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Cast Stainless Steel Technology Developments Raymond Monroe SFSA

Stainless Casting 6

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Page 1: Stainless Casting 6

Cast Stainless Steel Technology Developments

Raymond Monroe SFSA

Page 2: Stainless Casting 6
Page 3: Stainless Casting 6

CA 15 CB 7 CuCD4Cu

CF8

CN3MN

Page 4: Stainless Casting 6
Page 5: Stainless Casting 6

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

Page 6: Stainless Casting 6

Ferrite from Chemistry

• 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)

Schoefer Diagram

0.8

0.9

1

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2

2.1

2.2

0 10 20 30 40 50 60 70

Volume Percent Ferrite

Cr/N

i Com

posi

tion

Rat

io

77.2%)02.0N(26(%)Mn5.0(%)C30(%)Ni99.4(%)Nb(%)Mo4.1(%)Si5.1(%)Cr

NiCr

e

e

+−+++−+++

=

Page 7: Stainless Casting 6

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 non-

foundry)• Volume percent: 7• Use both methods: 2

Page 8: Stainless Casting 6

Identification of Phases by CompositionFERRITE

AUSTENITE

Page 9: Stainless Casting 6

Stainless Steels - Strength

Grade Yield (ksi) UTS (ksi)

CF8 70 30

CF3MN 75 37

4A(2205) 90 60

6A(Zeron 100) 100 65

Page 10: Stainless Casting 6

Stainless Steel - Corrosion

Grade Critical pitting temperature oC

CF8 5 (calculated)

CF3MN 29 (calculated)

4A(2205) 35 - 40

6A(Zeron100) 45 – 55

Page 11: Stainless Casting 6

Pseudo Phase Diagram for 68 % Fe – Cr Ni

Page 12: Stainless Casting 6
Page 13: Stainless Casting 6

CCT Diagram - CD3MN5oC/min 2oC/min 1oC/min 0.5oC/min 0.1oC/min 0.01oC/min

1 10 100 1000 10000 100000500

550

600

650

700

750

800

850

900

950

1000

1050

1100

Time (minutes)

CCT curves (non-equil. initial & final)

TTT curves(initial & final)

Tem

p. (C

elsi

us)

none

Cooling Rate=1oC/min,σ phase <<1%

Cooling Rate=0.5oC/minσ phase <1%

Cooling Rate=0.1oC/minσ phase =8.72% ±3.38

Cooling Rate=0.01oC/minσ phase =17.62% ±3.46

Page 14: Stainless Casting 6

CCT Diagram - CD3MWCuNV0.175mm/sec V0.150mm/sec V0.100mm/sec 5oC/min 2oC/min 1oC/min 0.5oC/min 0.1oC/min

1 10 100 1000500

550

600

650

700

750

800

850

900

950

1000

1050

1100

Time (minutes)

CCT curves (non-equil. initial & final)

TTT curves(initial & final)

Tem

p. (C

elsi

us)

none

Cooling Rate=5oC/minσ phase =3.61% ±2.64

Cooling Rate=2oC/minσ phase =7.10% ±2.12

Cooling Rate=1oC/minσ phase =10.09% ±1.13

Cooling Rate=0.5oC/minσ phase =10.37% ±2.22

Cooling Rate=0.1oC/minσ phase =10.60% ±2.82

Bridgman furnaceV=0.1mm/sec,σ phase<1%

Page 15: Stainless Casting 6

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

Wrought AL6XN As-SolidifiedAL6XNCN3MN

1150oC/4 hrs

0

2

4

6

8

10

0 10 20 30 40

Wt %

of e

lem

ent

Distance (µm)

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 σ phase

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

Page 16: Stainless Casting 6

Typical Homogenization Results

As Cast CK3MCuN

3

4

5

6

7

8

9

10

0 20 40 60 80 100 120 140 160 180Distance (microns)

Mol

ybde

num

Con

cent

ratio

n (w

t%)

MoDendrite Cores

1150 4 Hour CK3MCuN

3

4

5

6

7

8

9

10

0 50 100 150 200 250 300Distance (Microns)

Mol

ybde

num

Con

cent

ratio

n (w

%)

Mo

1205 4 Hour CK3MCuN

3

4

5

6

7

8

9

10

0 20 40 60 80 100 120 140 160 180

Distance (microns)

Mol

ybde

num

Con

cent

ratio

n (w

t% Mo

• 1205 °C/4 hours needed for complete homogenization

Page 17: Stainless Casting 6

5.4%

22.3%

18.0%

13.8%

18.3%

13.2%

5.0%

1.7%

0.0%

5.0%

10.0%

15.0%

20.0%

25.0%

AL6XN As CastCN3MN

1150 1 Hour 1150 2 Hour 1150 4 Hour 1205 1 Hour 1205 2 Hour 1205 4 Hour

Wei

ght L

oss

(%)

CN3MN Corrosion Results – ASTM G48A

AS

TM M

inim

um

Page 18: Stainless Casting 6

33.080 −= ελModel can be used as a predictive tool to determine effective heat treatment

times for CN3MN prepared with various cooling rates

Page 19: Stainless Casting 6

Need to establish acceptable cooling rate from the heat treatingtemperature to avoid formation of brittle secondary phase

Collaboration with Scott Chumbley (Iowa State)

Results from C. Muller and Scott Chumbley, Iowa State University

Impa

ct T

ough

ness

(ft-l

bs)

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.

Page 20: Stainless Casting 6

Charpy Impact Toughness decreases significantly with an extremely slow cooling rate (0.01°C/sec)

Charpy Impact Toughness is unaffected by cooling rate above 1°C/sec

Toughness and Corrosion Performance

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

Corrosion Performance is unaffected by cooling rate above 1°C/sec

Slow cooling rate sample shows evidence of grain boundary attack

CK3MCuN CN3MN

CK3MCuN CN3MN

Page 21: Stainless Casting 6

Corrosion of Welds in Super Austenitic Stainless Steel Castings

CN3MN 1205oC/4 hrs with Autogenous Weld

CN3MN As-Cast

CN3MN 1205oC/4 hrs

1 cm 1 cm

1 cmBase Metal Weld

Welding reintroduces the microsegregation profile

Percent Mass LossPercent Mass Loss

CN3MN As-Cast

CN3MN 1205°C/4hr

22% 2%

CN3MN 1205°C/4hr with Autogenous Weld

14%

Page 22: Stainless Casting 6

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

1cm

1cm

Base Metal

1cm

Weld Metal

6.2 wt% Mo

11.0 wt% Mo

12.4 wt% Mo

7.9 wt% Mo

1cm1 cm

14.0 wt% Mo

ASTM G48a Temperature: 75° C Solution: FeCl3 (Ferric Chloride)

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

Page 23: Stainless Casting 6

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

6.2 wt% Mo 20.6 wt% Cr

3.2 wt% Mo 31.5 wt% Cr

2.3 wt% Mo 34.9 wt% Cr

5.1 wt% Mo 24.4 wt% Cr

1cm

Weld Metal

Base Metal

1 cm1 cm

1 cm1 cm

1.3 wt% Mo 38.5 wt% Cr

ASTM G48a Temperature: 75° C Solution: FeCl3 (Ferric Chloride)

Corrosion performance increases with decreasing dilution levelIN72 Filler metal unable to avoid localized corrosion in weld

Page 24: Stainless Casting 6

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 1205°C/4hr produces the best corrosion resistance

Page 25: Stainless Casting 6

Air-Set Pouring

Page 26: Stainless Casting 6

Nondestructive Examination

• Surface– Visual– Magnetic particle examination (MT)– Liquid penetrant examination (PT)

• Volume– Radiographic examination (RT)– Ultrasonic examination (UT)

Page 27: Stainless Casting 6

Examination• Visual

– ASTM A802– MSS SP55

• Magnetic Particle– ASTM E709– ASTM E125– MSS SP53

• Liquid Penetrant– ASTM E165 Method– ASTM E433 Acceptance– MSS SP93

Page 28: Stainless Casting 6

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

Page 29: Stainless Casting 6

Inspection 1 Inspection 2O

pera

tor 1

Ope

rato

r 2

Casting 3

Page 30: Stainless Casting 6

Inspection 1 Inspection 2O

pera

tor 1

Ope

rato

r 2

Foundry 3

Page 31: Stainless Casting 6

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

Page 32: Stainless Casting 6

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.

Page 33: Stainless Casting 6

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.

Page 34: Stainless Casting 6

Casting Geometry 1AllInspector 3Inspector 1 Inspector 2

Standard Deviation95% confidence interval for mean0.0” to 0.04”

Standard Deviation Standard Deviation

Box-and-Whisker Plot

0.009 0.013 0.017 0.021 0.025

95% confidence interval for mean 0.0” to 0.2”

95% confidence interval for mean 0.0” to 0.02”

Standard Deviation

95% confidence interval for mean 0.01” to 0.5”

Box-and-Whisker Plot

0 0.1 0.2 0.3 0.4

Box-and-Whisker Plot

0 0.005 0.01 0.015 0.02 0.025

Box-and-Whisker Plot

0 0.1 0.2 0.3 0.4

Punch Line – The resolution for all inspectors is about 0.4”.

Page 35: Stainless Casting 6

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

Page 36: Stainless Casting 6

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

Page 37: Stainless Casting 6

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

side view cross-section

TGNy&

=

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

Page 38: Stainless Casting 6

Casting Simulation– Combine trial and simulation results:

• Trial results: X-ray level vs. FL

• Simulation of trials: Nymin vs. FL

• Combine by eliminating FL → X-ray level vs. Nymin

-1

0

1

2

3

4

5

6

-0.1 0.1 0.3 0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1

AST

M S

hrin

kage

X-r

ay L

evel

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

W/T = 2, CF-8M (20 Plates)W/T = 5.5, CF-8M (50 Plates)W/T = 8, CF-8M (30 Plates)W/T = 8, HH (20 Plates)W/T = 8, HP (20 Plates)W/T = 12, CF-8M (25 Plates)

Level 5: 25 PlatesLevel 4: 6 PlatesLevel 3: 12 PlatesLevel 2: 15 PlatesLevel 1: 24 PlatesLevel 0: 83 Plates

TOTAL: 165 Plates

25

6

70

9

11

14

15

13

0

-1

0

1

2

3

4

5

6

0 0.1 0.2

X-r

ay L

evel

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

0.074

0.005

0.022

0.024

Mean Minimum Niyama Values+/- One Standard Deviation

Page 39: Stainless Casting 6

0.0

0.5

1.0

1.5

2.0

2.5

0 1 2 3 4 5

Average X-ray Level Groupings

Ave

rage

One

-Sid

ed S

tude

nt-t

95%

Con

fiden

ce In

terv

al

39 x-rays

35 x-rays

27 x-rays

11 x-rays

8 x-rays

8 x-rays

Ave

rage

X-r

ay

Leve

l < 0

.5

0.5

< X

avg

< 1.

5

1.5

< X

avg

< 2.

5

2.5

< X

avg

< 3.

5

3.5

< X

avg

< 4.

5

Xav

g >

4.5

Data from all foundries Average one-sided student-t 95%confidence interval forall 128 x-rays = 1.42

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

Page 40: Stainless Casting 6

• 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

Page 41: Stainless Casting 6

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

Background

TGNy &=

Page 42: Stainless Casting 6

• 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)

Background

TGNy &=

log10(Ny)

Pore Volume (%)

0

micro-shrinkage

macro-shrinkage

NymicroNymacro

Pore

Vol

ume

(%)

Page 43: Stainless Casting 6

Case Study #3: Valve B

outer diameterof flange = 5”

Casting defect. Leaks around gasket• CG8M steel valve

cast in a silica sandshell mold

• After machining, 22%leaked around gasketon flange face duringpressure testing

• No shrinkage visibleon x-rays

Page 44: Stainless Casting 6

Case Study #3: Valve B

∼ 0.1 mm

• leaking castings weresectioned, andphotomicrographswere taken

• microporosity evidentin leaking area

Page 45: Stainless Casting 6

Case Study #3: Valve Boriginal rigging revised rigging

paddingadded

chillsetup

changed

Page 46: Stainless Casting 6

Case Study #3: Valve B

diameteras-cast

machineddiameter

outerdiameterof gasket

seat

Ny = 1.38Ny = 1.36

revised riggingflange face

Nymin = 1.4

Page 47: Stainless Casting 6

Case Study #3: Valve B

• Microporosity caused leaks in original rigging withNymin = 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

Page 48: Stainless Casting 6

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 customer’s pressure testing

• Leaker was returned to the foundry, with leak area circled

• Metallographic analysis (John Griffin, UAB)

leak

Page 49: Stainless Casting 6

Photographs of Defects in Leak Area

mid-plane18 mm below mid-plane

leak exit location

• Outer diameter (OD) of leak area:

mid-plane

18 mm belowmid-plane

1 mm

Page 50: Stainless Casting 6

Photographs of Defects in Leak Area• Casting through-thickness toward inner diameter (ID)

of leak area:

Page 51: Stainless Casting 6

Photographs of Defects in Leak Area• Polished through-thickness specimen toward ID of

leak area, showing shrinkage porosity:

Page 52: Stainless Casting 6

Niyama Values in Entire Valve

Page 53: Stainless Casting 6

Niyama Values in Region of Leak

mid-plane

mid-plane

ID

OD

Nymin = 0.69

Nymin = 0.58

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

Page 54: Stainless Casting 6

Niyama Values in Region of Leak

OD

ID

photos and simulation results are from the valve

mid-plane

Page 55: Stainless Casting 6

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.

Page 56: Stainless Casting 6

Additional Examination Areas

2

5

6

3

1

4

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

4

1

36 2

5

region of leak

Page 57: Stainless Casting 6

Comparison: Region #1

Page 58: Stainless Casting 6

Comparison: Region #2

A

B

B

A

A B

Page 59: Stainless Casting 6

Comparison: Region #3

A

BA B

A

B

Page 60: Stainless Casting 6

Comparison: Region #4

Page 61: Stainless Casting 6

Comparison: Region #5

A

B

C

D

D

B

A

C

A

B

C

D

Page 62: Stainless Casting 6

Comparison: Region #6

Page 63: Stainless Casting 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

Page 64: Stainless Casting 6

Leaker Case Study #2

leak (outside)

• 150# CN7M Valve Sand Casting:

leak (inside)

Page 65: Stainless Casting 6

Leaker Case Study #2

cross-section of leaking area

OD

ID

shrinkage, possibly segregation

Page 66: Stainless Casting 6

Case Study #2 Simulations• Original rigging:

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

OD

ID

Page 67: Stainless Casting 6

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.