STATE OF P91 STEEL FABRICATION IN INDIAN INDUSTRIES

DDN VERMA

General Manager – Quality Management (Welding & NDT), DEE PIPING SYSTEMS LTD., Prithla
– Tatarpur Road, Palwal, Haryana, India – 121102

ABSTRACT
Steam-temperature & pressure exiting S/H (Super heater) of a high capacity boiler is ~ 570
°C - 600 °C & 170 - 230 bar respectively. Final S/H & Pipes carrying steam to turbine must
withstand this extreme temperature & pressure. P91, presently is one such heat & creep
resistant material in power-industries. Equated to its predecessor; the grade 22, ‘Modified
P91’ exhibits high strength up to ~ 600 °C. It’s oxidation resistance confines are higher &
authorizes plant designers to plan components with lesser thickness contributing a higher
thermal fatigue life of ~ ten times. .

Grade 91 steel is absolutely intolerant to variations in its microstructure, unlike Grade 22 or

other grades. Any working on the steel would necessitate a precise heat treatment in order to
reinstate the lost microstructure back to its original conditions. In spite of all challenges &
confronts, the power-industry world-wide has embraced P91 today & the use of this steel
continues, & will continue to its successful journey.

This paper presents characteristic attributes of Grade 91 metallurgy & fabrication in Indian
industries including recent design considerations of this steel, welding, Heat Treatment,
influence of Delta ferrite, microstructures, SCC (Stress Corrosion Cracking)etc..

Key Words:Design of P91, Microstructure, Welding interruptions, Dissimilar welds, Delta Ferrite,
Type IV Cracks.

1.0 INTRODUCTION

Basic modification to the standard 9Cr1Mo alloy which generated Grade 91 involved a
controlled addition of vanadium, niobium and nitrogen. These elements impart precipitation
strengthening by formation of M23C6 carbides and MX (Nb,V) carbonitrides, which, in
addition to modest solid solution strengthening, produce an alloy with substantially greater
creep strength than the plain 9Cr1Mo steels.

The Nickel and Manganese content, even though in smaller percentages, have profound
effects on the critical temperatures & all heat treatments. Because of this, the composition of
the welding electrodes used should be in line with the parent material.

2.0 EXPERIENCES WITH GRADE 91

DDEL initiated fabrication of Grade 91 and other CSEF steels way back in the year 2007&
till date we have completed ~ 30-40,000 metric tons of fabrications in CSEF steels.
Experience says there have been little difference between what “theory” had predicted what
we actually encountered during fabrication & service of Grade 91 steel components.

Though already practiced in the USA [Ref. No.:1], there is a need for a programme in India
to specify scope of work required to address critical issues associated with the use of these
CSEF steels. The issues to be addressed are listed as below:
  Material procurement,
 Shop fabrication,
 Field erection,
 Appropriate quality assurance procedures to be applied during each of these phases of
implementation,
 Examination of in-service behaviour of both base and weld metal, with a particular
emphasis on provision for a comprehensive life assessment programme
 Optimization of maintenance etc..

This paper presents various aspects of P91 metallurgy & fabrication in Indian industries
including the recent reassessment of design-considerations of the steel [particularly with
respect to titanium], welding, Heat Treatment, effects of Delta ferrite, dissimilar welds,
Type IV Cracking, SCC etc..

3.0 REVISITING DESIGN OF P91

Under this section, we are going to discuss the state of a proposed modification in the present
Grade 91 steel particularly with respect to addition of Ti, Mn, N & Al [REF. No.:2].

Titanium produces stable carbides resulting in higher creep strength, long term
microstructural stability, and improved oxidation resistance by saving Chromium. With a
titanium content under 0.05 %, the desired effect cannot generally be obtained. However,
with a titanium content over 0.2 %, excessively large carbides may result in the matrix. These
large carbides are deleterious to mechanical properties as they typically act as stress
concentration risers. Therefore, the titanium content should be limited to within the range
0.05-0.2 wt. %, and preferably 0.05-0.15 wt. %. Note the proposed changes in the Ti content.
Max. Ti in the P91 is 0.01 % compared to the presently proposed Ti content of 0.05 – 0.15%.

Nitrogen (N):

Nitrogen, when present, combines with vanadium and niobium to form carbonitrides, which
are effective to improve creep strength. However, with a nitrogen content over 0.07 wt. %,
the formability and weldability are degraded. Therefore, nitrogen content should be limited to
less than 0.07 wt. %, and preferably 0.05 wt.% or less. Presently nitrogen content specified in
Grade 91 is 0.03-0.07%.

3.1 TITANIUM, THE DUAL CARBIDE FORMER

The Ti modified 9Cr-1Mo steel being discussed here exploits the propensity of “Ti” to form
high solubility stable carbides, wherein TiC [Titanium Carbide] is present as both primary
and secondary TiCs. The simultaneous presence of these two TiCs within the newly modified
9Cr-1Mo steel greatly increases its Creep and Oxidation Resistance over that of ASTM P91
and ASTM P92. Primary TiC are relatively large (0.5-3 µm) and are formed during steel
production prior to the heat treatment. Secondary Tic’s are relatively smaller and measure ~
(5-50 nm). Ti-modified 9Cr-1Mo steel thus contains secondary TiC and primary TiC in a
secondary to primary ratio of ~ 1:1 [Ref. No.:2].

The secondary TiC assists in maintaining a higher level of chromium in the finished steel for
increased oxidation resistance, and strengthens the novel heat treated material by impeding
the glide and climb of matrix phase dislocations throughout the microstructure.
This primary TiC controls grain growth by pinning grain boundaries and increasing grain
boundary strength and cohesion. The primary TiC resists its dissolution & also resists
austenitic grain growth at high temperatures during initial solidification, subsequent heat
treatments, and processes producing heat-affected zones, such as welding.

The novel 9Cr-1Mo steel described herein further generates secondary TiC thro’
‘Austenization’ & ‘Tempering’. Austenization is conducted in such a manner that ~ ½ of the
primary TiC is dissolved and Ti & C are placed in solution. During tempering, the titanium
precipitates out from solution forming secondary TiC homogeneously distributed throughout
the matrix of the alloy.

3.2 AUSTENIZATION

Heating the 9 Cr-1 Mo steel composition to a specific quench temperature serves two primary
purposes:

 Creating an austenite phase thereby enabling subsequent martensitic transformation,

 Dissolution of ~ 50% of the primary TiC in austenite to place Ti & C in solution prior
to rapid cooling. Typical austenization temperature is ~ 10500 C for ASTM P91 and
ASTM P92.

However, in Ti-modified 9 Cr-1 Mo steel, because dissolution of ~ 50% of the primary

TiC is required, and also because TiC has extremely low solubility at 10500 C, a higher
dissolution temp. than 10500 C is necessitated. The requisite temperature for a given
composition is determined thro’ computational simulation using a Material-Development
Software, namely THERMO-CALC.

An austenization temperature of ~ 1250+/-200C was maintained for ~ ten minutes [Ref.

No.:2]. This is sufficient for dissolution of ~50% of the primary TiC to dissolve Ti& C in
Austenite.

3.3 INSTANT COOLING AFTER AUSTENIZATION

Subsequent to austenization of the Ti-modified 9Cr1Mo steel to dissolve ~ 50% of the

primary TiC, it’s rapidly cooled. Rapid cooling serves two primary purposes:

 it produces martensite, and

 it suppresses the formation of secondary TiC particles which require both diffusion
and time unlike the martensite.

At cooling rates exceeding 20C/s the Ti-modified 9 Cr-1 Mo steel composition rapidly
reaches a temperature where the diffusivity of titanium is largely insufficient for
significant precipitation of TiC dispersions.

3.4 TEMPERING

Subsequent to instant cooling, the Ti-modified 9 Cr-1 Mo steel composition is tempered at a

temperature exceeding the anticipated service temperature of the steel.

Tempering serves two primary purposes:

 (i) rearrangement of the martensite microstructure to form ferrite, and
(ii) precipitation of secondary TiC.

The strong affinity of Ti for C results in preferential formation of the secondary TiC and
reduces the chances for formation of Chromium Carbides. This facilitates higher level of
chromium available for oxidation resistance. Additionally, the secondary TiC strengthens the
metal by impeding the movement of dislocations through the crystal structure.

4.0 ASSESSMENT & EVALUATION OF Ti

Ti-MODIFIED
MODIFIED 9Cr1Mo STEEL

4.1 OXIDATION-KINETICS

Oxidation rates of both the newly developed TiTi-modified 9Cr-1Mo

1Mo steel & the ASTM P91 &
P92 were examined & compared as a function of time in FIG. 1 [Ref. No.:2].. Each alloy
showed a parabolic oxidation
dation rate, and the mass gain of both specimens were due primarily to
growth of oxidation scale on the surface.

Fig.1: Oxidation rates of both the newly developed Ti

Ti-modified 9Cr-1Mo
1Mo steel & the ASTM
P91 [Ref. No.2].

The total mass gain of the Ti-modified

modified 9Cr-1
9Cr 1 Mo steel was ~ 5 times lower than that of
ASTM P91 !!!

4.2 TENSILE STRENGTH

Ti-modified 9Cr-1Mo
1Mo steel samples were subjected to tensile tests at temperatures of 550,
0
600 & 650 C at a loading rate of 0.5 mm/min. TenTensile
sile results are shown in Table 1 [Ref.
No.2]. For comparison, Table 1 also includes published results for the average yield strength
of commercial ASTM P91 steel at the various tested temperatures.

TABLE 1: Yield Stress of Ti-modified

modified 9Cr-1Mo
9Cr Vs. ASTM P91
1 at various temperatures.

Ti-MODIFIED 9Cr- ASTM P91

1Mo
TEMP., 0 C 550 600 650 550 600 650
YIELD STRESS, MPa 406 429 346 320 260 200
Result shows the yield strength of the Ti-modified
Ti 9 Cr-1
1 Mo steel was significantly higher
than that of commercial ASTM P91 steel, demonstrating highly astonishing improvements of
~ 27% at 550, 65% at 600 and 73% at 6500 C.

4.3 LARSON-MILLER
MILLER PARAMETER (LMP)

FIG. 2: Larson-Miller
Miller Parameter of Ti
Ti-modified 9Cr-11 Mo steel with those of the
standard values for ASTM P91 and P92 [Ref. No.:2].

FIG. 2 compares the Larson-Miller

Miller Parameter of the Ti
Ti-modified 9Cr-1 1 Mo steel with those
of the standard values for ASTM P91 and P92. Figure shows the superior time-to-rupture
time
properties of the new Ti-modified
modified 9Cr1Mo steel over that of the standard ASTM P91
P9 and P92
at times & temperatures examined.

5.0 GUIDELINES ON WELDING, METALLURGY & PWHT

This section provides guidelines on metallurgy, welding & heat treatment for Grade 91 steels.
Grade 91 being a hard formulation, iit’s important to use low residual fillers.
s. It’s imperative to
use E9015-B9B9 type of electrodes for shielded metal arc welding of Grade 91 steels since
EXX15 type electrodes contain no extra iron powder in the flux-coating
flux coating as EXX18 type of
electrodes do. This eliminates at least one source of contaminants.
contaminants. In any case, it’s important
to examine for occasional ‘crater’ or “solidification” cracks in the deposited weld metals in
order to decide on their correctness [Ref. No.:4].

For P91 and P92, the following must be incorporated in the specifications
specifications[Ref.
[Ref. No.:8]
No.:8]:

 Ni + Mn content of filler metal not exceed 1.5%. Ni + Mnaffects AC1 temp. of the
filler material.
 Nickel not to exceed 0.4%.
 Manganese-to-sulfur
sulfur ratio to be greater than 50.
 Nitrogen controlled to 0.02% minimum.
 Minimum toughness of filler afteraf PWHT of 20ft-lb at 210C.

With SAW, we should prefer to use abasicfluxsinceotherfluxtypes could

burnoutcarbonandpermitelevatedoxygenandnitrogenreducingstrengthandtoughnessof
theweldmetal.
Grade 91 being ahighly-hardenablealloy,it’s susceptible to hydrogencracking. We
must use E9015-B9-H4electrode. Weld jointshouldbeallowedtocoolslowlytoatleast
900C
afterweldingiscompletedtobesurethatalltheaustenitehasbeentransformedtomartensitepr
iortoPWHT. Else, thereisriskofmartensiteformationafterPWHT resulting inhard &
brittlewelds [Ref. No.:3].

AC1 temp. can be as low as 788°C, & once this exceeds during PWHT, the weld
should be allowed to cool to below 90°C followed by reheat treating or the
condition of the joints should be evaluated using microscopic examination &
hardness testing.

Since it is not possible to perform local normalizing & tempering, it is necessary to

cut out and replace the weld joint. Alternatively, normalize and temper the entire
assembly or justify the use of the joint based on properties of the material in the
annealed condition using the allowable stress values for Grade 9 instead of those
for Grade 91 for the joint [Ref. No.:5].

Surprisingly, Grade 91 is susceptible to attack by stress-corrosion cracking [SCC] in

the as-welded condition. Though the media that causes SCC has not yet been
identified fully, however, it appears to occur if the joint gets damped. Best is to post
weld heat treat the joint immediately or keep the joint warm and dry.

Any cold deformation must be limited to not more than 10% strain in the metal, and
if this limit is exceeded, the part should be renormalized and tempered. The strain
formula is % strain = 100 r/R where R is the radius of the bend and r is the radius of
the pipe.

For dissimilar metal welds between Grade 91 and lower chrome-moly steels, filler
metals corresponding to the lower chromium grade should be used. A large
difference in chromium causes a gradient that pulls carbon out of the lower-
chromium steel causing a depleted carbon band in the lower-chromium side of the
joint. It’s is preferred to have carbon depletion in the weld side rather than in the
parent metal. In any case, it has been shown to have no significant effect on creep
behavior when heat treatment time and temperature are not excessive. It’s to note
that width of the depleted/enriched band will get increased by excessively high or
long PWHT temperatures, therefore, PHWT should be done as per requirements of
the lower-chromium steel rather than those of the Grade 91[Ref. No.:6].

For Gr. 91 steel welds to austenitic stainless, nickel-based filler metals such as
ENiCrFe-2, ENiCrFe-3 or ERNiCr-3 should be used. If stainless steel is a stabilized
grade or a low-carbon grade, the completed joint can be given standard PWHT [Ref.
No.:7]. If the stainless is not a stabilized or low-carbon grade, the P91 side of the
joint should be buttered with at least 6.00 mm of nickel-alloy weld metal and heat
treated in the normal fashion. The buttered and heat treated end can then be welded
to the stainless steel using nickel alloy filler metal without preheat or PWHT.

P91 steels should contain a fully tempered martensitic microstructure.This needs a balance
of ferrite and austenite forming elements & this compositional balance is the foundation to
achieve a fully martensitic structure free of delta ferrite. Delta ferrite reduces creep
 ductility at high service temperature. Also, notch sensitivity of delta ferrite is harmful to
the impact toughness. Thus, it is important to avoid the formation of delta ferrite in grade
91 matrix.Some facts about delta ferrite are as follows: (1) Composition is the foundation
to ensure zero delta ferrite. Zero delta ferrite in Grade 91 is possible when Cr-Ni
equivalent value is < 10, and delta ferrite may form when Cr-Ni equivalent value is ≥
10.(2) Delta ferrite may form even though Cr-Ni equivalent value < 10 due to the
segregation of element such as Si, Mo and Cr etc..(3) The delta ferrite can be avoided by
the adjustment of composition and making process [Ref. No.:9]. (4) Once existed, delta
ferrite cannot be eliminated completely, however, the morphology of it can be changed and
the quantity of delta ferrite can be decreased by hot working and heat treatment.

6.0 CONCLUSION

1. Excellent creep rupture strength of Grade 91 allows the optimum use of this
material in temperature range ranging from 540 to 6000 C.

2. Titanium modified Grade 91 Steel with better corrosion & oxidation resistance,
Creep rupture & elevated temperature tensile properties will warrant a great future.

3. The role of secondary Titanium carbides in conservation of Chromium for

enhanced oxidation resistance has been an idea of high importance.

4. Grade 91 Steel is absolutely intolerant to variations in its microstructure.

5. The lower transformation temp. as well as the martensite finishing temperature

have to be kept in mind when heat treatment like tempering or cooling from
normalizing or welding are carried out.

6. Composition is the foundation to ensure zero delta ferrite. Zero delta ferrite in
Grade 91 is possible when Cr-Ni equivalent value is < 10, and delta ferrite may
form when Cr-Ni equivalent value is ≥ 10

7. Delta ferrite may form even though Cr-Ni equivalent value < 10 due to the
segregation of element such as Si, Mo and Cr etc..

8. The delta ferrite can be avoided by the adjustment of composition and making
process.

9. Once existed, delta ferrite cannot be eliminated completely, however, the

morphology of it can be changed and the quantity of delta ferrite can be
decreased by hot working and heat treatment.

REFERENCES

[1] EPRIGuidelines and Specifications for High-Reliability Fossil Power Plants

Best Practice Guideline for Manufacturing and Construction of Grade 91

Steel Components. 2011 TECHNICAL REPORT

[2] Jablonski Paul D.,Alman David, Dogan Omer, Holcomb Gordon, Cowen
Christopher.Publication number US8317944 B1, Application number

US 13/282,211, U.S. Department Of Energy, Nov. 27, 2012.

[3] Vallourec& Mannesmann Tubes, 1999, The T91/P91 Book, 1999.

[4]William F. Newell, Jr. P.E., Grade 91, Weld Filler Metal Development, EPRI
Report.

[5] Regev, Berger & Weiss, Technion, Israel, Investigation of Microstructure,

Mechanical & Creep Properties of Weldments between T91 & T22 Steels.

[6]Wachter& Ennis, Investigation of the properties of the 9%Cr Steel of the Type
9Cr-0.5Mo-1.8W-V-Nb, ISSN 0944-2952.

[7]Henry Jefrey F, Growing Experience with P91/T91 Forcing Essential Code

Changes, Combined Cycle Journal, First Quarter 2005

[8] Team CCJ, Much more to the design and welding of high-energy piping
systems than meets the eye, Combined Cycle Journal, October 29, 2012.

[9] Hemin Jing, Bo Wang, DangshengXiong, Yingeng Xu, et. al., Effect of
Composition and Temperature on The Formation of Delta Ferrite in the Billet for
P92 Steel, Advanced Materials Research Vols 194-196 (2011) pp 1280-1286.