DesignofDiffusionCoatingsDevelopedviaPackCementation

A.Naji,M.C.Galetz,M.Schtze
email:naji@dechema.de
Fundedby:BMWi viaAiF
Period:01.03.2012 28.02.2015

ConceptandGoaloftheCoatingDesign
Determinationof
PackProcessParameter

Coefficientofthermal
expansion(CTE)mismatch
betweencoatingandsubstrate

Fe2Al5

Coatingisbrittle

FeAl

FeAl

PowderComposition
ProcessTemperature
ProcessTime

Coatingthicknessistoohigh

interdiffusion zone

CoatingDesign

interdiffusion zone
material

material

ThermodynamicConsideration
KineticConsideration

Ni2Al3

IntermetallicPhases
(FeAlor NiAl phase)

InterdiffusionofAlintotheinner
substrate
Crackformationwithinthecoating

cracks
interdiffusion zone

NiAl

Prediction of Coating Structure

PredictionofCoatingStructure

Cyclicandisothermoxidation
Cyclic
and isotherm oxidation
ofAlcoatedmaterials

interdiffusion zone
material

CoatingThickness

material

Figure 2: Illustration of the coating design procedure.

Figure 1: Cross sections of an Al coated austenitic steel and

Nibase alloy with brittle phases and cracks.

Figure 3: Cross sections of an Al coated austenitic steel and

Nibase alloy with the desired phases without cracks.

ApproachoftheCoatingDesign
ThermodynamicConsideration

KineticConsideration
Kinetic considerations are based on Ficks first law
Linearization of the concentration gradient between the pack/coating and
coating/substrate interfaces (Figure 6) leads to an analytical, instead of a
numerical solution of the differential equation.

Pack Cementation Process

Gaseous diffusion step (Al chlorides diffuse from powder pack
to the substrate surface)
Solid state diffusion step (Al chlorides dissociate on the substrate surface
and Al diffuses into the substrate)
Solid state diffusion is assumed to be the rate limiting step
Fe

log10 (activity)

-2

Liquid
-2

Ni2Al3

Liquid

aAl

Ni3Al

-3

-3

NiAl

FeAl

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

-7
1.0 0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

aAl Ni2Al3

aAl in pack (1wt.%Al, 1wt.%NH4Cl, rest Al2O3

aAl in Pack (1wt.% Al, 1wt.%NH4Cl, rest Al2O3)

1E-3
aAl Fe2Al5

aAl FeAl
1E-3

Figure6:Illustrationofthelinearization
oftheAlactivitydifferences.

0,01

0,1

0,01

t:

resultingcoating
thickness
distance
diffusion
coefficientofAl
inthe intermetallic
phase
constant
Alactivitydifference
betweenthepack
andthesubstrate
processtime.

0,1

aAl FeAl3

aAl FeAl2

q:
a:

x
aAl

1.0

Figure4:ViaFactSagecalculatedAl,FeandNiactivities
withintheFeAlandNiAlsystemsat1000C.
1

substrate

aAl

Al

-6

-5
0

coating
FeAl

-5

FeAl2

pack

-4

Al

Fe2Al5
FeAl3

-4

x:
D:

Ni

-1

-1
1

aAl

Step2:
Calculationof
theAlactivity
withinthepack
h h
k
independence
oftheprocess
temperatureand
thepackpowder
composition
(diffusion
element,
activatorNH4Cl
andfillerAl2O3.

x:

aAl

Step1:
Calculationofthe
Al ti it ithi
Alactivitywithin
theintermetallic
phase,thatcan
occurduetothe
coatingprocess
(FeAl,NiAl,
Fe2Al5,Ni2Al3).

resultingcoatingthickness

Ficks firstlaw

aAl NiAl

1E-5
1E-6

1000 1050 1100 1150 1200 1250 1300

Step1: coatingofthematerialatthree
differentprocesstemperatures

aAl in pack (1wt.%AlF3, rest Al2O3)

1E-4

1E-7

Step2: determinationofthediffusion
coefficientD ofAlinFeAlorNiAl via
Matano analysisatthesetemperatures

aAl Ni3Al
1000 1050 1100 1150 1200 1250 1300 1350 1400

Temperature (K)

Temperature (K)

Step3: determinationoftheprefactorofD0
andtheactivationenergyEA forAldiffusionin Figure7:Plottingofthediffusion
coefficientvs.Temperature.
theintermetallicphasebyplottinglnD(T)vs.1/T

Figure5:ComparisonoftheAlactivitywithintheNiAlsystem
andtheAlactivitywithinthepack.

Applicationofthecoatingdesignmodel
DevelopmentofaFeAlcoatingonamaterial/diffusionelementcouple
1. Thermodynamic calculation of the appropriate pack powder mixture and
Table1:Comparisonofpredictedandmeasuredcoatingthicknesses.
process temperature in order to achieve a FeAl coating.
2. Three test coating procedures at different process temperatures
3. Determination of the diffusion coefficient D of Al in FeAl via Matano
analysis
4 Determination of D0 and the activation energy EA for Al diffusion in
4.
FeAl
FeAl by
plotting lnD(T) vs. 1/T

AISI 321

pack
composition
1wt.% Al,
1wt.% NH4Cl,
98wt.% Al 2O3

AISI 314

Alloy 800

800C

predicted
coating
thickness
12 m

measured
coating
thickness
11 m

predicted
coating
thickness
9 m

measured
coating
thickness
8.5 m

predicted
coating
thickness
3.9 m

measured
coating
thickness
3.5 m

900C
1000C

25.3 m
50 m

24 m
50 m

23m
51 m

22 m
51 m

19.9 m
54 m

18.5 m
54 m

5. Prediction of the coating properties for all other process parameters for every
alloy and coating

ProjectPartners
O.Pasdag,ZentrumfrBrennstoffzellenTechnikGmbH,Duisburg
A.Lderitz,InstitutfrFgetechnikundWerkstoffprfungGmbH,Jena

Acknowledgement
This work is financially supported by the German Ministry of Economics and Technology
(BMWi) via AiF under IGFcontract no. 16881 BG, which is gratefully acknowledged.