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CM 939 Weldable® Alloy

Conference Paper · January 2004


DOI: 10.1115/GT2004-53966

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Proceedings of ASME Turbo Expo 2004
Power for Land, Sea and Air
June 14-17 2004, Vienna, Austria

GT2004-53966

CM 939 WELDABLE ALLOY

Ken Harris, Jacqueline B. Wahl


Cannon-Muskegon Corporation
[A PCC Company]
Box 506, Muskegon, MI 49443-0506
Tel: (231) 755-1681 FAX: (231)755-4975
kharris@canmkg.com, jwahl@canmkg.com

ABSTRACT INTRODUCTION
IN 939 alloy, developed by the International Nickel Co. in IN 939 alloy (Table I [1]) was developed in the late 1960’s
the late 1960s, is a unique 22% Cr hot corrosion resistant γ’ by the International Nickel Company. This 22% chromium
strengthened, cast nickel-base superalloy. It is widely used in (Cr), hot corrosion resistant alloy has seen wide application in
industrial gas turbines for equiaxed vanes, vane segments and the industrial gas turbine (IGT) market for equiaxed vanes,
burner nozzles and is of interest to the aero turbine industry for segments and burner nozzles. (Alternate materials for these
LP and PT integral nozzles (vane rings) and high temperature applications include GTD 222 [2] and IN 738 LC). There is
turbine casings. However, IN 939 is considered difficult to also substantial interest in aero turbine engines for low pressure
weld repair without parent metal microcracking and can exhibit (LP) and pressure turbine (PT) integral nozzles (vane rings)
marginal ductility in heavy section castings. and high temperature casings (to replace Co-base X-40 alloy).
However, industry experience has found IN 939 castings in this
Cannon-Muskegon has developed a proprietary chemistry alloy difficult to weld repair due to marginal ductility and
modified version of IN 939 alloy designated CM 939 associated alloy chemistry design.
Weldable. Emphasis has been directed on optimizing aim
chemistry and ultra high purity manufacture using CM- Table I. Typical Chemistry of Alloys from
developed single crystal superalloy melting and raw material Comparable Applications
technology and subsequently on obtaining superior casting IN 939 GTD 222 IN 738 LC X-40
microstructure for improved weldability and mechanical C .15 .10 .09 .5
properties. Alloy purity and heat cleanliness will be discussed, Cr 22.5 22.5 16 25
along with a simplified two-step heat treatment cycle, resulting Co 19.0 19 8.5 Bal
in attractive microstructure, mechanical properties and repair W 2.0 2 2.5 7.5
weldability. Nb 1.0 0.8 0.8
Ta 1.4 1 1.7
Significant market interest has resulted in extensive Ti 3.7 2.3 3.5
vacuum casting experience throughout the gas turbine industry.
Al 1.9 1.2 3.5
Excellent results in terms of fluidity, casting cleanliness and
Zr .10 .012 .05
minimal microporosity have been obtained without any hot
tearing or hot cracking problems. B .01 .005 .01
Mo 1.7
Keywords: CM 939 Weldable, Ni-base Superalloy, Fe 1.5
Casting, Mechanical Properties, Weldability Mn 0.5
Si 0.5
CM 939 Weldable, CMSX-2, CMSX-3, CMSX-4, Ni Bal Bal Bal 10
CMSX-10K and CMSX are registered trademarks of the
Cannon-Muskegon Corporation

1 Copyright © 2004 by ASME


NOMENCLATURE
CM Cannon-Muskegon
GTA gas tungsten arc
HAZ heat affected zone
IGT industrial gas turbine
LP low pressure
PT power turbine
SEM scanning electron microscopy
TEM transmission electron microscopy
η eta phase

CM 939 WELDABLE ALLOY


As a result of the difficulties with standard IN 939 alloy
identified by casters in the gas turbine industry, Cannon- Figure 1. Typical As-Cast Microstructure of CM 939
Muskegon (CM) initiated work to develop a modified version Weldable Alloy
of IN 939 alloy for improved repair weldability and mechanical
properties, with emphasis on alloy ductility. A proprietary,
optimized aim chemistry, designated CM 939 Weldable alloy,
was devised and evaluated to examine the microstructure and
resulting mechanical properties, especially the anticipated
ductility improvement.

The as-cast microstructure showed minimal eta (η) phase


(Fig. 1), a undesirable Ni3(Ti,Cb,Ta) phase often found in high
Ti, Cr, Ta-containing alloys [3]. The baseline thermal treatment
consisted of a typical industry four stage heat treatment cycle
[4] which produced a very favorable microstructure (Fig. 2).
The primary γ’ size and small discrete grain boundary carbide
structure are key to obtaining good strength and alloy ductility
(Fig. 3) [5]. Note there is no evidence of eta phase in the heat
treated microstructure, which is indicative of improved alloy
stability (compared to standard IN 939). This is confirmed by a
typical PHACOMP value .11 lower than that for standard IN
939.

Figure 2. Typical Microstructure of CM 939 Weldable


Alloy following Baseline Four Stage Heat Treatment

2 Copyright © 2004 by ASME


Figure 4. Baseline Tensile Properties of CM 939
Weldable Alloy

Table III. Baseline Creep-Rupture Data –


Figure 3. SEM Photo of CM 939 Weldable Alloy CM 939 Weldable Alloy
following Baseline Heat Treatment showing Fine, Alloy Rupture Elong RA Time Time
Discrete Carbides Life, hrs % % 1% 2%
Creep Creep
816°C/207 MPa
MECHANICAL PROPERTIES CM 939 4011.4 5.4 6.3 1636.8 3000.1
Initial tensile and creep-rupture mechanical property data Weldable 3923.6 4.4 6.1 1418.1 2833.7
from equiax cast test bars of CM 939 Weldable alloy in the
GTD 222 Typ. 1510 6 13
baseline (four step) heat treat condition are shown in Tables II
and III and Fig. 4. Comparisons are made to standard IN 939 871°C/186 MPa
alloy [6] showing similar strength with improved ductility for CM 939 705.8 10.8 14.5 171.1 317.3
CM 939 Weldable. In contrast to GTD 222 [7], a weldable Weldable 690.8 8.7 15.1 151.4 305.5
high-Cr Ni-base alloy, CM 939 Weldable alloy has significantly IN 939 Typ. 645 5 5
improved strength with similar ductility.
899°C/138 MPa
CM 939 925.2 11.7 13.7 283.7 555.3
Table II. Baseline Tensile Data –
Weldable 968.8 10.4 17.4 253.7 587.0
CM 939 Weldable Alloy
Test Alloy 0.2% UTS Elong RA GTD 222 Typ. 235 8 13
Temp YS (ksi) (ksi) % % 899°C/172 MPa
20°C CM 939 107.8 163.6 10.0 10.0 CM 939 252.9 12.2 18.9 48.7 90.9
Weldable 109.0 164.4 10.4 10.7 Weldable 215.0 9.7 15.9 41.0 81.6
IN 939 Typ. 121 168 7 9 IN 939 Typ. 214 4 4
GTD222 Typ. 97 148 11 14 GTD 222 Typ. 45 14 34
760°C CM 939 89.4 127.2 6.7 8.2 927°C/83 MPa
Weldable CM 939 2674.7 12.4 12.1 1511.4 2028.4
IN 939 Typ. 100 111 2 4 Weldable 3178.6 12.5 14.7 1718.0 2309.1
GTD 222 Typ. 73 92 5 9 927°C/103 MPa
CM 939 1109.5 11.3 15.5 355.8 658.8
Weldable 1012.0 10.0 13.6 469.6 694.7

3 Copyright © 2004 by ASME


Larson-Miller curves of CM 939 Weldable rupture life shown in Table IV. As part of this study, as-cast properties
compared to vane alloy GTD 222 [7] and blade alloy IN 738LC were also assessed. Surprisingly good results were obtained in
[8] are shown in Fig. 5 and compared to Co-base vane alloy X- the as-cast condition. This will likely spur additional
40 in Fig. 6. These graphs demonstrate the strength capability examination of as-cast properties for low-stress non-rotating
of CM 939 Weldable alloy compared to alternate alloys which applications.
might compete for applications. CM 939 Weldable has a clear
strength advantage over GTD 222 and X-40 [9]. CM 939 Table IV. CM 939 Weldable Alloy Creep-Rupture
Weldable shows a debit in rupture life compared to IN 738 LC Properties in Pseudo-Production and As-cast
alloy; however, the benefit of the higher Cr (939 version) alloy Thermal Conditions
in uncoated hot corrosion resistance often is of greater Thermal Rupture Elong RA Time Time
importance in service applications [10]. Condition Life, hrs % % 1% 2%
Creep Creep
923°C/179 MPa
Pseudo- 62.1 6.3 12.1 38.8 50.4
Production 66.6 8.2 12.3 46.5 56.2
As-cast 58.7 7.0 11.7 39.7 49.6
56.1 6.8 10.8 37.4 47.3
899°C/234 MPa
Pseudo- 55.8 5.5 9.2 38.8 48.6
Production 57.4 5.6 10.5 41.4 50.1
As-cast 57.5 7.3 11.4 38.2 48.9
56.6 7.1 11.6 35.9 46.9
Figure 5. Baseline Stress-Rupture Life of CM 939
Weldable Alloy vs. GTD 222 and IN 738 LC
A number of alternate heat treatments were also examined.
The most promising thermal cycle is a simple, two-step heat
treatment, 1160°C (2120°F)/ 4 hours air cool + 845°C
(1553°F)/20 hours air cool [11]. An obvious benefit of this
heat treatment is the economic advantage of a simple, shorter
thermal cycle. A technical advantage was also observed:
properties that meet or exceed the baseline (four step) heat
treatment mechanical properties for rupture life and tensile
strength while maintaining reasonable ductility (Tables V and
VI and Fig.7). In addition to overall improvement in rupture
life, time to 1% creep dramatically increased with this thermal
processing.

Table V. CM 939 Weldable Alloy Tensile Properties


(Two Step Thermal Cycle)
Test Temp 0.2% YS UTS (ksi) Elong. % RA %
Figure 6. Baseline Stress-Rupture Life of CM 939
(ksi)
Weldable Alloy vs. X-40
20°C 132.9 165.9 4.1 5.1
HEAT TREATMENT OPTIONS 137.5 164.5 4.2 5.5
Once the ductility improvement goal of CM 939 Weldable 427°C 123.2 154.8 6.5 10.0
alloy was validated, further evaluation of alternate thermal 125.3 162.3 7.1 10.5
treatments were undertaken. The first variation was to 593°C 120.7 156.1 8.2 11.5
determine the effect of incorporating a 1080°C (1975°F) 117.4 159.3 10.0 13.1
coating diffusion cycle often necessary in the production 760°C 120.4 145.0 6.0 8.3
manufacturing process and to establish relevant heat 124.0 147.4 4.3 5.9
qualification (short duration) test conditions. 843°C 104.4 115.0 6.8 8.7
104.1 114.9 6.0 9.2
A five step, pseudo-production thermal cycle was
evaluated and representative short duration properties are

4 Copyright © 2004 by ASME


Table VII. CM 939 Weldable Alloy Tensile Properties
(Two Step + 1080°C Thermal Cycle)
Test Temp 0.2% YS UTS (ksi) Elong. % RA %
(ksi)
Room 130.9 174.9 6.6 11.0
20°C 130.7 177.0 8.2 9.2
427°C 121.1 159.8 9.0 14.1
124.3 156.8 6.1 9.9
593°C 119.5 151.7 7.6 13.5
119.7 156.5 8.2 14.5
760°C 120.7 144.9 4.8 6.5
121.0 144.6 3.8 7.4
843°C 104.5 111.2 4.0 6.2
99.6 110.0 6.4 7.4

Figure 7. Tensile Properties of CM 939 Weldable Alloy


with Two Step Thermal Cycle

Table VI. CM 939 Weldable Alloy Creep-Rupture Table VIII. CM 939 Weldable Alloy Creep-Rupture
Properties (Two Step Thermal Cycle) Properties (Two Step + 1080°C Thermal Cycle)
Test Rupture Elong RA Time 1% Time 2% Test Rupture Elong RA Time 1% Time 2%
Condition Life, hrs % % Creep Creep Condition Life, hrs % % Creep Creep
816°C/ 5197.1 2.0 2.9 5155.9 816°C/ 4758.1 3.1 5.0 4020.0 4663.6
207MPa 5156.9 2.3 2.6 4952.2 207MPa 4807.1*
871°C/ 893.7 6.3 10.8 686.3 792.9 871°C/ 999.8 9.3 12.7 697.6 821.3
186 MPa 1013.7 7.4 8.5 777.1 912.8 186 MPa 875.6 6.7 9.3 651.5 777.1
899°C/ 1177.9 10.3 14.1 777.0 952.7 899°C/ 1038.7 7.3 12.7 718.7 874.6
138 MPa 1085.1 10.1 14.8 702.1 866.5 138 MPa 943.3 6.5 10.0 718.2 844.1
899°C/ 380.5 11.2 11.5 262.3 306.8 899°C/ 385.5 11.4 16.4 265.8 306.9
172 MPa 447.3 7.4 16.3 325.2 381.8 172 MPa 343.9 5.6 11.9 269.2 308.2
430.2 12.2 19.3 291.8 342.2 927°C/ 2327.9 8.6 11.1 1374.9 1880.4
422.6 10.8 16.6 283.1 333.7 83 MPa 1900.6 4.6 5.7 1411.5 1783.0
927°C/ 2424.8 5.6 5.9 1705.2 2160.4 927°C/ 1008.8 9.2 12.6 646.2 800.7
83 MPa 2192.8 4.7 4.8 1582.3 1994.7 103 MPa 951.1 7.2 10.3 605.2 787.1
927°C/ 1042.6 6.7 6.6 718.1 889.3 * Test in progress at time indicated
103 MPa 916.9 6.6 11.3 655.3 812.8

Evaluation of the 1080°C (1975°F) simulated coating cycle METALLOGRAPHIC EVALUATION


added to the two step heat treatment (i.e., 1160°C (2120°F)/4 Due to the unusual improvement with the two step and two
hours air cool + 1080°C (1975°F)/4 hours air cool + 845°C step + 1080°C thermal cycles, the microstructures following
(1553°F)/20 hours) showed similar tensile data with a slight these heat treatments were examined. The typical SEM
reduction in rupture life (Tables VII & VIII). microstructures are presented in Figs. 8 and 9 and show blocky
carbides along the grain boundaries. It was difficult to resolve
Ductility is consistently favorable compared to standard IN the γ’ phase with standard metallographic techniques.
939 at all test conditions.

5 Copyright © 2004 by ASME


Figure 10. High Magnification SEM Microstructure of
CM 939 Weldable Alloy following Two Step Thermal
Cycle and Electro-Etching/Electro-Polishing

Figure 8. Typical SEM Microstructure of CM 939


Weldable Alloy following Two Step Thermal Cycle

Figure 11. High Magnification SEM Microstructure of


CM 939 Weldable Alloy in Dendrite Core following
Two Step Thermal Cycle + 1080°C and Electro-
Etching/Electro-Polishing

Figure 9. Typical SEM Microstructure of CM 939


Weldable Alloy following Two Step + 1080°C Thermal
Treatment

Subsequently, the samples were subjected to an electro-


polish and electro-etching procedure (at the Howmet Research Figure 12. High Magnification SEM Microstructure of
Corporation Laboratories) and examined by SEM at high CM 939 Weldable Alloy near Grain Boundary
magnification [12]. The two step thermal treatment sample following Two Step Thermal Cycle + 1080°C and
exhibited a very fine, uniform γ’ distribution (Fig. 10). The two Electro-Etching/Electro-Polishing
step + 1080°C sample shows a slightly finer γ’ distribution in
the dendrite core (Fig. 11), with a bi-modal γ’ distribution near
the grain boundary (Fig. 12).

6 Copyright © 2004 by ASME


(a) (a)

(b) (b)

(c) (c)
Figure 13. Bright Field TEM Images of γ’ Precipitates Figure 14. Bright Field TEM Images of γ’ Precipitates
at a) 260,000x, b) 160,000x and c) 52,000 x for Two at a) 120,000x, b) 89,000x and c) 52,000 x for Two Step
Step Thermal Cycle CM 939 Weldable Sample + 1080°C Thermal Cycle CM 939 Weldable Sample

7 Copyright © 2004 by ASME


TEM ANALYSIS
The deep etching technique utilized to resolve the γ’ gives
the appearance of greater volume fraction γ’ phase than is
typical or expected for this alloy. It was suspected that this is a
3D effect. To verify this, transmission electron microscopy
(TEM) examination of these samples was undertaken at the
University of Cambridge to characterize the volume fraction,
size, shape and distribution of the γ’ phase in these two
samples.

TEM specimens were prepared and examined using both


bright field and dark field diffraction conditions. To ensure a
representative sampling of the microstructure, six TEM foils
were made from each specimen. Typical TEM images are
shown in Figs. 13 and 14 [13].

For the two step thermal cycle sample, a fine unimodal Figure 15. Typical Microstructure of the Fusion Line
distribution of spherical γ’ precipitates was observed. The area and HAZ of C 263 Weld Deposit on CM 939 Weldable
fraction γ’ phase was calculated to be 36%, with an average γ’ Alloy Test Coupon
precipitate diameter of 51 nm. The two step + 1080°C sample
exhibited a bimodal distribution of spherical γ’ with average Follow-on welding trials evaluating the contribution of a
particle diameters of 261nm and 42 nm. A slightly higher area pre-weld overage thermal treatment and the two step heat
fraction of 43% γ’ was observed in this sample. treatment cycle are in progress. Based on the previous results,
manual GTA single and double layer welds were carried out
These microstructures parallel earlier metallographic/ using 60A weld current and C263 weld wire. Preliminary data
mechanical property evaluations, which noted that a fine γ’ indicates no evidence of HAZ cracking. Post weld heat
precipitate phase can improve strength in IN 939 alloy, at the treatment and further inspections, including metallography, are
expense of some reduction in ductility [10]. in progress.

WELDABILITY Further validation of alloy weldability is reported from


The feasibility of weld repair on castings produced from multiple casters who have routinely repair welded castings with
CM 939 Weldable alloy using gas tungsten arc (GTA) welding no indication of cracking problems.
has been examined by TWI Ltd. (Cambridge, UK). The initial
study was conducted on specimens subjected to the baseline PRODUCTION MANUFACTURING
four step thermal cycle. It is recognized that this is a non- Scale-up to production included manufacturing 23 5000#
typical condition for weld repair. In practice, weld repair and 15,000# heats of this alloy. In addition to optimizing the
would normally take place after a post-cast annealing aim chemistry, a critical factor in the ongoing success observed
treatment. However in this iteration, it was desired to evaluate with this alloy modification is utilization of Cannon-Muskegon
the material in the thermal condition in which the mechanical melting technology to produce premium quality alloy with
properties were generated to correlate the ductility of the alloy extremely low trace, tramp and gas levels for critical elements,
to the occurrence (or non-occurrence) of weld microcracking. such as S, P, N, O, Si and Fe (Table IX).

Bead on plate welding trails were carried out without pre- Table IX. CM 939 Weldable Alloy Critical Purity
heat. Single and double layer welding procedures, adopting a Results on Production Heats
stringer bead technique, were performed using two heat input Heat [N] [O] S P Si Fe
levels (40A [0.09-0.12kJ/mm] and 60A [0.15-0.20kJ/mm) and ppm ppm ppm ppm % %
two welding consumables (Alloy 625, for ductility and 4V1175 4 4 1 <10 <.02 .030
Nimonic 263, for higher weld strength). The samples were 4V1015 6 2 1 <10 <.01 .038
examined by fluorescent penetrant inspection (for the presence 6V1832 5 3 3 <15 .01 .044
of surface breaking defects) and metallographically in both the 6V1977 7 4 1 <15 .02 .039
as-welded and post weld heat treated condition. No evidence 6V2033 6 3 1 <15 .01 .040
of heat affected zone (HAZ) cracking was found on any weld 6V2103 4 3 1 <15 <.01 .038
repair coupons. Typical microstructure of a welded sample 6V2104 3 3 1 <15 <.01 .041
HAZ and fusion line is shown in Fig. 15 [14].

8 Copyright © 2004 by ASME


This technology was originally developed and REFERENCES
implemented by CM for superior quality single crystal alloys, [1] Bridges, P.J., Badger, P.J., Tottle, L.G. and Shaw,
such as CMSX-2, CMSX-3, CMSX-4, CMSX-10K and S.W.K., 1975, “Metallography of IN-939 A New Cast High
CMSX-10N utilized in the most demanding applications of Temperature, Corrosion Resistant Alloy,” Technical Publication
hot section gas turbines for advanced aero and IGT engines. No. P-BL. 292, International Nickel Limited, European
Key manufacturing/process considerations include raw material Research and Development Centre.
selection and control (to preclude the introduction of tramp
elements, gases, etc.), design of melting equipment and detailed [2] GTD-222 U.S. Patent #4,810,467 [GE].
manufacturing practices and procedures (to optimize the
vacuum induction refining process and ensure product [3] Muzyka, D.R., 1972, The Superalloys, John Wiley &
consistency), and advanced ceramic lining and tundish Sons, New York, pp.125-127, Cap. 4.
technology (to minimize reactivity and prevent ceramic
impurities). Implementation of CM alloy manufacturing [4] Shaw, S. [INCO] – Personal Conversation
capability on CM 939 Weldable alloy enhanced the
improvements achieved through optimized chemistry aims and [5] Cutler, C.P. and Shaw, S.W.K., 1979, “The
tight ranges. This technology has also enabled the transition to Interrelationship of γ’ Size, Grain Size and Mechnical
cost-effective blend heats without a reduction in casting yield Properties in IN-939, a Cast Nickel-Base Superalloy,”
or quality. Technical Publication No. P-BL. 378, INCO Europe Limited,
European Research and Development Centre.
CASTING EXPERIENCE
Extensive casting experience has been obtained at [6] Stickler, R., Osgerby, S. and Gibbons, T.B., May 1981,
numerous casting facilities on varied configurations. Results “European Concerted Action COST 50 – Materials for Gas
obtained indicate excellent fluidity with minimum repair and/or Turbines, Summary of the Properties and Characteristics of IN
yield issues (low microporosity with no apparent hot tearing or 939” Issue 1.
hot cracking problems).
[7] Cannon-Muskegon/Precicast S.A. Internal Data
SUMMARY
CM 939 Weldable alloy is a proprietary, modified [8] Department of Defense Aerospace Structural Metals
chemistry version of the hot corrosion resistant alloy IN 939. Handbook #5, Mar. 1984, Code 4217 IN-738, Section 3.04
The alloy has been developed to improve the repair weldability
and mechanical properties (particularly alloy ductility) for [9] Department of Defense Aerospace Structural Metals
application in large IGT vane segments, integral nozzles (vane Handbook #5, Dec. 1985, Code 4305 X-40/X-45, Section 3.04
rings) for aero and industrial gas turbines, and high temperature
capable (870°C) combustor and turbine casings, transition [10] Gibbons, T.B. and Stickler, R., 1982, “IN939:
ducts, heat shields, burner nozzles and turbine exit casings. Metallurgy, Properties and Performance,” High Temperature
Alloys for Gas Turbines 1982, R. Brunetaud et al., eds., D.
CM 939 Weldable demonstrates comparable strength to IN Reidel Publishing Company, Dordrecht, Holland, pp.369-393.
939 alloy, with improved ductility. Further improvements in
strength have been realized through a simple, economical two [11] McColvin, G.M., 1979, COST 50/2 UK 6 Henry
step heat treatment, that maintains reasonable ductility. Repair Wiggin, Report 3250.
weldability has been demonstrated through both welding trials
on sample coupons and caster experience on actual [12] Gu, B.P., 2004, “SEM Images of Gamma Prime Phase
components. Additional assessment of weldability in alternate in Samples LA-9581 & LA-9645,” Howmet Research
thermal conditions is ongoing. Corporation/Cannon-Muskegon Internal Report - Private.

Castability has been demonstrated through numerous [13] Tin, S., 2004, “TEM Analysis of LA 9645 & LA
evaluations and production applications within the casting 9581,” University of Cambridge/Cannon-Muskegon Internal
industry. Data – Private.

ACKNOWLEDGMENTS [14] Mulligan, S.J. and Gittos, M.F., 2002, “Weld Repair
Dr. Jean Pierre Zanghi, Precicast SA Feasibility of Modified IN 939 Castings,” TWI Report No:
Stephen Mulligan, TWI Ltd. 13895/1/02, Cannon-Muskegon – Private.
Bo Ping Gu, Howmet Research Corporation
Dr. Sammy Tin, University of Cambridge

9 Copyright © 2004 by ASME

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