含Fe和Mn的Ni30Cu70固溶体团簇模型与耐蚀性研究

11

Vol.45

No.11

2009

11

1390—1395ACTAMETALLURGICASINICANov.2009pp.1390–1395

Fe

Mn

Ni30Cu70

∗

(

,

116024)

Ni30Cu70(

,%)

,

Fe

Mn

.

,

Fe

Mn

Ni

12

(Fe1−xMnx)Ni12

.

Cu

,

[M1/13Ni12/13]30Cu70=[(Fe1−xMnx)Ni12]Cu30.3,M=(Fe1−xMnx).[(Fe1−xMnx)Ni12]Cu30.3

X

,

,

[(Fe0.75Mn0.25)Ni12]Cu30.3

,

3.5%NaCl

.

Cu–Ni

,Fe(Mn)

,

,

,

TG111,TG146

A

0412−1961(2009)11−1390−06

STUDYONTHECLUSTER–BASEDMODELOFNi30Cu70SOLIDSOLUTIONWITHFeANDMnANDITSCORROSIONRESISTANCE

ZHANGJie,WANGQing,WANGYingmin,DONGChuang

KeyLabofMaterialsModificationbyLaser,IonandElectronBeamsofMinistryofEducation,SchoolofMaterialsScience&Engineering,DalianUniversityofTechnology,Dalian116024

Correspondent:DONGChuang,professor,Tel:(0411)847083,E-mail:dong@dlut.edu.cn

SupportedbyNationalNaturalScienceFoundationofChina(Nos.50671018and50631010),National

BasicResearchProgramofChina(No.2007CB613902)andNationalHighTechnology

ResearchandDevelopmentProgramofChina(No.2007AA05Z102)

Manuscriptreceived2009–04–29,inrevisedform2009–07–31

ABSTRACTMinorFeandMnadditionsarenecessarytoenhancethecorrosionresistanceofcom-mercialCu–Nialloys.ThepresentpaperaimsatoptimizingtheadditionamountsofFeandMninCu70Ni30(atomicfraction,%)alloyusingacluster–basedsolidsolutionmodel.Inthismodelitas-sumedthatoneFe(Mn)atomandtwelveNiatomsformedaclusterconsistedofFe(Mn)–centeredandNi–surroundedcube–octahedronandthelimitsolidsolutionwouldbecomposedofisolatedFe(Mn)Ni12clustersembeddedintheCumatrix.TheratiooftheFe(Mn)atomsanditssurroundingNiatomsis112,andthelimitsolidsolutioncompositionofFe(Mn)–modifiedCu70Ni30alloyis[M1/13Ni12/13]30Cu70=[(Fe1−xMnx)Ni12]Cu30.3,M=(Fe1−xMnx).TheOM,XRDandelectrochemicalcorrosionmeasurementswereusedtocharacterizethemicrostructureandcorrosionresistanceper-formanceof[(Fe1−xMnx)Ni12]Cu30.3.Theresultsindicatedthatthesolidsolubilitylimitativealloys[(Fe0.75Mn0.25)Ni12]Cu30.3hasthebestcorrosionresistancein3.5%NaClaqueoussolution.

KEYWORDSCu–Nialloy,additionofFe(Mn),solidsolutionmodel,clusterstructure,

corrosion–resistance

70/30Cu–Ni(

*

,%,

)

50671018

50631010,

[1−3]

.

Ni

Fe

2007CB613902

2007AA05Z102

:2009–04–29,

:2009–07–31

:

,

,1979

,

[4,5]

Cu–Ni

70/30Cu–Ni0.5%—2.0%Fe

.90/10Cu–Ni,Fe,,Fe>2%

,

,

11

:

Fe

Mn

Ni30Cu70

1391

[6−9]

α,

.

Fe

Cu–Ni

,

0.5%—2.0%Mn[6]

.FeMnCu–Ni

,

Fe

Mn

Cu–Ni,

,

.

Fe

Mn70(Ni30Cu,%,

)

.

X(XRD)

,

.

1

,

,

+

,

[10,11]

.

,

,

,

,

,

,

,

,

[12]

[13]

.

Bragg–Williams

,

,

,

,

.

,

,

,

,

.

Cu–Ni

,

345.4

[14]

,

;FeCu,

[15]

600.1Cu–Ni–Fe[16]

800

FeNi=1

12

1Cu–Ni–Fe800[16]FeNi=1

12

Fig.1IsothermalsectionoftheCu–Ni–Fealloyphase

diagram[16]andtheFeNi=112composi-tionline

(

)

.

,Fe

Cu–Ni

Ni

,NiFe

Cu

,

Cu–Ni–Fe

FeNi=112

Fe

Cu,,

Cu–Ni–Fe

,Fe

NiFe

Ni≈112.

Fe

Ni30Cu70,Cu,Ni

Fe

0.128,0.1250.127nm,

,

,

.Ni–Fe,Cu–NiCu–Fe−2,413kJ/mol[17],,

,CuNiFe,Cu13,2a.FeNiFe

2fcc[(Fe1−xMnx)Ni12]Cu30.3

Fig.2Clustermodeloffcc[(Fe1−xMnx)Ni12]Cu30.3solid

solutionalloys

(a)(Fe1−xMnx)Ni12andCu13cube–octahedral

clusters

(b)neighboringbutisolated(Fe1−xMnx)Ni12clus-terscorrespondingtothesolubilitylimit

(c)Fe–Ni–Fe–Ni–typelong–rangeorderintheFeNi3

phase

(d)clustermodelfortheCu–Ni–Fesolubilitylimit

alloywheretheFe1Ni12atomicclustersareem-beddedinCumatrix

139245

,Ni12

Fe1Ni12

,Fe1Ni12,2b

,

···–Ni–Fe–Ni–Ni–Fe–Ni–···,FeNi=1

12.Fe,Fe1Ni12

,Ni,

···–Ni–Fe–Ni–Fe–Ni–···,

···–Ni–Fe–Ni–Fe–Ni–···FeNi3,FeNi3,2c.,FeNi30Cu70,

[Fe1/13Ni12/13]30Cu70,

[Fe1Ni12]Cu30.3.Fe/Ni[18]

,,FeNi=112Cu–Ni–Fe.

FeMnNi30Cu70

,Ni–MnCu–Mn−84kJ/mol[17].Fe,MnCu,Ni

,FeMn,(Fe1−xMnx)Ni12Cu1312

,2d.,Fe

MnCu70Ni30,

(Ni12/13M1/13)30Cu70,M=(Fe,Mn),[(Fe1−xMnx)Ni12]Cu30.3.FeMn

,Ni30Cu70FeMn

.

2

,

Ni13Cu30.3

(Ni30Cu70)FeMn[(Fe1−x-Mnx)Ni12]Cu30.3(x=0,0.25,0.5,0.751),

1.Cu99.98%,

Ni99.99%,Fe99.99%Mn99.98%.

8005h,.X(XRD,CuKα)

;(OM);EG&GM342

,,3.5%()NaCl,25,

1[(Fe1−xMnx)Ni12]Cu30.3Ni13Cu30.3

Table1Chemicalcompositionsof[(Fe1−xMnx)Ni12]Cu30.3

andNi13Cu30.3alloys

xAtomfraction,%Massfraction,%CuNiFeMnCuNiFeMn07027.692.31071.7226.202.0800.257027.691.730.5871.7326.201.560.510.57027.691.651.6671.7326.211.041.020.757027.690.581.7371.7326.210.521.1

7027.6902.3171.7426.2102.05Ni13Cu30.3

70

30

0

0

71.

28.36

0

0

60mV/min,,

(SCE),Pt,.

3.5%NaCl,240h

,v=(w1−w2)/St(,w1,w2,S

,t).

33.1

XRD3Ni13Cu30.3[(Fe1−xMnx)Ni12]Cu30.3(FeMnNi30Cu70)8005hXRD.fcc,Cu

,,,CuNi,FeMnCu,fcc.

3fcc

Ni13Cu30.3[(Fe1−xMnx)Ni12]Cu30.3

XRD

Fig.3XRDpatternsofthefccstructuralNi13Cu30.3and

[(Fe1−xMnx)Ni12]Cu30.3alloysafterannealingat800for5h

3.2

4Ni13Cu30.3[(Fe1−xMnx)Ni12]Cu30.38005h.4a,Ni13Cu30.38005h,100—250μm,.4bf,FeMn100—200μm.4c,deFeMn,

,50—100μm.Cu–Ni

Fe,Fe1Ni12

,,;

FeMn,Fe1Ni12Mn1Ni12

Fe/Ni,

.3.3

5Ni13Cu30.3[(Fe1−xMnx)Ni12]Cu30.3

(x=0,0.25,0.5,0.751)

.Tafel

[(FexMn1−x)Ni12]Cu30.3

11

:

Fe

Mn

Ni30Cu70

1393

4Ni13Cu30.3

[(Fe1−xMnx)Ni12]Cu30.3

800

5h

Fig.4OMimagesoftheNi13Cu30.3(a)and[(Fe1−xMnx)Ni12]Cu30.3alloyswithx=0(b),x=0.25(c),x=0.5(d),

x=0.75(e)andx=1(f)afterannealingat800for5h

2Ni13Cu30.3

[(Fe1−xMnx)Ni12]Cu30.3

Table2CorrosionparametersoftheNi13Cu30.3and[(Fe1−x-Mnx)Ni12]Cu30.3alloysin3.5%NaClsolutionob-tainedbyfittingthecurvesinFig.5

x00.250.50.75

EcorrV−0.137−0.123−0.133−0.152−0.175−0.212

icorrμA/cm210.97.512.122.5.385.5

βaV/dec0.1560.1940.1560.1950.1720.184

βcV/dec−0.091−0.099−0.101−0.120−0.125−0.143

5Ni13Cu30.3

[(Fe1−xMnx)Ni12]Cu30.3

1Ni13Cu30.3

Fig.5PotentiodynamicpolarizationcurvesoftheNi13Cu30.3and[(Fe1−xMnx)Ni12]Cu30.3al-loysin3.5%NaClsolution

Note:Ecorr—corrosionpotential,icorr—currentden-sity,βa—anodicTafelslope,βc—cathodicTafelslope

(βc)

(Ecorr)

(icorr),

(βa)

2.

2

Fe

,

Mn

Ni13Cu30.3

Ni30Cu70

,

1394

45

,

,

.

Mn[Mn1Ni12]Cu30.345.3μA/cm2,−0.175V,;FeMn[(Fe0.75-Mn0.25)Ni12]Cu30.3

(−0.123V)(8.5μA/cm2),

0.052V,36.8μA/cm2,

;

[(Fe0.5Mn0.5)Ni12]Cu30.30>[Fe1Ni12]Cu30.3>[(Fe0.25-Mn0.75)Ni12]Cu30.3

.,

Fe

Mn

,.

Mn[Mn1Ni12]Cu30.38005h,,(4f).

FeMn

[(Fe0.75Mn0.25)Ni12]Cu30.3

,

(4c),

,

[(Fe0.75Mn0.25)Ni12]Cu30.3.Cu–NiFeMn

FeMnCu–Ni,FeCu–Ni

[7].

3.4

,

[Fe1Ni12]Cu30.3

3.5%-NaCl

,

6.

,

,

,

,

,

,

,

,,

.[Fe1Ni12]Cu30.33.5%NaCl240h,0.0025μm/h.

,240h

.7FeMn[(Fe1−x-Mnx)Ni12]Cu30.3(x=0,0.25,0.5,0.751)

3.5%NaCl240hMn

.,FeMn

[Fe1Ni12]Cu30.3,FeMnCu70Ni30.[(Fe1−xMnx)Ni12]Cu30.3,Mn

x=0.25,[(Fe0.75Mn0.25)Ni12]Cu30.3

,0.0012μm/h,;Mn

x>0.25,,Mn,FeCu70Ni30

.FeCu70Ni30,

Fe

Mn[(Fe0.75Mn0.25)Ni12]Cu30.3

,

6[Fe1Ni12]Cu30.3

800

5h

3.5%NaCl

Fig.6Changesofmasslossandthecorrespondingcorro-sionrateofthe(Fe1Ni12)Cu30.3alloyafterannealingat800for5hin3.5%NaClsolutionwithtime

7[(Fe1−xMnx)Ni12]Cu30.3

Mn

Fig.7ChangesofstaticimmersioncorrosionratewithMn

contentxof[(Fe1−xMnx)Ni12]Cu30.3alloy(theda-tumofNi13Cu30.3isalsogivenascomparison)

Fe

Mn

,,

,

.

4

,

Fe

Mn

Ni30Cu70

,

(Fe1−xMnx)Ni12

Cu1312

fcc

,

[(Fe1−xMnx)Ni12]Cu30.3.

,

Mn

,x=0.25(Cu70Ni27.7Fe1.7Mn0.6(,%)=Cu–26.2Ni–1.6Fe–0.5Mn(,%)),800

5h,,50—100μm,3.5%NaCl,

0.0012μm/h.

11

:

Fe

Mn

Ni30Cu70

1395

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