工業プロセスで生じる硫酸及び HI流体環境下における耐 …jolissrch-inter.tokai-sc.jaea.go.jp/pdfdata/JAEA-Technology-2017... · Iodide, Rare Earth, Ellingham

JAEA-Technology

2017-027

DOI:10.11484/jaea-technology-2017-027

Xing L. Yan

HTGR Hydrogen and Heat Application Research CenterSector of Nuclear Science Research

December 2017

Japan Atomic Energy Agency

Noriaki HIROTA, Jin IWATSUKI, Yoshiyuki IMAI and Xing L. YAN

HI

FeNiDevelopment Plan of Austenitic Fe and Ni Based Alloys with Improved Corrosion

Resistance to Sulfuric Acid and HI Fluids of Industrial Processes

http://www.jaea.go.jp

This report is issued irregularly by Japan Atomic Energy Agency.Inquiries about availability and/or copyright of this report should be addressed toInstitutional Repository Section,Intellectual Resources Management and R&D Collaboration Department,Japan Atomic Energy Agency.2-4 Shirakata, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195 JapanTel +81-29-282-6387, Fax +81-29-282-5920, E-mail:[email protected]

Japan Atomic Energy Agency, 2018

319-1195 2 4 029-282-6387, Fax 029-282-5920, E-mail:[email protected]

i

JAEA-Technology 2017-027

HI

Fe Ni

Xing L. Yan

2017 10 25

Fe Ni

(SiC) Fe CuTa SiTi CuSi

Ni MoWTa Ti Ni MoW

311-1393 4002

i

ii


Development Plan of Austenitic Fe and Ni Based Alloys with Improved Corrosion

Resistance to Sulfuric Acid and HI Fluids of Industrial Processes

Noriaki HIROTA, Jin IWATSUKI, Yoshiyuki IMAI and Xing L. YAN

HTGR Hydrogen and Heat Application Research Center Sector of Nuclear Science Research

Japan Atomic Energy Agency Oarai-machi, Higashiibaraki-gun, Ibaraki-ken

(Received October 25, 2017)

In this study, austenitic Fe based alloys and Ni based alloys was developed as candidate structural materials for equipment operated in sulfuric acid and hydrogen iodide (HI) environment, which exists in various industrial processes including iodine-sulfur (IS) hydrogen production process and geothermal power generation process. The objectives of the study are to achieve the corrosion resistance performance sufficient under the working condition of these processes and to overcome the practical scale-up difficulty of the ceramic (SiC) material that is presently used in the processes due to the manufacturing size limitation of the ceramic. The chemical composition development plan for the austenitic Fe based alloys is threefold: reinforcement of matrix by addition of Cu and Ta, strength compensation of the surface film by addition of Si and Ti, and prevention of peeling of surface oxide by addition of rare earth elements. Because addition of Cu and Si is known to reduce the ductility of the material and thus manufacturability of the component, it is important to determine the allowable amount of each element to be added. On the other hand, the chemical composition development plan for the Ni based alloys is reinforcement of matrix by addition of Mo, W and Ta, strength compensation of the surface film by addition of Ti, and prevention of peeling of surface oxide by addition of rare earth elements. In particular, the addition of Mo and W to the Ni based alloy is expected to be effective in preventing dimensional deviation of structures from increasing during heating and cooling of process equipment. Various material specimens will be fabricated based on the above chemical composition development plans and tests on these specimens will then be carried out to confirm the corrosion resistance performance under the fluid conditions simulating each industrial process.

Keywords: Corrosion-Resistant Material, High Temperature, Sulfuric Acid, Hydrogen Iodide, Rare Earth, Ellingham Diagram

ii


iii

1. ---------------------------------------------------------------------------------------------------------------- 1 2. ------------- 2 3. ---------------------------------------------------------------------------------------------------- 2

3.1 -------------------------------------------------------------------------------------- 2 3.1.1 Fe Cu --------------------------------------- 2 3.1.2 Ni MoW ------------------------------------ 3 3.1.3 Fe Ni Ta --------------------------------- 4

3.2 ---------------------------------------------------------------------------------------- 4 3.2.1 Fe Si -------------------------------------------- 4

3.2.2 Fe Ni TiC ------------------------------------- 4 3.3 ------------------------------------------------------------------------------------------------- 5 3.3.1 Fe Ni ----------------- 5

3.4 Fe Ni --------------------------------------------------------- 5 4. ---------------------------------------------------------------------------------------------------------------- 6 ---------------------------------------------------------------------------------------------------------------------- 6 ---------------------------------------------------------------------------------------------------------------- 7

iii



iv

Contents 1. Introduction --------------------------------------------------------------------------------------------------- 1 2. Importance of matrix strengthening of alloy, use of surface compound phase and

prevention of peeling off of compound ------------------------------------------------------------------ 2 3. Development plan for chemical composition -------------------------------------------------------- 2

3.1 Matrix strengthening element ----------------------------------------------------------------------- 2 3.1.1 Promotion of Passivation by Formation of Cu Sulfide to -Fe based Alloy --------- 2 3.1.2 Solid solution strengthening by adding Mo and W to Ni based alloy,

and low thermal expansion ----------------------------------------------------------------------- 3 3.1.3 Promotion of passivation by adding Ta to -Fe based alloy and Ni based alloy -- 4

3.2 Elements that produce surface compounds ------------------------------------------------------ 4 3.2.1 Improvement of corrosion resistance by formation of Si oxides to the-Fe

based alloy --------------------------------------------------------------------------------------------- 4 3.2.2 Grain boundary reinforcement by TiC formation to -Fe based alloy and Ni

based alloy --------------------------------------------------------------------------------------------- 4 3.3 Peeling prevention element --------------------------------------------------------------------------- 5 3.3.1 Prevention of peeling of surface compounds by addition of rare earth to -Fe

based alloy and Ni based alloy ------------------------------------------------------------------- 5 3.4Development plan for chemical composition of -Fe based alloy and Ni based alloy 5

4. Conclusion ------------------------------------------------------------------------------------------------------- 6 Acknowledgment ---------------------------------------------------------------------------------------------------- 6 References ------------------------------------------------------------------------------------------------------------- 7

iv



- 1 -

1.

950

GTHTR300C1) 950HTTR2) HTTR-HTTR-GT/H2 3)

IS IS 3 4)

SO2(g) + I2(aq) + 2H2O(aq) 2HI(aq) + H2SO4(aq) , ca. 100 (1) H2SO4(g) H2O(g) + SO2(g) + 0.5O2(g) , ca. 850 (2) 2HI(g) H2(g) +I2(g) , ca. 500 (3)

HI HI 2 IS

HI

SiCHI Ni HasteloyC276 5)6) IS SiC Ni HI SiC

SiC Ni IS


- 1 -


- 2 -

7)

600 SiC SiC

SiC 8) SiC SiC

SiC Fe Ni HI

2.

Fe Ni -pH 9)

Fig. 1 25 1N FeNiCr 18Cr-8Ni SS 10)SS

SS Cr Ni IS

Fe Ni

3.

Fe Ni HI

3.1 3.1.1 Fe Cu

Cu


- 3 -

Fig. 2 4-6 Cu 4-6 Cu 11) Cu Fig. 3 20 Fe 18Cr-8Ni CuPtPd Cu 12) Fig. 4 6693 Cu Cu 13)

S Cu Cu 14) Ni Cu NiO Cu2O Cu2O NiO

15)16)Ni Cu NiO 3.1.2 Ni MoW

HI/I2/H2O 200400Hastelloy Ni 17)Fe Mo Mo SUS405SUS444SUS316L2 SUS329J1Ni Incoloy825HasteloyC276Carpenter20CbInconel625 Fig. 5 Mo Fe Ni Mo Fe Mo 5 18) 37massFig. 6 Thermo-Calc Fe-Mo2 Mo Mo Mo Fe2Mo 950 Mo 2mass% Mo Mo Fe 19) 10mass% Fe Fe HI

Ni Mo Fig. 7 Thermo-Calc Ni-Mo225mass% Mo Ni Mo Mo


- 3 -


- 4 -

Ni W Fig. 8

Ni-W Ni W 30 mass% 20) MoW Ni 21)

3.1.3 Fe Ni Ta

pH -pH AuAgPt WTaNb 9) Ta 22)2 Ta 0.06mass% 23) Ni 24)W pH Fe Fe2Mo Fe2W 25)Fe W 3.2 3.2.1 Fe Si

SiC Fe Fe-Si Si 26)Si 12.2% SiO4 SiC 0.07mm/y Si Fe-Si SiO4

Ni-Fe Si Fe11Ni15Si4 27)Si 11mass%Ni3Si 28)Ni Si Fe11Ni15Si4Ni3Si 3.2.2 Fe Ni TiC Fe Alloy800Ni Alloy600


- 4 -


- 5 -

TiC 29) TiCFig. 9 Ti 30)N TiN 31)32)33)C N 3.3 3.3.1 Fe Ni Fe Fe-20Cr

Fig. 10 1000 95h Fe-20Cr LaTiZrAlSiGdY 34)Si Si LaGdY 4h

Y YCrO3 Y Cr2O3 Fe Cr2O3 / Y2O3 35)Ni Ni9Y 36)37)

Fe-25Cr Y 1%Y2O3 YFe3

38)

3.4 Fe Ni Table 1 Fe Ni

TaTi Fe Cu Si Ni MoW IS Fe CuTa SiTi 5mass% Cu Si Ni MoW


- 5 -


- 6 -

Ta Ti FeNi IS

4.

SiC Fe Ni HI

1) IS

Fe Ni

2) Fe CuTa Si Si Ti TiC

3) Fe CuSi

Ti 4) Ni MoW Ta

Ti TiC

5) Ni MoW

IS

IS


- 6 -


- 7 -

1) K. Kunitomi, X. Yan, T. Nishihara, N. Sakaba and T. Mouri, "JAEA's VHTR for Hydrogen and Electricity Cogeneration: GTHTR300C," Nuclear Engineering and Technology, 39(1), pp.9-20, (2007). 2) S. Fujikawa, H. Hayashi, T. Nakazawa, K. Kawasaki, T. Iyoku, S. Nakagawa and N. Sakaba, Achievement of reactor-outlet coolant temperature of 950C in HTTR, J. Nucl. Sci. Technol., 41 pp.1245-1254 (2004). 3) H. Sato, J. Sumita, A. Terada, H. Ohashi, X. Yan, T. Nishihara, Y. Tachibana and Y. Inagaki, HTTR Demonstration Program for Nuclear Cogeneration of Hydrogen and Electricity, Proceedings of the 23th International Conference on Nuclear Engineering (ICONE23), ICONE23-1459, May 17 - 21, 2015, Chiba, Japan (2015). 4) , , , , , 62, pp.122-128 (2013). 5) , , , , 65(4), pp.262-265, (2001). 6) , , , , , 55(7), pp.320-324, (2006). 7) , , 35(3), pp.215-219, (1996). 8) , , (2017). 9) , , 16, , pp.64-67, (1973). 10) , , , , , p.7, (1986). 11) , , vol.6, No.1, pp.311-315, (1957). 12) N.D. Tomashov, Corrosion, 14, pp.229-236, (1958). 13) , , Vol.20, No.4, pp.178-191, (1971). 14) , , , , , Vo.36, No.3, pp.65-68, (1986). 15) , , , , 3 , 2 , pp.51-57, (1960). 16) , , , , 24, 5, pp.320-324, (1960). 17) , , , , , , 18, pp.49-54, (1993). 18) , , , 47 , 10 , pp.1493-1500, (1961). 19) , , , , , , 80 , 1 , pp.22-29, (2008). 20) , , 2009-64501, H21.3.26. 21) , , , , , , , Vol.90, No.1, pp.37-42, (2004). 22) , , , , , , , 46(2), pp.113-117, (1997).


- 7 -


- 8 -

23) , , , , , , , 64, pp.324-327, (2015). 24) , , 59, pp.222-227, (2010). 25) , , , , , , Vol. 40, No. 457 pp.1283-1289, (1991). 26) , , , , , , , , 46, pp.1041-1045, (1997). 27) , , , , Vol. 27, No. 1, pp.18-23, (1963). 28) A. T. Dutra, P. L. Ferrandini, R. Caram, Journal of Alloys and Compounds, 432, pp.167-171, (2007). 29) L. Tan, L. Rakotojaona, T. R. Allen, R. K. Nanstad and J. T. Busby, Materials Science and Engineering A, A528, Issue6, pp.2755-2761, (2011). 30) , , 8 , pp.49-57, (1969). 31) R. S. Dutta, R. Purandare, A. Labo, S. K. Kulkarni and G. K. Dey, Corrosion Science, 46, pp.2937-2953, (2004). 32) R. S. Dutta, R. Tewari and P. K. De, Corrosion Science, 49, pp.303-318, (2007). 33) R. S. Dutta, Journal of Nuclear Materials, 393, pp.343-349, (2009). 34) , , , , 42, pp.1138-1144, (1978). 35) , , 65 , 7 , pp.747-771, (1979). 36) , , , , , , 11 , pp.1110-1117, (1975). 37) Ingard A. Kvernes, Oxidation of Metals, Vol.6, No.1, pp.45-64, (1973). 38) J. M. Francis, W. H. Whitlow, Corrosion Science, Vol.5, pp.701-710, (1965).


- 8 -


- 9 -

Fig. 1 Anodic polarization curve at 25C. under 1N sulfuric acid environment 10)

Logarithm of reaction current log i (mA/cm2)

Ele

ctr

ode p

ote

ntial E (

V, S

CE)


- 10 -

Fig. 2 Changes in cavitation corrosion amount with temperature rise of 4-6 brass, pure Cu 11)

Liquid temperature ()

Boiling

Am

ount

of

cav

itat

ion c

orr

osi

on (

mg)

4-6 Brass

Steel

Cu


- 11 -

Fig. 3 The effect of addition of Cu, Pt and Pd on corrosion rate of 18Cr-8Ni steel with increasing

sulfuric acid concentration at 20C 12)

H2SO4 (%)

Corr

osi

on r

ate (

g/m

2/h)

No addition


- 12 -

Fig. 4 Changes in the degree of corrosion associated with the increase in the amount of Cu to stainless steel under 66C, 93C sulfuric acid environment 13)

H2SO4 (%)

Degr

ee o

f ero

sion (

mm

/y)


- 13 -

Fig. 5 Relationship between Corrosion rate and Mo addition amount of Various Alloys in HI / I2 / H2O Mixed Gas from 200C to 400C

Degr

ee o

f ero

sion (

mm

/y)

Mo content (mass%)

Ferrite Austenite

Ni alloy


- 13 -


- 14 -

Fig. 6 Fe-Mo phase diagram

Mo content (atom%)

Mo content (mass%)

Tem

pera

ture

(

)


- 14 -


- 15 -

Fig. 7 Ni-Mo phase diagram

Solid solution amount

Mo content (atom%)

Mo content (mass%)

Tem

pera

ture

(

)


- 15 -


- 16 -

Fig. 8 Ni-W phase diagram

Solid solution

amount

W content (atom%)

W content (mass%)

Tem

pera

ture

(

)


- 16 -


- 17 -

Fig.9 Ellingham diagram evaluating carbide forming ability 30)

Temperature (K)

Temperature (K)

Change

of

standar

d p

roducin

g fr

ee e

nerg

y (k

cal

)


- 18 -

Fig. 10 Influence of weight change on Fe-20Cr alloys containing La, Ti, Zr, Al, Si, Gd and Y added when kept at 1000C for 95 h 34)


- 19 -

-Fe based alloy Ni based alloy -Fe based alloy Ni based alloy

Cu Cu Sulfide

Peeling by Cu2O

Decline inprocessability

by Cu embrittlement

Acceleration of surfaceoxidation by Cu2O

MoW

Decrease incorrosion resistance

by Fe2Mo, Fe2W

Solid solutionstrengthening

of Mo, W

Fe2Mo, Fe2WEmbrittlement

Low thermalexpansion

by Mo, W content

Ta Ta Passive film

Ta Passive film

No effect No effect

Si SiO4 oxide


by Fe11Ni15Si4

Decline inprocessability by Si

embrittlement

Ni3SiEmbrittlement

Ti TiC

TiC

Improvement ofcreep strength by TiC


Prevention ofpeeling

Rareearth

Rare earth compound

Rare earth compound

Improvement oftoughness

by Rare earth


by Rare earth

: Obviously good effect: Those that will be adversely affected by excessive addition

Influence on corrosion resistance Influence on mechanical properties

Element thatproducesurface

compounds

Matrixstrengthening

element

Table1 Influence of each added element on corrosion resistance and mechanical properties for -Fe based alloy and Ni-based alloy


- 19 -

-Fe based alloy Ni based alloy -Fe based alloy Ni based alloy

Cu Cu Sulfide

Peeling by Cu2O

Decline inprocessability

by Cu embrittlement

Acceleration of surfaceoxidation by Cu2O

MoW


by Fe2Mo, Fe2W

Solid solutionstrengthening

of Mo, W

Fe2Mo, Fe2WEmbrittlement

Low thermalexpansion

by Mo, W content

Ta Ta Passive film

Ta Passive film

No effect No effect

Si SiO4 oxide


by Fe11Ni15Si4

Decline inprocessability by Si

embrittlement

Ni3SiEmbrittlement

Ti TiC

TiC



Prevention ofpeeling

Rareearth

Rare earth compound

Rare earth compound


by Rare earth


by Rare earth

: Obviously good effect: Those that will be adversely affected by excessive addition

Influence on corrosion resistance Influence on mechanical properties

Element thatproducesurface

compounds

Matrixstrengthening

element

Table1 Influence of each added element on corrosion resistance and mechanical properties for -Fe based alloy and Ni-based alloy


- 19 -

This is a blank page.

SI

1024 10-1 d1021 10-2 c1018 10-3 m1015 10-6 1012 10-9 n109 10-12 p106 10-15 f103 10-18 a102 10-21 z101 da 10-24 y

SI

SI min 1 min=60 s h 1 h =60 min=3600 s d 1 d=24 h=86 400 s 1=(/180) rad 1=(1/60)=(/10 800) rad 1=(1/60)=(/648 000) rad

ha 1 ha=1 hm2=104m2

Ll 1 L=1 l=1 dm3=103cm3=10-3m3

t 1 t=103 kg

SISI

SI eV 1 eV=1.602 176 53(14)10-19J Da 1 Da=1.660 538 86(28)10-27kg u 1 u=1 Da ua 1 ua=1.495 978 706 91(6)1011m

SISISI

SI Ci 1 Ci=3.71010Bq R 1 R = 2.5810-4C/kg rad 1 rad=1cGy=10-2Gy rem 1 rem=1 cSv=10-2Sv 1=1 nT=10-9T 1=1 fm=10-15m 1 = 0.2 g = 210-4kg Torr 1 Torr = (101 325/760) Pa atm 1 atm = 101 325 Pa

1 cal=4.1858J154.1868JIT4.184J

1 =1m=10-6m

10SI

cal

(a)SI(b)radsr(c)sr(d)(e)

(f)activity referred to a radionuclideradioactivity(g)PV,2002,70,205CIPM2CI-2002

aamount concentrationsubstance concentrationb

SI

Pa s m-1 kg s-1

N m m2 kg s-2

N/m kg s-2 rad/s m m-1 s-1=s-1 rad/s2 m m-1 s-2=s-2 , W/m2 kg s-3

, J/K m2 kg s-2 K-1 J/(kg K) m2 s-2 K-1 J/kg m2 s-2 W/(m K) m kg s-3 K-1

J/m3 m-1 kg s-2

V/m m kg s-3 A-1 C/m3 m-3 s A C/m2 m-2 s A C/m2 m-2 s A F/m m-3 kg-1 s4 A2

H/m m kg s-2 A-2

J/mol m2 kg s-2 mol-1

, J/(mol K) m2 kg s-2 K-1 mol-1

C/kg kg-1 s A Gy/s m2 s-3 W/sr m4 m-2 kg s-3=m2 kg s-3

W/(m2 sr) m2 m-2 kg s-3=kg s-3 kat/m3 m-3 s-1 mol

SI

SI

m2 m3 m/s m/s2 m-1 kg/m3

kg/m2

m3/kg A/m2 A/m (a) mol/m3 kg/m3 cd/m2 (b) 1 (b) 1

SI

SI

SI

SI

() rad 1 m/m () sr(c) 1 m2/m2 Hz s-1

N m kg s-2 , Pa N/m2 m-1 kg s-2 , , J N m m2 kg s-2 W J/s m2 kg s-3 , A sC , V W/A m2 kg s-3 A-1 F C/V m-2 kg-1 s4 A2 V/A m2 kg s-3 A-2 S A/V m-2 kg-1 s3 A2

Wb Vs m2 kg s-2 A-1 T Wb/m2 kg s-2 A-1 H Wb/A m2 kg s-2 A-2 () K

lm cd sr(c) cd lx lm/m2 m-2 cd

Bq s-1, ,

Gy J/kg m2 s-2

, ,,

Sv J/kg m2 s-2

kat s-1 mol

SISI

SI bar bar=0.1MPa=100 kPa=105Pa mmHg mmHg133.322Pa =0.1nm=100pm=10-10m M=1852m b b=100fm2=(10-12cm) =10-28m22

kn kn=(1852/3600)m/s Np

dB

SISI

SI

m kg s A K mol cd

SI

SI

SI erg 1 erg=10-7 J dyn 1 dyn=10-5N P 1 P=1 dyn s cm-2=0.1Pa s St 1 St =1cm2 s-1=10-4m2 s-1

sb 1 sb =1cd cm-2=104cd m-2

ph 1 ph=1cd sr cm-2 =104lx Gal 1 Gal =1cm s-2=10-2ms-2

Mx 1 Mx = 1G cm2=10-8Wb G 1 G =1Mx cm-2 =10-4T Oe 1 Oe (103/4)A m-1

CGS

aCGSSI

82006

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工業プロセスで生じる硫酸及び HI流体環境下における耐 …jolissrch-inter.tokai-sc.jaea.go.jp/pdfdata/JAEA-Technology-2017... · Iodide, Rare Earth, Ellingham