Cast Stainless Steel Technology Developments

Raymond Monroe SFSA

CN3MN

CF8 CD4Cu
CA 15

CB 7 Cu

Calculation of Chromium Equivalent and Nickel Equivalent

CrE = %Cr + 2 %Si + 1.5 %Mo + 5 %V NiE = %Ni + 0.5 %Mn + 30 %C + 0.3 %Cu

Ferrite from Chemistry

Schoefer Diagram
2.2 2.1 2 1.9 1.8

1.7 1.6 1.5 1.4 1.3 1.2 1.1 1 0.9 0.8 0 10 20 30 40 50 60 70 Volume Percent Ferrite
Cr e Cr (%) + 1 . 5 Si (%) + 1 . 4 Mo (%) + Nb (%) 4 . 99 = Ni e Ni (%) + 30 C (%) + 0 . 5 Mn (%) + 26 ( N 0 . 02 %) + 2 . 77

Chemistry: C=0.07, Mn=0.56, Si=1.30, P=0.028, S=0.009, Cr=19.5, Ni=10.7, Mo=2.18 (Cb ~ 0.05 and N ~ 0.04) ASTM A800 predicts 10.5 volume percent ferrite with a range of 6.5 to 14.5 (chromium equivalent to nickel equivalent = 1.19)

C r/N i C o m p o sitio n R atio

Means of Calculating Ferrite

Severn Gage: 11 Feritscope: 7 Magne-Gage: 2 Two different instruments: 5 Manual point count ASTM A800 1949 Schaeffler Diagram WRC Diagram

Unit of measure: FN: 8 (all 4 of the nonfoundry) Volume percent: 7 Use both methods: 2

Identification of Phases by Composition

FERRITE

AUSTENITE

Stainless Steels - Strength

Grade CF8 CF3MN 4A(2205) 6A(Zeron 100) Yield (ksi) 70 75 90 100 UTS (ksi) 30 37 60 65

Stainless Steel - Corrosion

Grade CF8 CF3MN 4A(2205) 6A(Zeron100) Critical pitting temperature oC 5 (calculated) 29 (calculated) 35 - 40 45 55

Pseudo Phase Diagram for 68 % Fe Cr Ni

CCT Diagram - CD3MN

5 C/min
1100 1050 1000 950
o

2 C/min

1 C/min

0.5 C/min

0.1 C/min

0.01 C/min

TTT curves (initial & final)

Temp. (Celsius)

900 850 800 750 700 650 600 550 500 1 10 100 1000 10000 100000

none

CCT curves (non-equil. initial & final)

Time (minutes)

Cooling Rate=1oC/min, phase <<1%

Cooling Rate=0.5oC/min phase <1%

Cooling Rate=0.1oC/min phase =8.72% 3.38

Cooling Rate=0.01oC/min phase =17.62% 3.46

CCT Diagram - CD3MWCuN

V0.175mm/sec V0.150mm/sec o o o 5 C/min 2 C/min 1 C/min 1100 V0.100mm/sec o o 0.5 C/min 0.1 C/min

1050 1000 950

Temp. (Celsius)

900 850 800 750 700 650 600 550 500 1

TTT curves (initial & final)

Cooling Rate=0.1oC/min phase =10.60% 2.82

none

CCT curves (non-equil. initial & final)

10

Time (minutes)

100

1000

Cooling Rate=0.5oC/min phase =10.37% 2.22

Bridgman furnace V=0.1mm/sec, phase<1%

Cooling Rate=5oC/min phase =3.61% 2.64

Cooling Rate=2oC/min phase =7.10% 2.12

Cooling Rate=1oC/min phase =10.09% 1.13

PROBLEM - Corrosion of High Alloy (6 wt% Mo) Stainless Steel Castings

Wrought AL6XN

AL6XN

1150oC/4 hrs

CN3MN As-Solidified

10

Dendrite cores

Mo

Current minimum required heat treatment 1150 C/ 1hr (ASTM Standards A743 and A351) Cast alloys and welds not as corrosion resistant due to: microsegregation presence of phase

Wt % of element

6 4

2 0 0 10 20 30

OBJECTIVE: Develop heat treating schedules and welding procedures that restore the corrosion resistance of castings and welds to a level comparable to that of wrought counterpart alloys 40

Distance (m)

Typical Homogenization Results

1205 4 Hour CK3MCuN
10
M ) M olybdenumCConcentration (wt% olybdenum oncentration (wt% MolybdenumConcentration (w
10 10

As Cast CK3MCuN 1150 4 Hour CK3MCuN

Dendrite Cores

9
9 9

Mo Mo

Mo

8
8 7 6
8 7 6 5 4

7 6

% )

55 44

33 3 00

20 20

50

40 40

60 60 100

80 80

Distance (Microns) Distance (microns)

Distance (microns)

150

100 100

120 120 200

140 140

250

160 160

180 180 300

1205 C/4 hours needed for complete homogenization

CN3MN Corrosion Results ASTM G48A

25.0% 20.0% 15.0% 10.0%

22.3% 18.0%
ASTM Minimum

W eig h t L o ss (% )

18.3% 13.8% 13.2%

5.4%
5.0%

5.0% 1.7%

0.0%
AL6XN As Cast CN3MN 1150 1 Hour 1150 2 Hour 1150 4 Hour 1205 1 Hour 1205 2 Hour 1205 4 Hour

 = 80

0.33

Model can be used as a predictive tool to determine effective heat treatment times for CN3MN prepared with various cooling rates

Need to establish acceptable cooling rate from the heat treating temperature to avoid formation of brittle secondary phase Collaboration with Scott Chumbley (Iowa State)
Results from C. Muller and Scott Chumbley, Iowa State University

Impact Toughness (ft-lbs)

Impact toughness

Grain boundary precipitates

Impact toughness decreases significantly with time at 870 oC, which could occur for large castings cooled slowly from the heat treating temperature Need to establish critical cooling rates in order to avoid embrittlement.

CK3MCuN

CN3MN

Toughness and Corrosion Performance

Charpy Impact Toughness decreases significantly with an extremely slow cooling rate (0.01C/sec) Charpy Impact Toughness is unaffected by cooling rate above 1C/sec

Corrosion Performance decreases at an extremely slow cooling rate (0.01C/sec)

CK3MCuN

CN3MN

Corrosion Performance is unaffected by cooling rate above 1C/sec Slow cooling rate sample shows evidence of grain boundary attack

Corrosion of Welds in Super Austenitic Stainless Steel Castings

CN3MN As-Cast

CN3MN 1205oC/4 hrs

CN3MN 1205oC/4 hrs with Autogenous Weld

Base Metal 1 cm Weld

Welding reintroduces the microsegregation profile 1 cm 1 cm Percent Mass Loss CN3MN 1205C/4hr with Autogenous Weld 14% Percent Mass Loss CN3MN As-Cast 22% CN3MN 1205C/4hr 2%

Corrosion Resistance as a Function of Dilution (IN686 Filler Metal Welds on CN3MN)

ASTM G48a
1 cm

Temperature: 75 C
1cm

Solution: FeCl3 (Ferric Chloride)

1cm 1cm

6.2 wt% Mo

Weld Metal

Base Metal

7.9 wt% Mo
1cm

11.0 wt% Mo 14.0 wt% Mo 12.4 wt% Mo

Corrosion performance increases with decreasing dilution level Corrosion performance of weld can restored to level of cast material at dilution levels below ~ 50%

Corrosion Resistance as a Function of Dilution (IN72 Filler Metal Welds on CN3MN)

ASTM G48a
1 cm

Temperature: 75 C
1 cm

Solution: FeCl3 (Ferric Chloride)

5.1 wt% Mo 24.4 wt% Cr 6.2 wt% Mo 20.6 wt% Cr

3.2 wt% Mo 31.5 wt% Cr

Base Metal
1 cm 1 cm

Weld Metal
1cm

1.3 wt% Mo 38.5 wt% Cr

2.3 wt% Mo 34.9 wt% Cr

Corrosion performance increases with decreasing dilution level IN72 Filler metal unable to avoid localized corrosion in weld

Corrosion Results: IN686 Filler Metal Heat Treatments have a significant effect on corrosion performance Post weld heat treatments (PWHT) will mitigate negative effects of dilution Heat treatments should be done after welding, if possible (no need to control dilution) Post Weld Heat Treatment at 1205C/4hr produces the best corrosion resistance

Air-Set Pouring

Nondestructive Examination
Surface
Visual Magnetic particle examination (MT) Liquid penetrant examination (PT)

Volume
Radiographic examination (RT) Ultrasonic examination (UT)

 Visual

Examination

ASTM A802 MSS SP55

Magnetic Particle
ASTM E709 ASTM E125 MSS SP53

Liquid Penetrant
ASTM E165 Method ASTM E433 Acceptance MSS SP93

Visual Examination
Equipment required: surface comparator, pocket rule, straight edge, workmanship standards Enables detection of: surface flaws cracks, porosity, slag inclusions, adhering sand, scale, etc. Advantages: low cost, can be applied while work is in process to permit correction of faults Limitations: applicable to surface defects only, provides no permanent record Remarks: should always be the primary method of inspection, no matter what other techniques are required

Inspection 1 Operator 1

Inspection 2

Casting 3 Operator 2

Inspection 1 Operator 1

Inspection 2

Foundry 3 Operator 2

Liquid Penetrant Examination

Equipment required: commercial kits containing fluorescent or dye penetrants and developers, application equipment for the developer, a source of ultraviolet light if fluorescent method is used Enables detection of: surface discontinuities not readily visible to the unaided eye Advantages: applicable to magnetic and nonmagnetic materials, easy to use, low cost Limitations: only surface discontinuities are detectable

Methodology
To determine the resolution of the process
Only data from a minimum of three inspections per casting for each inspector was used. An indication must be detected at least 50% of the time or the data was not considered so results are a best case situation.

The results were grouped by casting type, if multiple geometries were used, and also by inspector (to eliminate variation from inspector to inspector). Sample standard deviation was used as a measure of resolution.

Foundry 3
High alloy steel, visible liquid penetrant. One casting shape, 10-15 lb cast weight. Three Inspectors. Twenty-four pieces per part type. Three runs per inspector Measured length and sketched location of indications on part drawing. A total of 216 inspections were made.

Casting Geometry 1
Inspector 1
Box-and-Whisker Plot

Inspector 2
Box-and-Whisker Plot

Inspector 3
Box-and-Whisker Plot

All
Box-and-Whisker Plot

0.009

0.013

0.017

0.021

0.025

0.1

0.2

0.3

0.4

0.005 0.01 0.015 0.02 0.025

0.1

0.2

0.3

0.4

Standard Deviation 95% confidence interval for mean 0.0 to 0.04

Standard Deviation 95% confidence interval for mean 0.0 to 0.2

Standard Deviation 95% confidence interval for mean 0.0 to 0.02

Standard Deviation 95% confidence interval for mean 0.01 to 0.5

Punch Line The resolution for all inspectors is about 0.4.

Radiographic Examination
Equipment required: commercial x-ray or gamma units made especially for inspecting welds, castings, and forgings with film and processing facilities Enables detection of: internal macroscopic flaws cracks, porosity, blow holes, non-metallic inclusions, shrinkage, etc. Advantages: when the indications are recorded on film, gives a permanent record Limitations: cracks difficult to detect, requires safety precautions, requires skill in choosing angles of exposure, operating equipment, and interpreting indications Remarks: radiographic inspection is required by many codes and specifications, useful in qualification of processes, its use should be limited to those areas where other methods will not provide the assurance required because of cost

Results for Unanimous Agreement in X-Ray Ratings

Unanimous agreement in shrinkage type: 37% (47/128) 14 Level 0 (no type) 20 CB 7 CA 6 CC Unanimous agreement in shrinkage level: 17% (22/128) 14 Level 0 1 Level 1 1 Level 2 1 Level 3 5 Level 5 Unanimous agreement in level and type: 12.5% (16/128) 14 Level 0 2 CB5

Casting Simulation
Each trial plate was simulated with recorded casting conditions Niyama values (Ny) were measured
minimum Ny area of Ny < 0.1 (K-s)1/2mm-1 top view cross-section

Ny =

G & T

G: temperature gradient (K/mm) T: cooling rate (K/s)

side view cross-section

Casting Simulation
Combine trial and simulation results:
6

W/T = 2, CF-8M (20 Plates) Trial results: X-ray level vs. FL

5

Simulation of trials: Ny
25 6

X-ray Level

ASTM Shrinkage X-ray Level

4 Combine by eliminating FL X-ray level vs. Nymin 3 2 1 0 -1 0 0.1 0.2 0.022 0.024 0.074

W/T = 5.5, CF-8M (50 Plates) W/T = 8, CF-8M (30 Plates) min W/T = 8, HH (20 Plates) W/T = 8, HP (20 Plates) W/T = 12, CF-8M (25 Plates) Level 5: 25 Plates Level 4: 6 Plates Level 3: 12 Plates Level 2: 15 Plates Level 1: 24 Plates Level 0: 83 Plates

Mean Minimum Niyama Values +/- One Standard Deviation

vs. FL 5
0.005

11
2

14
1

TOTAL: 165 Plates

Nymin (K1/2s1/2mm-1)

15
0

13 70
-1 -0.1

0.1

0.3

0.5

0.7

0.9

1.1

1.3

1.5

1.7

1.9

2.1

Minimum Niyama Criterion Value, Nymin (K1/2s1/2mm-1)

Variation in the Ratings: Confidence intervals of x-ray level ratings grouped by average x-ray level
2.5

Data from all foundries Average One-Sided Student-t 95% Confidence Interval 27 x-rays
2.0

11 x-rays 35 x-rays

Average one-sided student-t 95% confidence interval for all 128 x-rays = 1.42

8 x-rays

1.5

1.0

2.5 < Xavg < 3.5

0.5 < Xavg < 1.5

Average X-ray Level < 0.5

1.5 < Xavg < 2.5

3.5 < Xavg < 4.5

39 x-rays

0.5

8 x-rays Xavg > 4.5

5

0.0 0 1 2 3 4

Average X-ray Level Groupings

Background
The root cause of leaks in fluid-containing castings can be shrinkage porosity that extends through a wall. Sometimes, porosity is so small that it cannot be detected using industrial radiography. No method available to assure quality.

Background
The Niyama criterion, a common output from a casting computer simulation, can be used to predict shrinkage porosity.

Ny = G

& T

Background
What is the critical Niyama below which shrinkage porosity forms? (especially for high-Ni alloys)
o Micro-porosity, Nymicro (not visible on radiograph) o Macro-porosity, Nymacro (visible on radiograph)
Pore Volume (%)

Pore Volume (%)

macro-shrinkage

micro-shrinkage

0 log10(Ny) Nymacro Nymicro

Ny = G

& T

Case Study #3: Valve B

CG8M steel valve cast in a silica sand shell mold After machining, 22% leaked around gasket on flange face during pressure testing No shrinkage visible on x-rays
Casting defect. Leaks around gasket

outer diameter of flange = 5

Case Study #3: Valve B

0.1 mm

leaking castings were sectioned, and photomicrographs were taken microporosity evident in leaking area

Case Study #3: Valve B

original rigging revised rigging

padding added chill setup changed

Case Study #3: Valve B

revised rigging flange face
Ny = 1.36 Ny = 1.38

diameter as-cast

machined diameter

outer diameter of gasket seat

Nymin = 1.4

Case Study #3: Valve B

Microporosity caused leaks in original rigging with Nymin = 0.5 - 0.7 Nymin = 1.4 for revised rigging Valves cast since rigging revised: none have leaked none have had any shrinkage indications on x-ray

Leaker Case Study #1

Leaker was a 20# investment cast M35-1 valve 8 valves were cast and shipped to the customer, and one leaked during the customers pressure testing Leaker was returned to the foundry, with leak area circled Metallographic analysis (John Griffin, UAB)
leak

Photographs of Defects in Leak Area

Outer diameter (OD) of leak area:
leak exit location 1 mm

18 mm below mid-plane

mid-plane

mid-plane 18 mm below mid-plane

Photographs of Defects in Leak Area

Casting through-thickness toward inner diameter (ID) of leak area:

Photographs of Defects in Leak Area

Polished through-thickness specimen toward ID of leak area, showing shrinkage porosity:

Niyama Values in Entire Valve

Niyama Values in Region of Leak

Nymin = 0.58 ID

Nymin = 0.69 OD

mid-plane mid-plane Niyama values are in units of (C-s)1/2/mm

Niyama Values in Region of Leak

ID

OD

photos and simulation results are from the valve mid-plane

Case Study #1 Summary

Simulation suggests potential for leak in valve
At valve mid-plane: Nymin = 0.58 (C-s)1/2/mm at ID, Nymin = 0.69 at OD

These low Niyama values (Nymin < 1) correspond well with shrinkage porosity observed in metallographic sections.

Additional Examination Areas

After examining the leaking area, additional areas were selected for metallographic examination (all regions on valve mid-plane):

3 3 6 2 2 1 6 1 5 region of leak 4 5

Comparison: Region #1

Comparison: Region #2
A A B

Comparison: Region #3
B A B

Comparison: Region #4

Comparison: Region #5
A A C D B D C B

A B

Comparison: Region #6

Additional Region Summary

In general, areas with Ny < 1 show a significant amount of porosity (macroporosity) In general, areas with 1 < Ny < 2 show a noticeable amount of microporosity
Region #4 was a slight exception, with no substantial microporosity in a region with 1.5 < Ny < 1.8

In general, areas with Ny > 2 were free from shrinkage porosity

Leaker Case Study #2

150# CN7M Valve Sand Casting:

leak (outside) leak (inside)

Leaker Case Study #2

cross-section of leaking area

OD

ID

shrinkage, possibly segregation

Case Study #2 Simulations

Original rigging:
OD

ID

Nymin = 1.6 at OD, Nymin = 0.5 at ID visible macro-porosity for Nymin < 1.0

Conclusions
In general, areas with Ny < 1 show a significant amount of porosity (macroporosity) In general, areas with 1 < Ny < 2 show a noticeable amount of microporosity In general, areas with Ny > 2 were free from shrinkage porosity It appears that the Niyama criterion can be used for quality assurance, especially if shrinkage porosity is so small that it cannot be detected by radiography. Note for MAGMAsoft users: the valves had only minimal feeding indications (porosity %); the shrink seen in the valves was only predicted using Niyama criterion.