Metallogr. Microstruct. Anal.
(2015) 4:261–272
DOI 10.1007/s13632-015-0209-1
TECHNICAL ARTICLE
Microstructural Comparison of Spray-Formed
and Conventionally Cast 2.5C–19Cr High-Chromium White Iron
Juho Lotta1 • Simo-Pekka Hannula1
Received: 9 February 2015 / Revised: 27 April 2015 / Accepted: 22 May 2015 / Published online: 13 June 2015
Ó Springer Science+Business Media New York and ASM International 2015
Abstract A billet of hypoeutectic high-chromium white
iron (2.5% C, 19% Cr) was spray formed using gas-to-
metal ratios of *0.9, *1.0, and *1.1. The as-sprayed
material was close to full density and contained fine
(Fe,Cr)7C3 carbides (27–30 vol%) uniformly distributed in
a matrix consisting of pearlite and ferrite. Length of the
carbides rarely exceeded 30 lm. This was in stark contrast
to a conventionally cast starting material, which contained
coarse (Fe,Cr)7C3 carbides (*22 vol%) non-uniformly
distributed in a matrix consisting of austenite and marten-
site. Length of the carbides in the cast material occasion-
ally exceeded 100 lm. Varying gas-to-metal ratio between
0.9 and 1.1 did not result in any significant changes in
carbide morphology, although slightly coarser carbide
morphology was produced with the gas-to-metal ratio of
0.9. Regardless of the gas-to-metal ratio, the finest carbide
morphology was found in the surface region of the spray-
formed billet.
Keywords Spray forming  High-chromium white iron 
Carbides  Quantitative metallography
Introduction
High-Chromium White Irons (HCWIs) are ferrous
alloys that typically contain 11–30 wt.% chromium,
1.8–3.6 wt.% carbon, and minor additions of other alloying
elements such as molybdenum, manganese, silicon, copper,
& Juho Lotta
juho.lotta@aalto.fi
1 carbides in the spray-formed material improve the flow of
Department of Materials Science and Engineering, School of
Chemical Technology, Aalto University, P.O. Box 16200,
FI-00076 Aalto, Finland
and nickel. They are widely used in industrial applications
in which high abrasion resistance is required (e.g., mining
and mineral processing). The good abrasion resistance
arises from the presence of considerable amount of hard
chromium-rich eutectic and/or primary carbides, typically
of type M7C3, in a steel matrix [1, 2]. Conventional casting,
however, produces coarse carbide structures, which are
detrimental to properties such as impact resistance, fracture
toughness, and fatigue resistance. The coarse carbide
structures cannot be refined to any significant degree by
heat treatments, while the attempts to avoid their formation
by modifying cast conditions or utilizing alloying additions
have only achieved limited success [1].
Spray forming technology, which was pioneered in the
early 1970s, is an advanced melt processing technique in
which gas atomized metal droplets are deposited onto a
substrate to form a high-density preform [3–5]. The rapid
cooling rates prior to deposition and high kinetic energy of
the accelerated droplets promote development of fine and
uniform microstructure, which is free of macro-segrega-
tion. This not only improves the mechanical properties as
compared to conventionally processed material, but also
makes spray forming suitable for many otherwise difficult-
to-process materials [5].
Spray-formed HCWIs feature much finer and more
uniform carbide morphology than cast HCWIs [6–11].
Hanlon et al. [6] found that the rolling/sliding wear rate of
conventionally cast HCWI was significantly higher than
that of spray-formed material when tested at a temperature
range of 20–500 °C. The poor performance of cast material
was attributed to the extensive cracking of coarse carbides.
In another study, Hanlon et al. [7] showed that the discrete
matrix around the carbides in forging. Unlike the cast
material, the spray-formed material could be forged
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without carbide fracture or void formation. Ted Guo et al.
[8] did not observe any considerable difference between
the dry sliding wear performances of spray-formed and cast
materials in a pin-on-disk test, but noted that the spray-
formed material showed better fracture resistance than the
cast material. Matsuo et al. [9] reported similar type of
findings in their respective study of spray-formed and cast
HCWIs. Both of the studies concluded that the enhanced
fracture resistance of the spray-formed material was due to
finer carbide morphology. Kasama et al. [10] found the
abrasive wear resistance of spray-formed material to be
comparable to that of cast material. The investigation by
the current authors [11] found that cast material outper-
formed spray-formed material in abrasive wear resistance
when coarser abrasive was being used.
This paper presents an extensive analysis of carbide
morphology of spray-formed and conventionally cast
hypoeutectic HCWI, described in a more general level
earlier in [11] where abrasion resistance of the materials
was presented. The primary objective of the present con-
tribution is to quantify the refinement of carbide mor-
phology resulting from the use of spray forming as opposed
to conventional casting. The effect of spraying conditions,
which were varied within the typical range of gas-to-metal
ratios, is also evaluated.
Experimental
Spray Forming Procedure
A billet of hypoeutectic HCWI was spray formed at the
University of Bremen, in a plant described in [12]. The
conventionally cast starting material (141.3 kg), whose
composition is listed in Table 1, was first induction melted
(150 °C superheat) under argon atmosphere and then
poured into an alumina tundish. An outlet (ø5 mm) at the
bottom of the tundish allowed the melt to flow to the
atomization zone (scanning free-fall atomizer) where it was
disintegrated into fine droplets by a gas-jet of nitrogen
(scanning frequency = 15 s-1, scanning amplitude = 4°).
Size of the atomized droplets could not be determined
during the in-flight period, but the following values were
measured for size distribution of overspray powder by laser
diffraction technique: d0.1 = 11 lm, d0.5 = 37 lm, and
d0.9 = 100 lm. The gas atomized droplets were deposited
Table 1 Chemical composition (wt.%) of the cast starting material determined by optical emission spectroscopy
C Si S P Mn
2.55 1.23 0.01 0.02 0.88
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Metallogr. Microstruct. Anal. (2015) 4:261–272
onto a rotating steel substrate (rotation fre-
quency = 2.45 s-1, inclination = 35°). Spraying distance
(435 mm) was maintained constant by moving the sub-
strate downwards along its axis of rotation. A schematic
representation of the spray forming process is provided in
Fig. 1(a). Immediately following the end of the spray run,
the billet (106.6 kg) was covered with an insulating blanket
to minimize the risk of thermal cracking.
Overall solid fraction on the deposition surface of a
billet is dependent on the relative rates of heat input and
output. The heat input rate is determined by the average
enthalpy of droplet spray and its mass arrival rate, while
the heat output rate is determined by convective cooling
conditions, preform thermal conductivity, and thermal
gradients. The balance between these two and the subse-
quent macroscopic heat flow controls the evolution of the
spray-formed microstructure [5]. In the present case,
deposition conditions were modified by varying Gas-to-
Metal Ratio (GMR) during the spray forming process;
GMR is defined as the ratio between the mass flow rates of
atomizing gas and molten metal. The changes to GMR
were realized by maintaining the flow rate of atomizing gas
at 992 kg/h, while changing melt level in the tundish to
achieve melt flow rates of 879, 983, and 1077 kg/h. As
illustrated in Fig. 1(b), this resulted in a billet which con-
sisted of layers sprayed with the GMRs of 0.92 (*0.9),
1.01 (*1.0), and 1.13 (*1.1). Lowering of GMR was
expected to increase the average enthalpy of the droplet
spray and thus promote microstructural coarsening.
Sample Preparation and Materials Characterization
Three samples (5 9 15 9 15 mm3) were cut from each of
the layers sprayed with different GMRs (see Fig. 1b). The
surfaces of interests (15 9 15 mm2), which were parallel
to the longitudinal surface of the billet, were located at the
approximate radial positions of 0, 40, and 80 mm with
respect to the center axis of the billet (i.e., approximately
100, 60, and 20 mm beneath the surface). Sample identi-
fiers, which are listed in Table 2, consist of digits referring
to the GMR and a letter indicating the radial distance to the
center axis of the billet (a = 0 mm, b = 40 mm, and
c = 80 mm). The samples with the same radial position are
additionally referred to as center axis (0.9a, 1.0a, and 1.1a),
mid-radius (0.9b, 1.0b, and 1.1b), or surface samples (0.9c,
1.0c, and 1.1c). The study also included a sample
Ni Cr Mo Cu V Fe
0.18 19.31 0.55 0.16 0.07 Bal.
Metallogr. Microstruct. Anal. (2015) 4:261–272 263

were used for chemical analysis. Phase identification

was based on x-ray diffraction (Cu–K a radiation).
Density (Archimedes’ principle) and Rockwell C
hardness were evaluated by performing ten measure-
ments per sample.
Quantitative characterization of porosity was carried out
using software-assisted image analysis on optical micro-
graphs. A total of 10 fields (*21.5 mm2) were analyzed
per sample. Software-assisted image analysis was also used
on scanning electron micrographs for quantitative charac-
terization of carbide morphology. In order to cover an
adequately large area without sacrificing resolution, four
backscattered electron fields were combined into one
composite image. A total of 10 composite images were
analyzed per sample. The composite images originating
Fig. 1 (a) A schematic representation of the spray forming process. from the spray-formed material (magnification 93500)
(b) The spray-formed billet was produced using gas-to-metal ratios covered a total area of *0.023 mm2 per sample, while the
(GMRs) 0.9, 1.0, and 1.1. The darker shade of gray indicates material ones originating from the cast material (magnification
that was discarded from the study
91000) covered a total area of *0.278 mm2.
Carbide size and shape were quantified by analyzing a
Table 2 Sample designation system minimum of 800 carbides per sample. Analysis of carbide
GMR Radial position (mm) Sample identifier morphology excluded the carbides which extended outside
the field of view, while the area fractions were determined
0.9 0 0.9a by including all the carbides within the field of view,
0.9 40 0.9b regardless of whether they extended outside the field of
0.9 80 0.9c view or not. Quantification of carbide size involved con-
1.0 0 1.0a verting software-determined cross-sectional areas to circle
1.0 40 1.0b diameters of equivalent area. Shape was quantified by
1.0 80 1.0c assigning each of the cross-sectional carbide a circularity
1.1 0 1.1a value; circularity for a perfect circle is 1.0, while for a line
1.1 40 1.1b it is 0. Circularity was calculated with the following
1.1 80 1.1c formula:
N/A N/A cca 4pA
C¼ ; ð1Þ
a
Obtained from the cast starting material bar P2
in which A is area and P is perimeter.

(2 9 7 9 15 mm3) obtained from one of the cast starting

material bars (ø80 mm). Its surface of interest
(7 9 15 mm2) was located close to the mid-radius and was
parallel to the longitudinal surface of the cast bar.
The spray-formed and cast materials were studied in the
as-sprayed and as-cast conditions, respectively. The sur-
faces of interest were first ground with SiC papers (P120,
P240, P400, and P1200) and then mechanically polished
with diamond paste (6, 3, and 1 lm). The polished surfaces
were either etched with Nital (qualitative metallography) or
fine polished mechanically with colloidal silica (quantita-
tive metallography).
The microstructures were characterized by light and
scanning electron microscopy. Energy-dispersive x-ray
spectroscopy (acceleration voltage = 15 kV, probe
current & 500 pA) and optical emission spectroscopy
Results
Phase Identification and Chemical Composition
Table 3 lists the chemical composition of the materials
sprayed with different GMRs. The results indicate that the
variation of GMR had no impact on the overall chemical
composition. Compositional similarity between the spray-
formed and cast materials (see Table 1) furthermore indi-
cates that the chemical composition was not very sensitive
to the spray forming process.
Figure 2(a) shows a typical example of x-ray diffraction
pattern obtained from the spray-formed material (sample
1.0a). The pattern indicates the presence of M7C3-type
carbides and ferrite. The x-ray diffraction pattern obtained

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264 Metallogr. Microstruct. Anal. (2015) 4:261–272

Table 3 Chemical composition

GMR C Si S P Mn Ni Cr Mo Cu V Fe
(wt.%) of the spray-formed
material determined by optical 0.9 2.52 1.06 0.01 0.03 1.00 0.10 19.15 0.57 0.22 0.09 Bal.
emission spectroscopy
1.0 2.54 1.06 0.01 0.03 0.98 0.10 19.10 0.57 0.22 0.09 Bal.
1.1 2.53 1.06 0.01 0.03 0.98 0.10 19.14 0.57 0.22 0.09 Bal.

Fig. 2 Typical examples of x-ray diffraction patterns obtained from the (a) spray-formed (1.0a) and (b) cast materials

from the cast material, shown in Fig. 2(b), indicates the
presence of M7C3-type carbides, retained austenite, and
martensite. The presence of retained austenite and
martensite instead of ferrite indicates that the cast material
was subject to faster cooling rate than the spray-formed
material at the end of the solidification. The distinction
between martensite and ferrite was in both cases based on
observations made in metallographic studies.
Table 4 lists the chemical composition of the carbides
and matrix in the spray-formed (sample 1.0a) and cast
materials. Each composition represents the mean of 10
separate analyses (normalized to 100%) carried out by
energy-dispersive x-ray spectroscopy. The finest carbides
Table 4 Chemical composition (at.%) of the carbides and matrix
determined by energy-dispersive x-ray spectroscopy
Phase Element Sample
1.0a
and matrix locations with tight spacing between the car-
bides were not included in the analysis to ensure that the
signal was coming either from the carbides or matrix. The
results exclude carbon due to poor suitability of energy-
dispersive x-ray spectroscopy for quantitative analysis of
light elements. Copper, molybdenum, nickel, and vana-
dium, which were found at low concentrations (B0.5 at.%),
are excluded from the results because energy-dispersive
x-ray spectroscopy is not well suited for quantitative
analysis of low concentrations. The results show that there
is no major compositional difference between the carbides
of the cast and spray-formed materials, chromium and iron
being the main alloying elements in both cases. The matrix
of the cast material has slightly lower Fe/Cr ratio (6.6 vs.
8.4) than the matrix of the spray-formed material. Quali-
tative comparison furthermore indicated that the matrix of
the cast material contains more carbon than the matrix of
cc the spray-formed material.

Carbide Cr 58.7 59.5 Qualitative Metallography

Mn 1.3 1.2
Fe 40.0 39.3 The cast material underwent sluggish solidification, which,
Matrix Si 2.8 2.6 as illustrated in Fig. 3, resulted in coarse M7C3-type car-
Cr 10.2 12.8 bides non-uniformly distributed in a matrix consisting of
Mn 1.0 1.0 retained austenite and some martensite. The martensite was
Fe 86.0 83.6 concentrated in the vicinity of the carbides, most probably
The results (normalized to 100%) exclude carbon and elements with because these areas were sufficiently depleted in alloying
low concentration (B0.5 at.%) elements to allow austenite to transform to martensite.

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Metallogr. Microstruct. Anal. (2015) 4:261–272
Fig. 3 (a) An optical and (b) a secondary electron micrograph
showing the Nital etched microstructure of the cast material. In both
micrographs, the net-like features with well-defined borders corre-
spond to M7C3-type carbides (C). The dark shaded areas in the
Length of the carbides ranged from a micron to above
100 lm, the large carbides being on average more elon-
gated and irregular in shape than the small ones.
The microstructure of the spray-formed material, as
illustrated in Fig. 4, contained fine M7C3-type carbides
uniformly distributed in a matrix consisting of ferrite and
pearlite. Length of the carbides ranged from a few hundred
nanometers up to *30 lm, the large carbides being on
average more elongated and irregular in shape than the
small ones. The GMR of 0.9 produced slightly coarser
carbide morphology than the GMRs of 1.0 and 1.1, which
produced carbide morphologies indistinguishable from
each other. The center axis and mid-radius samples of a
given layer were indistinguishable from each other as well,
while the surface samples featured the finest carbide mor-
phology. Figure 5 illustrates radial variation of carbide
morphology in the layer sprayed with the GMR of 1.0.
Fig. 4 (a) An optical and (b) a secondary electron micrograph
showing the Nital etched microstructure of the spray-formed material
(sample 0.9b). The light shaded areas with well-defined borders in
the optical micrograph correspond to M7C3-type carbides (C), while
265
optical micrograph and the light shaded areas in the backscattered
electron micrograph correspond to martensite (a0 ). The remaining
areas are retained austenite (c)
The microstructure of the spray-formed material con-
tained a large number of circular formations (typically
ø10–40 lm) with very fine carbide morphology. These, as
illustrated in Fig. 6, seem to be the remnants of droplets
that solidified during the in-flight period and were subse-
quently embedded in the billet. The microstructure of the
gas atomized overspray powder particles was observed to
feature a very fine dendritic solidification structure, which
consisted of austenite and M7C3-type carbides. In rare
occasions, the dendritic structures were still faintly visible
in the carbide morphology of the embedded droplets. In
most cases, however, microstructural coarsening during the
post-deposition period resulted in carbide morphology
which bore little resemblance to the solidification structure
observed in the overspray particles.
A marked increase in the number of embedded droplets
was observed near the surface of the billet. It also appeared
the dark shaded areas correspond to pearlite (P). The dark shaded
features with well-defined borders in the secondary electron micro-
graph correspond to M7C3-type carbides (C), while the light shaded
areas correspond to pearlite (P). The remaining areas are ferrite (a)
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Fig. 5 Secondary electron micrographs illustrating radial variation of
microstructure (Nital etching) within the spray-formed billet. (a) Sam-
ple 1.0a. (b) Sample 1.0c. The features with well-defined borders in
Fig. 6 (a) An optical micrograph showing circular formations which
correspond to droplets that solidified during the in-flight period and
were subsequently embedded in the microstructure of the spray-
formed material (sample 1.1c, Nital etching). (b) A secondary
electron micrograph illustrating the fine carbide morphology
that the layers sprayed with the GMRs of 1.0 and 1.1
contained a somewhat higher number of embedded dro-
plets than the layer sprayed with the GMR of 0.9. It should
be pointed out that not all of the fine carbides were con-
centrated in the circular formations. Many of the fine car-
bides were instead found in irregularly shaped clusters (see
Fig. 4b), which are likely to trace their origin back to the
material that solidified prior to deposition.
Density, Porosity, and Hardness
Figure 7(a) shows the measured densities and approximate
porosity levels. The spray-formed material was close to full
density apart from a porous surface layer (*10 mm). The
changes to GMR had no impact on either density or
porosity levels apart from the surface region, where a
modest increase of porosity occurred with increasing
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Metallogr. Microstruct. Anal. (2015) 4:261–272
the micrographs correspond to M7C3-type carbides (C), while the
light shaded areas correspond to pearlite (P). The remaining areas are
ferrite (a)
characteristic to the embedded droplets (sample 1.1c, Nital etching).
The features with well-defined borders in the secondary electron
micrograph correspond to M7C3-type carbides (C). The surrounding
matrix is ferrite (a)
GMR. The results indicate that the theoretical density of
the spray-formed material is in the range of 7.52–7.54 g/
cm3. The cast material was close to full density as well,
although in this case the results indicate that the theoretical
density is closer to 7.60 than 7.50 g/cm3.
The cast material had significantly higher hardness than
the spray-formed material as can be seen from Fig. 7(b),
which shows the measured Rockwell C hardness values.
This is consistent with the fact that its microstructure
consisted of austenite and martensite instead of pearlite and
ferrite found in the microstructure of the spray-formed
material. In case of the spray-formed material, the GMR of
1.0 produced slightly higher hardness than the GMRs of 0.9
and 1.1. This could be related to spraying order (see
Fig. 1b) as post-deposition cooling rate increases toward
the substrate. No clear correlation can be established
between radial position and hardness.
Metallogr. Microstruct. Anal. (2015) 4:261–272 267

Fig. 7 Bar graphs showing the measured (a) densities and (b) Rockwell C hardness values (mean ± SD). The numerical values in the density
graph indicate the approximate porosity levels (vol%)

Quantitative Study of Carbide Morphology

Carbide Content

Figure 8 shows the carbide area fractions determined by

image analysis. Although the results do not indicate clear
correlation between the carbide content and GMR, there is
some indication that the carbide content tend to increase
with radial distance to the center axis of the billet. Most
notably, however, the carbide content of the spray-formed
material is 5–8 vol% higher than that of the cast material.

Carbide Size

Figure 9 shows a typical example of a carbide diameter Fig. 9 An example of a typical carbide diameter distribution
histogram, which is heavily skewed toward the small histogram (sample 1.0a)
diameters. The shape of the histogram indicates that car-
bide diameter is approximately log-normally distributed.

Fig. 10 A stacked bar graph showing the total carbide area densities
Fig. 8 A bar graph showing the carbide area fractions (mean ± SD) as well as the area densities of carbides below and above 1.5 lm,
determined by image analysis respectively

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Figure 10 shows the total carbide area densities as well
as the area densities of carbides with diameter below and
above 1.5 lm, respectively. The area densities were cal-
culated by dividing the number of analyzed carbides with
the total area of the analyzed fields; the carbides extending
outside the field of view were excluded from the analysis.
The threshold value of 1.5 lm was chosen after studying
the carbide size distribution of an embedded droplet
(*ø25 lm, sample 1.0c). The formation, which was fairly
similar to that shown in Fig. 6(b), was determined to have
an arithmetic mean carbide diameter of 0.50 ± 0.31 lm,
carbide area density of *360 9 104 mm-2, and carbide
area fraction of *28%. Carbides with diameter below
1.5 lm were determined to constitute *99% of all the
carbides in the formation. In case of the spray-formed
material, the coarse carbides (C1.5 lm) are considered to
represent material that formed in the billet during the
elimination of residual melt, while most of the fine carbides
(\1.5 lm) are considered to represent material that solid-
ified during the in-flight period and did not undergo re-
melting during the post-deposition period.
In agreement with the observations made in the metal-
lographic studies, the carbide area density of the cast
material (*4 9 103 mm-2) was substantially lower than
that of the spray-formed material (see Fig. 10). Diameter of
most of the carbides in the spray-formed material was
below 1.5 lm, while the opposite was true in case of the
cast material (*3 9 103 vs. *1 9 103 mm-2). The
dominance of fine carbides was particularly overwhelming
in the surface samples of the spray-formed material. This is
in agreement with the observation that the surface samples
contained the highest number of embedded droplets.
Figure 11 shows the arithmetic mean carbide diameters
determined by image analysis. The large standard devia-
tions associated with the mean values reflect the nature of
Fig. 11 Arithmetic mean carbide diameters determined by image
analysis. The numerical values associated with each bar are the mean
and standard deviation
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Metallogr. Microstruct. Anal. (2015) 4:261–272
the carbide size distributions, which, as illustrated in
Fig. 9, bear resemblance to log-normal distribution. The
results confirm the substantially finer carbide morphology
of the spray-formed material. Although the results show
that the GMR of 0.9 produced coarser carbide morphology
than the GMRs of 1.0 and 1.1, there is no indication that
any refinement occurred as GMR was increased from 1.0 to
1.1.
Figure 12a and b shows the arithmetic mean diameters
of fine (\1.5 lm) and coarse (C1.5 lm) carbides, respec-
tively. The cast material, as expected, is set apart from the
spray-formed material by its noticeably higher mean
diameter. The changes to GMR or spraying order appear to
have had no clear impact on the mean diameter of the fine
carbides. The only noteworthy trend is the slight decrease
in mean diameter near the surface of the billet. The mean
diameter of the coarse carbides correlates with spraying
order (see Fig. 1b) rather than with GMR in the interior of
the billet. This changes near the surface of the spray-
formed billet where the mean diameter of coarse carbides
increases with decreasing GMR.
The ratio between carbide perimeter and analyzed area
(P/A ratio) provides an alternative approach for comparing
between carbide morphologies. Figure 13 shows the P/
A ratios plotted as a function of arithmetic mean diameters,
with higher P/A ratio indicating finer carbide morphology.
In the interior of the billet, P/A ratio increases toward the
substrate, whereas in the surface region P/A ratio increases
with GMR. The observation is in agreement with the
conclusion made from Fig. 12(b).
As is evident from Fig. 13, the relationship between P/A
ratio and carbide diameter can be described reasonably
well with a power law. The most straightforward way to
show that this is not a coincidence is to limit the investi-
gation to a circle. The P/A ratio of a circle can be expressed
as follows:
Pc Pc Dc p
¼ ¼f 2
¼ 4fD1
c ; ð2Þ
A Ac =f ð0:5Dc Þ p
in which Pc is the perimeter of the circle, A is the area of the
field that contains the circle, Ac is the area of the circle, f is the
area fraction of the circle, and Dc is the diameter of the circle.
The formula, which describes a power law relationship, is not
applicable to non-ideal cases as such (e.g., non-constant
carbide shape and content). It nevertheless demonstrates the
applicability of power law for describing the relationship
between carbide size and P/A ratio.
Carbide Shape
The circularity distribution histograms, like the one shown
in Fig. 14(a), had a shape characteristic to a log-normally
distributed variable. The region of high frequency in the
Metallogr. Microstruct. Anal. (2015) 4:261–272
Fig. 12 Bar graphs showing the arithmetic mean diameter of (a) fine (\1.5 lm) and (b) coarse (C1.5 lm) carbide size fractions, respectively
Fig. 13 Carbide perimeter-to-area ratios (P/A ratio) plotted as a
function of arithmetic mean carbide diameter
Fig. 14 (a) An example of a typical circularity distribution histogram (sample 1.1a). (b) Diameter of individual carbides plotted as a function of
circularity (sample 1.1a)
269
histogram correlates with fine carbide size, as is evident
from Fig. 14(b).
Figure 15 shows the arithmetic mean circularity values
determined by image analysis. The cast material has
noticeably lower mean circularity than the spray-formed
material. The changes to GMR appear to have had no
impact on the overall mean circularity. The only noticeable
trend is the very slight increase of mean circularity with
radial distance to the center axis of the billet in materials
sprayed with the GMRs of 0.9 and 1.0.
Figure 16 shows the mean circularity values of carbides
with diameter below and above 1.5 lm, respectively. The
results indicate that the fine carbides (\1.5 lm) have higher
mean circularity than the coarse carbides (C1.5 lm). This is
in agreement with the observations made in the metallo-
graphic studies. Interestingly, Fig. 16 indicates no signifi-
cant difference between the mean circularities of the cast
and spray-formed materials, even though Fig. 15 shows a
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270
Fig. 15 Arithmetic mean circularities determined by image analysis.
The numerical values associated with each bar are the mean and
standard deviation
clear difference between the two materials. The contradic-
tory observation is explained by the fact that the cast
material contains higher number of coarse than fine carbides
(*3 9 103 vs. *1 9 103 mm-2), the opposite being the
case with the spray-formed material (see Fig. 10).
The mean circularity of the fine carbides increases toward
the surface of the spray-formed billet, while the opposite is
true for the coarse carbides. There appears to be no clear
correlation between the mean circularity of the fine carbides
and GMR (see Fig. 16a). The mean circularity of the coarse
carbides on the other hand decreases with increasing GMR
in the surface region of the billet (see Fig. 16b).
Discussion
The billet produced by spray forming was close to full
density (see Fig. 7a). In agreement with the observations
reported in literature [6–10], spray forming resulted in
much finer carbide morphology than conventional casting
Fig. 16 Bar graphs showing the mean circularity of (a) fine (\1.5 lm) and (b) coarse (C1.5 lm) carbide size fractions
123
Metallogr. Microstruct. Anal. (2015) 4:261–272
(see Figs. 3, 4, and 11). The microstructural refinement is
primarily due to rapid cooling of atomized droplets during
the in-flight period. It creates a large number of solidifi-
cation nuclei, whose number further increases as a result of
fragmentation that occurs if the droplets are semi-solid
when they impact the deposition surface [5].
Carbide content of HCWI is known to increase with
increasing carbon and chromium contents [1, 2]. The fol-
lowing empirical formula, which was established by Doğan
et al. [13], uses carbon and chromium contents as input
values to produce an estimate for the eutectic carbide
volume fraction of cast HCWI:
CVF(% ) ¼ 14:05C þ 0:43Cr  0:22: ð3Þ
In this case, the equation yields 22.1 vol% for the car-
bide volume fraction of the cast material. The value is very
close to the carbide content determined by image analysis
(see Fig. 8), but underestimates the carbide content of the
spray-formed material by 5–8 vol%. This suggests that
carbide content not only depends on the carbon and chro-
mium contents, but also on the solidification conditions.
Dupin and Schissler [14] reported a similar type of trend,
observing higher carbide content near the surface of a
casting where the highest cooling rate is expected. Hanlon
et al. [7] and Matsuo et al. [9] on the other hand found no
evidence of higher carbide content in spray-formed mate-
rial as compared to cast material.
In conventional casting, solidification of hypoeutectic
HCWI starts with the formation of primary austenite den-
drites (Liquid ? c-Fe) and continues with the precipitation
and growth of eutectic carbides (Liquid ? c-Fe ? M7C3)
once the eutectic temperature is reached [1]. The observa-
tion that the overspray powder particles feature dendritic
microstructure consisting of retained austenite and M7C3-
type carbides indicates that this was the solidification
sequence also during in-flight period. Considering that the
post-deposition cooling conditions resemble more closely
Metallogr. Microstruct. Anal. (2015) 4:261–272
those encountered in conventional casting, it seems likely
that this was the solidification sequence in the billet as well.
Despite the considerable difference in solidification
conditions, the carbides in the spray-formed material were
compositionally (see Table 4) almost identical to the car-
bides in the cast material. This is in agreement with the
observation by Hanlon et al. [7]. The matrix of the cast
material, however, was found to contain more chromium
and carbon than the matrix of the spray-formed material,
indicating that sluggish solidification promotes matrix with
higher carbon and chromium contents. This is probably
because sluggish solidification increases the mean free path
for diffusion of carbon and chromium, thus limiting the
contribution of free carbon and chromium to the volume of
eutectic carbides during the post-solidification period.
Cooling rate within spray-formed billet increases toward
substrate and surface [15]. The results (see Figs. 12b, 13)
indicate that longitudinal gradient in cooling conditions was
enough to overshadow the influence of GMR variation on
solidification conditions in the interior of the billet. It
appears that this is not the case in the surface region of the
billet, where an increase in GMR resulted in a decrease in
the mean diameter of the coarse carbides (see Fig. 12b) and
an increase in the P/A ratio (see Fig. 13). The observation
contradicts that reported by Hanlon et al. [7] as they found
no correlation between carbide size and GMR despite testing
a wider range of GMRs (0.97–1.69) than the present study.
In case of the spray-formed material, the results indicate
that the mean circularity of the fine carbides (\1.5 lm)
correlates neither with the spraying order nor with the
GMR variation, but tends to increase with radial distance to
the center axis of the billet (see Fig. 16a). The radial
increase in the mean circularity is probably due to radial
increase in cooling rate. It not only increases the number of
embedded droplets (see Fig. 6), but also inhibits the solid-
state growth of the fine carbides found in the material
solidified prior to deposition. This increases mean circu-
larity because finer carbides tend to be more circular than
coarser carbides (see Fig. 14b). In addition to limiting
diffusion, faster cooling rate near the surface of the billet
accelerates the disappearance of residual melt. The results
(see Fig. 16b) indicate that this gave rise to lower mean
circularity in case of the coarse carbides (C1.5 lm). Cooler
deposition conditions (i.e., higher GMR) appeared to have
similar effect on the mean circularity of the coarse carbides
in the surface region of the billet (see Fig. 16b).
Conclusions
Close to fully dense billet of hypoeutectic HCWI was
produced by spray forming. Spray forming resulted in
considerable refinement of carbide (M7C3, M = Cr, Fe)
271
morphology as compared to the cast material having the
same composition and considerably larger carbide content
than casting. While the cast material contained carbides
which occasionally exceeded 100 lm in length, the carbide
length in the spray-formed material rarely exceeded 30 lm.
In addition to the coarser carbide morphology, the cast
material contained 5–8 vol% less carbides than the spray-
formed material. We suggest that this is because casting
results in larger mean free path for diffusion of free carbon
and chromium and thus inhibits diffusion of carbon and
chromium from matrix to the eutectic carbides during the
post-solidification period. Despite the major differences in
solidification conditions and carbide content, there was no
significant compositional difference between the carbides
of the two materials.
Marked refinement of carbide morphology occurred near
the surface of the spray-formed billet. This coincides with
the fastest cooling rates occurring in the surface region of
the billet. A considerable part of the refinement was due to
the increase in the number of embedded droplets (typically
ø10–40 lm), which featured significantly finer carbide
morphology than rest of the material. Refinement of carbide
morphology with increasing GMR was most noticeable in
the surface region of the billet. In the interior of the billet,
the GMR of 1.1 produced slightly coarser carbide mor-
phology than the GMR of 1.0. This was most likely due to
longitudinal gradient in cooling conditions, which was sig-
nificant enough to suppress refinement of carbide morphol-
ogy that was expected to occur as GMR was raised from 1.0
to 1.1. The results also indicate that rather than promoting an
overall increase in circularity, faster cooling rates increase
the fraction of very fine carbides with high circularity while
lowering the circularity of coarse carbides.
Acknowledgments This work was supported by the Graduate
School for Advanced Materials and Processes of the Academy of
Finland.
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