PWHT 2.25%Cr Steel

The new generation of CrMo(V) steel plates
base material - welding
I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 1
Content
1. Introduction
2. Application trends and resulting requirements for CrMo(V) steels

3. Metallurgical limits for PWHT- conditions
4. Processing
5. Summary

1. Introduction

„conventional“
A broad variety of CrMo(V) steels is commercially available
1Cr½Mo ASTM/ASME A/SA 387-12-1/2

EN 10028-2: 1992, 2003 13CrMo4-5
1¼Cr½Mo ASTM/ASME A/SA 387-11-1/2

EN 10028-2: 1992, 2003 13CrMoSi5-5
2¼Cr1Mo ASTM/ASME A/SA 387-22-1/2

A/SA 542-A/B-3/4/4a
EN 10028-2: 1992 10CrMo9-10

11CrMo9-10
EN 10028-2: 2003 10CrMo9-10
12CrMo9-10
2¼Cr1Mo¼V ASTM/ASME A/SA832-22V

A/SA 542-D-4/4a
EN 10028-2: 2003 13CrMoV9-10
3Cr1Mo¼V ASTM/ASME A/SA832-23V

A/SA 542-E-4/4a
EN 10028-2: 2003 12CrMoV12-10

„enhanced“

EN 10028-2: 1992, 2003 13CrMo4-5

EN 10028-2: 1992, 2003 13CrMoSi5-5

A/SA 542-A/B-3/4/4a
EN 10028-2: 1992 10CrMo9-10

11CrMo9-10
EN 10028-2: 2003 10CrMo9-10
12CrMo9-10

A/SA 542-D-4/4a
EN 10028-2: 2003 13CrMoV9-10

A/SA 542-E-4/4a
EN 10028-2: 2003 12CrMoV12-10

„new generation“

EN 10028-2: 1992, 2003 13CrMo4-5

EN 10028-2: 1992, 2003 13CrMoSi5-5

A/SA 542-A/B-3/4/4a
EN 10028-2: 1992 10CrMo9-10

11CrMo9-10
EN 10028-2: 2003 10CrMo9-10
12CrMo9-10

A/SA 542-D-4/4a
EN 10028-2: 2003 13CrMoV9-10

A/SA 542-E-4/4a
EN 10028-2: 2003 12CrMoV12-10

2. Application trends and resulting
requirements for CrMo(V) steels

Application and trends for the use of CrMo(V) steels
Application:
• typical applications are hydrotreating reactors
• operating temperatures up to 480 °C
• hydrogen partial pressures up to 180 bar or even higher

Trends:
• ever bigger and heavier reactors (already more than 1000t per unit)
• higher operating temperatures and pressures resulting in higher
wall thicknesses
• increasing demand due to expansion or new construction of plants

Special requirements for more sophisticated steels
● Increasing thickness with high demand in thickness over 100mm
● Larger dimensions to allow for more freedom in vessel design
● PWHT requirements including 3 or often even 4 cycles
● Chemical restrictions exceeding those of the standards
● Improved resistance against hydrogen
● Specifying J- and X-factor for ultra clean steels

● Specifying toughness values at low temperatures in combination with PWHT
● Additional requirements in regard to grain size and microstructure
● Hardness restrictions
● Specifying step cooling test
● Additional tensile test at elevated temperatures
● ...
Many additional requirements; often in combination

3. Metallurgical limits

for PWHT conditions

General influence of a PWHT on the mechanical properties
of CrMo-steels
Rm before Av after
Av, Rm, Rp0,2
Av before
Rp0.2 before Rm after

Rp0.2 after
Before After
PWHT PWHT
HP-Factor

Tensile- and yield strength of enhanced 2¼CrMo steels (N+AC+T)
1000
Thickness > 200 mm

900
Rp0,2 resp. Rm [N/mm2]
Tempering PWHT-Min PWHT-Max

800
740 °C/30‘ 690 °C/8h 690 °C/24h
700 12CrMo9-10

600
Rm
12CrMo9-10
500
Rp0.2
400
12CrMo9-10
300
19,8 20,0 20,2 20,4 20,6 20,8 21,0 21,2
HP-Factor

Tensile- and yield strength of enhanced 2¼CrMo (V) steels (N+AC+T)
1000
Thickness > 200 mm

900
800
+ 0,25% V
700
Rm “V-m

odified“
600
Rm “enhanced“
500
Rp0.2 “enhanced“
400
300
19,8 20,0 20,2 20,4 20,6 20,8 21,0 21,2
HP-Factor

1000
Thickness > 200 mm

900
800
700
Rm “V-m

odified“
+ 0,25% V
600
500 Rp0.2 “V-m

odified“
Rp0.2 “enhanced“
400
300
19,8 20,0 20,2 20,4 20,6 20,8 21,0 21,2
HP-Factor

1000
Thickness > 200 mm

900
Tempering PWHT-Min PWHT-Max
715 °C/250‘ 705 °C/8h 705 °C/24h
800
A542-D-4a
700
Rm “V-m

odified“
600 A542-D-4a
500 Rp0.2 “V-m

odified“
400 A542-D-4a
300
19,8 20,0 20,2 20,4 20,6 20,8 21,0 21,2
HP-Factor

Estimated impact toughness of
enhanced 2¼CrMo(V) steels (N+AC+T)
350 350
Thickness > 200 mm Thickness > 200 mm

300 300
+20 °C
250 250
Impact Toughness [J]

Impact Toughness [J]
+20 °C
0 °C
0 °C

200 200
150
2¼CrMo 150
-20 °C 2¼CrMoV
-40 °C
-20 °C
100 100
-60 °C
50 50
-40 °C
0 0
19,8 20,0 20,2 20,4 20,6 20,8 21,0 21,2 19,8 20,0 20,2 20,4 20,6 20,8 21,0 21,2
HP-Factor HP-Factor

SA 387-22-2: Feasibility in dependence of HP, Rm, Re, Ch-V,
hardness and plate thickness of 2¼CrMo steel
21,2 21,2
21,0
Average ≥ 31 J
21,0
N+AC+T 195 HB
20,8 20,8
200 HB 195 HB 190 HB 200 HB

20,6 20,6
N+AC+T 20,4
205 HB
Hollomon parameter
20,4
Hollomon parameter
N+T -40 °C N+T

20,2 20,2
205 HB
20,0
-29 °C 20,0
-18 °C -18 °C u. -29 °C 210 HB 210 HB

19,8 19,8
19,6 19,6
-10 °C 215 HB
19,4 19,4 215 HB
19,2 19,2
19,0 19,0
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200
Plate thickness [mm] Plate thickness [mm]

2¼ CrMo(V), Q + T, plate delivery dimensions of Dillinger Hütte GTS
250
up
225 on
ag
ree
me
200
nt
up
to
175 42
t
N + AC + T
Thickness[mm]
150
(Q + T) As rolled

125
up to 37 t
(plates for
100
hot-forming)
75
Depending on grade & thickness up to 37 t up to 37 t
50
up to 28 t
25
0
1,50 1,75 2,00 2,25 2,50 2,75 3,00 3,25 3,50 3,75 4,00 4,25 4,50 4,75 5,00 5,25
Width [mm]
Maximum thickness is often limited by requirements from specifications

Conclusion 1
• CrMo steels with ¼V offer improved performance for petro-

chemical reactors compared to enhanced 2¼Cr1Mo steels.
• Plates are commercially available up to about 250 mm thickness.

The steels tolerate very high temperatures 690 - 710 °C for post
weld heat treatment.
• DH-GTS is a long term supplier with plenty of know how for

highly sophisticated steels
• A wide range of dimensions can be supplied.

4. Processing

4. Processing - Index
4.1 Reference to API 934 - Recommended Practice
4.2 Impact toughness requirements test conditions
4.3 Step cooling
4.4 Flame cutting
4.5 Forming and subsequent thermal treatment
4.6 Welding

– Weld design
– Welding procedure qualification
– Production testing
– Preheat and minimum interpass temperature
– HAZ-hardness
– Welding consumables
– Production tests
4.7 Post weld heat treatments
– Intermediate post weld heat treatments
– PWHT - „final PWHT”
Title and introduction of API 934
API recommended practice 934 : 2000

Materials and Fabrication Requirements for 2¼ Cr-1Mo & 3Cr-1Mo
Steel Heavy Wall Pressure Vessels for High Temperature, High
Pressure Hydrogen Service *
“....Introduction

This recommended practice applies to new heavy wall pressure vessels in
petroleum refining, petrochemical and chemical facilities in which hydrogen
or hydrogen-containing fluids are processed at elevated temperature and
pressure.
Materials covered by this recommended practice are conventional steels
including standard 2-¼Cr-1Mo and standard 3Cr-1Mo steels, and advanced
steels including enhanced 2-¼Cr-1‘Mo, 2-¼Cr-1Mo-¼V, 3Cr-1Mo-¼V-Ti-B,
and 3Cr-1Mo-¼V-Cb-Ca steels. The interior surfaces of these heavy wall
pressure vessels may have an austenitic stainless steel weld overlay to
provide additional corrosion resistance. ...”

Impact test - step cooling
Additional to the PWHT condition impact tests are

required after “step cooling”:
on the base material (each heat)

•on welding consumables (each batch)

•on HAZ
for the qualification of welding procedures

and the verification on production welds
What is step cooling and why is it applied ?

impact transition curve
impact
energy before service
after high
temperature service

54J
∆T
test temperature
Service embrittlement - step cooling
trace elements are responsible
Parent material
J = (Si + Mn) x (P + Sn) x 1000

Weld metal
X = (10P + 5Sb + 4Sn + As) / 100 API 934 X < 15
harmful elements must be restricted to provide good

toughness properties through the life time.

Step cooling - heat treatment
1 6 °C/h
2 6 °C/h
3 6 °C/h
Heating 4 3 °C/h
rate 5 28 °C/h
56°/h

316°C
1h 15h 24h 60h 100h

6h 6h

Step cooling- impact transition curve
impact
after
energy initial
step
cooling

after service
54J
∆TSC ∆Ttot
∆Ttot = 2.5 x ∆TSC
test temperature
4.6 Welding

HAZ hardness comparison of CrMo- and CrMoV-steel
HV10
400
2¼CrMo¼V
as welded

2¼CrMo
as welded
250
usual range cooling time t8/5

Coarse grained HAZ microstructure
For the usual welding

conditions we obtain
Martensite in the
coarsed grained HAZ
and
high as welded

hardness
~400 HB
as welded coarse grained HAZ

t8/5 22s - essentially Martensite
Cold forming
Bend test to check cold forming
(cross section 200 x 50 mm) with severe
deformation
•no cracks on the machined side even for
bending at ambient temperatur
• a small crack in the flame cut edge after
bending at 170°C

Hydrogen induced cold cracking
Weld metal and HAZ in the as welded condition are

susceptible to hydrogen induced cold cracking
how to avoid this defect ?
• dry and clean weld bevels
• select low hydrogen consumables and treat them properly
to minimise hydrogen input (rebaking, storage, heated

quivers ...)
• keep the weld at sufficiently high temperatures until the
weld is completed (>180°C)
• lower the concentration of residual hydrogen by heat
treatment immediately after welding (300-350°C)
• lower the hardness and cracking susceptibility by PWHT
(~700°C) or „intermediate PWHT“ (~650-670°C)
HAZ hardness comparison of CrMo- and CrMoV-steel
HV10
400 2¼CrMo¼V
as welded
650°C-10h

675°C-10h
2¼CrMo
as welded
250 650°C-10h
235 700°C-10h
725°C-10h 675°C-10h
700°C-10h
usual range cooling time t8/5

Development of carbides during PWHT

0,5µm 0,5µm 0,5µm
As welded 620°C - 15’ 730°C - 8h

no carbides M3C few M23C6 M7C3, M23C6,
TEM micrographs on carbon extraction replica 21/4CrMoV fine V4C3, M2C
Ref.: Lundin,C.D. and K.K.Khan, WRC Bulletin 409
5. Summary

Summary
• Parent metal toughness: sufficient safety margin against the requirements

at -29°C and taking into account the step cooling. Limited step cooling
embrittlement is achieved by extremely low level of trace elements.
• HAZ toughness: after PWHT impact at -29°C and “after lifetime” at +10°C
satisfactory thanks to ultra low trace elements.
• HAZ hardness 248HV10 (235 HB) is achieved by proper PWHT at 705°C
• 235HV10 is difficult to achieve

• weld metal toughness: Very few potential suppliers. Rather important
scatter of impact results at -29°C, and at +10°C after “lifetime” more difficult
than for CrMo-Steel. (with regard to the lowest anticipated service
temperature some relaxation should be possible). Development is ongoing.
• hydrogen induced cracking can safely be prevented -> needs good
workmanship, careful personal and well controlled processing conditions
• PWHT for 8-10 hours 705°C - 710°C is experienced to be the best

compromise for the properties in the welded construction. In case of
repeated PWHT the sum of holding times shall not exceed 24 h.
Thank you for your attention

and welcome to our workshops

PWHT 2.25%Cr Steel

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The new generation of CrMo(V) steel plates

base material - welding

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

2. Application trends and resulting requirements for CrMo(V) steels

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 2

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

1Cr½Mo ASTM/ASME A/SA 387-12-1/2

1¼Cr½Mo ASTM/ASME A/SA 387-11-1/2

2¼Cr1Mo ASTM/ASME A/SA 387-22-1/2

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

2¼Cr1Mo¼V ASTM/ASME A/SA832-22V

3Cr1Mo¼V ASTM/ASME A/SA832-23V

The new generation of CrMoV-steel plates - base material, welding 4

1Cr½Mo ASTM/ASME A/SA 387-12-1/2

1¼Cr½Mo ASTM/ASME A/SA 387-11-1/2

2¼Cr1Mo ASTM/ASME A/SA 387-22-1/2

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

2¼Cr1Mo¼V ASTM/ASME A/SA832-22V

3Cr1Mo¼V ASTM/ASME A/SA832-23V

The new generation of CrMoV-steel plates - base material, welding 5

1Cr½Mo ASTM/ASME A/SA 387-12-1/2

1¼Cr½Mo ASTM/ASME A/SA 387-11-1/2

2¼Cr1Mo ASTM/ASME A/SA 387-22-1/2

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

2¼Cr1Mo¼V ASTM/ASME A/SA832-22V

3Cr1Mo¼V ASTM/ASME A/SA832-23V

The new generation of CrMoV-steel plates - base material, welding 6

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 8

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

Many additional requirements; often in combination

The new generation of CrMoV-steel plates - base material, welding 9

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 10

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 11

Thickness > 200 mm

Tempering PWHT-Min PWHT-Max

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 12

Thickness > 200 mm

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 13

Thickness > 200 mm

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

500 Rp0.2 “V-m

The new generation of CrMoV-steel plates - base material, welding 14

Thickness > 200 mm

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

500 Rp0.2 “V-m

The new generation of CrMoV-steel plates - base material, welding 15

Thickness > 200 mm Thickness > 200 mm

Impact Toughness [J]

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

The new generation of CrMoV-steel plates - base material, welding 16

200 HB 195 HB 190 HB 200 HB

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium

-18 °C -18 °C u. -29 °C 210 HB 210 HB

Plate thickness [mm] Plate thickness [mm]

The new generation of CrMoV-steel plates - base material, welding 17

I. Detemple and F. Hanus, Dillinger Pressure Vessel Colloquium