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The Application andProperties of ATI NuShieldBorated Stainless Steels
CharlesStinnerManager, Market and Project Development
ATI Nuclear Energy
Technical and Commercial Center
1300 Pacific Ave
Natrona Heights, PA 15065
USA
T: 724-226-6173
Tony DenardoProduct Development Metallurgist
ATI Allegheny Ludlum
1300 Pacific Ave
Natrona Heights, PA 15065
USA
T: 724-226-6317
Biography
Charles Stinner is the Manager of Market
and Project Development at ATI Nuclear
Energy. His responsibilities include research
and development of new products as well
as business development of the Electrical
Energy market. His current area of focus is
development of materials for the Nuclear
Energy market as well business development
of nuclear energy accounts. Mr. Stinner
received his PhD in Metallurgical and
Materials Engineering from the University of
Pittsburgh.
Abstract
ATI has begun production of a family of borated
stainless steel products, being branded as ATI
NuShield Borated Stainless Steel. These
products use powder metallurgy processing
which imparts a homogenous microstructure
resulting in properties superior to cast and
wrought products. This paper discusses the
application and properties of these products,
with emphasis on ATI 304B7P/M Alloy.
Keywords
ATI NuShield
Borated Stainless Steel
304B7
spent fuel
neutron absorption
spent fuel rack
neutron attenuation
enriched boron
Introduction
Commercial nuclear reactors rely on the fission
of uranium and/or plutonium compounds to
produce radiation that is converted into heat.
Fission in power reactors is the process where
fissile isotopes, mostly 235U and 239Pu, absorb
a neutron and split into two or more nuclei,
releasing energy, gamma radiation, and free
neutrons. The free neutrons may later be
absorbed by other fissile atoms triggering
further fission events, which in turn release
more neutrons. Control of this chain reaction
is the key to safely harnessing nuclear energy
for power production.
Control of the nuclear chain reaction
is possible by affecting the energy and
availability of neutrons. Within nuclear
reactors, neutron moderators such as water or
graphite are used to reduce the velocity of fast
neutrons such that they become lower energy
thermal neutrons, which are more likely to be
absorbed and create fission events. Similarly,
neutron absorbers may be used to reduce the
number of neutrons available to participate
in fission events, which slows or prevents
the nuclear chain reaction from proceeding.
Neutron absorbers are used in control rods
within the fuel assemblies to control the rate
of power production, or to halt the fission
process during shutdown. Neutron absorbersare also a key component for handling and
storing used fuel, where they are used to
isolate the fuel allowing for the slow decay of
heat and radiation.
The effectiveness of neutron absorbers is
characterized by their neutron cross-section,
which is measured in barns. One barn is equal
to 10-28m2, which is approximately the cross-
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sectional area of a uranium nucleus. The
higher the neutron cross-section of a given
atom, the greater is the ability of the atom
to absorb a neutron. Table 1 gives a list of
elements along with their neutron absorption
cross-sections [1]. Due to cost and availability,
the most common neutron absorbing elementused today is boron. Natural boron contains
approximately 19.9 atomic percent 10B, which
is the isotope responsible for absorption of
thermal neutrons. Boron compounds enriched
in 10B are available commercially, but are not
commonly employed due to the very high price
of this raw material.
Boron may be used in many forms,
including elemental powder, boron carbidepowder, boron carbide in metal matrix
composites, boron carbide in ceramics, or
as a boride rich phase in stainless steels.
Most boron containing materials require
physical containment or attachment, and are
not suitable for structural members due to
strength and ductility issues. Borated stainless
steels (BSS) have a strength and ductility
advantage over other materials, which makes
them uniquely suited to be used for structural
application such as spent fuel racks.
Used Nuclear Fuel
In a commercial nuclear reactor, power is
generated through the transfer of heat to a
heat transfer medium, such as borated water,
which is used to produce steam that is used
to turn a turbine-generator set. The equipmentthat is used to convert heat into steam can
differ depending on the design of the reactor.
While there have been many different nuclear
reactor designs deployed around the world,
the most common commercial nuclear
reactors in service or under construction are
the pressurized water reactor (PWR) and the
boiling water reactor (BWR).
In these reactor designs, and most others,
power is produced through the fission of
uranium enriched in the fissionable isotope235U. An exception is the AECL designed Candu
reactor, which uses natural uranium (un-
enriched) for fuel. The uranium fuel, in the form
of UO2, is contained within seamless zirconium
tubes called fuel rods. The fuel rods are placed
into fuel assemblies typically containing 50-
264 fuels rods each depending on the type
and size of the reactor core. A PWR will have
120-300 fuel assemblies per core. A BWR fuel
assembly is smaller than that of a PWR, and
will have up to 370-800 assemblies per core2.
The fuel assemblies are arranged within the
reactor core such that the burn-up efficiency
of the fuel in the fuel rods is maximized. After
approximately 12-24 months, nuclear fuel
must be replaced by fresh fuel due to the build-
up of fission products that absorb neutrons.
Typically, one third of the fuel assemblies for
a PWR, and one quarter of the assemblies of a
BWR, are replaced during a refueling outage.
The disposition and storage of this spent fuel
is one of the most challenging aspects of the
operation of a commercial nuclear power plant.
This spent fuel must be carefully contained
as it continues to emit dangerous levels of
radiation and heat for many years.
During a refueling outage, used fuelassemblies are removed from the reactor core
and placed in racks within a spent fuel pool. The
spent fuel pool is a stainless steel lined tank
typically containing a minimum of 6.1 m (~20')
of water (see Figure 1). The water is used to
shield the environment from gamma radiation
and also provide a heat transfer medium to
cool the fuel assemblies. The used fuel will
remain in the spent fuel pool at least until it
Table 1.Neutron cross-section of selected
elements.
Element Neutron A bsorption
Cross-section (Barns)
B (natural) 764
10B 3835
11B 5.5 x 10-3
Cd 2520
Dy 940
Er 159
Eu 4565
Hf 104
In 194
Ag 63.3
Gd 48890
Ni 1.15
Fe 2.56
Zr 0.185
Table 2.Half-life of some common isotopes
found in spent nuclear fuel.
Isotope Half Life
Fission Products
129I 1.57 x 107years
131I 8 days
134Cs 2 years
137Cs 30.1 years
90Sr 28.5 years
99Tc 4.2 x 106years
144Ce 284 days
147Sm 1.06 x 1011years
144Nd 2.29 x 1015years
Actinides
239Pu 24,000 years
241Pu 14.4 years
234U 2.45x105years
235U 7 x 108years
236U 6561 years
238U 4.47 x 109years
241Am 433 years
237Np 2.14 x 106years
Figure 1. Spent fuel storage pool.
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has lost enough heat to be safely transferred
to another facility. Typically, a minimum time
of one year is required [2]. In the US and other
countries that dispose of used fuel after one
cycle, spent fuel remains in pools at the reactor
site until the pools near their capacity. The
spent fuel is then transferred from the spentfuel pool to on-site dry storage in casks. O ther
countries will store spent fuel in pools for an
extended period and then transfer the spent
fuel to a reprocessing facility.
It is important to note that used fuel contains
a significant amount of radioactive isotopes,
some with very long half-lives. Typical used
fuel is about 95% 238U, 1% 235U that has not
undergone fission, about 1% plutonium and
3% of various fission products. Some fission
products, such as isotopes of iodine and
cesium, have relatively short half-lives but
are highly radioactive. These isotopes are
responsible for most of the heat generated by
used fuel. Uranium and plutonium, along with
the minor actinides americium, neptunium,
and californium have lower radioactivity, but
have extremely long half-lives. The half-lives of
some of the isotopes that make up spent fuel
are summarized in Table 2[3].
Due to the large amount of fissile materialcontained in used fuel, there is a potential
for criticality to be reached, resulting in an
uncontrolled reaction and potential meltdown.
In order to reduce the chances of criticality, the
fuel assemblies are isolated through the use
of neutron absorbing materials. These may be
mechanically attached to the support structure,
or in the case of borated stainless steels, used
as the structural support material. Borated
stainless steels are used as the material of
construction for racks and baskets in the spent
fuel pools and casks used for transport and
storage, and as neutron absorbing inserts in
some designs.
General Characteristics of
Borated Stainless Steels
Borated stainless steels (BSS) are covered by
the specification ASTM A887-89 [7]. The grade
of borated stainless is characterized by itsboron content, per Table 3. The compositions
are similar in many respects to 304 stainless
steels, with the main exception of the high boron
content. The alloys also have higher nickel
content. The increase in nickel is intended to
compensate for the effects of boron on the
properties and micro-constituents. Nickel is
added to improve ductility and workability.
An optical micrograph of ATI 304B7P/M is
shown in Figure 2. The microstructure consists
of chromium rich boride particles (darker
phase) in an austenite matrix. The boride
phase for similar alloys was researched by
Goldshmidt[4,5]and others [6]and was found to
Figure 2. Optical (a) and SEM micrograph (b) illustrating morphology and distribution of boride precipitates in ATI 304B7P/M alloy.
a b
Table 3.Composition limits for borated stainless steels per ASTM A877-89[7].
UNS Type C Mn P S Si Cr Ni B Other
S30460 304B 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 0.20-0.29 0.10N
S30461 304B1 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 0.30-.049 0.10N
S30462 304B2 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 0.50-0.74 0.10N
S30463 304B3 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 0.75-0.99 0.10N
S30464 304B4 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 1.00-1.24 0.10N
S30465 304B5 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 1.25-1.49 0.10N
S30466 304B6 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 1.50-1.74 0.10N
S30467 304B7 0.08 2.00 0.045 0.03 0.75 18.00-20.00 12.00-15.00 1.75-2.25 0.10N
CONCENTRATIONS ARE THE MAXIMU M, UNLESS A RANGE OR MINIM UM IS INDICATED.COBALT CONCENTRATION SHALL BE 0.2 MAX , UNLESS A LOWER CONCENTRATION IS AGREED UPON BETWEEN THE PURCHASER AND THE SU PPLIER.
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have the approximate proportions of Cr:Fe:Ni
of approximately 11:11:1 with an orthorhombic
crystal structure of the type Cr2B.
The precipitation of chromium rich borides
locally depletes the surrounding austenite
of chromium. This degrades the corrosion
resistance somewhat, especially in the presence
of chlorides. The minimum chromium content is
raised so that depletion effects are reduced.
The carbon content is typically kept below
0.03 wt% maximum in order to avoid forming
chromium carbides, which would further
deplete the austenite of chromium resulting in a
further decrease in corrosion resistance. These
alloys are generally less resistant than typical300 series stainless steels, but have good
resistance in the spent fuel pool environment.
Research has shown that alloys produced
using the powder metallurgy (P/M) process
have generally superior corrosion resistance
to ingot cast and wrought materials of similar
composition [8]. Some corrosion testing results
for ATI 304B7P/M in a simulated spent fuel
pool environment may be seen in Table 4.
The mechanical properties of borated
stainless steels as specified by ASTM A887
may be seen in Tables 5 and 6. The properties
for P/M alloys are given as Grade A and
those of ingot cast and wrought products are
designated Grade B. The higher values for
the minimum properties reflect the improved
performance of the P/M material.
Table 5.Mechanical testing requirements of borated stainless steels per ASTM A887-89 [7]. Grade A: P/M produced, Grade B: cast and wrought.
UNS
Designation
Type Grade Tensile Strength, min Yield Strength, min Elongation, min Hardness, max
MPa ksi MPa ksi % Brinell Rockwell B
S30460 304B A 515 75 205 30 40.0 201 92
B 515 75 205 30 40.0 201 92
S30461 304B1 A 515 75 205 30 40.0 201 92
B 515 75 205 30 35.0 201 92
S30462 304B2 A 515 75 205 30 35.0 201 92
B 515 75 205 30 27.0 201 92
S30463 304B3 A 515 75 205 30 31.0 201 92
B 515 75 205 30 19.0 201 92
S30464 304B4 A 515 75 205 30 27.0 217 95
B 515 75 205 30 16.0 217 95
S30465 304B5 A 515 75 205 30 24.0 217 95
B 515 75 205 30 13.0 217 95
S30466 304B6 A 515 75 205 30 20.0 241 100
B 515 75 205 30 9.0 241 100
S30467 304B7 A 515 75 205 30 17.0 241 100
B 515 75 205 30 6.0 241 100
Table 4.Modified ASTM G 48 Practice B crevice test and Practice A pitting testresults for ATI 304B7P/M alloy. Solution: 10 ppm Cl- (as NaCl) and 12,000
ppm boric acid solution, exposure time: 72 hours, temperature: 24C (75F).
Modified G48 Practice A
Sample Code Test Temperature
(C)
Weight Loss
(g )
Weight Loss
(g/cm2)
Deepest Pit
and Location
420-A1 24 0.0003 0.000009 None
420-A2 24 0.0003 0.000010 None
Modified G48 Practice B
Sample Code Test Temperature
(C)
Weight Loss
(g )
Weight Loss
(g/cm2)
Deepest Pit
and Location
420-B1 24 0.0004 0.000013 None
420-B2 24 0.0002 0.000010 None
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ATI NuShield Products
The careful, highly specialized processing of
ATI NuShield products allows for superior
properties over competing products.
ATI begins wi th powder metal lurgy processing
which imparts a homogenous microstructure,leading to higher ductility and toughness,
along with improved neutron absorption
performance. The material may be used as-
consolidated as a near net shape, or further
processed into plate, sheet or strip.
Powder Metallurgy
Processing
The powder metallurgy processing used
to produce ATI NuShield products is
performed at the production facilities of ATI
Powder Metals. The process begins with
induction melting and inert gas atomization.
Similar to conventional metallurgy, the
composition is attained in the melt furnace,
and not via elemental blending of powders.
Once chemistry is confirmed and refining
is complete, rather than pouring the molten
metal into ingots or molds, the material is
diverted through a nozzle where the stream is
impinged by high velocity inert gas (typically
nitrogen or argon), rapidly solidifying
the material and eliminating segregation
that would occur with conventional ingot
metallurgy. The high-purity, homogenous,
and spherical powder particles (see Figure 3)
are collected at the bottom of the chamber for
subsequent processing. Again, each powder
particles shares a common chemistry, and
can be thought of as a micro-ingot.
Following atomization, which yields a wide
size range of powder particles, the material
is classified to a desired particle size by
way of sieving. This screening operation is
performed in clean room conditions under apositive pressure of filtered air. Next, the yield
of multiple heats are blended together, both to
homogenize the particle size distribution and
normalize any compositional variations. The
former is of utmost importance for production
of consolidated product, as it influences
packing density in the containers and
consequently distortion during consolidation.
Once the powder has been screened,
Table 6.Impact testing requirements of borated stainless steels per ASTM A887-89 [7].
Grade A: P/M produced, Grade B: cast and wrought.
UNS
Designation
Type Grade Charpy V-Notch Energy, min
J ft-lb
S30460 304B A 65 88
B 40 54
S30461 304B1 A 60 81
B 35 47
S30462 304B2 A 48 65
B 16 22
S30463 304B3 A 38 52
B 10 14
S30464 304B4 A 30 41
B
S30465 304B5 A 23 31
B
S30466 304B6 A 16 22
B
S30467 304B7 A 10 14
B
Figure 3. Scanning electron microscope (SEM) micrograph of inert gas atomized powder.
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Figure 4. Schematic of powder metallurgy processing.
Melting & Atomization Screening Blending Loading Hot Isostatic Pressing
Figure 5. Microstructures of borated stainless steel produced by (a,b) ingot metallurgy, cast and wrought structures and (c,d) powder metallurgy.
a b
c d
Cast + Wrought 1.1% Boron Cast + Wrought 1.65% Boron
P/M with 1.1% Boron P/M with 1.85% Boron
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blended, and fully classified, custom-
engineered containers are fabricated for
optimum integrity and loaded with the powder
on vibratory tables to maximize packing, again
to control the extent of shrinkage and distortion
that occur during consolidation. The final step
in the process is hot isostatic pressing (HIP),
where the compacts are loaded into ATI Powder
Metals autoclave, and heat and pressure
are simultaneously applied per established
procedures. A processing schematic is shown
in Figure 4. HIP consolidation achieves full
theoretical density of the P/M material. The
consolidated material, termed a compact, may
be used as a near net shape or can be further
worked at ATI manufacturing operations to
produce the final product.
Properties of ATI
NuShield Products
A comparison of the microstructure and
properties of borated stainless steel produced
by powder metallurgy and ingot cast +
wrought processes is given in Figure 5.
The microstructure shown in Figure 5d is of
mill produced ATI 304B7 flat-rolled sheet
product. All other materials shown in this
figure were produced in 20 kg heat lots and
processed at ATI production facilities. The
fine distribution of borides of the P/M product
leads to the higher ductility and toughness
noted in Table 7.
Typical mechanical properties of ATI
304B7P/M are given in Table 8. This grade
is currently available in flat rolled products
from ATI Allegheny Ludlum as plate, sheet, and
strip. Other product forms and compositions
are available on request.
Neutron Absorption
Neutron absorption testing of ATI 304B7
P/M was performed on a university researchreactor. Several samples were tested in order
to determine the ability of the ATI 304B7
P/M material to attenuate neutrons. Two
control samples of commercially available
type 304L were also run for comparison. The
results of the testing are shown in Table 9.
The ratio I/Io is a measure of the intensity of
the transmitted neutron beam to the incident
beam with no sample present. It is noted that
significant neutron attenuation was achieved
for all of the borated stainless steel samples.
Very few neutrons were able to pass through
the discrete plate samples labeled as PMP-1
and PMP-2.
Fabrication
Borated stainless steels have higher strength
and lower ductility than 300 series stainless
steels and special precautions are needed to
prevent cracking or degradation of properties.
ATI NuShieldalloys are generally weldable
using standard techniques. However, some
degradation in properties of the heat affected
zone should be expected. The use of AWS ER
308/309 filler metal is recommended for best
results. Low heat inputs should be used tominimize base metal dilution. A photograph of
3mm thick sheet of ATI 304B7 P/M that has
been butt welded using MIG with ER 308 filler
wire and low heat input may be seen in Figure
6. The weld joint was able to be bent through
approximately 145 without cracking.
ATI NuShieldproducts can be cold formed
by bending although the angle and radius may
be limited. The edges should be ground and
Table 7.Property comparison between P/M and cast + wrought products. All materials were produced in 20 kg heat lots and processed at ATI facilities.
Identification UTS MPa (ksi) YS MPa (ksi) Elongation % Impact J (ft-lb)
ATI 304B7 P/ M
1.8% Boron738 (107) 338 (49) 25 22 (16 ft-lb)
C&W 304B61.65% Boron
648 (94) 351 (51) 11 9 (6.5 ft-lb)
P/M 304B5
1.4% Boron772 (112) 303 (44) 35 38 (28 ft-lb)
C&W 304B5
1.4% Boron634 (92) 303 (44) 18 14 (10 ft-lb)
P/M 304B4
1.14% Boron689 (100) 283 (41) 35 65 (48 ft-lb)
C&W 304B4
1.1% Boron710 (103) 462 (67) 21 18 (13 ft-lb)
ASTM 887-89
304B7 Grade A
515 (75) 205 (30) 17 14 (10 ft-lb)
ASTM 887-89
304B7 Grade B
515 (75) 205 (30) 6
GRADE A PROPERTIES ARE FOR P/M PRODUCED MATERIAL.
GRADE B ARE FOR CAST + WROUGHT.PROPERTIES LISTED ARE AVERAGE OF TESTS ON 6MM -THICK MILL-PRODUCED PLATE.PROPERTIES ARE FOR LAB ORATORY PRODUCED MATERIAL.
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free of area of stress concentration such as
gouges, burrs, dents, etc. This is especially
true of the grades with higher boron content,
which tend to be highly notch sensitive. Some
bend testing data for ATI 304B7P/M may be
seen in Figure 7 and Table 10.
Hot working should be performed between
927-1,093C (1,700-2,000F). To restore
properties, hot or cold worked products
should be annealed at a temperature range of
1,038-1,093C (1,900-2,000F) followed by
rapid cooling.
ConclusionBorated stainless steels are very effective
neutron absorbers and possess properties
that allow these alloys to be used for structural
applications such as spent fuel racks and
baskets. ATI NuShieldborated stainless steel
products are made using P/M processing,
which results in a very fine, homogenous
distribution of boride precipitates. The
homogenous microstructure leads to high
ductility and toughness, improved neutron
absorption, and better corrosion performance
than conventional ingot cast products. ATINuShield alloys are available as flat rolled
products from ATI Allegheny Ludlum.
References
1. ASTM C1233-98, Standard Pract ice for
Determining Equivalent Boron Contents
of Nuclear Materials, American Society
Figure 6. Welded ATI 304B7P/M sheet that was bent through ~145 without cracking.
Table 9.Results of neutron attenuation testing. I/Io is the ratio of the transmitted beam to the incident beam.
Sample Thickness mm (in) Boron wt% Areal Density (g/cm2) I/Io
304-1 2.67 (.105) 0.0001 0.00038 0.938
304-2 3.30 (0.130) 0.0001 0.00047 0.867
S-1 2.72 (0.107) 1.84 0.007 0.258
S-2 3.30 (0.130) 1.80 0.008 0.217
PMP-1 6 (0.236) 1.80 0.015 0.098
PMP-2 10 (0.394) 1.80 0.026 0.063
Table 8.Typical mechanical properties of ATI 304B7P/M alloy.
Identification UTS MPa (ksi) YS MPa (ksi) Elongation % Impact J (ft-lb)
Sheet 758 (110) 335 (48) 19 N/A
Plate 738 (107) 338 (49) 24 22 (16 ft-lb)
ASTM 887-89
304B7 Grade A
515 (75) 205 (30) 17 14 (10 ft-lb)
TYPICAL EXPECTED PROPERTIES FOR SHEET 2 MM THICKNESS.TYPICAL EXPECTED PROPERTIES FOR HOT-ROLLED PLATE BETWEEN 5MM AND 12MM THICKNESS.
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for Testing and Materials, 2010.
2. International Atomic Energy Agency,
Storage and Disposal of Spent Fuel
and High Level Radioactive Waste,
Fact Sheet.
3. G. Radulescu, I.C. Gauld, and G. Ilas,
Scale 5.1 Predictions of PWR Spent
Nuclear Fuel Isotopic Compositions,
ORNL, ORNL/TM-2010/44, March
2010.
4. H.J. Goldschmidt, Effects of Boron
Additions to Austenitic Stainless Stee ls,
Journal of the Iron and Steel Insitute,
209, 1971.
5. H.J. Goldschmidt, Effects of Boron
Additions to Austenitic Stainless Stee ls.
Part II Solubility of Boron in 18% Cr,
15% Ni Austenitic Steels, Journal of the
Iron and Steel Insitute, 209, 1971.
6. E.A. Loria, and H.S. I saacs, Type
304 Stainless Steel with 0.5% Boron
for Storage of Spent Fuel, Journal of
Metals, December, 1980.
7. ASTM A887-89, Standard Speci fication
for Borated Stainless Steel Plate, Sheet,
and Strip for Nuclear Applications,
American Society for Testing and
Materials, 2010.
8. T.E. Lister, R.E Mizia, A.W. Erikson, and
B.S. Matteson, General and Localized
Corrosion of Borated Stainless Steels,
NACE, Corrosion 2008, 2008.
n n n
Table 10.Bend testing results for ATI 304B73 mm (0.125") thick sheet.
Test Specimen Transverse Longitudinal
12.7 mm radius to 180 Pass Pass
6.4 mm radius to 180 110 Pass
6.4 mm radius to 90 Pass Pass
3.2 mm radius to 90 83 77
Figure 7. 3 mm (0.125") thick ATI 304B7P/M sheet bent to 90 at a radius of 6.4 mm (0.25")
and 12.7 mm (0.5").