materials
Article
Effect of the Biodegradable Component Addition to the
Molding Sand on the Microstructure and Properties of Ductile
Iron Castings
Katarzyna Major-Gabryś 1 , Małgorzata Hosadyna-Kondracka 2, * , Adelajda Polkowska 2
and Małgorzata Warmuzek 2






Citation: Major-Gabryś, K.;
Hosadyna-Kondracka, M.;
Polkowska, A.; Warmuzek, M. Effect
of the Biodegradable Component
Addition to the Molding Sand on the
Microstructure and Properties of
Ductile Iron Castings. Materials 2022,
15, 1552. https://doi.org/10.3390/
ma15041552
Academic Editor: José A.F.O. Correia
Received: 27 December 2021
Accepted: 14 February 2022
Published: 18 February 2022
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Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2022, 15, 1552. https://doi.org/10.3390/ma15041552
1 Faculty of Foundry Engineering, AGH University of Science and Technology, Mickiewicza 30,
30-059 Krakow, Poland; katmg@agh.edu.pl
2 Łukasiewicz Research Network-Krakow Institute of Technology, Zakopiańska 73, 30-418 Krakow, Poland;
adelajda.polkowska@kit.lukasiewicz.gov.pl (A.P.); malgorzata.warmuzek@kit.lukasiewicz.gov.pl (M.W.)
* Correspondence: malgorzata.kondracka@kit.lukasiewicz.gov.pl
Abstract: In this work, the results of the examinations of the effect of the mold material and mold
technology on the microstructure and properties of the casts parts of ductile cast iron have been
presented. Four different self-hardening molding sands based on fresh silica sand from Grudzen Las,
with organic binders (no-bake process), were used to prepare molds for tested castings. A novelty
is the use of molding sand with a two-component binder: furfuryl resin-polycaprolactone PCL
biomaterial. The molds were poured with ductile iron according to standard PN-EN 1563:2018-10. The
microstructure of the experimental castings was examined on metallographic cross-sections with PN-
EN ISO 945-1:2019-09 standard. Observations were made in the area at the casting/mold boundary
and in a zone approximately 10 mm from the surface of the casting with a light microscope. The tensile
test at room temperature was conducted according to standard PN-EN ISO 6892-1:2016-09. Circular
cross-section test pieces, machined from samples taken from castings, were used. In the present
experiment, it was stated that interactions between the mold material of different compositions and
liquid cast iron at the stage of casting solidification led to some evolution of casting’s microstructure
in the superficial layer, such as a pearlite rim observed for acidic mold sand, a ferritic rim for
alkaline sand, and graphite spheroids degeneration, especially spectacular for the acidic mold with
polycaprolactone (PCL) addition. These microstructural effects may point to the interference of the
direct chemical interactions between liquid alloy and the components released from the mold sand,
such as sulfur and oxygen. Particularly noteworthy is the observation that the use of molding sand
with furfuryl resin with the addition of biodegradable PCL material does not lead to an unfavorable
modification of the mechanical properties in the casting. The samples taken from Casting No. 2,
made on the acidic molding sand with the participation of biodegradable material, had an average
strength of 672 MPa, the highest average strength UTS-among all tested molding sands. However,
the elongation after fracture was 48% lower compared to the reference samples from Casting No. 1
from the sand without the addition of PCL.
Keywords: metal casting; ductile cast iron; molding sand; organic binder; biodegradable additive
1. Introduction
Cast iron accounts for about 70% of the total production of castings, which confirms
that it is the most used alloy in the industry [1]. Cast iron castings are widely used in
the automotive industry, in sea and rail transport, in the energy industry, agriculture,
and construction, as products that do not carry loads, mainly of gray cast iron (cylinders,
ingot molds, pistons); more loaded castings of malleable and nodular cast iron (parts
of agricultural machinery, car parts, fittings, camshafts, crankshafts, gears, machine tool
spindles), as well as castings with the high abrasion resistance of white cast iron (mill balls,
https://www.mdpi.com/journal/materials
Materials 2022, 15, 1552 2 of 14

brake pads). The advantages of cast iron castings are high durability and strength, resistance
to abrasion, good ability to dampen vibrations, the possibility of obtaining various and
complicated shapes of castings as well as low production costs. The production of a large-
size casting with a complex shape, characterized by high quality while maintaining the
required functional properties, involves many stages of the production process. These
stages are interdependent and ultimately determine the quality and competitiveness of the
manufactured elements. The main stages of the large-size castings manufacturing process
include:
− The selection of the chemical composition of the casting;
− The proper selection of mold and core technology;
− The preparation, smelting and refining of the liquid alloy (modifiers);
− The post-casting treatment, i.e., removal of gating systems, treatment heat, finishing
(polishing, shot blasting) of the raw surface of castings;
− The quality control of the finished product.
This paper presents the impact of the type of molding sand used in the mold tech-
nology on the properties of the produced iron casting. Four different molding and core
sands, dedicated to the production of large-size castings, were selected for the tests. They
are molding sands with organic binders. Furthermore, in one molding sand, the addition
of biodegradable material to the binder was used in order to accelerate the process of
biodegradation of the binder waste remaining after the casting process. The authors’ earlier
studies proved an increased biodegradability of post-production residues of the binding
material in the case of using a new two-component binder in relation to the analogous
molding sand without the additive [2]. This approach to the issue of improving the ecology
of the process is particularly important in the case of large-size castings production, where
the amount of waste binding material is large.
The rapid increase recently observed in the production of heavy castings of cast
iron, both vermicular and nodular, also places special demands on the quality of molding
materials. While molding sands with furfuryl resins are very well suited for the production
of small and medium-sized castings, their use for the production of heavy castings will
require significant technological modifications. Thus, the constant improvement of molding
technologies is still an important challenge.
The latest trends in foundry technologies focus on improving the dimensional accuracy
and functional quality of castings and on meeting the environmental protection require-
ments introduced in the European Union. Subsequent generations of molding materials are
elaborated, including their second generation based on sands bound with various binders,
which can also be used for the production of both foundry molds and cores [3].
The second-generation molding technologies mainly use organic binders based on
synthetic resins, but the inorganic ones based on hydrated sodium silicate can also be
used [3–5]. At present, molding technologies with the use of alkyd resins hardened by
catalyst based on isocyanates and alkaline phenolic resin hardened by esters are becoming
a serious alternative in the heavy steel castings industry, mainly due to their less harmful
environmental impact [5]. Among the basic advantages of the molding sands with alkyd
binder, there is [3]: the possibility of using a very high proportional fraction of reclaim
in the mixture (up to 90%); high plasticity of the sand during contraction of the steel
casting (as opposed to phenolic and furfuryl resins); no nitrogen content, no addition of
formaldehyde and water to their composition; a lower amount of gases emitted during
pouring of molten metal and low level of the toxic compounds formed during mixing and
setting of sands (as opposed to furfuryl resins). Unfortunately, using more coarse sands
requires the application of protective coatings (hydrous or alcoholic).
Another group of materials for second-generation molds are those based on loose
self-hardening sands with furfuryl resins. These are materials based on grains of silica sand
and/or their reclaim, with furfuryl resin and an acid hardener, such as organic sulfonic
acids, sometimes in combination with orthophosphoric acid, and inorganic sulfuric or
Materials 2022, 15, 1552 3 of 14

phosphoric acids. The silica sand used for these materials should contain a maximum of
0.2% of the clay and its pH should be close to 7 [6].
Since the time of solidification and cooling of heavy castings, from the moment the
liquid metal is poured into the mold, takes up to several days, local interactions between
the mold material and the liquid alloy, and then the cooling-down casting may affect
its properties to a much more significant extent than in the case of small castings [7,8].
Especially in the case of using molds made of self-hardening sands with furfuryl resins
hardened with acid hardeners, their negative influence on the graphite spheroidization
process in the casting surface layer was observed. This phenomenon depends on the sulfur
content in the molding or core sands and the conditions of the oxidation process of the
solidifying surface casting [8–12]. The sulfur-containing gases released from the molds
materials are absorbed by the liquid metal. Therefore, a reduction in the effectiveness of
the magnesium modifier is observed due to the formation of magnesium sulfide. Sulfur
saturation of surface zones of castings made in molds of loose self-hardening molding/core
sands with furfuryl resins is also observed in steel castings [10,11]. The effects of the
interaction between the cast iron and the mold material are manifested as casting skin,
including roughness of the casting surface and other microstructural effects, is considered
to be unfavorable [6,8,9].
According to the tendencies observed in recent years, molding processes must meet
high requirements connected to environmental protection including problems related to
the disposal of waste from used molding materials [1,13].
The idea of K. Major-Gabryś [1] is to introduce an additive of biodegradable material
to the commercial organic binder. The trend causing a gradual replacement of binding
materials produced from a petrochemical origin with biomaterials is observed in foundry
technologies development [14–17]. In the 900 s General Motors Co. (Detroit, MI, USA)
elaborated a new binding system based on protein composition GMBONDTM [14]. The
materials in the protein binder come from natural renewable resources and consist of
polypeptide chains, which are ecologically friendly. The binder is well soluble in water
and the binding process begins during the dehydration reaction of wet molding sand.
The technological experiments using the protein binder showed good enough castings
properties, though the binder quantity was reduced by 45% in comparison to the furfuryl
resin binder quantity used in core production by hot-box technology [14]. Another ex-
ample of using biodegradable materials in molding sands technologies was proposed by
K. Rusin’s scientific group [15]. The usage of biogenic binders based on proteins obtained
from by-products of pharmacy industry production was tested. The binders were water
soluble non-toxic polymers, including different polypeptide molecules with long amino
acids chains. There is no chemical reaction in the process, only the reaction of dehydration
during the heating process. This kind of molding sand can be used for light alloys like alu-
minum castings [15]. B. Grabowska [16,17] proposed the usage of aqueous biodegradable
polymeric compositions consisting of acrylic derivatives and modified natural polymers as
foundry molding sands’ binders (BioCo binders). Molding sands with BioCo binders can
be used in iron castings production [17]. K. Major-Gabryś investigated the possibility of
using biodegradable materials, such as PLA, PHB, or PCL as binders for molding sands
production. Research results showed lower toxicity and greater capacity for mechanical
reclamation of molding sands with biodegradable materials as binders [1].
The idea of improving molding sand presented in this paper is to introduce an ad-
ditive of biomaterial to the commercial organic binder. Therefore, molding sand with a
two-component binder: furfuryl resin and biodegradable PCL, will be also used and the
influence of the biodegradable additive on changes in the microstructure and properties of
the casting will be tested.
Literature data [18–22] shows the possibility to use biomaterials as additives to
petroleum binders in order to cause biodegradation of materials from the petrochemi-
cal industry. Various synthetic resins can be fragmentized and biologically assimilated,
however, most of these processes could take tens or even hundreds of years. According to
Materials 2022, 15, 1552 4 of 14

research results of G. Scott [19], one of the solutions for this problem is a partial replacement
of the resins with oxy-biodegradable polymers characterized with short decomposition
time. Oxy-biodegradation of polymers is possible, thanks to special pro-oxidant addi-
tives which are usually compounds of iron, nickel, cobalt, or manganese together with
carefully formulated stabilizers [19]. These additives can dissociate the bonding between
carbon atoms. An example is PCL (polycaprolactone), which is compatible with many
other polymers. It is partially compatible or mechanically compatible with polymers,
such as polyvinyl acetate (PVAc), polystyrene (PS), polycarbonate, etc., and with other
polymers, such as polyvinyl chloride (PVC), styrene acrylonitrile copolymer (SAN), poly
(hydroxy ether), etc. This feature of polycaprolactone enables the formation of various
“bio-destructive” mixtures using it as a biodegradable component [20]. Initial studies of
“bio-destructive” polymer blends using PCL as a biodegradable component relate to a PC
polyolefin blend system based on polyolefins, such as LDPE (low density polyethylene)
and PP (polypropylene). More extensive studies on the biodegradability of PCL/polyolefin
blends, including the relationship between biodegradability and phase structure, have been
presented by A. Iwamoto and Y. Tokiwa [23].
The main objective of the research presented in the article was to analyze the mi-
crostructural effects related to the interaction with the mold material in ductile iron cast-
ings, in the surface layer, and inside the cross-section, depending on the type of molding
material, with acid and alkaline hardeners. The characteristics of the matrix microstructure
and graphite morphology in two zones on the casting cross-section, near the surface and
inside the casting, were determined to distinguish and estimate the specific effects of the
interaction of the liquid metal with the tested molding materials.

2. Materials and Methods

The molding mixtures based on fresh silica sand from Grudzen Las (Slawno, Poland)
were characterized by the following parameters: granulation 0.20/0.32/0.40; d50 = 0.31 mm;
pH = 7. The composition of the molding mixtures is presented in Table 1. The molding
materials were prepared in a laboratory mixer LM-R1, using mixing times: sand and
hardener—60 s and sand, hardener and binder—50 s.

Table 1. The composition of molding sands used in the test.

silica sand 100 parts by mass

Molding sand No. 1 furfuryl-resole resin 1.1 parts by mass
hardener-a mixture of sulfuric acids in an aqueous solution 0.55 parts by mass
silica sand 100 parts by mass
furfuryl-resole resin 1.1 parts 95%
Molding sand No. 2
PCL polycaprolactone by mass 5%
hardener-a mixture of sulfuric acids in an aqueous solution 0.523 parts by mass
silica sand 100 parts by mass
Molding sand No. 3 alkyd resin 1.1 parts by mass
hardener-catalyst based on isocyanates 0.275 parts by mass
silica sand 100 parts by mass
Molding sand No. 4 alkaline phenolic resin 1.1 parts by mass
hardener-esters 0.22 parts by mass

To reveal the possible effects of metal/mold interactions, the mold design, as well
as sampling area, were determined based on literature data from Linke and Sluis [12].
The dimensions of the experimental casting were 195 mm × 175 mm × 120 mm. The
characteristic U-shape allowed obtaining the highest possible concentration of gas released
from the mold material. A scheme of the casting is shown in Figure 1. Standard tensile tests
with circular cross-section test pieces and microstructure observations were carried out
for test samples taken from the experimental castings in the area of the assumed intense
interactions between mold and casting surface.
 ing surface.

Materials 2022, 15, 1552
A scheme of the casting is shown in Figure 1. Standard tensile tests with circular cross-section
test pieces and microstructure observations were carried out for test samples taken from the
experimental castings in the area of the assumed intense interactions between mold and 5 of 14
cast-
ing surface.

Figure 1. The scheme of the experimental casting with marked sampling site for metallographic (red
area) and mechanical properties (green mark) examinations; drawing and dimensions of circular
cross-section test pieces on right [5,12,24].
Figure1.1.The
Figure Thescheme
schemeof ofthe
theexperimental
experimentalcasting
castingwith
withmarked
markedsampling
samplingsite
sitefor
formetallographic
metallographic(red
(red
area)and
area) andmechanical
mechanicalproperties
properties(green
(greenmark)
mark)examinations;
examinations;drawing
drawingand
anddimensions
dimensionsofofcircular
circular
Experimentalcross-section
castings were
cross-section made
testpieces
test pieces of ductile
onright
on right [5,12,24].cast iron according to standard PN-EN
[5,12,24].
1563:2018-10 “Founding-Spheroidal graphite cast irons” [25]. The chemical composition
was 3.30% C, 2.61% Si,Experimental
0.38% Mn, castings
Experimental castingsP,
0.04% were
were
0.01%made
made S,ofofductile
ductile
0.06% cast
Cr,cast iron
ironaccording
0.07% according
Ni, 0.06% to
tostandard
standard
Mg, 0.07%PN-EN
PN-EN
1563:2018-10
1563:2018-10“Founding-Spheroidal
“Founding-Spheroidalgraphite graphitecast castirons”
irons”[25].
[25].The
Thechemical
chemicalcomposition
composition
Cu, 0.02% V, 0.02% wasAl,3.30%
0.01%
was3.30%
Ti and0.38%
C,C,2.61%
2.61%Si,Si,
the
0.38%
rest-Fe
Mn,
Mn, 0.04% (as
0.04%
estimated
P, 0.01%
P, 0.01%S, 0.06% by
Cr,optical
S, 0.06% 0.07%
Cr, Ni,
0.07%
emission
0.06% Mg,spec-
Ni, 0.06% 0.07%
Mg, Cu,
0.07%
trometry method, 0.02%
ARL MA
V,
Cu, 0.02%0.02%spectrometer
V, Al, 0.01%
0.02% Al, 0.01% (Thermo
Ti and theand
Ti Scientific).
rest-Fe
the (as Metal
(as estimated
rest-Fe melting
by optical
estimated wasemission
byemission
optical carriedspec-
spectrometry
out in the Radynemethod,
furnaceARL
trometry AMF MA45/150
method, ARL MAofspectrometer
spectrometer medium
(Thermofrequency
Scientific).
(Thermo induction
Metal melting
Scientific). Metal furnace with
was carried
melting a in
out
was carried
the Radyne
out in theof
crucible of 100 kg capacity furnace
Radyne
charge AMF
furnace 45/150 of
AMF 45/150
and neutral medium
liner. frequency
of medium induction
frequency and
Spheroidization furnace
induction with a crucible
furnace with a
modification
of 100 kg of
crucible capacity
100 kg of chargeofand
capacity neutral
charge and liner.
neutralSpheroidization
liner. and modification
Spheroidization and were
modification
were performed in a slender ladle, using a FeSiMg9 modifier (Elkem, Norway)
performed in a slender
were performed ladle, using
in a slender ladle, ausing
FeSiMg9 modifier
a FeSiMg9 (Elkem,(Elkem,
modifier Norway) Norway)
The molds were poured
The
Themolds
with
moldswere
ductile
werepoured
iron
pouredwith
with
withductile
a drain
ductileironironwith
temperature
withaadrain
of about 1420
draintemperature
temperatureofofabout
°C
about1420
◦C
1420 °C
and a pouring temperature of temperature
about 1370of°C. Figure ◦ 2°C.
includes
and
andaapouring
pouring temperature about
of about1370
1370C. Figure
Figure 2photographs
2 includes photographs
includes of the
photographs exam-
of the
of examined
the exam-
molds,
ined molds, produced produced
ined from
molds,molding from molding
producedsands sands with
with composition
from molding composition presented
presented
sands with composition in Table
in Table
presented 1.
in 1.
Table 1.

Figure 2. Molds used for experimental castings.

Figure 2. Molds usedFigureThe microstructure

for experimental of the experimental castings was examined on metallographic
castings.
2. Molds used for experimental castings.
cross-sections, etched with 4% Nital reagent (POCH, Gliwice, Poland), under Zeiss Axio
Observer
Theof Z1m light microscope
microstructure (Jena, Germany).
of the experimental Observations
castings was examinedwere on
made in the area at
metallographic
The microstructure the experimental castings was examined on from
metallographic
cross-sections, etched with 4% Nital reagent (POCH, Gliwice, Poland), under Zeiss of
the casting/mold boundary and in a zone approximately 10 mm the surface the
Axio
cross-sections, etched withQuantitative
casting. 4% Nital reagent (POCH,
microstructure Gliwice, Poland),
characteristics were under
carried out Zeiss Axio
utilizing the com-
Observer Z1m light microscope (Jena, Germany). Observations were made in the area
Observer Z1m light microscope
atmercial
the (Jena,
system for
casting/mold Germany).
analysis
boundary of the in Observations
andmicroscope images were made
Axio Vision
a zone approximately in
10 mm(version
fromthethe
area atZeiss,
4.8.2.0,
surface of
Jena,
the casting/mold boundary
the Germany).
casting. and in a zone
Quantitative approximately
microstructure 10 mm from
characteristics were the surface
carried of the the
out utilizing
casting. Quantitative The tensile
commercial test
system
microstructure foratanalysis
room temperature
characteristics was conducted
of the microscope
were images Axio
carried according
out Vision to standard
(version
utilizing the PN-EN
4.8.2.0,
com- Zeiss,
ISO
Jena, 6892-1:2016-09,
Germany). method B [24]. Circular cross-section test pieces of 14 mm diameter
mercial system for analysis of the microscope images Axio Vision (version 4.8.2.0, Zeiss,
The tensile test at room temperature was conducted according to standard PN-EN
Jena, Germany). ISO 6892-1:2016-09, method B [24]. Circular cross-section test pieces of 14 mm diameter
The tensile test at room
(drawing and temperature was conducted
dimensions on Figure 1), machinedaccording
from samples totaken
standard PN-ENwere
from castings,
ISO 6892-1:2016-09, method
used. B [24].were
Three pieces Circular cross-section
tested for test pieces of
each casting. Examinations 14 carried
were mm diameter
out on EU-20
strength testing machine (VEB, Leipzig, Germany) with a range of 0–200 kN. The strain rate
 strength testing machine (VEB, Leipzig, Germany) with a range of 0–200 kN. T
rate for tensile testing was 16 MPa/s. The percentage elongation after fracture A
culated from Equation (1) [24]:
Materials 2022, 15, 1552 6 of 14
–
A= ∙ 100 %
for tensile testing was 16 MPa/s. The percentage elongation after fracture A was calculated
Lo the from
original gauge length;
Equation (1) [24]:
Lu is the final gauge length afterA fracture.
=
Lu –Lo
·100% (1)
Lo
L the original gauge length;
3. Results andLoDiscussion
is the final gauge length after fracture.
u

The photos of the experimental castings (Figure 3a) and the area with traces
3. Results and Discussion
action of the liquid metal
The photos with
of the the mold
experimental surface,
castings remain
(Figure 3a) and the on
areathe
withcasting surface (Fi
traces of interac-
An area oftion
increased roughness
of the liquid metal with theappeared
mold surface,on theonsurface
remain the castingof all the
surface examined
(Figure 3b). An cas
area of increased roughness appeared on the surface of all the examined castings, reported
ported previously as a typical effect for such molding technology. Hence, it is n
previously as a typical effect for such molding technology. Hence, it is necessary to estimate
to estimatethe
the range
range of interactions
of interactions in the
in the material of thematerial of the tested casting.
tested casting.

Figure 3. (a)Figure
Experimental castings
3. (a) Experimental 195195
castings mm mm××175 mm× ×120
175 mm 120
mm;mm; area
area at at interface
interface mold/cas
mold/casting
arrows) (b) (blue
indicated areas
arrows) (b) withareas
indicated traces of interaction
with traces of interactionliquid metal/mold.
liquid metal/mold.

3.1. Experimental Castings Microstructure

3.1. Experimental
The Castings Microstructure
microstructure of the ductile cast iron formed in the examined castings is presented
in Figures 4–7. The observed morphology and phase composition of the microstructure is
The microstructure
typical for ductile ironof according
the ductile to [25]cast
with iron formed
the chemical in the used
composition examined
for testingcasting
sented in Figures 4–7.
castings, i.e., The observed
pearlitic–ferritic morphology
matrix with andFerrite
graphite spheroids. phase composition
forms characteristic of th
envelopes around graphite spheroids. Graphite nodules observed in these castings have
structure isbeen
typical
ascribedfor ductile
to classes iron
V and according
VI (Figure to [25]
8), according with theinchemical
to designation composit
standard PN-EN
for testing ISO
castings, i.e.,[26].
945-1:2019-09 pearlitic–ferritic matrix
Nevertheless, a variation with graphite
in microstructural spheroids.
effects was observed, Ferri
related to the type of material used for the casting molds.
characteristic envelopes around graphite spheroids. Graphite nodules observed
The revealed microstructural effects were observed in two zones of wall section: in
castings have beenlayer
the surface ascribed to classes
(casting skin) V of
and the area and VIfrom
10 mm (Figure 8), according
the surface. The descriptionto of design
the microstructural evolution in these zones concerned the
standard PN-EN ISO 945-1:2019-09 [26]. Nevertheless, a variation in microstruc local phase composition of the
metal matrix and the shape of graphite.
fects was observed, related to the type of material used for the casting molds.
15, x FOR PEER REVIEW 7 of 14
15, x FOR Materials 2022, 15, 1552
PEER REVIEW 7 of 14 7 of 14

Figure 4.
Figure 4. Casting
Casting No.
No. 1, prepared
Figure
1, prepared
4. Casting in No.
in acidic1,molding
acidic molding sand
preparedsand No. 1,
in acidic
No. 1, LM
LM etched
moldingetched with 1,
sand with
No. 4%LM
4% Nital; (a) mi-
etched
Nital; (a) mi- 4% Nital;
with
crostructure of alloy, microscope
(a)microscope
crostructure of alloy, microstructure magnification 100 ×,
of alloy, microscope
magnification (b) microstructure
100 ×, (b)magnification of
100×
microstructure the
of, the superficial zone
(b) microstructure (S),
of (S),
superficial zone the superficial
microscope magnification
zone 1000
(S),
microscope magnification 1000 ×. ×.
microscope magnification 1000 × .

Figure 5.
Figure 5. Casting
Casting No.
No. 2, prepared
Figure
2, prepared in acidic
5. Casting
in acidic molding
No. 2,molding sand
prepared No. 2,
in acidic
sand No. 2,molding
LM etched
LM etched with
sandwith 4%
No.4% Nital;
2, Nital; (a) mi-
LM etched
(a) mi-with 4% Nital;
crostructure of alloy, microscope magnification
microstructure of alloy, 100 ×,
microscope(b) microstructure
magnification 100 of
× the superficial zone
crostructure of alloy, microscope magnification 100 ×, (b) microstructure of the superficial zone the superficial
(a) , (b) microstructure of
(S), microscope
(S), microscope magnification
magnification 1000 ×.
1000 ×. magnification 1000×.
zone (S), microscope

Figure 6.
Figure 6. Casting
Casting No.
No. 3, prepared
Figure
3, prepared in alkyd
6. Casting
in alkyd
No. 3, molding sand
prepared
molding sand No. 3,
in No. 3, molding
alkyd LM etched
LM etched
sandwith
with 4%3,Nital;
No.4% Nital; (a) micro-
LM etched
(a) micro-
with 4% Nital;
structure of alloy, microscope
(a) magnification
microstructure of alloy, 100100 ×,
microscope (b) microstructure
magnification of
100,100 ×the
, (b)superficial zone
microstructure
structure of alloy, microscope magnification 100100 ×, (b) microstructure of the superficial zone (S), of(S),
the superficial
microscope magnification 1000
zone (S),1000
microscope magnification ×.
microscope
×. magnification 1000×.
 Materials 2022, 15, x FOR PEER REVIEW

15, x FOR Materials

PEER REVIEW
2022, 15, 1552 8 of 14 8 of 14

Figure 7. Casting No. 4, prepared in alkaline molding sand No. 4, LM etched with
Figure 7. Casting No. 4, prepared in alkaline molding sand No. 4, LM etched with 4% Nital;
Figure 7. CastingNital;
No. 4,(a) microstructure
prepared in alkalineofmolding
alloy, microscope
sand No. 4, LM magnification
etched with 100 4% ×, (b) microstructu
(a) microstructure of alloy, microscope magnification 100×, (b) microstructure of the superficial zone
Nital; (a) microstructure
the of alloy, zone
superficial microscope magnification
(S), microscope 100 ×, (b) microstructure
magnification 1000 × of
(S), microscope magnification 1000×.
the superficial zone (S), microscope magnification 1000 ×

Figure 8. Graphite Figure

nodules Graphite
morphology in the
nodules
examinedincastings,
morphology
LM, castings,
the examined
non-etchedLM,
cross sections,
non-etched cross sections,
Figure8.100
microscope magnification 8. Graphite
×.; (a) nodules
Casting No. morphology
1 (acidic in the
molding examined
sand No. 1), castings,
(b) Casting LM,
No. 2non-etched cross
microscope magnification 100×; (a) Casting No. 1 (acidic molding sand No. 1), (b) Casting No. 2
microscope
(acidic molding sand magnification
No. 2), (c) Casting 100 molding
No. 3 (alkyd ×.; (a) Casting
sand No.No. 1 (acidic
3), (d) Castingmolding sand No. 1), (b) Castin
No. 4 (alkaline
(acidic molding sand No. 2), (c) Casting No. 3 (alkyd molding sand No. 3), (d) Casting No. 4 (alkaline
(acidic molding sand No. 2), (c) Casting No. 3 (alkyd molding sand No. 3), (d) Casting No. 4 (
molding sand No. 4).
molding sand No. 4).
molding sand No. 4).
The revealed microstructural
In castings No.effects 1 andwere
No. 2, observed
which were in two
bothzones
made of of wall section: in
acid molding sand molds,
in theThe
the surface layer (casting matrix
skin) microstructure
and the area in
of the
10 mmsurface
from layer
the (skin),
revealed microstructural effects were observed in two zones
surface. different
The effects
description wereof found.ofInwall sec
the microstructural Casting No. 1 typical pearlite skin (about 5 µm) was revealed as reported previously
theevolution
surface layer in these zones concerned
(casting skin) and the the local
area phase
of 10 mmcomposition
from theofsurface.
the The descrip
metal matrix andthe in [10]. The layer
themicrostructural of material with degenerate graphite nodules
shape of graphite.evolution in these zones concerned the local phase compositio (classes IV and V) was
thicker (approx. 200 µm, Figure 4). In Casting No. 2, from mold No. 2, in which part
In castings No.
metal 1 and No. 2,
matrix andwhich shape
were both made of acid molding sand molds, in
of the hardener wasthereplaced with of graphite.
PCL polycaprolactone, no visible pearlite skin was
the matrix microstructure
observed. inInthe
In castings thesurface
No. 1layer
superficial and (skin),
No.
layer, 2,different
thickerwhich
than in effects
were were
both
Casting No. found.
made ofInacid
1 (approx. Cast-
500molding
µm), theresand m
ing No. 1 typical was
pearlite skin
degenerated (about 5
graphite µm)in was
flake revealed
form (classasI,reported
Figure previously
5). In castings in
No. [10].
3 and No. 4,found. I
the matrix microstructure in the surface layer (skin), different effects were
The layer of material
madewith degenerate
in molds of alkaline graphite
materials, nodules
the main (classes IV and V)
microstructural wasinthicker
effect the surface layer
ing
(approx. 200 µm, was
No.
Figure
1 typical pearlite
4). In Castingi.e.,
decarburization,
skin (about
No.reduction
2, from mold in the No.
5 µm) was
2, infraction
volume
revealed
which of part
as hard-
reported
of the(Figures
pearlite
previously
6 and 7;
ener was replaced The
Table layer
with2).PCL ofpolycaprolactone,
However, material
while inwith
Casting degenerate
noNo. graphite
3, degenerate
visible pearlite skinnodules
graphite (classes
wasobserved.
was visible in the IV and V) was
Insuperficial
(approx. 200 µm, Figure 4). In Casting No. 2, from
the superficial layer, thicker than in Casting No. 1 (approx. 500 µm), there was degener- with the
layer (class IV and V, Figure 6), in the superficial layer the mold
Casting No.
No. 2,
4, in
alongwhich part of th
almost
ener
ated graphite in flake wascomplete
form replaced
(class ferritization
with5).
I, Figure ofInthe
PCL matrix (Figure
polycaprolactone,
castings No. 3 and 7, Table
No.no2), also the
4,visible
made graphite
pearlite
in molds skin particles
was obser
disappeared (Figure 7). The thickness of the casting skin in castings No. 3 and No. 4 was
the superficial
of alkaline materials, layer, thickereffect
the main microstructural than in in the
Casting
surface No. 1 (approx.
layer 500 µm), there was d
was decarburi-
ated in
zation, i.e., reduction graphite
the volume in flake formof(class
fraction pearlite I, Figure
(Figures5).6 Inand castings
7; TableNo. 3 and No. 4, made in
2). How-
ever, while in Casting No. 3, degenerate graphite was visible in the superficial
of alkaline materials, the main microstructural effect in the surface layer was dec layer (class
IV and V, Figure zation,
6), in thei.e.,
superficial
reduction layer
in the
theCasting
volumeNo. 4, alongofwith
fraction the almost
pearlite (Figures com-6 and 7; Table 2)
Materials 2022, 15, 1552 9 of 14

about 500 µm, which can be compared with the result given in [6,10] for castings produced
in molds with a protective coating.

Table 2. Morphological characteristics of the microstructure in the experimental castings.

Specimen No. 1 Specimen No. 2 Specimen No. 3 Specimen No. 4

Decarburization, Decarburization,
Microstructure effects in Despheroidization,
Despheroidization Ferrite skin-local Ferrite skin depleted
the superficial layer Pearlite skin
despheroidization in graphite
Fraction of spheroids of
0.2 0.1 0.3 -
roundness > 0.5
VvF 0.1 0.3 0.7 1.0
Microstructure in casting Pearlite and ferrite Pearlite and ferrite Pearlite and ferrite Pearlite and ferrite
VvF 0.2 0.1 0.2 0.8
ECD, µm 132 140 126 103
max FD, µm 187 192 166 132
Fraction of spheroids of
0.6 0.6 0.6 0.5
roundness > 0.5
VvF volume fraction of ferrite; ECD equilibrium circle diameter; max FD value of maximum Feret (mean value).

The observed changes in the matrix microstructure can be considered by the effect
of the superposition of the diffusion of the mold components into the liquid alloy and its
oxidation. The formation of the thin pearlitic rim in Casting No. 1 can be explained by the
enrichment of the alloy with sulfur and carbon coming from the mold material. On the
other hand, the oxygen produced by the contact of the hot metal with the mold leads to
the oxidation of the carbon from liquid alloy. This may result in such a degree of carbon
depletion of the alloy on the mold/casting interface that a completely decarburized layer is
formed, observed in Casting No. 4 (Figure 7) as a ferritic rim, without graphite particles.
The degeneration of the shape of graphite nodules in the casting skin can be explained by
the bonding of Mg from the used modifier with sulfur released from the mold material
as described in [5,7,10]. Although graphite degeneration was found in castings No. 1, 2
and 3, it was most intense in Casting No. 3 where flake graphite appeared. Magnesium
oxidation can be considered as an additional factor contributing to the weakening of the
spheroidization effect, observed in the examined castings [7,10].
Microstructural effects in the material inside the examined castings were recognized
as changes in the metal matrix phase composition (Figures 4–7) and morphology of the
graphite nodules (Figures 8 and 9). The ratio VvF /VvP of volume fraction of ferrite VvF
to perlite VvP in the examined castings was different (Table 2). These microstructural
differences can be attributed to the actual temperature field created during the solidification
of the casting, which is subordinate to the thermal conductivity of the mold material.
However, one should also take into account the possibility of decarbonization of the liquid
alloy in the depths of the casting, as a result of long-term in situ interactions with the mold
surface and with the released gaseous reaction products. Although the visual analysis
did not reveal differences in the morphology of the graphite nodules, especially between
castings 1, 2 and 3, more detailed image analysis allowed for their identification. The nodule
size distribution (Figure 9) and roundness coefficient R (R = 4 Aa/(πFDmax )2 , R = 0–1),
where: Aa—the area of particle cross-section, FDmax —the value of maximum Feret diameter,
for the randomly chosen population of graphite particles (Table 2), showed the effect of
molding sand composition on the morphological characteristics of the graphite spheroids.
OR PEER REVIEW 10 of 14
Materials 2022, 15, 1552 10 of 14

Figure 9. DistributionFigure Distribution

of the9.ECD of the of the ECD nodules
graphite of the graphite
in thenodules in the examined
examined castings;castings; (a) Casting
(a) Casting No. No. 1
(acidic molding sand No. 1), (b) Casting No. 2 (acidic molding sand No. 2),
1 (acidic molding sand No. 1), (b) Casting No. 2 (acidic molding sand No. 2), (c) Casting No. 3 (alkyd (c) Casting No. 3 (alkyd
molding sand No. 3), (d) Casting No. 4 (alkaline
molding sand No. 3), (d) Casting No. 4 (alkaline molding sand No. 4). molding sand No. 4).

In the castings No. 1 and No. 2, made in acidic molds, graphite nodules were larger
In the castings than
No. those
1 andin No. 2, made
the castings in acidic
made in alkyd molds,
molds graphite nodules
(castings No. 3 and 4,were
Figure larger
9, Table 2).
than those in the castings
Although made
in theinsuperficial
alkyd molds
layers (castings
an importantNo.difference
3 and 4,inFigure
graphite9,morphology
Table 2). was
observed,layers
Although in the superficial in material inside all the
an important examined in
difference castings,
graphitethe roundness
morphology of graphite
was ob- nodules
was similar. In castings No. 1, 2, 3, the volume fraction of nodules with roundness
served, in material inside all the examined castings, the roundness of graphite nodules was
R > 0.5 was 0.6 and only in specimen No. 4 slightly lower than 0.5. Nevertheless, graphite
similar. In castings No. 1, 2,populations
nodules 3, the volume fraction specimens
in the examined of nodules with
differ notroundness
only by theirRmean
> 0.5size,
wasdefined
0.6 and only in specimen
here asNo.max4 ECD
slightly lower than
(equilibrium circle0.5. Nevertheless,
diameter, Figure 9)graphite
and FD maxnodules
(Table pop-
2) but also
by distribution
ulations in the examined specimens of the sizenot
differ of the
onlynodule, visible
by their meanin microstructure
size, definedimages
here as (Figure
max8). In
castings No. 1, 2, 3 (Figure 9a–c) distribution of the graphite nodule size is typical for that
ECD (equilibrium circle diameter, Figure 9) and FD max (Table 2) but also by distribution
observed usually in ductile cast iron, i.e., there is one fraction of large spheroids of similar
of the size of the nodule,
diametervisible
and the insecond
microstructure images (Figure
one, more numerous–of 8). In castings
very dispersed particles,No. 1, 2,<310 µm.
of ECD
(Figure 9a–c) distribution
Castingof No.the4 Isgraphite
dominated nodule size is of
by the fraction typical for thatparticles
small graphite observedwithusually
an ECD < in10 µm
ductile cast iron, i.e., there is one fraction of large spheroids of similar diameter and theshown
(Figures 8d and 9d). Thus, based on the results of microscopic observations, it was
that the microstructure
second one, more numerous–of of the metal
very dispersed matrix and
particles, ofthe
ECDmorphology
< 10 µm.of graphite
CastinginNo. Casting
4 IsNo. 4,
made in a mold with an alkaline phenolic resin, differed significantly from those revealed in
dominated by the fraction of small graphite particles with an ECD < 10 µm (Figures 8d and
other castings, both in the surface layer and inside the casting. Morphological characteristics
9d). Thus, based onofthe results of microscopic
the microstructure observed inobservations,
the experimental it castings
was shown that the micro-
were summarized in Table 2.
structure of the metal matrix and the morphology of graphite in Casting No. 4, made in a
3.2. Results of the Standard Tensile Test
mold with an alkaline phenolic resin, differed significantly from those revealed in other
The mechanical properties measured for the examined specimens taken from the
castings, both in the surface layer and inside the casting. Morphological characteristics of
experimental castings are presented in Table 3. The results are also graphically depicted
the microstructure observed
in Figure 10.in The
the obtained
experimental
results,castings were
in reference summarized
to the inindicate
standard [25], Table 2.the material
designation of EN-GJS-500-7C with relevant wall thickness in the range of 60–200 mm. The
3.2. Results of the Standard
minimalTensile Teststrength should be 260 MPa, tensile strength 400 MPa and elongation
0.2% proof
The mechanical properties measured for the examined specimens taken from the ex-
perimental castings are presented in Table 3. The results are also graphically depicted in
Figure 10. The obtained results, in reference to the standard [25], indicate the material
Materials 2022, 15, x FOR PEER REVIEW
Materials 2022, 15, 1552 11 of 14

sand without the addition of PCL. It can be observed that samples from acidic m
after fracture 3%. The samples taken from Casting No. 2, made on the acidic molding
sands have higher UTS strength at the level 656–672 MPa than those from alkali m
sand with the participation of biodegradable material, had the highest average strength
sands with 542–589
UTS—among MPa. sands—of 672 MPa. However, the elongation after fracture
all tested molding
was 48% lower compared to the reference samples from Casting No. 1 from the sand
Table 3. the
without Tensile test results
addition of PCL. of the be
It can specimens
observedfrom the examined
that samples castings
from acidic (average
molding sandsof 3 resu
have higher UTS strength at the level 656–672 MPa than those from alkali molding sands
with 542–589 MPa. 0.2% Proof Strenght Tensile Strenght Elongation after Fr

Table 3. Tensile test results of theYS, MPa from the examinedUTS,

specimens MPa
castings (average of 3 results). A, %
Casting No. 1
0.2% Proof Strenght YS, MPa
356 (SD = 17)
Tensile Strenght UTS, MPa
656Elongation
(SD = 15) 6.9 (SD = 1.6
after Fracture A, %
Casting No. 1 356Casting
(SD = 17) No. 2 333 656
(SD(SD
= 6)
= 15) 672 (SD = 18)
6.9 (SD = 1.6) 3.6 (SD = 1.2
Casting No. 2 333 (SD = 6)
Casting No. 3 290 672
(SD(SD = 18)
= 4) 3.6 (SD = 1.2)
589 (SD = 24) 8.0 (SD = 2.1
Casting No. 3 290 (SD = 4) 589 (SD = 24) 8.0 (SD = 2.1)
Casting No. 4 334 (SD = 5) 542 (SD = 9) 7.7 (SD = 2.7
Casting No. 4 334 (SD = 5) 542 (SD = 9) 7.7 (SD = 2.7)
SD—standard deviation.
SD—standard deviation.

10.The
Figure 10.
Figure Themechanical
mechanicalproperties of the tested
properties of thesamples
testedobtained
samplesinobtained
the tensile in
test.
the tensile test.
The results of the standard tensile test signalize that the measured mechanical proper-
Theinfluenced
ties were results ofbythe thestandard tensile
characteristics test
of the signalize that
microstructure, andthe measured
thus, mechanica
indirectly also
erties
by usedwere
mold influenced
materials. Two bytypes
theofcharacteristics
material effects can of be
theindicated:
microstructure, and thus, ind
increased material
strength in castings No. 1 and 2 made in molds with an acid
also by used mold materials. Two types of material effects can be indicated: hardener compared to that inc
obtained in castings No. 3 and 4, made in molds based on alkali resins,
material strength in castings No. 1 and 2 made in molds with an acid hardener com increased ductility
of the material in castings No. 3 and 4. (Tables 1–3). Simultaneously, these effects can be
to that obtained in castings No. 3 and 4, made in molds based on alkali resins, inc
related to microstructure characteristics. The measured increase in UTS can be assigned
ductility of theeffect
to the common material in castings
of the lower No. 3 and
ferrite fraction (VvF )4.and
(Tables
larger 1–3). Simultaneously,
graphite nodules, while these
can be related
increased to microstructure
elongation to fracture–to thecharacteristics. The measured
effect of higher ferrite fraction (VvFincrease in UTS can
) and smaller
graphite nodules. In each group of castings (1. made in molds with
signed to the common effect of the lower ferrite fraction (VvF) and larger graphite acid hardener and 2. n
made in mold based on alkaline resin), some increase in yield strength value was related to
while increased elongation to fracture–to the effect of higher ferrite fraction (V
the presence of smaller graphite nodules (Tables 2 and 3). Hence, the influence of graphite
smaller
morphologygraphite
shouldnodules.
be assumed,In each group
although of castings
the studies (1. made
conducted so farin moldsa with
indicate weak acid ha
and 2. made in mold based on alkaline resin), some increase
relationship between the size of spheroids and the yield stress. The microstructural de- in yield strength val
termination
related to theof the mechanical
presence properties
of smaller of ductilenodules
graphite iron has not been identified
(Tables 2 and 3).so far as the in
Hence,
reported in Refs. [27–29]; therefore, the results obtained in this study should be considered
of graphite morphology should be assumed, although the studies conducted so fa
as the initial stage of research.
cate a weak relationship between the size of spheroids and the yield stress. The
structural determination of the mechanical properties of ductile iron has not been
fied so far as reported in Refs. [27–29]; therefore, the results obtained in this study
be considered as the initial stage of research.

4. Conclusions
Materials 2022, 15, 1552 12 of 14

4. Conclusions
Based on the analysis of the results of the examination carried out in this work the
following conclusions can be formulated:
• The microstructural effects in the tested castings were revealed in two zones, depend-
ing on the area of observation: in the surface layer (casting skin) and in the zone
approximately 10 mm from the surface of the casting. These effects manifested them-
selves through changes in the phase composition of the metal matrix and the shape of
graphite spheroids. The effects of the superficial zone on mechanical properties can be
considered in two aspects, related to a. Material and b. Cast part.
a. Material effects result from the diffusive exchange of elements at the metal/form
interface. The resulting concentration gradient of individual components in the
liquid alloy affects the final image of the microstructure of the material. This
impact concerns both the matrix composition and graphite morphology, and
then the observed differentiation of properties (Tables 2 and 3).
b. Different ranges of superficial zone of different matrix and graphite morphol-
ogy observed in the examined cast parts can influence on useful properties of
cast parts during specific exploitation conditions.
• Experimental castings were characterized by a different thickness and microstructure
of the surface layer. The microstructural effects in the superficial layer, such as the
pearlite rim observed for acidic mold sand, the ferritic rim for alkaline, and graphite
spheroids degeneration, especially spectacular for acidic mold with PCL addition,
may point to the interference of the chemical interactions between liquid alloy and
components released from mold sand, such as sulfur and oxygen.
• The microstructural effects observed on the cross-section of the examined castings, in
10 mm from the surface, such as a change in the volume fraction of ferrite in metal
matrix and changes in the morphological characteristics of graphite spheroids, indicate
the possibility of a long-term, indirect influence of the used mold materials, modified
by adding various binders and hardener fractions to silica sand (Table 1).
• Two types of material effects can be indicated: 1. increased material strength in
castings No. 1 and 2 made in molds with an acid hardener compared to that obtained
in castings No. 3 and 4, made in molds based on alkali resins, and 2. increased ductility
of the material in castings No. 3 and 4. The obtained results indicate the possibility of
optimizing the composition of the mold material, i.e., the selection of additives used
as binders and hardeners to control the mechanical properties of the casting.
• Quantitative image analysis revealed some differences in graphite morphology, not
always accounted for in the visual analysis results. From a comparison of the his-
tograms in Figure 9b, it follows that the spheroidal size distribution is bimodal, i.e.,
there are probably two sets of nodules: in sample 2 (Figure 9b) the first with a diame-
ter of 120–140 mm and the second with a diameter of 30–50 mm, while in sample 3
(Figure 9c)—the first with a diameter of 90–100 mm and the second, probably not very
numerous, with a diameter of about 130 mm. This difference in the size distribution of
spheroids can be considered a factor of the synergy effect of both components of the
microstructure, i.e., graphite and matrix, on the mechanical properties (Table 3).
• At this stage of the research, it can be assumed that the difference in the matrix
microstructure results indirectly from:
a. Direct diffusion interactions at the metal/mold interface, which are influenced
by the composition of the molding sand,
b. The temperature field occurring in the casting at the subsequent stages of
solidification, when the microstructure is formed, is determined by the thermo-
physical properties of the mold depending on the components used. As these
presented results concern of initial stage of research, these phenomena are still
under examination.
Materials 2022, 15, 1552 13 of 14

Author Contributions: Conceptualization, K.M.-G. and M.H.-K.; methodology, K.M.-G., M.H.-K. and
M.W.; validation, K.M.-G., M.H.-K. and M.W.; formal analysis, M.W.; investigation, K.M.-G., M.H.-K.,
A.P. and M.W.; resources, K.M.-G., M.H.-K., A.P. and M.W.; writing—original draft preparation,
K.M.-G., M.H.-K. and M.W.; writing—review and editing, K.M.-G., M.H.-K. and M.W.; supervision,
K.M.-G.; project administration, K.M.-G. and M.H.-K.; funding acquisition, K.M.-G., M.H.-K. and A.P.
All authors have read and agreed to the published version of the manuscript.
Funding: The research was financed by AGH Research Project No 16.16.170.654 and the Research
Project No. 8007/00 financed by Ministry of Science and Higher Education.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Conflicts of Interest: The authors declare no conflict of interest.

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