zirconium Grade Zr700 Zr702 Zr705
ASTM Designation R60700 R60702 R60705
Zr+Hf, minimum 99.5 99.2 95.5
Hafnium, maximum 4.5 4.5 4.5
Fe+Cr, maximum 0.2 0.2 0.2
Sn, maximum -- -- --
Hydrogen, maximum 0.005 0.005 0.005
Nitrogen, maximum 0.025 0.025 0.025
Carbon, maximum 0.05 0.05 0.05
Niobium - -- 2.0-3.0
Oxygen, maximum 0.10 0.18 0.18

Table 4. Mechanical properties of zirconium alloys.

Zirconium Grade 700 702 705
ASTM Designation R60700 R60702 R60705
Tensile Strength , MPa (ksi) 379(55) max. 379 (55) min. 552(80) min.
Yield Strength, MPa (ksi) 305 (45) max. 207 (30) min. 379(55) min.
% Elongation, 0.2% Offset 20 min . 16 min. 16 min.
Min. Bend Test Radius 5T 5T 3T

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28 PAPER 1B - THE FORMABILITY OF REACTIVE METAL S

854°C (1570°F) for zirconium. At the
transformation temperatures, the
structure transforms to a body-
centered cubic (BCC) structure,
termed beta phase . The HCP
structure is more densely packed
than that of the body or face-
centered structures which
contributes to less formability than
that of the carbon or stainless steel
materials.
Titanium alloys used for the
chemical processing industry are
generally the alpha grades. Some
higher strength alpha-beta alloys
such as titanium Grade 9, titanium
Grade 5, and titanium Grade 38 are
being used in some specific
chemical processing applications
where greater mechanical strength
is needed.
Zirconium alloys used for the
chemical processing industry are
also typically alpha alloys, with the
exception of the Grade 705 alloy.
The Zr 705 grade is a 2-phase
structure with alpha zirconium and
beta niobium. This alloy has
zirconium and 2-3% niobium which
increases the strength of the
material by about 30% over that of
the Zr 702 grade.
Deformation Mechanisms
The primary mode of deformation in
both zirconium and titanium is by
"slip". The most common
crystallographic slip planes in
titanium and zirconium materials are
the pyramidal , prismatic, and basal
planes in the close-packed direction.
Figure 1 shows the primary
deformation systems for titanium
and zirconium . Deformation due to
slip in these alloys depends on the
alloy composition, temperatu re,
grain size , st ructure, and crystal
orientation{f]. Deformation also
occurs by "twinning " which is
favored over slip by factors including
course grain size, high purity, and
low temperature deformation.
Figures 2A and 2B show the
appearance of twinning in titanium
and zirconium alpha alloys.
Elastic Springback
Characteristics
Spring back is defined as the elastic
recovery after cold forming, which
can be considerable for reactive
metals. Both zirconium and titanium
will experience significant
springback characteristics due to
their low modulus of elasticity. It has
been noted that springback of

Table 5. Alloys systems and primary characteristics for titanium alloys.

"Commercially Pure" Titanium Grades
Characteristics: Good corrosion resistance, non-heat treatable . good weldability. generally good
workability/formability. Ti Grade 1 best.
Examples: CP Grades 1-4.
Alpha Titanium Alloys
Characteristics: Non-heat treatable. good weldability. generally poor workability.
Examples: Ti-6AI-2Sn-4Zr-2Mo-0 .1Si (Ti 6242). Ti-SAI-2.SSn(Gr. 6). Ti-Ni-Mo (Gr. 12).
Alpha-Beta Titanium Alloys
Contains 1 or more alpha and 1 or more beta stabilizers.
The high temperature alloys in this alloy group generally contain aluminum. tin and vanadium.
Characteristics: Heat treatable (can be strengthened by heat treatment).
Examples: Ti-S (Ti-6AI-4V). Ti-9 (Ti-3AI-2.SV). Ti-23 (Ti-6AI-4V- ELI). Ti-38 (Ti-4AI-2 .5V).

Table 6. Alloys systems and primary characteristics for zirconium alloys.

ALPHA ZIRCONIUM
Unalloyed Zirconium
Characteristics: Highly formable. easily explosion clad, weldable.
Example: Zr700 Grade.
Zirconium Grade 702
Alloyed with oxygen for strength.
Characteristics: Less formability than Zr700. weldable .

2 PHASE ALLOY
Alpha Zirconium - Beta Niobium
Zirconium Grade Zr705
Zircon ium alloyed with 2-3% niobium.
Characteristics: 30% greater strength than Zr702 grade. improved formability over Zr702 grade.
Weldable but must be heat treated after welding .

CORROSION S OLUTION S · CONFE R ENCE 2 0 0 9 - PROCEEDINGS

 PAPER 1B - THE FORMABILITY OF REACTIVE METALS 29

Figure 1. The primary deformation systems of titanium and zirconium.

twal Pole
<0001> Twin Direction
<1010>
IlasaI Plane
(0001)
TwinOirectioa
<1010>

Twio Plane
TctUion
(1011) (1121) Twin PWx:
Tension
(lOll)

Slijllpirecborl
(I010)ftaiJr

Slip Systems Twin Systems

Figures 2A and 28. Twinning in titanium and zirconium.

15-25% could be expected formed where scratches (notches)

depending on the forming
temperature and actual configuration
of the part being formed{4). This
effect can be overcome by "over-
bending" the material in the forming
dies or by the application of heat
during the forming process.
Notch Toughness
Both titanium and zirconium are
susceptible to notch induced
cracking. This occurs since the notch
toughness for some of the titanium
and zirconium alloys is very low. This
is an important factor if a part is
Figure 3. The effect of notches
are present perpendicular to the (scratches) on a bend test. The sample of
forming direction. Figure 3 shows the the left was formed on a 2T bend radius
effect of notches on bend samples. mandrel where the sample on the right
was formed on a 3T bend radius mandrel.
Hot Forming of Titanium and
Zirconium
Both zirconium and titanium can be
formed either at ambient (room)
temperature or at elevated
temperatures . If thicker parts are
required or tighter bend radii are
needed, the materials may require
warm or hot forming. In the higher
strength alloys, it is imperative that
the parts be heated or cracking will

CORROSION SOLUTIONS ' CONFERENCE 2009 - PROCEEDINGS

30 PAPER 1B - THE FORMABILITY OF REA CTIVE METALS

occur. Titanium and zirconium can
be formed at room temperature to
those bend rad ii as shown in Table
7, up to about 19mm (0 .7S"),
depending on a number of factors.
These factors include surface finish ,
actual bend radius , die
configuration, and roughness,
forming speed, and part dimension,
to name a few. These bend radii are
however, only guaranteed to form at
room temperature, per the ASTM
specification, up to 4.74mm (0.187")
in thickness. If the parts cannot be
formed at room temperature then
hot forming may be required. Table
8 shows the typical forming
temperatures for titanium and
zirconium . Elevated temperatures
will increase the ductility of the
metals significantly. Figures 4-6
show the reduction in mechanical
Table 7. Minimum Bend Radius for
Material up to 0.187" thick (4.75mm) as
shown in ASTM B 265 (Titanium) and
strength as the temperature is
increased. This decrease in
mechanical strength and increase in
elongation will significantly improve
the formability of these materials. It
is always cautioned that when
reactive metals such as titanium or
zirconium are heated, the heating
processes should be carefully
reviewed to prevent detrimental
effects on the material. In addition,
hot forming requires that safety
measures be taken to insure that the
personnel are protected from these
higher temperatures.
Heating Methods
Heating material for hot forming may
be done using localized heating
Figure 4. Typical Mechanical Properties as a function of temperature for Zr 102 grade.
Temperature· F
77 100 200 300
600
(87)
~ 60
sources or through furnace heating.
Localized heating will include those
processes where the heating source
is by combustion burners and / or
high temperature quartz lamps. It is
important, when heating the
material , that the heat is well
distributed (heated evenly)
throughout the material. Improper
or inadequate heating may cause
deformation or cracking in the part
being formed . When hot forming is
used, the material and the dies
should be heated. Cold (ambient
temperature) dies will cause a local
surface chilling effect on the plate
surface which could initiate surface
cracks in the part being formed.
Often, localized heating is also used
400 500 600 700
70

----
ASTM B 551 (Zirconium). 500
V
-; (73)
- ~ / ~
lion
~
Alloy Bend Radius 50
400
f"'-..
Ti-1 2T i(58)
- -- -- X C:
40 o
Ti-2
Ti-3
Ti-9
2.5T
2.5T
3T
I: 300
~
~ (44)
~ 200 -- ~
~ '"--- -
...........
Ilimate Tens e Streng1h

r--
30
;:l
IV
~
o
iii
~

-
20

'--
(29)
Yield Siren th
Ti-12
Ti-38
2T
4.ST
.c:
~ 100
:IE (14)
o
- 10

o
Zr700 5T
25 38 93 150 200 260 315 370
Zr702 ST
Temperature· C
Zr705 3T

Table 8. Hot Forming Temperatures for Reactive Metals.

Common Designation ASTM Grade Forming Temperature, OF (0C)
Titanium Grade 1 R502S0 900-1000 (482-S38)
Titanium Grade 2 R50400 900-1000 (482-S38)
Titanium Grade 3 RSOSSO 900-1000 (482-S38)
Titanium Grade 9 RS6320 900-1000 (482-S38)
Titanium Grade 12 RS3400 900-1000 (482-S38)
Titanium Grade 38 RS4250 900-14S0 (482-788)
Zirconium Grade 700 R60700 900-14S0 (482-677)
Zirconium Grade 702 R60702 900-14S0 (482-677)
Zirconium Grade 70S R6070S 900-12S0 (482-677)

CORR O S I O N SO LUTI O N S · CONF ER ENC E 2009 - P ROC EEDING S

 PAPER 1B - THE FORMABILITY OF REACTIVE METALS 31

to keep the material being formed Figure 5. Typical Mechanical Properties as a function of temperature for Zr 705 grade.
and I or the dies heated during the
Temperature - F
forming process . Figures 7 and 8 n 200
100 300 400 500 600 700
show an oxyacetylene torch 600 40
(rosebud) being used for localized
heating of the material. ~ 500
(87)
- r-- ~v ElonnJtion 35
Sometimes it is advantageous,
or even essential, to place the
-;; (73)

~
i 400 / ~ 30

~
material into a furnace, allowing it to
evenly heat or soak prior to forming.
5i
(58)

300
--.:
- >< ~ U1timat Tensile Sire g t h - c
20ij
25
c

The furnace used could either be

electric or fuel-fired . This process
will create very uniformly heated
material and may provide a more
Ci (44)
~
.~
~
~ 100
200
(29)
~

----- ----
...............
I---
--
Yield Siren tit
-
15 .E

10
Cl
C

consistent formability of the part. 5

::E (14)
While electric furnaces are preferred
o o
for reactive metals to prevent
25 38 93 150 200 260 315 370
hydrogen pick-up, fuel-fired furnaces
Temperature· C
are by far the most common. If oil or
gas-fired furnaces are used, the
atmosphere must be maintained
with an oxidizing or neutral flame. A Figure 6. Typical Mechanical Properties as a function of temperature for titanium Grade 2.
reducing atmosphere should never Temperature· F
be used because of the potential for n 100 200 300 400 500 600 700
hydrogen pick-up!2]. 600 50

---
(87) 45
.--.-
Heating Procedures for ~ 500 - '
Elon~_
40
~
Forming Reactive Metals
When reactive metals such as
'" (73)
~ 400 V 35
~
titanium and zirconium are heated for l:. (58)
><V ~ 30 .:
forming, it is especially important that
iii
5i 300 r--- "'- Ilbmate lens e:sttengtb
25 ij
c

~
...........
Ci 01
certain procedures be developed to
insure the heating process is not ~
(44)

200 "-... I'-- r-- 20 2i

iii
detrimental to the material being
heated . Proper cleanliness of the
.~ (29)
~
u 100
...........
r--- r-- Yield SIren jh
r-
15
10

furnace and the material surface is ~ (14) 5

critical to a successful and non- o o
contaminated part being formed. 25 38 93 150 200 260 315 370
Before the material is placed in the Temperature· C
furnace, it should be clean and free

Figure 7. Heating of a Plate Zirconium Blank. Figure 8. Initial Localized Heating of a Zirconium Blank.

CORROSION SOLUTIONS ' CONFERENCE 2009 - PROCEEDINGS

32 PAPER 1B - THE FORMABILITY OF REACTIVE METALS

of any oils, greases or other residue .
It is critical that the furnace and
material is properly thermocoupled
to avoid overheating. The time in the
furnace should also be monitored to
minimize the oxide thickening . Some
forming operations may require
reheating (either by placing the
material back in the furnace or locally
heating) during the operation to allow
for continued formability.
Forming Speed or Strain Rate
In reactive metals the forming speed
(strain rate) is important to successful
forming of the part. Some titanium
(e.g. Ti-2 or Ti-3) or zirconium alloys
can be formed using stamping
techniques, where other less
formable alloys must be formed very
slowly or cracking will take place.
Heating the parts may allow for a
faster forming speed.
Forming Processes
There are a number of forming
techniques available for forming
these materials including roll
forming, press break forming, die
forming, hydro-forming, superplastic
forming, and others. Figures 9 and
10 show some processes for
cylindrical forming of material.
Rolling or break press forming is
generally performed in stages.
Figures 11-14 show the pipe being
rolled to final cylinders and the
resultant piping spools.
TYPES OF FORMING
Tube Forming (Bending)
Titanium and zirconium tubing can
be formed using conventional
methods and equipment. Standard
tube bending processes such as
press, compression or rotary draw
equipment have been used for
titanium and zirconium tubing .
Tubing is generally formed at
ambient or room temperature.
When heat exchanger tubing is
formed for U-tubes, it is generally
performed using rotary draw bend
tooling with ball mandrels and wiper
dies e3]. Primarily, tubing for heat
exchangers is fabricated in
accordance with requirements
specified in TEMA (Tubular
Exchanger Manufacturers
Association) standards. The softer
the material is, the more easily it
tends to collapse during bending.
The softer materials will require
better support on the 10 with the use
of ball mandrels. Other important
factors in tube bending include the
use of proper die clearances,
lubrication, wiper dies configuration,

Figure 9. Hydraulic break press forming of plate. Figure 10. 3-roll double pinch plate roller.

Figure 11. Initial forming process for titanium pipe Figure 12. Final formed cylinder for pipe welding.

CORROSION SOLUTIONS · CONFERENCE 2009 - PROCEEDINGS

 PAPER 1B - THE FORMABILITY OF REACTIVE METALS 33

and mandrel materials . Since Figure 13. Final formed cylinder for pipe welding.
titanium and zirconium are soft
materials, they may tend to smear
or gall if the proper procedures are
not established. Lubrication can be
used to minimize the smearing.
Soaps or lubricants that can be
easily removed should be
considered. Primary considerations
of bending titanium and zirconium
include ovality and wall thinning. If
the wall thinning exceeds that
allowed in the TEMA specification,
then heavier wall thickness tube
might be required for that particular
bend tube radius. As occurs in other
types of forming operations, titanium
or zirconium is prone to some
spring back which can be overcome
by slightly overbending the tube .
Some of the tube bending radiuses
used for titanium and zirconium are
shown in Table 9.
Figure 14. Final pipe spool showing multiple formed pipe bends.
Pipe & Fittings Forming
(Bending)
Piping can be formed at room
temperature or elevated
temperatures depending on the pipe
dimensions and radius needed.
When titanium or zirconium pipe is
bent during fabrication of piping
systems, it may be required to heat
the area to be bent using localized
heating methods. These heating
methods may include torch heating,
blanket heaters or induction heating.
If pipe bends are needed they may
be formed in individual elbows either
by forming and welding clam shells
or using a solid die process. When
elbows are formed either by cold or
warm forming, it may be advisable
to perform a stress relief anneal to
remove residual stresses caused
during the forming process. These

Table 9. Tube bending radius for titanium or zirconium.

Material Tube Diameter, in. Wall Thickness, in . Minimum Bend Radius
Zr 702 0.75 0.049 1.2" 30mm
Zr 702 0.75 0.069 1.5" 38mm
Zr702 0.75 0.090 1.6" 40mm
Ti Gr2 1.0 0.098 2.0" 50mm

CORROSION SOLUTIONS ' CONFERENCE 2009 - PROCEEDINGS

34
elbows are generally welded onto a
straight section of pipe to produce
a piping system. Figure 14 shows a
piping spool in the final stages of
fabrication.
Surface Preparation Before
and After Forming Parts
It is important to properly prepare
the material surface prior to the
forming process. The surface of the
material should be examined initially
for any scratches, gouges, large
pits, or notches. These surface
defects should be removed by light
grinding or polishing using a fine
abrasive. Sometimes it may be
necessary to weld repair surface
defects and grind the area smooth.
Figure 15. Construction of a sectional
head.
Figure 18. Example of zirconium structured packing.
CORROSION
PAPER 1B - THE FORMABILITY OF REACTIVE METALS
The material should not have any
significant scale on the surface.
Generally the standard mill products
will be provided descaled (without a
surface scale). If a thick scale
remains on the surface, it can be
removed using methods such as grit
blasting or steel shot blasting. If steel
shot blasting is used, this process
must be followed by acid cleaning
or pickling. Acid baths using nitric -
hydrofluoric - water mixtures can be
used to pickle the blasted surface.
The steel shot blasting residue must
be removed from the material
surface because surface iron may
cause corrosion problems to occur.
A ferroxyl test (See ASTM A 380) is
sometimes used to verify any
Figure 16. Examples of zirconium
column internals.
SOLUTIONS ' CONFERENCE 2009
residual iron remaining on the
surface of the material after cleaning.
After forming is completed,
depending on the type of part
formed, cleaning and inspection may
be required.
Head Forming
Processes for head forming have
been established for titanium and
zirconium. The processes used will
depend on the head type and
construction method. Heads can be
produced from either solid or
explosive clad blanks. Generally the
thinner heads are formed using a
solid titanium or zirconium plate,
where the thicker heads are
constructed using explosion
Figure 17. Examples of zirconium sieve
trays for use in a column.
Figure 19. Example of zirconium surface
cracking of a formed half-shell.
Figure 20. Example of zirconium
cracking on thick-wall pipe cylinder.
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 PAPER 1B - THE FORMABILITY OF REACTIVE METALS 35

cladded materials. In addition, Figure 21. Example of head cracking.

heads can be produced in single or
multiple sections. The most
common head designs for use in
reactive metal pressure vessels are
flanged and dished, hemispherical,
and 2:1 elliptical.
In production of solid heads,
either single plates or multiple plates
can be welded together as starting
blanks depending on the final size
of head required. When using
multiple plates joined together, it is
recommended that any notches (toe
of weld) or weld reinforcement be
ground smooth and flat to remove
any potential for crack propagation
during forming.
Where sectional heads are
produced, the individual "petals" are Figure 22. Example of head deformation.
formed and then welded together.
It is critical that these petals are
formed correctly to allow good
match-up of the sections. Figure 15
shows sectional head petals being
welded together.
Explosion clad heads may be
formed using die forming (smaller
heads) or using a process called
"bump and spinning" This technique
is one where curved male and
female dies are used to form a flat
plate into a dished head. This
process forms or "bumps" the
circular head blank in small
increments and then spins the plate
to an adjacent area until the total
dished head is formed . It usually carbon steel base metal below the Surface defects include surface
takes a number of forming steps and lower critical temperature'}. tears, cracks, thinning, laps,
tighter radius dies until the final head embedded material while internal
shape is achieved. This may occur Tray and Internals Forming defects may include strain induced
in many steps and may also require Titanium and zirconium are porosity (SIP), grain separation,
some localized heating. commonly produced into internals for intermetallic compound formation,
When heads are formed, it is distillation columns. These parts may and segregation.
extremely important that a process include sieve or valve trays, random
be developed before the head packing, structured packing, or other Surface Cracking
formation begins. In most cases the internal devices. Figures 16-18 show Surface cracking can occur if
process is performed at elevated some examples of column trays and improper procedures are used
temperatures. Studies have shown internals that have been produced during forming. In most cases
that the optimum temperature to from reactive metals(5}. these problems can be overcome
form explosion clad heads is in the by developing and following proper
range of 600-800 o e (111 0-1470°F), Forming Defects procedures. Figures 19-23 show
but in practice, titanium and There are certain surface and examples where unsuitable forming
zirconium heads have been formed internal defects that can be caused techniques have resulted in surface
below 700 e (1290°F) to keep the
0
by improper forming techniques . cracking.

CORROSION SOLUTIONS ' CONFERENCE 2009 - PROCEEDINGS


36
Strain Induced Porosity
(internal pores or cavities)
Strain induced porosity (SIP) are
undesirable cavities that form during
hot or cold working of metallic
materials. The cavities usually
nucleate at grain boundaries (the
boundaries between crystals) as a
result of local stresses and strains
induced by sliding that occurs along
the boundaries at cold and hot-
working temperatures. Depending
on the precise state of stress and
strain, the cavities grow to various
sizes (from nano to micrometers)
and, in extreme cases, may lead to
fracture(6}. Although internal,
micrometer-scale cavities are
Figure 23. Example of head cracking.
Figures 24A and 24B. Internal porosity on zirconium Grade 702 bend samples
formed at 1.2T bend radius.
CORROSION
PAPER 1B - THE FORMABILITY OF REACTIVE METALS
extremely difficult to detect using
non-destructive techniques,
avoiding internal cavity formation
and growth during hot working is
nevertheless important for avoiding
the harmful effect of SIP on
subsequent processing or service.
Figures 24A and 24B show the
appearance of strain induced
porosity in zirconium.
CONCLUSIONS
• Titanium and zirconium have
one of the most difficult
crystal structures and quite
often don't lend themselves to
standard forming techniques .
SOLUTIONS · CONFERENCE 2009
t -
• These materials, however, can
be formed even into complex
parts if the proper equipment
and procedures are used.
• It is important to develop a
procedure for the specific
titanium and zirconium alloy
and strictly follow it.
• Often times the production of
a mock-up part is helpful and
desirable.*
REFERENCES
1 . Jack Tosdale and Richard
Jenkins, "The Forming of
Heads and Parts," Zirconium /
Organics Conference,
Salishan Lodge, Gleneden
Beach, OR, Wah Chang,
September 8-10, 1997
2. Richard C. Sutherlin,
"Procedures for Heat -Treating
Fabricated Reactive Metals
Equipment," Corrosion
Solutions Conference 2005,
Sunriver, OR, ATI Wah Chang,
September 11-15, 2005.
3. Ronald R. Strange, "Lean Time
Call for Mean Tactics: A Tube
Bender's Tools of the Trade,"
TPJ-The Tube and Pipe
Journal, September 14, 2004.
4. Curtis Prothe and John Banker,
"Metallurgical Considerations in
the Manufacture of Clad
Heads," Corrosion Solutions
Conference 2009, The
Canyons Resort, Park City,
Utah, ATI Wah Chang,
September 21-23,2009.
5. B.J. Sanders, "Design and
Procurement of Zirconium
Column Internals," Reactive
Metals in Corrosion
Applications Conference,
Sunriver Resort, Sunrive~
Oregon, Wah Chang,
September 12-16, 1999.
6. Roland Tricot, "Zirconium in
Chemical Engineering:
Principal Metalworking
Characteristics," Materiaux Et
Techniques, April-May 1989.
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