05-01-2010 Daido Steel Co.

,Ltd

Daidos New Materials for Petrochemical industry And Energy industry

1.EST (Ethylene Super Tube) 2.BST (Boiler Super Tube) 3.DSA760 (Ni-38Cr-3.8Al )

DAIDO STEEL CO., LTD.

EST (Ethylene Super Tube)

Ethylene Furnace
Fe e d
N a ph th a E tha ne C 3,C 4

Ste am 500-600 Frac tio n atio n

Furnace)

Eth yle n e , e tc
Furnace Temp. 1100-1200 Coil Temp.(TMT 1080-1120 (Quencher)

Radian t Co ils (EST )

OutletTemp.(COT) 800-850

DAIDO STEEL CO., LTD.

Introduction
History of radiant coils for ethylene pyrolysis furnace material: A constant struggle for longer life & run length at higher temperature & severity
2007 18Cr-8Ni (304) 25Cr-20 (310)
DAIDO STEEL CO., LTD.

25Cr-20Ni (HK) INCO 800

25Cr-35Ni (HP)

25Cr-35Ni-Nb (HP-Nb) 35Cr-45Ni

Our Solution: EST (Ethylene Super Tube) = PPW (Plasma Powder Weld) Overlaid Tube Base Tube
-Material: Conventional (HK, HP-Nb, 35Cr-45Ni, etc.) Centrifugally cast (Daido)

PPW layer
- Material: 45Cr-50Ni-1Mo Gas atomized & PPWd (Daido) - Thickness: 1 - 3 mm

Main Benefits
- Anti Catalytic Coke - Anti Carburization
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PPW (Plasma Powder Welding)

Gas atomized 45Cr-50Ni-1Mo powder

PPW layer Base Metal

As weld overlaid
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Machine finished

Anti-Carburization
The PPW layer stops carburization into the base tube by the Dam-Effect.

Furnace A: Naphtha Feed

Samples taken after 9 years of operation

Coils with EST have been used since 2000.

DAIDO STEEL CO., LTD.

Appearance of EST (After 9 years)

- Green colored surface is recognized. (same as the sample after 24 months) - No-erosion or damage is observed.
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Cross Section Composition Analysis

HP-Nb, after 2 years of operation
- Fully carburized. - [C]: 4.7% (ID), 1.1% (OD)
HP-Nb

[C]

[Ni]

[O]

[Cr]

[Fe]

Cross section composition analysis EST, after 6 years of operation

- Carburization stops at the PPW layer - No-carburization in the base tube
3

PPW Layer Base metal Weld by 35Cr-45Ni Weld by 45Cr-54Ni-1Mo

[C]

[Cr]

[Fe]

[Ni]

High Cr% is kept in the PPW layer

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EPMA (Electron Probe Microanalysis)

Actual Carburization Comparison

HP-Nb 7% [C]%
(onset of graphite formation)

EST
onset of graphite formation)

[C]%

4
C (4 years)

Onset of carburization into the base tube (Carburization)

EU Plant (6 years) Japan plant (9 years)

2
(Carburization)

D (2 years) A (4 years) (original)

2 0

(original)
PPW overlay Base tube Japan plant (48 months)

ID

OD

ID

OD

Dam-Effect by the PPW layer

DAIDO STEEL CO., LTD.

Japan Plant (14 months)

Mechanism of Dam-effect
Base tube: HPmod HP mod. (total C = 0.4%): Original C in metal matrix = 0.02%

0.35
C C

PPW overlay
HPmod composition

0.3 C% in matrix 0.25 0.2 0.15 0.1 0.4% 0.05 0 0 2

HPmod

PPW

PPW HP HPmod -M
3% Carburization progresses when C in metal matrix ( exceeds 0.02%

Metal matrix

Cr carbides

4 6 Total C (%)

10

Dam-effect can only be expected in the clad tubes, not in solid tubes.

Lack of carburization in EST can prevent physical distortion and help maintain stable operation.

DAIDO STEEL CO., LTD.

Anti Catalytic Coke

An Fe free, Cr-oxide film on the PPW layer reduces catalytic coke formation with Self Healing Effect.

Coke Resistance
Laboratory screening
Metal coupons in hot gas stream accumulate coke as experiment proceeds. Coupon EST is prepared by PPW process

96hrs Coke Production (mg/m2/hr) 2500 2000 1500 1000 500 0

192hrs 500hrs

Simulated process gas environment

25Cr-35Ni 45Cr-50Ni-1Mo 35Cr-45Ni Material

Inconel690

Ni

DAIDO STEEL CO., LTD.

Furnace B: Gas Feed

TLE No.2 TLE No.1 Tube Metal Temperature

35Cr-45Ni
DAIDO STEEL CO., LTD.

Coils with EST

(2 out of 10 passes )

Furnace B: TMT
(Flat means less coke formation)
2000 1080 1060 1950

1040 TMT (deg.C) 1020

1850 1000 980 1800

Coil A (35Cr-45Ni)
960 940 04/15/05 05/15/05 06/14/05 07/14/05 08/13/05 Date
DAIDO STEEL CO., LTD.

Coil C (EST) Coil D (EST)

1750

Coil B (35Cr-45Ni)

09/12/05

10/12/05

11/11/05

12/11/05

TMT (deg.F)

1900

Furnace C/D: Gas Feed

Furnace C: EST used for 50% of full coil
(EST) (35Cr-45Ni)

Furnace D: Identical furnace with 35Cr-45Ni

(35Cr-45Ni)
DAIDO STEEL CO., LTD.

(HK4M)

Furnace C/D: Pressure Drop

(Flat means less coke formation)
0.20 Delta P (MPa) 0.15 0.10 0.05 0.00 0 20 40 60 80 100 Days 0.20 Delta P (MPa) 0.15 0.10 0.05 120 140 160 180 200 Furnace D (Conventional)

36 days

34 days

29 days

35 days

34 days

Furnace C (EST)

52 days
0.00 0 20 40 60

52 days
80 100 Days 120

68 days
140 160 180 200

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Lower pressure increase continue through years by Self Healing Effect of EST
2 years
0.19000 0.17000 0.15000 0.13000 0.11000 0.09000 0.07000 0.05000 2005/12/14 2006/3/24 2006/7/2 2006/10/10 2007/1/18 2007/4/28 2007/8/6 2007/11/14

D e lta Pre s

300B 300A

FurnaceC : EST

FurnaceD : 35Cr 45Ni

Surface composition mapping of 35Cr/45Ni after 3.3 years

Near ID surface

100mm

[Cr] [Fe] [Si] [Mn]

[Ni]

[Mo]

35-45 surface oxides contain Fe or Feoxide (catalyst for coke formation)

[C] [O]
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[Nb]

Surface composition mapping of EST after 9 years

Near ID surface

100mm

[Cr]

[Fe]

[Ni]

[Si]

[Mn]

[Mo]

EST surface is covered by pure Cr-oxide, same as after 2 years

[O]

[C]

DAIDO STEEL CO., LTD.

EPMA (Electron Probe Microanalysis)

Mechanism of Self-healing
Cr2O3 HPmod As the alloy is carburized, Cr in metal matrix will be depleted (forming Cr-carbides) and lose the ability to form surface Cr2O3. 45 C C Cr% in Matrix 40 35 30 25 20 15 10 5 0 0 2 4 Total C% 6
EST(EU) 13 months EST(Japan) 14 months 48 months 6 years

EST HPmod
HPmod will lose Cr in matrix quickly to the level where enough Cr2O3 cannot be made. PPWs Cr in matrix stays high, enough to re-create Cr2O3 after each decoking cycle.

HPmod

PPW

Metal matrix

HPmod (EU) 2, 4 8 years

10

Cr carbides

Due to high Cr in the PPW layer, surface Cr2O3 can be re-created and reinforced after each decoking cycle: Self-healing effect

Summary
EST has, Extremely high carburization resistance Extended tube life (Twice or more) Ability to run at higher severity Maintained ductility (can survive emergency shutdowns) Suppression of catalytic coke formation Extended run length (Twice in ethane furnace) Higher pricing than conventional tubes, but Pay back In a year can be expected. (EST is in operation at over 10 commercial plants)
DAIDO STEEL CO., LTD.

BST (Boiler Super Tube)

Outer surface overlay
Overlay and bending

Waste to Energy plant

Benefits of BST (Boiler Super Tube)

Plasma Powder Welding Original metal powder

Boiler Super Tube BST Production Line

Anti-corrosion to corrosive fired gas in high temperature Higher steam temperature for Higher efficiency of power generation

History of BST (Boiler Super Tube)

1960-1964 Union Carbide Co. in USA developed welding application of plasma energy and powder metallurgy. 1973-1991 Daido Steel developed automatic Plasma Powder Welding (PPW) equipment for engine valves. Plasma arc generator, gas controller, powder metal feeder, and particle size control were patented by Daido. 1992More than 150 PPW equipment for engine valves have been shipped to automotive engine valve manufacturers. 1994Daido developed Boiler tubes with PPW overlay for the waste to energy plant through a Japanese National Project. 1998Daido started commercial manufacturing of boiler tubes with PPW overlay as 1st Generation Boiler Super Tube "BST276BST625" for Japanese waste to energy plants. Daido developed new process for PPW overlay on the inner surface. 2009Daido developed New "BST1" for higher temperature operation.

1st generation "BST 276 and BST 625"

(Steam Temperature: ~400oC) Chemistry of Weld overlay (typical)
C BST276 BST625 0.01 0.01 Si 0.8 0.2 Mn 0.2 0.1 Ni Bal. Bal. Cr 20.8 21.8 Mo 13.2 9.2 Co 2.2 2.0
(wt%)

W 3.1 -

Fe 1.0 1.2

Actual corrosion depth in the waste to energy plant (550oC x 6000 hrs)
PPW overlaid Boiler Tube
BS T2 76 BS T6 25 Alloy6 25 30 Cr-40 Ni S US 347 H S TBA24

(Ref.) Mechanical Properties of Boiler tubes STB340 + H-276M(PPW) R.T. T/S El Base tube 620 28.8 With PPW 601 41.2 (Base 5m/m + PPW 2m/m)

Max. Ave.

2 4 Corrosion Depth (mm)

Applications of BST625 and BST276 in Japan

Size Grade PPW overlay Thickness Grade OD: f38.1 - 114.3 mm, Thickness: 3.5 - 6.0 mm, L (shipping length): 0.9 - 7.4 m STB340, STB410, SUS310J1 2 - 2.5 mm 276 modified, Inco625, 625modified

Base tube

Installation

24 Waste to Energy Plants in Japan (Locations: Tokyo, Osaka, Nagoya, Hokkaido, Tochigi, Kyoto, Kagawa, Toyama, Chiba, etc)

Remarks

Over 8000 pcs are in operation now. Maximum years in operation is 9 years. (2009)

for higher temperatures and longer tube life

(Steam Temperature: over 400oC)
(1) Chemistry of PPW overlay
C BST1 BST625 BST276 Ad. 0.01 0.01 Si Ad. 0.8 0.2 Ni Bal. Bal. Bal. Cr 27 22 21 Mo 9 13 Co 2 2 W Ad. 3

New generation "BST1"

(wt%)
Al Ad.

(2) Concept of BST1 - Chemistry of BST1 is originally developed and applied for commercial Air-heater for Gasification and Ash Melting System. (Metal temperature: 800oC (1,142oF)) - Higher corrosion resistance with higher Cr than BST625 or BST276. - Higher W than BST276 prevents the formation of Cr-depleted zones. - Added Si, Al prevent corrosion by Cl through grain boundaries. - Adequate C makes fine grains to protect against corrosion through grain boundaries.

Results of Corrosion Test

JIS Z 2293
Methods for high temperature corrosion test of metallic materials by dipping and embedding in molten salts
Salts
Mol. % Na2SO4 K2SO4 Fe2O3 PbCl2 FeCl2 NaCl KCl 3 3 2 3 3 2 2 Wt. % 16.8 20.6 12.6 28.15 12.85 3.95 5.05
oC oF

Dipping temperature and time

400 752

600 1,112 100 hours

800 1,472

time

Weight loss Weight loss of BST105 at 800oC is remarkably smaller than BST276 or 625 Appearance after the test
400oC x 100 h

3 2.5 2 1.5 1 0.5 0

(g)

400

600

800

BST1

BST625

BST276

600oC x 100 h

800oC x 100 h

BST1

BST625

BST276

Almost no corrosion of BST1 even at 800oC

Conclusions
- With higher contents of Cr, W, Al, and Si (with no Mo and Co), a new generation BST1 has been developed. - A high temperature (800oC or 1,472oF) molten salt test revealed higher corrosion resistance of BST1 as compared with BST276 or BST625 against oxide and chloride formations. - BST1 is expected to enable higher steam temperatures with longer tube life, resulting in higher efficiency for waste to energy plant operation.

DSA760 ( Ni-38Cr-3.8Al)
Characteristics - High hardness in AG condition by precipitation of aCr and g phases - Wear resistance comparing with AISI 440C - Corrosion resistance in comparable with AISI 316 - Easy to machine and cold work in ST condition - Non-magnetic

Development History of DSA760

1972 (Japan) Ni-40Cr-4Al (mass%) was developed by Toshiba for gas turbine parts, which had high hardness and good corrosion resistance. 1974 (Russia) Ni-40Cr-3.8Al was introduced as high hardness and non-magnetic permeability alloy in a Russian paper. 1990 (UK) Ni-40Cr-3.8Al was introduced again as the Russian Ni alloy and applied to a non-magnetic pressure cylinder. Manufacturing process was cast due to low hot workability. 1999 - (DAIDO) DSA760 was developed for forging and rolling process to product many kind of products for every industry by Daido process technology

Hardness and Corrosion Resistance

<condition> 3.5%NaCl 30
excellent 800 Pitting Potential (mV vs SCE) 600 316 400 304 200 0
Non-magnetic

DSA760 Inconel X750

Corrosion Resistance

Austenitic SS

-200 poor -400 0

Magnetic

< > Martensitic SS 3.5%NaCl 30 420

440C

200

400 Hardness (HV)

600

800

Ageing Hardness
800

700

Hardness (HV)

600

500

400

300 ST : 1150 200 ST 400 500 600 700 /0.5hrWQ

Ageing Temperature ( /16hrAC)

Mechanical Properties at R.T.

Tensile properties
2500 TS 2000
Diameter : 7 Gage Length : 28 Screw chuck : M18

Charpy Impact Value

100 250 Hardness 60

80

200

1500 1000

0.2% PS

60 40 RA EL

150 100

50

40 20 0 900 50 Impact Value

Charpy specimens Size : 10x10 10R notch

500 0 500

600

700
o

800

0 500

600

700
o

800

30 900

Ageing Temperature (T Cx24h/AC)

Ageing Temperature (T Cx24h/AC)

Microstructure after ST-AG

SEM images
Solution treatment (ST) : 1150deg.C x over0.5hr / WC Aging (AG) : 550deg.C x over16hr / AC

x50,000

x100,000
aCr g (Ni3Al)

1mm

500nm

Hard phase consists of lamellar aCr and g/g' phases

g' Ni3Al

Hot Hardness
800

600
Hardness (HV)

DSA760

400

Nimonic80A

200 0 200 400 600 [ (C) ] Temperature 800 1000

Wear Resistance
0.1 Pin
<Test condition> Test temperature : RT Contact force : 10kg Distance : 10km Rev. speed : 1m/s Lubricant : dry Partner disc : AISI 52100 (62HRC)
Force Pin Force

0.05

0 DSA760 (58HRC) AISI 440C (60HRC) AISI 52100 (62HRC)

Disc

Pin-on-disc wear test

Acid Corrosion Resistance

1x10 10
4

5%H 1x10 10 . 10 1x10

2 3

SO

(RT)

1%HCl(RT) Immersion time:6hr

1

1x10 10

10 1x10

0.33 0.12 0.16

1x10 10

-1

1x10 10

-2

<0.01

<0.01

<0.01 Alloy751 AISI 304

DSA760

Hot Corrosion Resistance

High temperature oxidation
12 10 8 6 4 2 0 700 Alloy751 Alloy80A Alloy625 DSA760
0 50 100 150
S-attack(90%Na2SO4+10%NaCl)

Hot corrosion by salt coating

V-attack(85%V2O5+15%NaCl) 800deg.Cx20h

A286

800 900 1000 1100 Temperature (deg.Cx200hr)

DSA760

Alloy80A

Hardness and Magnetic Permeability

1x10 1
g type stainless steel

AISI 420

AISI 440C

(Cold worked) 1x10

0

AISI 304 AISI 201

1x10 -1

g type stainless steel (ST)

1x10

-2

AISI 303 AISI 316 Titinium alloy

Ni-based superalloy Alloy80A Alloy718 400 600 800 DSA760

1x10 -3

200

Hardness (HV)

Examples of Application (Tools) - High hardness (High temperature) - Excellent corrosion resistance
Weld Overlay by DSA760

Die tool to make drug tablets

Hot die punch

Overlay:55HRC

Base:36HRC DAC3

Examples of Application (Wire, Bearings)

High Strength Wires Dot pin, Dental tool Non-magnetic Bearings Magnetic Resonance Imaging System (MRI) Electromagnetic Clutch

Wire (0.3mm in diameter)

Bearings

Thank you so much for your attention