coatings

Article
Sulfur and Oxygen Effects on High-Si Ductile Iron
Casting Skin Formation
Denisa Anca, Mihai Chisamera, Stelian Stan, Iuliana Stan * and Iulian Riposan
Materials Science and Engineering Faculty, Politehnica University of Bucharest, 313 Spl. Independentei,
060042 Bucharest, Romania; denisa_elena.anca@upb.ro (D.A.); chisameramihai@gmail.com (M.C.);
constantin.stan@upb.ro (S.S.); iulian.riposan@upb.ro (I.R.)
* Correspondence: iuliana.stan@upb.ro




Received: 27 May 2020; Accepted: 27 June 2020; Published: 29 June 2020


Abstract: The main objective of the present paper is to evaluate by thermal (cooling curve) analysis the
solidification pattern and the occurrence of the layer of degenerate graphite at the surface of ductile
iron castings (3.15% Si, typically as 450-18 grade, ISO 1563/2011), with or without a mold coating,
including S or O, and different agents (carbonic material, iron powder), supposed to act to block their
diffusion into the iron melt. It is found that the mold coating materials temperately influence the
parameters of the solidification cooling curves and, more visibly, the occurrence and the thickness of
the undesired skin layer. Different graphite morphologies comparable to the casting body are present,
at a large range of thicknesses, from 50 up to 200 µm. The sulfur presence in the mold coating will
promote a higher skin thickness compared to oxygen (up to 50% by oxygen and 2.5–3.3 times for
sulfur action), despite the fact that in the casting body, the graphite nodularity undergoes a limited
decrease (from 85% up to 82%–83% level). Carbonic material or iron powder supplementary addition
decreases these undesired effects, but the solidification undercooling compared to the equilibrium
system is increased. It is found that carbonic material is more efficient at limiting oxygen than iron
powder is at limiting the negative effects of sulfur on the casting skin thickness. More experiments
are necessary to quantify their capacity to block the oxygen or sulfur transfer into the iron melt.

Keywords: thermal analysis; solidification cooling curves; eutectic undercooling; ductile cast iron;
mold coating; sulfur; oxygen; degenerated graphite surface layer; structure

1. Introduction
Ceramic molds, used in metal castings production, are usually coated in order to control the
metal–mold chemical interaction and to decrease the casting surface roughness. In Mg-treated iron
castings, the coating is also important to control the graphite degeneration process in the surface layer.
The surface layer with degenerated graphite causes stress raisers in the casting, similar to a notch, so
all the mechanical properties are reduced. In a technical literature review, Boonmee and Stefanescu [1]
found that the yield strength and elongation of cast ductile iron samples lied below the ASTM standard
line, and only after machining, a significant number of samples lied above the standard, as the casting
skin was removed. The casting skin effect on fatigue properties is expected to be more pronounced
than the static properties because in thin-wall ductile iron castings, a reduction of 16.3% in the fatigue
strength is observed. A deleterious effect of the casting skin in compacted graphite iron casting is also
identified, suggesting that both the graphite degradation layer and surface roughness were responsible
for the reduction in tensile properties.
The applied coating on the active surface of the mold in order to improve the casting surface
quality also influences the solidification characteristics of the casting body and graphite degeneration
in the casting surface layer (skin formation). These mold coatings will favor skin formation, in the

Coatings 2020, 10, 618; doi:10.3390/coatings10070618 www.mdpi.com/journal/coatings

Coatings 2020, 10, 618 2 of 15

presence of available sulfur or oxygen, to diffuse into the surface iron melt layer. Contrarily, inorganic
materials expected to act as desulphurization items (Al2 O3 , CaCO3 , basic slag, CaF2 , Talc, Mg) are
favorable for decreasing skin thickness [1–7].
In previous experiments [8–13], the graphite degeneration process in the surface layer of Mg-treated
iron castings (0.020 to 0.054 wt.% Mgres ) was considered, for solidification in coated or nonceramic molds,
including or excluding a sulfur source. The decrease in the residual magnesium content aggravated
the degeneration of the surface graphite, five times more in mold including sulfur. The application of a
mold coating strongly influenced graphite deterioration in the surface layer of castings, promoting
graphite degeneration for the S-bearing coating, or conversely, limiting the surface layer thickness
using desulphurization-type coatings, with Mg-bearing coatings as performance.
The main objective of the present paper is to evaluate the solidification pattern and the occurrence
of graphite degeneration in the surface layer of relatively-high-silicon ductile cast iron (3.15%Si,
typically as 450-18 grade, ISO 1563/2011), solidified in a ceramic mold without sulfur contribution, as
the influence of the mold coating (with or without S or O-content, and with or without supplementary
addition (iron powder or carbonic material)). It is supposed that these materials could have the
capacity to delay the sulfur or oxygen diffusion from the coating into the iron melt. High silicon, 450-18
ISO 1563/2011 grade, could be considered an attractive material for many applications, including
heavy ductile iron castings for the windmills industry. The presence of oxygen or sulfur in the coating
composition is simulated by the intentional addition of materials including these elements (Fe2 O3 or
FeS2 ), usually used in metallurgy as sources of oxygen or sulfur due to their high capacity to supply
these elements to the steel and cast iron melt.

2. Materials and Methods

Experimental cast iron is obtained by electrically melting, in a graphite crucible induction furnace
(10 kg, 8000 Hz), using high-purity pig iron as the base charge material and 1565 ◦ C temperature
superheating. Table 1 includes the two main alloys selected for the double treatment, specifically for
ductile cast iron production.

Table 1. Treatment alloys, wt.%.

Treatment Alloy Addition Addition

Si Ca Al TRE* Mg Ba Fe Amount
Role Type Technique
(wt.%)
Si alloying FeSi90 Min. 90 Max. 1.0 Max. 0.5 - - - Max. 10 2.0 Furnace
Tundish -
Nodulizer FeSiCaMgRE 46 1.87 0.85 1.1 8.2 - bal 2.0
Cover
Inoculant FeSiCaBaAl 75 1.0 1.1 - - 1.0 bal 0.8 Pouring Ladle
* TRE-total rare earth elements.

Mg-treatment (graphite nodularization) was recorded by the tundish-cover technique (1500 ◦ C

treatment, 8 kg iron melt, 2.0 wt.% FeSiCaMg8RE alloy addition), followed by an inoculation during
the transfer of Mg-treated iron into the pouring ladle (0.8 wt.% FeSiCaBaAl alloy addition, 1430 ◦ C).
This covered ladle method, as a tundish cover removable type, which is used in this experiment,
limits the oxygen volume available during the hot metal reaction with the Mg-bearing alloy, which
is not done with open ladle methods, resulting in important benefits: Reduction of smoke and flare,
improved Mg-recovery, reduced temperature losses, better consistency of final Mg. A pocket is made
in the bottom of the ladle, to receive Mg-bearing FeSi, while the liquid base iron is delivered from the
tundish through a calibrated hole, in a ladle with a 2:1 ratio between height and diameter.
The solidification pattern of the obtained Mg-treated and inoculated ductile cast iron is evaluated by
standard thermal (cooling curve) analysis, QuiK-Cup® (Heraeus Electro-Nite International, Houthalen,
Belgium) [14], which is a disposable measurement test cup that is securely attached to the contact
block of the QuiK-Cup® holder. The system measures the cooling attributes of the molten iron poured
into the QuiK-Cup® . Various types of QuiK-Cups® are available depending on measurement type
Coatings 2020, 10, 618 3 of 15

and iron grade. In the present work, it was used as a ceramic cup, with a 7.3 mm cooling modulus
and 0.35 kg mass. This mold media is without free sulfur or oxygen for supplying to the iron melt
before solidification, to affect the structure characteristics. This experimental procedure is selected as
this thermal analysis system is a quick, simple, reliable, and low-cost method for shop floor control of
molten iron, with a large application in the world foundry industry [14].
Different coatings are prepared for the inner surface of the ceramic cup, based on polystyrene and
toluene solution (4 g polystyrene and 10 mL toluene): S-bearing coating (0.6 g FeS2 ); O-bearing coating
(0.6 g Fe2 O3 ); Fe-powder-bearing coating (1.12 g iron powder); carbonic-material (MC)-bearing coating
(1.0 g carbonic material powder, 99% C).
After S or O-bearing coating application on the inner surface of the ceramic cup and its drying,
a new Fe-powder or MC-bearing coating is applied on the first one. It is assumed that the Fe-powder
or MC-powder included in the second coating will block the sulfur or oxygen diffusion from the FeS2
or Fe2 O3 -bearing coating into the iron melt, before solidification.
The experiments could be grouped in the following variants: (a) Uncoated mold, without oxygen
or sulfur available to diffuse into the iron melt, as reference variant; (b) coated mold, including oxygen
(Fe2 O3 -bearing coating) or sulfur (FeS2 -bearing coating), as potential sources of these active elements to
react with iron melt, before solidification, at least in the superficial layer of casting; (c) supplementary
addition of other substances (carbonic material-MC or iron powder-Fe) on the previous Fe2 O3 - or
FeS2 -bearing coatings, as potential blockage of oxygen or sulfur diffusion into the iron melt.
For a structure analysis, in the surface layer and casting body, samples obtained in the thermal
analysis ceramic
Coatings 2020, 10, xcup
FORare used
PEER (Figure 1a). The structure is analyzed in the as-cast state, without4 of
REVIEW etching
16
(graphite analysis) and after Nital etching (metal matrix analysis).

(a) (b)

(c)
Figure 1. Metallographic sample drawn (a), analysis points on the sample section (b) and surface
Figure 1. Metallographic sample drawn (a), analysis points on the sample section (b) and surface layer
layer thickness (c) evaluation [15].
thickness (c) evaluation [15].
3. Results and Discussion

3.1. Chemical Composition

According to Table 2 data, the final cast iron, after Mg-treatment and ladle inoculation, occupies
a hyper-eutectic position, as carbon equivalent CE = 4.6%, at normal contents of the elements usually
Coatings 2020, 10, 618 4 of 15

The occurrence of the surface layer (casting skin) as position and thickness is extremely variable,
depending on a lot of influencing factors. For this reason, it is not recommended to consider only
one evaluated point as representative of the results in specific solidification conditions. Consequently,
only a large number of measurements could offer an image of casting skin formation, as their average
value. It is also known that as the cast structure is relatively un-homogeneous also in the casting body,
an average value of structure characteristics is more representative for each considered parameter.
The average values of measurements are plotted in the graphs, and typical structures, selected as
representative for each tested variant, are considered.
To evaluate the structure characteristics in the casting body, three analysis directions are considered,
each one with 5 analysis points (15 analyses in total), placed in the same positions, outside the surface
layer and casting center, to avoid their influence (Figure 1b). The end effect is avoided, so a 22 mm
analysis length is used on each side. For each side, the layer thickness is measured in points 100 µm
apart (Figure 1c). The final result is expressed as the average of all measurements (220 measurements
on each side, 880 in total) [15]. A metallographic microscope is used for the measurements of the
surface layer, at a magnification of 100:1.

3. Results and Discussion

3.1. Chemical Composition

According to Table 2 data, the final cast iron, after Mg-treatment and ladle inoculation, occupies a
hyper-eutectic position, as carbon equivalent CE = 4.6%, at normal contents of the elements usually
present in the base chemical composition, including residual magnesium (0.049%Mgres ). According to
the size characteristics of the test samples, graphite flotation phenomena are not registered. High-purity
charge materials lead to limited content of minor elements, typically as (wt.%): 0.08Cr, 0.05Mo, 0.072Ni,
0.002Al, 0.02Cu, 0.016V, 0.004W, less than 0.002Pb and Bi, less than 0.005Sn, Sb, As, Sb, Ti. Consequently,
the experimental ductile cast irons are characterized by low antinodularizing potential (K < 0.8) and
low sensitivity of pearlite formation (Px < 1), according to Thielemann equations [16].

Table 2. Chemical composition of Mg-treated and inoculated cast iron.

Carbon Equivalent * Antinodulizing Pearlitic

Chemical Composition, wt.%
% Factor ** Factor ***
C Si Mn P S Mg CE K Px
3.65 3.15 0.1 0.013 0.004 0.049 4.6 0.72 −0.22
* CE = %C + 0.3(%Si + %P) + 0.4(%S) − 0.027(%Mn); ** K = 4.4 (%Ti) + 2.0(%As) + 2.4(%Sn) + 5.0(%Sb) + 290(%Pb)
+ 370(%Bi) + 1.6(%Al) [14]; *** Px = 3(%Mn) − 2.65(%Si − 2) + 7.75(%Cu) + 90(%Sn) + 357(%Pb) + 333(%Bi) +
20.1(%As) + 9.60Cr + 71.7(%Sb) [14].

3.2. Thermal (Cooling Curves) Analysis

Figure 2 [17] illustrates the representative events on the cooling curve, as temperatures and
undercooling degrees, respectively, for applied standard thermal (cooling curve) analysis for
commercial ductile cast iron, solidified in nonequilibrium conditions, typically for industrial metal
castings production.
3.2. Thermal (Cooling Curves) Analysis
Figure 2 [17] illustrates the representative events on the cooling curve, as temperatures and
undercooling degrees, respectively, for applied standard thermal (cooling curve) analysis for
commercial ductile
Coatings 2020, 10, 618 cast iron, solidified in nonequilibrium conditions, typically for industrial metal
5 of 15
castings production.

ΔT2 ΔT1

ΔT3

Time, τ, sec
Figure
Figure2.2. Representative
Representativesolidification
solidificationtemperatures
temperaturesand andundercooling
undercoolingdegrees
degrees(ΔT)(∆T)compared
comparedtoto
equilibrium temperature in stable (graphitic) (T
equilibrium temperature in stable (graphitic) (Tst ) and metastable (carbidic) (Tmst ) systemsofofductile
st) and metastable (carbidic) (Tmst) systems ductile
cast
castiron
iron[17].
[17].

Equilibrium temperatures TTststand

Equilibriumtemperatures andTTmst
mstare
areinfluenced
influencedbybymany
manyelements,
elements,present
presentininthe
thechemical
chemical
composition, as increasing
composition, as increasingoror decreasing
decreasing by different
by different powers,
powers, usuallyusually withassilicon
with silicon the mostasinfluencing
the most
influencing element. Consequently,
element. Consequently, these are
these temperatures temperatures are calculated
calculated depending depending
on the on the
silicon content, silicon
according
content, according
to Equations (1) andto (2)
Equations
[18,19]: (1) and (2) [18,19]:
Tst = 1153 + 6.7 (wt.%Si) (°C), (1)
Tst = 1153 + 6.7 (wt.%Si) (◦ C), (1)

Tmst== 1147
Tmst 1147 −− 12
12 (wt.%Si)
(wt.%Si) ((°C),
◦
C), (2)(2)
TEU represents the lowest temperature of the eutectic reaction, attended below the equilibrium
TEU represents the lowest temperature of the eutectic reaction, attended below the equilibrium
temperature in the stable (graphitic) system Tst, at a difference defined by the maximum eutectic
temperature in the stable (graphitic) system Tst , at a difference defined by the maximum eutectic
undercooling degree ΔTm = Tst − TEU. This temperature could be above or below the equilibrium
undercooling degree ∆Tm = Tst − TEU. This temperature could be above or below the equilibrium
temperature in a metastable system, Tmst.
temperature in a metastable system, Tmst .
The eutectic reaction will continue after TEU time with heat generation (austenite and eutectic
The eutectic reaction will continue after TEU time with heat generation (austenite and eutectic
formation), causing the temperature to rise until TER (the highest eutectic reaction temperature) is
formation), causing the temperature to rise until TER (the highest eutectic reaction temperature) is
reached. The TER − TEU = ΔTr difference is defined as eutectic recalescence. Solidification will
reached. The TER − TEU = ∆Tr difference is defined as eutectic recalescence. Solidification will
continue with decreasing temperature. The solidification of the last part of the liquid iron is marked
continue with decreasing temperature. The solidification of the last part of the liquid iron is marked by
by TES (temperature of the end of solidification), usually determined by the help of the first
TES (temperature of the end of solidification), usually determined by the help of the first derivative of
derivative of the cooling curve (corresponding to the lowest level of the first derivative, the first
the cooling curve (corresponding to the lowest level of the first derivative, the first derivative at the
derivative at the end of solidification (FDES) position).
end of solidification (FDES) position).
TEU and TER parameters are important to express the sensitivity of cast iron to graphite or
TEU and TER parameters are important to express the sensitivity of cast iron to graphite or carbides
carbides formation and graphite morphologies characteristics, while the TES value is important to
formation and graphite morphologies characteristics, while the TES value is important to evaluate
evaluate the sensitivity to inter-eutectic cell carbides and micro-shrinkage formation in the last
the sensitivity to inter-eutectic cell carbides and micro-shrinkage formation in the last solidified iron
solidified iron melt, at the end of solidification. Commercial/industrial iron castings (with more than
melt, at the end of solidification. Commercial/industrial iron castings (with more than 30 elements
30 elements in chemical composition) solidify in nonequilibrium conditions (solidification cooling
in chemical composition) solidify in nonequilibrium conditions (solidification cooling rate many
times higher than in equilibrium conditions), which affect the quality and the soundness of castings,
especially as free carbides and micro-shrinkage formation in the inter-eutectic cell areas, at the end of
solidification. Several elements segregate to the rest melt and lower TES. A low TES increases the risk
for inverse chill, i.e., formation of primary carbides at the last phases to solidify. In this respect, the TES
Coatings 2020, 10, x FOR PEER REVIEW 6 of 16

rate many times higher than in equilibrium conditions), which affect the quality and the soundness
of castings, especially as free carbides and micro-shrinkage formation in the inter-eutectic cell areas,
at the end
Coatings 2020, of
10, solidification.
618 Several elements segregate to the rest melt and lower TES. A low6 of TES
15
increases the risk for inverse chill, i.e., formation of primary carbides at the last phases to solidify. In
this respect, the TES parameter is very important: Lower TES values, or a more negative T3
parameter is very important: Lower TES values, or a more negative ∆T3 undercooling parameter,
undercooling parameter, means high sensitivity to form these defects. More information on the
means high sensitivity to form these defects. More information on the evaluation parameters at the
evaluation parameters at the end of solidification, such as TES, FDES-the first derivative at the end of
end of solidification, such as TES, FDES-the first derivative at the end of solidification (the lowest pick
solidification (the lowest pick on the first derivative, which corresponds to TES on the cooling
on the first derivative, which corresponds to TES on the cooling curve), or graphitization factors GRF2
curve), or graphitization factors GRF2 (as angle of the first derivative curve at FDES) are offered in
(as angle of the first derivative curve at FDES) are offered in papers [18,19]. For example, high GRF2
papers [18,19]. For example, high GRF2 indicates an increased risk for micro-shrinkages and
indicates an increased risk for micro-shrinkages and detrimental undercooled graphite shapes (type D
detrimental undercooled graphite shapes (type D and E) in grey cast iron.
and E) in grey cast iron.
At the beginning of the thermal analysis application in cast iron solidification control in the
At the beginning of the thermal analysis application in cast iron solidification control in the foundry
foundry industry, Tst – TEU = Tm (as the maximum undercooling referring to stable equilibrium
industry, Tst – TEU = ∆Tm (as the maximum undercooling referring to stable equilibrium temperature)
temperature) and TER-TEU (as recalescence) are used. They are also used currently, in solidification
and TER-TEU (as recalescence) are used. They are also used currently, in solidification simulation
simulation systems. However, over time, it has been observed that the referring of the cooling curve
systems. However, over time, it has been observed that the referring of the cooling curve events to the
events to the metastable (carbidic) temperature (Tmst) offered direct and clearer information. The
metastable (carbidic) temperature (Tmst ) offered direct and clearer information. The positions of the
positions of the representative temperatures TEU, TER, and TES compared to the eutectic
representative temperatures TEU, TER, and TES compared to the eutectic equilibrium temperature in
equilibrium temperature in the metastable (carbidic) solidification system (Tmst) are expressed by
the metastable (carbidic) solidification system (Tmst ) are expressed by specific undercooling degrees
specific undercooling degrees (Figure 2):
(Figure 2):
∆TΔT
1 =1 TEU
= TEU
− −Tmst
Tmst, , (3)
(3)

∆TΔT
2 =2 TER − −Tmst
= TER Tmst, , (4)
(4)
∆T3 = TES − Tmst , (5)
ΔT3 = TES − Tmst, (5)
The values of these undercooling degrees allow us to evaluate the structure characteristics and
The values of these undercooling degrees allow us to evaluate the structure characteristics and the
the quality of the iron castings, such as:
quality of the iron castings, such as:
• ∆T1 < 0 and ∆T2 < 0: Only carbides, not graphite formation (white cast iron);
• ΔT1 < 0 and ΔT2 < 0: Only carbides, not graphite formation (white cast iron);
• ∆T1 < 0 and ∆T2 > 0: Carbides at the beginning and graphite at the end of eutectic reaction
• ΔT1 < 0 and ΔT2 > 0: Carbides at the beginning and graphite at the end of eutectic reaction
(mottled cast iron);
(mottled cast iron);
•• ∆T
ΔT11 >>00 and ∆T22>>0:0:Only
and ΔT Onlygraphite
graphiteformation
formation(graphitic
(graphiticcast
castiron);
iron);
•• ∆T
ΔT33 << 00 usually,
usually, as TES <
as TES <TTmst for most of the commercial cast irons, solidified in industrial
mst for most of the commercial cast irons, solidified in industrial
conditions
conditions (the lower the TES (more negative),
(the lower the TES (more negative), the
the higher
higher the
the incidence
incidence of
of inter-cells
inter-cells events
events
formation).
formation).
Figure 3 shows
shows the aspect
aspect of
of typical
typical solidification
solidification cooling curves obtained in the present
present
experimental program,
program, with representative temperatures TEU, TER, and TES included in Figure4.4.
with representative temperatures TEU, TER, and TES included in Figure

Figure 3. Solidification
Solidification cooling
cooling curves
curves of
of tested
tested ductile
ductile cast
cast irons,
irons, for
for uncoated
uncoated and
and different
different inner-
cups.
coated ceramic cups.
Coatings 2020, 10, 618 7 of 15
Coatings 2020, 10, x FOR PEER REVIEW 7 of 16

1190
Tst Tmst TEU TER TES
1180
Fe2O3-Coating
TEMPERATURE, oC
Un- FeS2-Coating
1170
Coating Fe2O3
Fe2O3+
FeS2
FeS2+ FeS2+
MC Fe MC
1160

1150

1140

1130

1120

1110

1100

Figure 4.
Figure The lowest
4. The lowest (TEU) and and the
thehighest
highest(TER)
(TER)temperatures during
temperatures eutectic
during reaction
eutectic andand
reaction at the
at end
the
of solidification (TES) for uncoated and different inner coated ceramic cups, compared to stable
end of solidification (TES) for uncoated and different inner coated ceramic cups, compared to stable (T st )
and metastable (T
(Tst) and metastable ) equilibrium eutectic temperatures.
(Tmst) equilibrium eutectic temperatures.
mst

ItIt is
is supposed
supposedthat in the
that in present experimental
the present program,
experimental the solidification
program, parameters
the solidification of inoculated
parameters of
ductile iron,
inoculated identified
ductile iron, by thermalby
identified (cooling
thermalcurve) analysis,
(cooling curve)could be influenced
analysis, by two important
could be influenced by two
factors. For
important the same
factors. For used moldused
the same media mold (ceramic
mediacup), with cup),
(ceramic defined
withthermal-physical properties
defined thermal-physical
(Table 3) [20], different coatings, applied on the inner mold surface, could be influencing
properties (Table 3) [20], different coatings, applied on the inner mold surface, could be influencing factors on
the solidification
factors cooling rate,
on the solidification and rate,
cooling also,and consequently, the cooling
also, consequently, the curves
coolingparameters, due to their
curves parameters, due
different thermal-physical properties (Table 3). Higher thermal diffusivity
to their different thermal-physical properties (Table 3). Higher thermal diffusivity could could be a premise befor a
higher solidification
premise cooling rates.
for higher solidification cooling rates.
On the other hand, the presence of active materials in the coating composition, such as Fe2O3,
Table 3. Typical thermo-physical properties of used materials.
FeS2, carbonic material powder (MC), or iron powder (Fe) could influence the solidification pattern,
according to their capacity to diffuse intoDiffusivity
Thermal the iron meltSpecific
themself,
Heat or depending on their capacity
Thermal Conductivity Densityto
Material 1/2 /m2 K)
block the diffusion of other substances. (W s (J/kg K) (W/m K) (kg/m3 )
Ceramic cup 1487 1280 1.08 1600
S-bearing coatingTable 3. Typical thermo-physical
3585 547 of used materials.5
properties 4700
O-bearing coating 2044 650 1.26 5100
Fe-powder-bearing coating Thermal 16,221 450 Heat Thermal74.4
Diffusivity Specific Conductivity 7870
Density
Material
Carbonic-material-bearing coating 14,410 710 129 2267 3
(W s /m K)
1/2 2 (J/kg K) (W/m K0 (kg/m )
Ceramic cup 1487 1280 1.08 1600
OnS-bearing coating
the other hand, the presence of 3585
active materials in547 5
the coating composition, 4700
such as Fe 2 O3 ,
O-bearing coating 2044 650 1.26
FeS2 , carbonic material powder (MC), or iron powder (Fe) could influence the solidification pattern,5100
Fe-powder-bearing
according coating to diffuse into
to their capacity 16,221 450
the iron melt themself, 74.4on their capacity
or depending 7870 to
Carbonic-material-bearing coating 14,410 710 129 2267
block the diffusion of other substances.
ItIt is
is expected
expectedthat oxygen
that oxygenandand
sulfur diffused
sulfur into the
diffused ironthe
into meltiron
will melt
have awill
complex
have contribution
a complex
on the graphite phase: As active elements in graphite formation, by their contribution
contribution on the graphite phase: As active elements in graphite formation, by their contribution in the three-stage
formation
in of graphite
the three-stage nucleation
formation sites (sulfides–silicates–graphite)
of graphite [21], favoring the solidification
nucleation sites (sulfides–silicates–graphite) [21], favoringat
lower
the undercooling
solidification (usually
at lower as higher TEU,
undercooling TER, as
(usually TES); but TEU,
higher also inTER,
degeneration
TES); butof nodular/spheroidal
also in degeneration
graphite,
of as these elements
nodular/spheroidal will consume
graphite, part of thewill
as these elements nodulizing
consumeelements, decreasing
part of the nodulizing them under a
elements,
critical level.
decreasing them under a critical level.
Consequently, itit isis expected
Consequently, expected that
that the
the tested
tested coating
coating variants
variants could
could have
have aa complex
complex action,
action,
contributing to the increase in the solidification cooling rate, by their higher thermal
contributing to the increase in the solidification cooling rate, by their higher thermal diffusivity, but diffusivity, but
at the
at the same
same time,
time, to
to the
the decrease
decrease in
in the
the solidification
solidification cooling
cooling rate,
rate, byby their
their contribution
contribution in in graphite
graphite
formation (as a result of supplied O and S), without
formation (as a result of supplied O and S), without the necessity the necessity of higher undercooling.
The lowest
The lowest eutectic
eutectic temperature
temperature (TEU),
(TEU), registered
registered inin the
the first
first part
part of
of the
the eutectic
eutectic reaction,
reaction, is
is
affected by
affected by mold
mold coating
coating application,
application, but
but inin different
different ways
ways and
and power. Generally,
Generally, thethe increase
increase in
in
TEU level is a positive effect of potential influencing factors, at least for decreasing the sensitivity to
free carbide formation. The Fe2O3-bearing coating increased (1145.87 versus 1144.53 °C) and the
 mold solidification. MC-carbonic material supplementary addition led to the visible decrease in
values for both Fe2O3 (1140.73 versus 1145.87 °C) and FeS2-bearing coating (1141.39 versus 1143.40
°C) applications, according to its capacity to increase the thermal properties of these coatings and
cooling rate, respectively; iron powder addition also decreased the TEU level, for the same reason.
The 10,
Coatings 2020, highest
618 eutectic temperature, as a result of the eutectic recalescence, TER, is only a little8bit of 15
increased by the oxygen-bearing coating (1156.22 versus 1156.01 °C), but it is not affected by the
sulfur-bearing coating. The carbonic material visibly decreases the recalescence temperature for the
TEU Felevel is a positive effect of potential influencing factors, at least for decreasing the sensitivity
2O3 coating (1153.34 versus 1156.22 °C), but only at a limited level for the FeS2-bearing coating.
to free
Iron powderformation.
carbide The Fe2the
visibly decreases O3 -bearing
TER levelcoatingfor FeSincreased (1145.87 versus 1144.53 ◦ C) and the
2-bearing coating application (1152.96 versus
FeS1155.59 ◦
2 -bearing °C).coating decreased (1143.40 versus 1144.53 C) the TEU level, compared to uncoated
mold solidification.
The temperature MC-carbonic
at the end material supplementary
of solidification TES is at aaddition
lower level ledfor
to the visible
all the decrease
tested in TEU
mold coating
values for both Fe O (1140.73 versus 1145.87 ◦ C) and FeS -bearing coating (1141.39 versus 1143.40 ◦ C)
variants, compared 2 3 to the uncoated mold solidification. 2 It decreases from 1107.17 °C for the
applications,
uncoated to according
1106.39 °C tofor
its the
capacity
Fe2O3 to increase
coating andthe up thermal
to 1105.7properties
°C for the FeSof these coatings
2 coating. and cooling
Supplementary
rate, respectively;
carbonic materialironorpowder
iron powderaddition also decreased
addition decreasesthe theTEU level, for much
temperature the same more reason.
at the end of
solidification.
The highest At the end
eutectic of solidification,
temperature, when of
as a result thethe casting is solidified
eutectic recalescence, in theTER,outeris region,
only a the
little
bit coating
increased doesbynot
theact anymore as a supplier
oxygen-bearing coatingof oxygenversus
(1156.22 and sulfur, ◦ C), but
beneficial
1156.01 foritgraphite formation
is not affected by at
the
lower undercooling,
sulfur-bearing coating. butTheitcarbonic
will contribute
material tovisibly
the increase
decreasesin the thecasting cooling temperature
recalescence rate, by its higher
for the
Fe2thermal
O3 coating diffusivity,
(1153.34resulting
versus in a decrease
1156.22 ◦ C), in
butthe TESatparameter.
only a limited level for the FeS2 -bearing coating.
If the representative temperatures
Iron powder visibly decreases the TER level for FeS TEU, TER, and-bearing
TES are coating
referred application
to the equilibrium
(1152.96eutectic
versus
2
temperature
1155.59 ◦ C). in the metastable (carbidic) solidification system, Tmst, ΔT1, ΔT2, and ΔT3 solidification
undercooling
The temperature degrees (Equations
at the (3)–(5)) will result
end of solidification TES (Figure 5). level for all the tested mold coating
is at a lower
Positive values for both ΔT1 and ΔT2 sustain graphitic solidification of ◦the experimental
variants, compared to the uncoated mold solidification. It decreases from 1107.17 C for the uncoated
double-treated (Mg-treatment + inoculation) cast iron, at relatively higher silicon contents (more
to 1106.39 ◦ C for the Fe2 O3 coating and up to 1105.7 ◦ C for the FeS2 coating. Supplementary carbonic
than 3% Si). The negative values for ΔT3 (−2, …, −8 °C) show that the temperature of the end of
material or iron powder addition decreases the temperature much more at the end of solidification.
solidification (TES) remains below, but closer than, Tmst. Figure 5 illustrates a good relationship
At the end of solidification, when the casting is solidified in the outer region, the coating does not act
between the undercooling degree at the lowest eutectic temperature TEU, in the first part of the
anymore as a supplier of oxygen and sulfur, beneficial for graphite formation at lower undercooling,
eutectic reaction (ΔT1) and at the end of solidification (ΔT3); and between the undercooling degree at
buttheit will
highest contribute to thetemperature
(recalescence) increase inTER the (ΔT
casting cooling rate, by its higher thermal diffusivity,
2) and at the end of solidification ΔT3, respectively. If
resulting
the appliedin a decrease
coatings indothe
notTES parameter.
change these expected relationships, it is found that at the beginning of
eutectic reaction, the relationship (ΔT1 −TEU,
If the representative temperatures ΔT3) TER, and TES
is stronger thanare referred
at the maximum to the equilibrium
recalescence eutectic
rate (ΔT2
temperature in the metastable (carbidic) solidification
− ΔT3), but with results at a larger distribution. On the other hand, system, T , ∆T , ∆T
mst it is 1visible , and ∆T
2 that a coating
3 solidification
variant
undercooling
could have degreesdifferent(Equations (3)–(5)) to
positions referring ΔTresult
will 1 and ΔT(Figure
2, such 5).
as FeS2-included coatings.

Figure
Figure5. Relationship
5. Relationship between
betweenthe thesolidification
solidificationundercooling
undercooling at the
the lowest
lowest (ΔT
(∆T1)1 )and
andthe
thehighest
highest
(∆T(ΔT
2 ) eutectic reaction
2) eutectic andand
reaction at theat end
the of solidification
end (∆T3 ) (ΔT
of solidification compared to metastable
3) compared (carbidic)
to metastable eutectic
(carbidic)
eutectic temperature
temperature (Tmst) for uncoated
(Tmst ) for uncoated and different
and different inner-coated
inner-coated ceramic ceramic
cups. cups.

Positive values for both ∆T1 and ∆T2 sustain graphitic solidification of the experimental
double-treated (Mg-treatment + inoculation) cast iron, at relatively higher silicon contents (more
than 3% Si). The negative values for ∆T3 (−2, . . . , −8 ◦ C) show that the temperature of the end of
solidification (TES) remains below, but closer than, Tmst . Figure 5 illustrates a good relationship
between the undercooling degree at the lowest eutectic temperature TEU, in the first part of the eutectic
reaction (∆T1 ) and at the end of solidification (∆T3 ); and between the undercooling degree at the
highest (recalescence) temperature TER (∆T2 ) and at the end of solidification ∆T3 , respectively. If the
applied coatings do not change these expected relationships, it is found that at the beginning of eutectic
Coatings 2020, 10, 618 9 of 15

reaction, the relationship (∆T1 − ∆T3 ) is stronger than at the maximum recalescence rate (∆T2 − ∆T3 ),
but with results at a larger distribution. On the other hand, it is visible that a coating variant could
have different positions referring to ∆T1 and ∆T2 , such as FeS2 -included coatings.
Mold coating status has an important effect on the undercooling degree levels and relationship.
Solidification in the uncoated mold is characterized by a high level of ∆T1 , ∆T2 , and ∆T3 (less negative)
parameters. The lowest level of these parameters is generally obtained by carbonic material or iron
powder addition to the oxygen or sulfur-bearing coatings. Limited effects and, in any case, apparent
Coatings 2020, 10, x FOR PEER REVIEW 9 of 16
contradictions reported for these coatings as their influence on the cooling curves morphology are
evidence that Moldthis is notstatus
coating the most
has animportant contribution,
important effect from thedegree
on the undercooling two possible
levels and effects, mentioned
relationship.
before: Solidification
Influence oninthe thesolidification
uncoated mold is characterized
pattern by a high level
or their contribution of ΔT1, ΔT
in graphite 2, and ΔT3 (less
degeneration.
negative) parameters. The lowest level of these parameters is generally obtained by carbonic
material
3.3. Structure or iron powder addition to the oxygen or sulfur-bearing coatings. Limited effects and, in
Analysis
any case, apparent contradictions reported for these coatings as their influence on the cooling curves
morphology
3.3.1. Casting Bodyare evidence that this is not the most important contribution, from the two possible
effects, mentioned before: Influence on the solidification pattern or their contribution in graphite
Thedegeneration.
microstructures included in Figure 6 show the effect of the coating of the ceramic mold on the
structure of the obtained body of ceramic cup casting (see Figure 1b), in unetched (graphite phase)
3.3. Structure
and Nital-etched Analysis
(metal matrix) conditions. The graphite characteristics are evaluated with Automatic
Image Analysis (OMNIMET
3.3.1. Casting Body ENTERPRISE and analySIS® FIVE Digital Imaging Solutions software).
For graphite nodularity (N), this software uses Equation (6):
The microstructures included in Figure 6 show the effect of the coating of the ceramic mold on
the structure of the obtained body
X of ceramicX cup casting
X (see Figure 1b), in unetched (graphite
N = [( A NG +1/2 A IG / Atot ]·100
phase) and Nital-etched (metal matrix) conditions. The graphite [%]
characteristics are evaluated with (6)
Automatic Image Analysis (OMNIMET ENTERPRISE and analySIS FIVE Digital Imaging Solutions
®

where: software). For graphite nodularity (N), this software uses Equation (6):

ANG is the area of particles classified N = as

[(∑A NG+1/2 ∑A
nodules (RSF = tot0.625
IG/∑A ]∙100 − 1.0);
[%] (6)

AIG —area of particles classified as intermediates (RSF = 0.525 − 0.625);

where:
Atot —area
ANGof all area
is the graphite particles;
of particles classified as nodules (RSF = 0.625 − 1.0);
RSF = 4A/(π
AIG—arealm2of); particles classified as intermediates (RSF = 0.525 − 0.625);
A—areaAof tot—area of all graphite particles;
the graphite particle in question;
RSF = 4A/(π lm2);
lm—maximum
A—area of axis
thelength
graphite ofparticle
the graphite particle in question (maximum distance between two points
in question;
on the graphite
lm—maximum particle
axisperimeter).
length of the graphite particle in question (maximum distance between two
points on the graphite particle perimeter).

S/O Source Protective Samples

Coating Coating Unetched Nital-etched

Un-Coating Un-
[UC] Coating [UC]

Oxygen
(Fe2O3-
bearing coating)

Fe-
powder coating

Figure 6. Cont.
Coatings 2020, 10, 618 10 of 15
Coatings 2020, 10, x FOR PEER REVIEW 10 of 16

MC-
powder coating

Sulphur
Fe-
(FeS2-
powder coating
bearing coating)

MC-
powder coating

FigureFigure 6. Typical structure characteristics in the casting body (unetched and Nital-etched).
6. Typical structure characteristics in the casting body (unetched and Nital-etched).
In all the cases, a good nodular graphite cast iron is obtained, with a more than 85% graphite
In all the cases, a good nodular graphite cast iron is obtained, with a more than 85% graphite
nodularity level in the uncoated mold casting. The Fe2O3 and FeS2-bearing coating has a limited
nodularity level
effect in the
on the uncoated
graphite moldinside
nodularity casting. The Feby
the casting, 2 Oreducing
3 and FeS 2 -bearing
the nodularitycoating has82%–83%
up to the a limited effect
on the graphite
level. Application of the carbonic-material- or iron-powder-bearing supplementary coating on the level.
nodularity inside the casting, by reducing the nodularity up to the 82%–83%
Application of the
previous carbonic-material-
oxygen or sulfur-bearing orcoating
iron-powder-bearing
acted in a positive supplementary coatingnodularity
manner, as graphite on the previous
increased up to 83.5%–84%, but in a different association formula.
oxygen or sulfur-bearing coating acted in a positive manner, as graphite nodularity Better results are obtained by up to
increased
carbonic material addition on the Fe2O3-bearing coating and iron powder on the FeS2-bearing
83.5%–84%, but in a different association formula. Better results are obtained by carbonic material
coating, respectively. The presence of oxygen or sulfur in the mold coating appears to favor the
additionformation
on the of Felower-sized
2 O3 -bearing coating and iron powder on the FeS2 -bearing
graphite nodules, while the carbonic material included
coating, respectively.
in the mold coating
The presence
leads to an increased amount of higher-sized graphite nodules in the casting body structure.of lower-sized
of oxygen or sulfur in the mold coating appears to favor the formation
graphite nodules, whileis the
Metal matrix carbonic
mainly ferritic material included
type, at less than 15% in pearlite,
the mold coating
without the leads
presenceto of
anfree
increased
carbides, according to the lower pearlitic potential
amount of higher-sized graphite nodules in the casting body structure. of the chemical composition (high content of
silicon and low content of manganese and minor elements). A higher ferrite amount
Metal matrix is mainly ferritic type, at less than 15% pearlite, without the presence of free carbides, (>90% ferrite)
accompanies the lower size and higher graphite particles count favored by the oxygen or
according to the lower pearlitic potential of the chemical composition (high content of silicon and
sulfur-bearing mold coating. A lower graphite nodularity level, which means a higher incidence of
low content of manganese
non-spheroidal and
graphite minor elements).
particles, resulting from A the
higher ferrite
action amount
of mold coating(>90% ferrite)
including accompanies
oxygen or
the lower size and higher graphite particles
sulfur, also contributes to ferrite formation. count favored by the oxygen or sulfur-bearing mold
coating. A lower graphite nodularity level, which means a higher incidence of non-spheroidal graphite
3.3.2.
particles, Surface Layer
resulting fromofthe Castings
action of mold coating including oxygen or sulfur, also contributes to
ferrite formation.
Figure 7 shows the structure of the experimental ductile cast iron in the surface layer of
castings, in all test variants, as effects of mold coatings application. Figure 8 illustrates the larger
3.3.2. Surface
casting Layer
surfaceof Castings
structure, for S-bearing coating application.

Figure 7 shows the structure of the experimental ductile cast iron in the surface layer of castings,
in all test variants, as effects of mold coatings application. Figure 8 illustrates the larger casting surface
structure, for S-bearing coating application.
Coatings 2020, 10, x FOR PEER REVIEW 11 of 16

Coatings 2020, 10, 618 11 of 15

S/O Source Protective Samples

Coating Coating Unetched Nital-etched

Un- Un-
Coating [UC] Coating [UC]

Oxygen
Fe-
(Fe2O3-
powder
bearing
coating
coating)

MC-
powder
coating

Sulphur
Fe-
(FeS2-
powder
bearing
coating
coating)

MC-
powder
coating

Figure 7. Typical
Figure 7. structure of
Typical structure of the
the Mg-treated
Mg-treated and
and inoculated
inoculated cast
cast iron
iron in
in the
the casting
casting surface
surface layer.
layer.
Coatings 2020, 10, 618 12 of 15
Coatings 2020, 10, x FOR PEER REVIEW 12 of 16

Coatings 2020, 10, x FOR PEER REVIEW 12 of 16

(a) (b)
(a) (b)
Figure 8. Unetched
Unetched (a)
(a) and
and Nital-etched
Nital-etched (b)
(b) casting surface structure, at larger pictures (S-bearing
Figure 8. Unetched (a) and Nital-etched (b) casting surface structure, at larger pictures (S-bearing
coating).
coating).
Typically, for
Typically, for the
theMg-treated
Mg-treatediron ironcastings,
castings, there
there is the
is the presence
presence of a of a surface
surface layerlayer (casting
(casting skin)
skin) Typically,
with an alteredfor the Mg-treated
structure as iron
the castings,phase
graphite there is the presence of
morphology. a surface
This means layer
a (casting skin)
decreased graphite
with an altered structure as the graphite phase morphology. This means a decreased graphite phase
phasewith an altered structure
compactness as the graphite phasebetween
morphology. This means a decreased graphite the
phase
compactness degree,degree,
with awith a transition
transition between nodular nodular (spheroidal)
(spheroidal) graphite graphite
in the incastingcasting
body
compactness
body through degree,
mixture with a transition
morphologies between
(nodular, nodular
compacted, (spheroidal)
lamellar graphite
graphite) in the casting
atcasting
the casting bodysurface.
through
through mixture morphologies (nodular, compacted, lamellar graphite) at the casting surface. The The
mixture morphologies (nodular, compacted, lamellar graphite) at the surface.
The presence
presence of theof casting
the casting
skinskin is visibleboth
isisvisible in both unetched and Nital etching samples conditions, but
presence of the casting skin visiblein unetched
in both unetched andNital
and Nital etching
etching samples
samples conditions,
conditions, but atbut at
at different
different levels
levels
different
depending
depending
levels depending
on
ononthe the mold
themold
coating
moldcoating
status (Figure
status(Figure
coating status
9).
(Figure9).9).
In In
In the
thethe
unetched
unetched
unetched
structure,
structure,
structure,
only the
only the
only the
graphite
graphite phase
phase
graphite is considered.
is considered.
phase In this
is considered.InInthis case,
thiscase, the
case, thedegenerated graphite
degeneratedgraphite
the degenerated graphite layer
layer
layer thickness
thickness
thickness is considered
is considered
is considered up
up up to
thethe
to nodular
tonodular graphite
the nodular
graphite morphology
graphite morphology
morphology appearance,
appearance,
appearance, without
without
without other
othervisible
othervisible
visiblegraphite
graphite morphologies,
morphologies,
graphite morphologies,suchsuch as
such
lamellar
as and
lamellarcompacted
and graphite.
compacted
as lamellar and compacted graphite. graphite.

250
250
Un- Fe O -Coating FeS2-Coating
Un- Fe22O33-Coating FeS2-Coating
Casting Skin Thickness, μm

Coating
Casting Skin Thickness, μm

Coating Fe2O3 Fe2O3 +Fe Fe2O3+MC FeS2 FeS2+Fe FeS2+MC

200 Fe2O3 Fe2O3 +Fe Fe2O3+MC FeS2 FeS2+Fe FeS2+MC
200
Un-etchingh
N ital etching
Un-etchingh
150 N ital etching
150

100

100

50

50
0

Figure
Figure 9. Averagegraphite
9. Average graphitedegenerated
degenerated surface
surfacelayer
layer(casting skin)
(casting thickness
skin) of experimented
thickness of experimented
ductile0irons.
ductile irons.
Figure 9. Average graphite degenerated surface layer (casting skin) thickness of experimented
In theIn Nital
the Nital etching
etching structure,
structure, notonly
not onlygraphite
graphite but alsoalsometal
metalmatrix
matrixis is
considered.
considered.There exists
There exists a
ductile irons.
a difference between the surface layer and casting body not only as graphite
difference between the surface layer and casting body not only as graphite morphology but also as morphology but also as
metalmetal
Inmatrix
matrix
the Nital
make-up.
make-up. In thecasting
etchingInstructure,
the castingsurface
surface layer,
layer,formed
not only graphite formed lamellar
but also
graphite
lamellar graphite
metal matrix
promotes pearlite
promotes
is considered.
whilewhile
pearlite
There exists
very fine lamellar graphite and compacted graphite promote ferrite, resulting in a layer not only
avery fine lamellar
difference between
with a mixture
graphite
of graphite
and compacted
the surface layer andgraphite
morphologies casting
but
promote ferrite,
also body
with anot asresulting
only of
mixture graphite
metal
in
matrix
a layer not only
morphology but
constituents. The
withasa
also
mixture
metal of graphite
matrix make-up. morphologies
In the castingbutsurface
also with a mixture oflamellar
metal matrix constituents. The thickness
thickness of this surface layer is considered inlayer, formed
the Nital etching graphite
conditions. promotes pearlite while
of this surface
very fineDespite layer
lamellar is considered
graphite
this, in the
and compacted
in the present Nital
experiments, etching
graphite conditions.
the usedpromote
ceramic ferrite,
mold is resulting
not able toinsupply
a layer not only
active
Despite
withagents forthis,
a mixture ofingraphite
the present
nodularizing experiments,
morphologies
elements butthe
consumption used
also ceramic
intowith
the moldand
a mixture
iron melt, is metal
of not able tolayer
supply
matrix
a surface active agents
constituents.
at different The
for nodularizing
thickness elements
of this surface consumption
layer into
is considered inthe
theiron
Nitalmelt, andconditions.
etching a surface layer at different graphite
Despite this, in the present experiments, the used ceramic mold is not able to supply active
agents for nodularizing elements consumption into the iron melt, and a surface layer at different
 The lowest thickness of the surface layer (skin) is obtained without mold coating, at an average
ze at 52.3 µm for unetched (graphite phase evaluation), and 54.97 µm for Nital etching (metal
atrix evaluation). A higher level of skin thickness as metal matrix evaluation compared to the
aphite phase evaluation is present in all of the experimented variants. This situation is confirmed
so in other researchCoatings
works 2020,
[22,23]. Both oxygen or sulfur included in the mold coating increase the
10, 618 13 of 15
sting skin thickness, but at different powers: Up to 50% by oxygen and 2.5–3.3 times for sulfur
tion, respectively, despite the fact that in the casting body, the graphite nodularity decreases only
om 85% up to 82%–83%. morphologies
Supplementarycompared to the casting
iron powder addition, body is present,
supposed butoxygen
to block at a large range of thicknesses, from 50 up
or sulfur
ffusion from the mold coating
to 200 µm. into the iron melt, is efficient, as the skin thickness decreases from
.93 to 58.68 µm for the oxygen-bearing
The lowest thicknesscoatingof andtheespecially
surface layer from (skin)
133.75 is
toobtained
56.34 µmwithout
for sulfur
mold coating, at an average
esence in the moldsize coating, forµm
at 52.3 unetched samples(graphite
for unetched evaluation. phaseForevaluation),
metal matrixand evaluation
54.97 µm (Nital
for Nital etching (metal matrix
ching samples), a decrease from 103.73
evaluation). A higherto 83.06
levelµm is found
of skin for theas
thickness oxygen-bearing
metal matrix coating and compared to the graphite
evaluation
om 178 to 77.81 µmphase for theevaluation
sulfur-bearing coating. Similarly, positive effects are also
is present in all of the experimented variants. This situation obtained by is confirmed also in
rbonic material addition.
other research works [22,23]. Both oxygen or sulfur included in the mold coating increase the casting
Some visible structure characteristics could also be observed for the casting body just below the
skin thickness, but at different powers: Up to 50% by oxygen and 2.5–3.3 times for sulfur action,
rface layer (skin) for the test variants. Larger-sized nodules and degenerated graphite
respectively, despite the fact that in the casting body, the graphite nodularity decreases only from 85%
orphologies (like spiky-graphite) could be noted for the uncoated mold, and small-sized nodules
r coated molds. Theup to 82%–83%.
ferritic structure Supplementary
characterizes all the ironanalyzed
powderstructures.
addition, supposed to block oxygen or sulfur diffusion
from thethe
Figure 10 summarizes mold coatingresults,
obtained into the as iron
the melt,
effectsis ofefficient,
the moldas the skin thickness
coating on the decreases from 73.93 to
58.68 µm for the oxygen-bearing coating and especially
lidification parameters, expressed by the undercooling degree at the lowest eutectic temperature, from 133.75 to 56.34 µm for sulfur presence
the first part of solidification (ΔT1) and at the end of solidification (ΔT3) on the one hand, and the evaluation (Nital etching
in the mold coating, for unetched samples evaluation. For metal matrix
sting skin thickness,samples),
resulting afrom
decrease from 103.73
the influence of the to 83.06
tested is foundon
µmcoatings,
mold forthe
theother
oxygen-bearing
hand. coating and from 178
espite this, the applied
to 77.81 coatings
µm for the influence the solidification
sulfur-bearing pattern not
coating. Similarly, positiveonlyeffects
by their
are also obtained by carbonic
ermal-physical properties,
materialinfluencing
addition. the solidification cooling rate in this way, but also as
ossible sources for activeSome substances, supposed characteristics
visible structure to be able to diffuse could alsointo be
theobserved
iron melt,forbefore
the casting body just below the
lidification; to affect structure
surface layerformation,
(skin) for thethe test
casting skin Larger-sized
variants. formation appears nodules to and
be attributed
degenerated graphite morphologies
ainly to the second (like
influencing factor.
spiky-graphite) could be noted for the uncoated mold, and small-sized nodules for coated molds.
The highest thickness of the graphite surface degeneration layer (casting skin) resulted from the
The ferritic structure characterizes all the analyzed structures.
esence of sulfur in the mold coating, despite the fact that the casting solidification is characterized
Figure 10 summarizes the obtained results, as the effects of the mold coating on the solidification
a medium undercooling in the first part of the eutectic reaction and at the end of solidification.
parameters, expressed by the undercooling degree at the lowest eutectic temperature, in the first part
on powder or carbonic material addition to the S- or O-bearing coating increases the undercooling
gree, lowering both of solidification
ΔT1 and ΔT3 (more (∆T1 ) negative),
and at thebut endthe of casting
solidification (∆T3 ) onsensitivity
skin formation the one hand, and the casting skin
creases. thickness, resulting from the influence Coatingsof the10,tested
2020, mold
x FOR PEER coatings, on the other hand.
REVIEW 14 of 1

(a) (b)

Figure 10. Casting skin thickness forFigure 10. Casting

uncoated skin thickness
and different for uncoated
inner-coated and different
ceramic inner-coated
cups, in unetchedceramic cups, in unetched
(graphite)
(graphite) and Nital etching (metal matrix) and Nital conditions
evaluation etching (metal ∆T1 ; (b)
(a)matrix) ∆T3 relationship.
evaluation conditions (a) ΔT1; (b) ΔT3 relationship.

4. Conclusions
Despite this, the applied coatings influence the solidification pattern not only by their
thermal-physical properties, influencingThethelowest eutectic temperature
solidification cooling rate (TEU) is slightly
in this way, but increased by the O-bearing coating an
also as possible
decreased by the S-bearing coating, while carbonic material or iron
sources for active substances, supposed to be able to diffuse into the iron melt, before solidification; to powder supplementary additio
leads to a visible TEU decrease.
affect structure formation, the casting skin formation appears to be attributed mainly to the second
The highest (recalescence) eutectic temperature TER is only increased a little bit by th
influencing factor. O-bearing coating, but it is not affected by the S-bearing coating; the carbonic material visibl
The highest thickness of the graphite
decreases surface degeneration
TER for the layer (casting
O-bearing coating, but only atskin) resulted
a limited level from
for thethe
S-bearing coating, whi
presence of sulfur in the mold coating, despite the
the Fe-bearing fact that
coating the
visibly castingTER
decreases solidification
for S-bearing is coating
characterized by
application.
a medium undercooling in the first part Theoftemperature
the eutecticat the end of solidification
reaction and at the end TES is
ofatsolidification.
a lower level forIron
all the tested mold coatin
variants, compared to the uncoated mold solidification. Supplementary carbonic material or iro
powder or carbonic material addition to the S- or O-bearing coating increases the undercooling degree,
powder addition decreases the temperature of the end of solidification much more.
lowering both ∆T1 and ∆T3 (more negative), but the casting skin formation sensitivity decreases.
The O- or S-bearing coating had a limited effect on the graphite nodularity inside the casting, b
reducing it, while the application of the carbonic material or iron powder acted in a positive manne
Better results are obtained by carbonic material addition on the O-bearing coating and iron powde
on the S-bearing coating.
A surface layer at different graphite morphologies compared to the casting body is present, at
large range of thicknesses, from 50 up to 200 m, with a higher level as metal matrix evaluation. Th
lowest thickness of the surface layer (skin) is obtained without mold coating, while O or S include
Coatings 2020, 10, 618 14 of 15

4. Conclusions
The lowest eutectic temperature (TEU) is slightly increased by the O-bearing coating and decreased
by the S-bearing coating, while carbonic material or iron powder supplementary addition leads to a
visible TEU decrease.
The highest (recalescence) eutectic temperature TER is only increased a little bit by the O-bearing
coating, but it is not affected by the S-bearing coating; the carbonic material visibly decreases TER
for the O-bearing coating, but only at a limited level for the S-bearing coating, while the Fe-bearing
coating visibly decreases TER for S-bearing coating application.
The temperature at the end of solidification TES is at a lower level for all the tested mold coating
variants, compared to the uncoated mold solidification. Supplementary carbonic material or iron
powder addition decreases the temperature of the end of solidification much more.
The O- or S-bearing coating had a limited effect on the graphite nodularity inside the casting, by
reducing it, while the application of the carbonic material or iron powder acted in a positive manner.
Better results are obtained by carbonic material addition on the O-bearing coating and iron powder on
the S-bearing coating.
A surface layer at different graphite morphologies compared to the casting body is present, at
a large range of thicknesses, from 50 up to 200 µm, with a higher level as metal matrix evaluation.
The lowest thickness of the surface layer (skin) is obtained without mold coating, while O or S included
in the mold coating increases the casting skin thickness, but at different powers: Up to 50% by oxygen
and 2.5–3.3 times for sulfur action, respectively, despite that fact that, in the casting body, the graphite
nodularity had a limited decrease.
Despite this, the mold coatings influence the solidification pattern not only by their
thermal-physical properties (solidification cooling rate), but also as possible sources for active
substances, supposed to be able to diffuse into the iron melt; to affect structure characteristics,
the casting skin formation appears to be attributed mainly to the second influencing factor.
The negative role of oxygen and, especially, of sulfur in graphite degeneration in the surface
casting layer could be counteracted by the addition of materials able to block the diffusion of these
elements into the iron melt. It is found that carbonic material is more efficient at limiting oxygen
negative effects, and iron powder is more efficient at limiting sulfur negative effects. More experiments
are necessary to quantify their capacity to block the oxygen or sulfur transfer into the iron melt.

Author Contributions: D.A., M.C., S.S., I.S. and I.R. contributed equally in conceiving, designing and performing
the experiments; analyzing the data; and writing the paper. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by the Operational Programme Human Capital of the Ministry of European
Funds through the Financial agreement 51668/09.07.2019, SMIS code 124705.
Conflicts of Interest: The authors declare no conflict of interest.

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