Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.

43

DIFFRACTING

PARTICLE SIZE ANALYSIS OF MARTENSITE

AUSTENITE MICROSTRUCTURES.

- RETAINED

J. D. Makinson, W. N. Weins, T. W. Snyder, and R. J. De Angelis

Center for Materials Researchand Analysis
Department of Mechanical Engineering
University of Nebraska-Lincoln
Lincoln, NE 68588
ABSTRACT

Case carburized steels containing a martensite-retained austenite microstructure are typically

analyzedfor the amountof eachphaseusing x-ray diffraction techniqueswhich arewell established.
In addition, however, analysis of the diffracting particle size of both the retained austeniteand the
martensiteprovides additional detailed information aboutthe microstructure. The diffracting particle
size of the martensite was measuredas a function of depth of four end-quenchspecimens(Jominy
bars) ranging from 0.22 to 0.83 weight percent carbon. In addition ,difFi-actingparticle size of 53
casecarburized sampleswas measuredat a constant carbon composition, as a function of retained
austenite content. Analysis of the data indicates that the diffracting particle size of the austenite
becomesrefined asthe amount of martensitetransforming from the austeniteincreases.This effect
is due to the austenite being cut by the martensite and plastic deformation of the austeniteby the
martensiteat lower temperatures.The martensitedX&actingparticle sizeremainsrelatively constant
during transformation at a given carbon level, regardless of the degree of transformation. The
martensitediffracting particle size does,however, increaseasthe morphology changesto a diffusion
controlled transformation.
I
INTRODUCTION

Engineered components and structureswhich utilize steel as a material along with a quench and
temper heat treatment will experience different cooling rates as a function of location during the
quenching process.In addition, the product may have a variable carbon content as a function of
location, dueto processessuch as carburization or decarburization of the surfaceof the component.
The two phaseswhich are most prevalent in this type of microstructures include martensite and
retained austenite. While the amount of each phase is of great importance and is certainly the
parameterwhich is most often measuredusing x-ray difiaction, the diffracting particle size of both
the martensite and retained austenite as a function of carbon content and cooling rate are also of
interest and can be determined at the sametime generally using the same data. If the diffracting
particle size can be correlated with the cooling rate and carbon content, it can be used as a method
for checkingthe consistencyof aparticular heattreatmentprocess,or to determine information about
the processingparametersused for a particular heat treatment operation.

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Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43

EXPERIMENTAL
End-Quench

PROCEDURE

Test

The specimensstudied were standardJominy bars machined from symmetrical positions of a single
AISI-SAE 4320H gradesteelbar, carburized,and then homogenizedwhich resulted in carbonlevels
of 0.22,0.34,0.46, and.O.84%. Chemistry of the starting material is listed in Table 1. Thesefour
carbon levels were achieved by carburizing the specimens0, 20, 40, and 120 hours respectively.
Homogenization was carried out at 1200C for 192 hours in a neutral atmosphereof argon. The
grain sizewas then refined by two thermal cycling treatmentsafter of the homogenization treatments
Jereemployed.

Element
Nickel
Manganese
ChOmiUm

Molybdenum
Silicon
Carbon
Phosphorous
Sulphur
Copper
Aluminum

The Jominy bars were austenitized at 857C, held at

temperaturefor 40 minutes, andthen end-quenchedas
per ASTM A255. [I1 Water temperature was 16C.
Flats were ground on the longitudinal sides of the
Jominy bars and Rockwell hardness profiles were
performed.

Weight %
1.69%
0.61%
0.57%
0.23%
0.30%
0.22%
0.021%
0.020%
0.14%
0.05%

Table 1: Chemical analysis of the

4320H steel used for this investigation.

X-ray diffraction measurements were made by

grinding to severaldepths from the quenchedend of
the four Jominy bars. Surface roughness after
grinding measuredlessthan 0.8 microns. The surface
damagedlayer was then removed by electropolishing
at 25 to 35 volts for 120 secondsin a 6% perchloric,
35% buteoxyethanol, 59% methanol solution cooled
by an ice water bath. This procedureremovedeight to
16 pm of material. Finally, the electopolishedsurface
was inspectedusing an optical microscope to ensure
an uniform removal of material.

A Philips x-ray diffractometer was used with a copper anode tube powered at 40 kV and 30 mA.
The diffractometer was outfitted
with a graphite diffracted beam
monochromator and a variable
divergent slit. Sincethe cooling rate
M(211)
is a function of distance from the
1
quenched end, copper k, radiation
A(200)
was selected to minimize x-ray
I
penetration depth. This decreased f _
M(200)
the range of cooling rates averaged =
into eachx-ray measurement.
Higher carbon content in the steel
increasesthe tetragonality of the asquenchedmartensite unit cell. This

40

60

80
70
Two-Theta Degrees

is
cka.dy
seen
in
the
x-ray
p lgure 1: X-ray diffraction patterns of as-quenched
diffraction pattern firom the as- 0.84% carbon steel.

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Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43

328

quenched0.84% carbon specimen in Figure 1. Becausethe amount of tetragonality dependson

several factors such as carbon content and thermal history, the diffraction profile is affected to
varying degrees. Although inexact, an assumption was made that the diftiaction profiles are
symmetrical, therefore a method of reflecting the high angle side datato the low side was used,thus
removing the asymmetric effect of the tetragonalality on the diffraction profile.
A single-profile Fourier analysis technique was used to determine the diffracting particle size L2].
This techniqueemploys the Stokescorrection for instrumentalbroadening.I31Profiles from the NIST
660 LaB, standardreferencematerial provide the instrument broadening function. The effective
particle size was determined from the martensite M(200) reflection. Ferrous martensite contains
very high dislocation densities in the order of 1Ol to 1012per cm2. r41 With this heavy defect
structureof the martensite, the x-ray line broadening is predominantly produced by small coherent
particles.
Experimental Case Carburized Specimens
Fifty three 4320H steel specimenswere casecarburized with a 1.O%carbonpotential gas,cooledto
room temperature then austenitized, followed by an oil quench. Finally, the specimens were
tempered at 176C for three hours. The processingparameterssuch as austenitizing temperature,
quenchtemperature,etc., were varied slightly to produce retained austenite contentsranging from
17 to 31%. Using a surface grinder, 500 pm of material was removed from the surface, then
electropolishedto remove the effects of grinding. Diffracting particle size was calculated from the
retained austenite A(200) and martensite M(200) reflections. Because these specimens were
temperedno teteragonality of the unit cell was present,therefore, it was not necessaryto symmetrize
the diffraction peak.
Retained austenite measurementswere
accomplished employing a four peak
The integrated
analysis method.
intensities of two retained austenite,
A(200) & A(220) and two martensite,
M(200) & M(211) diffi-action peaks
were used to calculate the retained
austenite content. [51 These peaks are
indexed and shown in Figure 1.
RESULTS AND DISCUSSION

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of distance from the Figure 2: Rockwell C hardnessprofile of the four end-

quenched end are shown in Figure 2. quenchedspecimens.

As expected, hardness increases with
increasingcarboncontent. The lower carbonspecimensexhibit decreasedhardenability ascompared
to the higher carbon specimens. Both the 0.46% and 0.83% C specimensare through-hardened,
maintaining their hardness50 mm from the quenchedend. Hardnessof the 0.22 % C specimen

Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43

329

beginsto decreaseat a depth 14 mm from the quenchedsurface,while the 0.34% C specimenbegins

to decreaseat 25 mm.
The diffracting particle size of the martensite as a function of distance from the quenchedend for
all carbon levels are shown in Figure 3a. Figure 3b is enlarged area from Figure 3a. An overall
decreasein diffracting particle size is observedwith increasing carbon content; however, very little
difference between the 0.46% and 0.83% carbon specimensis observed. For all specimens,there
is a sharp decreasein the diffracting particle size in the first couple of millimeters towards the
quenchedend. This decreasein diffracting particle size approachingthe quenchedend is due to a
faster cooling rate effect. These faster cooling rates increasethe amount of undercooling which
occursbefore transformation. Consequently,this increasesthe number of active sitesfor martensite
nucleation. It is reasonableto expect that the length of crystal coherencebecomes smaller as the
density of martensite nucleation sites increases.
The martensite start temperature, M, , may be calculated for low alloy steels by the empirical
equation;

or for these specimens,M, (C) = 437 - 333 C, where the alloying elements are given as weight
percentages.t6] The M, temperaturedecreasesTom approximately 363C for the 0.22% C to 157C
for the 0.84% C specimens. The amount of undercooling createdby the quenchwith 16C water is
greaterin the lower carbon specimenswhen the M, temperatureis highest. This combination of high
M, temperature and positions near the quenchedend where the cooling rate is faster produce the
largest difference in diffracting particle size.
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Figure 3: (a) Diffracting particle size measuredfrom the martensite (200) as a function of
distancefrom the quenchedend. (b) Enlarged areafrom outlined in Figure 3(a).

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Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43

An increase in the martensite

diffracting particle size occurs
where diffusion
controlled
transformation of austenite begins.
c7]This is observed in the lower
carbon specimens at depths which
coincide with a decrease in
hardness.No increasein martensite
diffracting particle size is observed
in the through hardened, higher
carbon,specimensat depthsup to 50
mm.
Experimental
Specimens

Case Carburized

85

83

81

330

Percent Martensite
79 77 75 73

71

69

67

210
190

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Diffracting: narticle size of the

50
austenite kd martensite phases is
r(r
~a 17 19 21 23 25 27 29 31 33
plotted as a function of retained
Percent Retained Austenite
austenite content in Figure 4. The
diffracting particle size of the Flgure 4: DifEacting particle size of retained austenite and
martensite Phase remains constant martensite as a function of percent retained austenitefor the
as a function of retained austenite experimental casecarburized specimens.
content. However, the retained
austenite diffracting particle size decreaseswith increasing amount of martensite formed. This
decreaseis consideredto be due to two effects. First, the increaseamount of plastic deformation of
the austenite as larger amounts of martensite is formed. Second, cutting of the austenite by the
martensite as it forms.
CONCLUSIONS

From the results of this investigation the following conclusions can be made:
End-quench

Test

The martensite diffracting particle size decreaseswith increasing carbon content and with
increasing cooling rate. A large increasem diffracting particle size is observedwhere diffusion
controlled martensitic transformations begin to occur.
Experimental

Case Carburized

Specimens

Martensite: Diffracting particle size remainsconstantwith increasingamountsof retained austenite.

Scatterof data are indicative of processingcontrol.
RetainedAustenite: Diffracting particle decreaseswith increasingamount of martensite. This is an
indication of austenite particle cutting by the martensite plates during transformation and the
increasingplastic deformation in the austenitedue to larger amount of martensite formed.

Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43

REFERENCES
1.

Standard Method for End-Quench Test for Hardenability of Steel, A255-89, Annual
Book of ASTM Standards.

2.

Kuo, H. K., Ganesan,P., and De Angelis, R. J., A Method to Study Sintering of a

SupportedMetal Catalyst, Microstructural Science,vol. 8, Elsevier North Holland, 1980.

3.

Warren, B. E. , X-ray Diffraction, Dover Publications Inc. 1969, 1990 pp 258-260

4.

Honecombe, R.W. K., Steels,Edward Arnold Publishers London, 1981, p86

5.

Jatczak, C. F., Larson. J. A., and Shin, S. W., Retained Austenite and Its Measurementby
X-Ray Diffraction, Society of Automotive Engineers, 1980

6.

Carapella, L.A., Computing A or MS from Analysis, Metals Progress,46, 1944, ~108

7.

Makinson, J. D., Weins, W. N., and De Angelis, R. J., The Substructureof Austenite and
Martensite Through a Carburized Surface, Advances in X-Ray Analysis, 34, 1991

331