Professional Documents
Culture Documents
The Formability of Reactive Metals
The Formability of Reactive Metals
25
PAP E R 1 B
The Formability of
Reactive Metals
taken into consideration to help meet the minimum ASTM highly alloyed alpha -beta grades.
insure a successful result. Important mechanical property requirement. The lower strength alpha titanium
factors to consider when these Any concerns with improvement of grades are primarily used for
reactive metals are formed are the formability due to forming direction chemical processing equipment of
physical and mechanical properties. could be overcome by other means all types where some higher
When alloying elements are added such as establishing and following strength alpha-beta titanium alloys,
to titanium or zirconium, the proper or alternate procedures. such as titanium Grade 5 (Ti-6AI-4V)
mechanical and physical properties are used primarily in pump and valve
may change depending on the appl ications. The chemical and
particular element added. REACTIVE METALS FOR USE mechanical properties of select
Both zirconium and titanium are IN CPI APPLICATIONS titanium alloys used in the CPI are
anisotropic materials. Anisotropic is shown in Table 1 and Table 2.
defined as a material exhibiting Titanium Alloys For the chemically pure (CP)
different mechanical properties in Titanium alloys are commonly used titanium alloys, the formability of
different directions. This means that in a large number of chemical these will generally depend on their
the transverse and rolling direction processing applications due to their mechanical strength since the lower
are different in mechanical strength good corrosion resistance in strength materials will form more
and ductility. Because of this, the chemical media . The application easily than that of the high-strength
material will exhibit a greater ductility areas for titanium consist of alloys. For example, titanium Grade
in one direction than in the other. chemical plants, pulp and paper, 1 is commonly used in the
Normally, companies do not petrochemical , waste treatment , production of plate and frame heat
consider the preferential forming of and metal fin ishing. The titanium exchanger panels and for explosive
materials in a specific direction for alloys used in chemical processing clad plate which require maximum
chemical processing equipment industry range from the very low ductility due to the severe forming
since the design properties always interstitial unalloyed grades to the requirements . The higher strength
alloys have the lowest elongation used primarily for the explosive of Platinum Group Metals (PGM)
and require larger bend radii during welding (cladding) process onto elements added for improved
forming. In regards to the ASME steel or stainless steel and where corrosion resistance. The CP alloys
Boiler and Pressure Vessel high formability is required. The Zr are generally very fabricable. The
construction code, solid titanium 702 grade comprises, by far, the alpha-beta titanium alloys, on the
vessels can be produced using highest quantity of zirconium alloys other hand, contain elements
alloys Ti-1, Ti-2, Ti-3, Ti-9 , Ti-11, used in the CPI. The Zr 705 alloy is (aluminum) to stabilize and
Ti-12, Ti-17, and Ti-38 (through a primarily used for fasteners, valves, strengthen the alpha phase and
code case). and pumps. Although the Zr 705 beta stabilizers (vanadium) to give
alloy has a higher strength than that solid solution strengthening . These
Zirconium Alloys of the Zr 702 grade, it also has alloys also have fairly good
Zirconium alloys are also used in a better bend ductility due to its 2- fabricability. The more common
number of chemical processing phase alloy composition. Table 3 titanium and zirconium grades and
applications due to their excellent and Table 4 show the chemical and their characteristics are shown in
resistance to severe corrosive mechanical properties of common Tables 5 and 6.
media. The application areas for zirconium alloys.
zirconium consist of chemical and Crystal Structure of Titanium
petrochemical plants because of Effect of Alloying and Zirconium
zirconium's resistance to organic Both titanium and zirconium have a Both zirconium and titanium are
acids (acetic, formic), mineral acids strong affinity for oxygen, nitrogen, allotropic. At ambient temperatures,
(sulfuric acid, nitric acid, and hydrogen. This reactivity leads the chemically pure grades exist as
hydrochloric acid), and other media to a strengthening effect of the hexagonal close-packed (HCP)
such as chloride solutions and urea. materials as these interstitial structures. These commercially pure
Zirconium alloys used in the elements increase . The (CP) alloys are termed alpha phase
chemical processing industry commercially pure (CP) titanium structures. The alpha phase exists
consist of the unalloyed Zr 700 alloys are all alpha grades with in the CP or pure alloys at
grade, the Zr 702 grade, and the Zr essentially only oxygen added for temperatures up to about 885°C
705 grade . The Zr 700 grade is strength or alloys with small levels (1625°F) for titanium and about
854°C (1570°F) for zirconium. At the chemical processing industry are slip in these alloys depends on the
transformation temperatures, the also typically alpha alloys, with the alloy composition, temperatu re,
structure transforms to a body- exception of the Grade 705 alloy. grain size , st ructure, and crystal
centered cubic (BCC) structure, The Zr 705 grade is a 2-phase orientation{f]. Deformation also
termed beta phase . The HCP structure with alpha zirconium and occurs by "twinning " which is
structure is more densely packed beta niobium. This alloy has favored over slip by factors including
than that of the body or face- zirconium and 2-3% niobium which course grain size, high purity, and
centered structures which increases the strength of the low temperature deformation.
contributes to less formability than material by about 30% over that of Figures 2A and 2B show the
that of the carbon or stainless steel the Zr 702 grade. appearance of twinning in titanium
materials. and zirconium alpha alloys.
Titanium alloys used for the Deformation Mechanisms
chemical processing industry are The primary mode of deformation in Elastic Springback
generally the alpha grades. Some both zirconium and titanium is by Characteristics
higher strength alpha-beta alloys "slip". The most common Spring back is defined as the elastic
such as titanium Grade 9, titanium crystallographic slip planes in recovery after cold forming, which
Grade 5, and titanium Grade 38 are titanium and zirconium materials are can be considerable for reactive
being used in some specific the pyramidal , prismatic, and basal metals. Both zirconium and titanium
chemical processing applications planes in the close-packed direction. will experience significant
where greater mechanical strength Figure 1 shows the primary springback characteristics due to
is needed. deformation systems for titanium their low modulus of elasticity. It has
Zirconium alloys used for the and zirconium . Deformation due to been noted that springback of
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 .
Twio Plane
TctUion
(1011) (1121) Twin PWx:
Tension
(lOll)
Slijllpirecborl
(I010)ftaiJr
occur. Titanium and zirconium can strength as the temperature is sources or through furnace heating.
be formed at room temperature to increased. This decrease in Localized heating will include those
those bend rad ii as shown in Table mechanical strength and increase in processes where the heating source
7, up to about 19mm (0 .7S"), elongation will significantly improve is by combustion burners and / or
depending on a number of factors. the formability of these materials. It high temperature quartz lamps. It is
These factors include surface finish , is always cautioned that when important, when heating the
actual bend radius , die reactive metals such as titanium or material , that the heat is well
configuration, and roughness, zirconium are heated, the heating distributed (heated evenly)
forming speed, and part dimension, processes should be carefully throughout the material. Improper
to name a few. These bend radii are reviewed to prevent detrimental or inadequate heating may cause
however, only guaranteed to form at effects on the material. In addition, deformation or cracking in the part
room temperature, per the ASTM hot forming requires that safety being formed . When hot forming is
specification, up to 4.74mm (0.187") measures be taken to insure that the used, the material and the dies
in thickness. If the parts cannot be personnel are protected from these should be heated. Cold (ambient
formed at room temperature then higher temperatures. temperature) dies will cause a local
hot forming may be required. Table surface chilling effect on the plate
8 shows the typical forming Heating Methods surface which could initiate surface
temperatures for titanium and Heating material for hot forming may cracks in the part being formed.
zirconium . Elevated temperatures be done using localized heating Often, localized heating is also used
will increase the ductility of the
metals significantly. Figures 4-6
Figure 4. Typical Mechanical Properties as a function of temperature for Zr 102 grade.
show the reduction in mechanical
Temperature· F
77 100 200 300 400 500 600 700
Table 7. Minimum Bend Radius for 600 70
Material up to 0.187" thick (4.75mm) as (87)
shown in ASTM B 265 (Titanium) and
~ 60
----
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
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
----- ----
...............
I---
--
Yield Siren tit
-
15 .E
10
Cl
C
---
(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)
Figure 7. Heating of a Plate Zirconium Blank. Figure 8. Initial Localized Heating of a Zirconium Blank.
of any oils, greases or other residue . Forming Processes press, compression or rotary draw
It is critical that the furnace and There are a number of forming equipment have been used for
material is properly thermocoupled techniques available for forming titanium and zirconium tubing .
to avoid overheating. The time in the these materials including roll Tubing is generally formed at
furnace should also be monitored to forming, press break forming, die ambient or room temperature.
minimize the oxide thickening . Some forming, hydro-forming, superplastic When heat exchanger tubing is
forming operations may require forming, and others. Figures 9 and formed for U-tubes, it is generally
reheating (either by placing the 10 show some processes for performed using rotary draw bend
material back in the furnace or locally cylindrical forming of material. tooling with ball mandrels and wiper
heating) during the operation to allow Rolling or break press forming is dies e3]. Primarily, tubing for heat
for continued formability. generally performed in stages. exchangers is fabricated in
Figures 11-14 show the pipe being accordance with requirements
Forming Speed or Strain Rate rolled to final cylinders and the specified in TEMA (Tubular
In reactive metals the forming speed resultant piping spools. Exchanger Manufacturers
(strain rate) is important to successful Association) standards. The softer
forming of the part. Some titanium the material is, the more easily it
(e.g. Ti-2 or Ti-3) or zirconium alloys TYPES OF FORMING tends to collapse during bending.
can be formed using stamping The softer materials will require
techniques, where other less Tube Forming (Bending) better support on the 10 with the use
formable alloys must be formed very Titanium and zirconium tubing can of ball mandrels. Other important
slowly or cracking will take place. be formed using conventional factors in tube bending include the
Heating the parts may allow for a methods and equipment. Standard use of proper die clearances,
faster forming speed. tube bending processes such as 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.
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
elbows are generally welded onto a The material should not have any residual iron remaining on the
straight section of pipe to produce significant scale on the surface. surface of the material after cleaning.
a piping system. Figure 14 shows a Generally the standard mill products After forming is completed,
piping spool in the final stages of will be provided descaled (without a depending on the type of part
fabrication. surface scale). If a thick scale formed, cleaning and inspection may
remains on the surface, it can be be required.
Surface Preparation Before removed using methods such as grit
and After Forming Parts blasting or steel shot blasting. If steel Head Forming
It is important to properly prepare shot blasting is used, this process Processes for head forming have
the material surface prior to the must be followed by acid cleaning been established for titanium and
forming process. The surface of the or pickling. Acid baths using nitric - zirconium. The processes used will
material should be examined initially hydrofluoric - water mixtures can be depend on the head type and
for any scratches, gouges, large used to pickle the blasted surface. construction method. Heads can be
pits, or notches. These surface The steel shot blasting residue must produced from either solid or
defects should be removed by light be removed from the material explosive clad blanks. Generally the
grinding or polishing using a fine surface because surface iron may thinner heads are formed using a
abrasive. Sometimes it may be cause corrosion problems to occur. solid titanium or zirconium plate,
necessary to weld repair surface A ferroxyl test (See ASTM A 380) is where the thicker heads are
defects and grind the area smooth. sometimes used to verify any constructed using explosion
Figure 15. Construction of a sectional Figure 16. Examples of zirconium Figure 17. Examples of zirconium sieve
head. column internals. trays for use in a column.
Figure 18. Example of zirconium structured packing. Figure 19. Example of zirconium surface
cracking of a formed half-shell.
Strain Induced Porosity extremely difficult to detect using • These materials, however, can
(internal pores or cavities) non-destructive techniques, be formed even into complex
Strain induced porosity (SIP) are avoiding internal cavity formation parts if the proper equipment
undesirable cavities that form during and growth during hot working is and procedures are used.
hot or cold working of metallic nevertheless important for avoiding • It is important to develop a
materials. The cavities usually the harmful effect of SIP on procedure for the specific
nucleate at grain boundaries (the subsequent processing or service. titanium and zirconium alloy
boundaries between crystals) as a Figures 24A and 24B show the and strictly follow it.
result of local stresses and strains appearance of strain induced • Often times the production of
induced by sliding that occurs along porosity in zirconium. a mock-up part is helpful and
the boundaries at cold and hot-
working temperatures. Depending
desirable.*
on the precise state of stress and CONCLUSIONS
strain, the cavities grow to various • Titanium and zirconium have REFERENCES
sizes (from nano to micrometers) one of the most difficult 1 . Jack Tosdale and Richard
and, in extreme cases, may lead to crystal structures and quite Jenkins, "The Forming of
fracture(6}. Although internal, often don't lend themselves to Heads and Parts," Zirconium /
micrometer-scale cavities are standard forming techniques . Organics Conference,
Salishan Lodge, Gleneden
Figure 23. Example of head cracking. 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
Figures 24A and 24B. Internal porosity on zirconium Grade 702 bend samples Canyons Resort, Park City,
formed at 1.2T bend radius. 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.