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Journal of Materials Processing Technology 246 (2017) 3041

Contents lists available at ScienceDirect

Journal of Materials Processing Technology


journal homepage: www.elsevier.com/locate/jmatprotec

Thermomechanical behavior of resin bonded foundry sand cores


during casting
Hiba Bargaoui a,b, , Farida Azzouz a , Delphine Thibault b , Georges Cailletaud a
a
Mines ParisTech, PSL Research University, MAT-Centre des matriaux, UMR CNRS 7633, BP 87, F-91003 Evry, France
b
MONTUPET, 3 rue de Nogent, 60290 Laigneville, France

a r t i c l e i n f o a b s t r a c t

Article history: Foundry sand cores and bonding resin behaviors were investigated between room temperature and
Received 3 January 2017 450 C. A series of experiments including DMA, DSC, TGA, dilatometry, tensile tests and creep tests were
Received in revised form 2 March 2017 conducted on the resin. Sand core samples were tested under four-point bending loading with various
Accepted 3 March 2017
thermomechanical histories and the tension-compression asymmetry was investigated by turning upside
down the specimen. The deformation mechanisms as well as the effect of temperature, heating rate and
Keywords:
applied load were studied. The microstructure variation-resin thermal aging relationship was discussed
Casting
and established. It was found that the evolution of resin properties due to both thermal degradation and
Sand cores deformation
Polyurethane resin
crosslinking depending on temperature history has a direct impact on core deformation.
Thermomechanical behavior 2017 Elsevier B.V. All rights reserved.

1. Introduction mately generate leaks or premature cracking during the life of


the component. Nevertheless, just poor material database exists
In foundry, for certain types of castings, internal cavities of the in the literature and in commercial softwares. Besides, the sand
metallic parts are obtained using sand cores. They are placed in core was, for decades, considered as a non-deformable part in
the metallic die just before casting. The core is dened as a het- metal casting modeling, even if, few studies have been performed,
erogeneous material formed of three phases: a refractory matrix, a in Azzouz (1995) a work was made to characterize and model
bonding resin and air. Many types of processes and resin binders are the thermo-hydro-mechanical behavior of single-phase green sand
used depending on the cast part. For aluminum cylinder heads and molds, while Motoyama et al. (2012) and Inoue et al. (2013) devel-
other engine parts, founders opted for processes such as the Cold- oped an experimental setup to measure the mould rigidity and the
Box process studied in the present work. It offers high precision for force during casting operation. For chemically bonded sands, the
thin and complex core production. In this process, silica sand and only existing works as in Gonzlez et al. (2011), the authors focused
an organic polyurethane thermoset resin are used. The binder cure on varying the type of binder and its amount and studied their
is made at room temperature by injection of gaseous amine catalyst effect on various properties of the sand core, while Thiel (2008)
during coremaking. During casting, the core is subjected to severe investigated the evolution of mechnaical properties such as the
loading conditions (high temperatures, metallo-static pressure. . .). elastic modulus and high temperature strength of different types
The resin goes through thermal degradation and chemical decom- of bonded sands made using different processes. In Mahnken and
position. This sometimes leads to the core destruction and enables Caylak (2011), experimental investigation of the thermomechani-
its extraction from the solidied metallic part. cal behavior of cold-box cores was done for solidication modeling.
The thermomechanical study of the metal solidication and Uniaxial compression and tensile tests were performed at differ-
cooling raises experimental and numerical problems. In the par- ent temperatures but without any investigation of the material
ticular case of the sand cores, with the development of thin and behavior mechanisms. Recently, authors were interested in the
complex designs as in Antonelli et al. (2016), controlling the defor- thermal degradation of the phenolic binders (Giese et al., 2009)
mation during casting becomes a challenge in order to prevent and investiagted the principal decomposition stages. Models for
dimensional inaccuracies/defects on the nal part, that could ulti- the resin pyrolysis were developed in order to prevent defects due
to gas emission during casting (Jomaa et al., 2015). In a recent
study, Stauder et al. (2016) investigated the properties of sand
Corresponding author. cores with four different types of binders. They were focused on
E-mail address: hiba.bargaoui@mines-paristech.fr (H. Bargaoui). the core behavior at room temperature and different storage times.

http://dx.doi.org/10.1016/j.jmatprotec.2017.03.002
0924-0136/ 2017 Elsevier B.V. All rights reserved.
H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041 31

Fig. 1. Structure of resin bonded sand showing silica sand particles and resin bridges (circled in blue). (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of this article.)

Three point bending tests were used to evaluate the core strength respectively at the upper and lower, thin parts of the core, at the
and elastic modulus. The obtained results show an elasto-plastic center, while T3 and T5 were at the edges of the core, thicker parts,
behavior prior to fracture with dependence to the loading rate. close to the metallic die. The evolution of the temperature as a
Nevertheless, the mechanical behavior of the sand core at high function of time is plotted in Fig. 2.
temperature is still poorly documented and the thermomechani- The temperature of the liquid aluminum is about 700 C before
cal behavior of the binder and its inuence on the overall material casting operation. During lling, it was found to reach 600 C. In the
response are neglected. sand core, the highest temperature values (450 C) were obtained
The present work aims at modeling the thermomechanical in the thin section, at the center of the core (thermocouples T2
behavior of chemically bonded sand cores. An experimental char- and T4). The temperature rate is about 220 C/min. In the thicker
acterization has to be carried out to understand the deformation zone (thermocouples T3 and T5), a thermal gradient of 80 C was
mechanisms induced by process parameters such as pressure and found compared to the central area. From this instrumentation,
heat transfer between the metal and the sand core. the thin parts at the center of the core were found to reach high
temperatures during casting and can be identied as critical areas
in the core. Once the sand core is in contact with the liquid alu-
2. Experimental studies
minum, the core temperature increases. The resin goes through
chemical changes and thermal degradation process leading to the
2.1. Materials and sand cores production
formation of char structure. This is chemical aging, which is present
The sand cores studied in the present work are made with the
cold-box process for aluminum casting applications. In this pro-
cess, pure dry silica sand is mixed with polyurethane binder at
room temperature. The binder represents 1 wt% of the sand. It is
made of a two-component system chemically composed of a polyol
(phenolic resin) and a polyisocyanate resin dissolved in organic sol-
vents. Both resins are added in equal weight percentages to the
silica sand, all mixed and introduced into the corebox by shooting.
Amine catalyst in the gaseous state is then sprayed into the core-
box to accelerate the condensation of the polyurethane. The formed
solid polymer is a thermosetting resin, it has the structure of a 3D
macromolecular network. SEM observations of sand core show that
the polyurethane resin forms linking bridges between sand parti-
cles as shown in Fig. 1. As one can see, the bonding resin is porous.
More pores are found in the center of the bridge.
An industrial core used to cast cylinder head part was instru-
mented. This water jacket sand core was equipped with 5
thermocouples. The rst thermocouple T1 was used to measure the Fig. 2. Temperature evolution of the aluminum and inside the sand core during
temperature of aluminum. Thermocouples T2 and T4 were located casting.
32 H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041

in polymers at high temperatures. It is characterized by complex


mechanisms of polymeric chain scission and further crosslinking
which are hardly discriminated (Pielichowski and Njuguna, 2005).
Specically, polyurethane decomposition starts with volatil com-
ponents release, then splitting and depolymerisation phenomena
take place. Three different phases can be observed in the resin
decomposition during casting (Torralba, 2011). Once the sand core
Fig. 3. Resin specimen for tensile tests.
gets into contact with the liquid metal, during the rst seconds,
the binder undergoes thermal cracking and splitting of the molec-
ular chains due to thermal shock. Before the core becomes totally parameters, such as the temperature, aging and strain rate was
surrounded by the metal, it remains in contact with oxygen and investigated.
the combustion phase takes place for a very short period. The
pyrolysis is the most important phase, it lasts until the metallic 2.2.6. Creep tests
part is totally cooled down. In this phase, volatil components are Tensile creep tests were performed at different temperatures
released by rst order reactions, then new fragments and smaller using the specimen geometry given in Fig. 3. A 1 kN cell load Instron
molecules are obtained accompanied by degassing phenomena. machine was used. It enables to switch mode from stress control
Second order reactions take place later on between the new frag- during heating to strain control until a target stress, and nally
ments and molecules which can recombine to produce secondary stress control again to perform the creep test. The strain measure-
elements. Understanding the sand core behavior during casting ment was made by means of a video extensometer. The specimens
requires a set of thermophysical and thermomechanical analyses were heated up to different temperatures 70 C, 200 C and 210 C
on both bonding resin and sand core. at zero stress. They were next loaded at a strain rate of 103 s1 up
to a stress level of 1.1 MPa slightly, above the yield stress. The creep
2.2. Experimental tests for resin characterization test was then performed.

2.2.1. Differential scanning calorimetry (DSC) 2.3. Experimental tests for core characterization
The aim of the DSC analysis is to observe any change or
transformation in polyurethane during heating (since no change 2.3.1. Dilatometry
can be observed in silica sand at this temperature range up to The dilatometry tests were conducted on sand core under the
450 C). Tzero Q2000 TA instruments machine was used. Small rigid same experimental conditions as for the resin detailed in Sec-
polyurethane disks, weighting 10mg, were prepared with 1:1 phe- tion 2.2.3.
nolic resin:hardener mass ratio. An empty crucible was used as a
reference. The specimens were heated continuously at different 2.3.2. Four-point bending tests
heating rates (2 C/min, 5 C/min and 10 C/min) under nitrogen For the modeling of the sand core behavior and the development
atmosphere. of the constitutive equations, a comprehensive characterization of
the thermomechanical behavior and properties of the sand core is
2.2.2. Thermogravimetric analysis (TGA) necessary. The following aspects were studied:
Thermogravimetric analysis (TGA) was used to evaluate the
mass loss during heating. Polyurethane (PU) samples weighting Sand core behavior under four-point bending;
5mg were analyzed using Netzsch STA 449 F3 Jupiter. The pyrolysis Effect of heating rate, temperature, strain rate and applied load.
was studied under inert atmosphere using Argon as a purge gas at
two heating rates 2 C/min and 10 C/min. The silica particles used have a average grain size around 350 m.
The sand cores were prepared by mixing silica sand with 1:1 phe-
2.2.3. Dilatometry nolic resin:polyisocyanate mass ratio in total of 1 wt% of the whole
The investigation of the material thermal expansion was sand mass. The specimens are left 24 h before testing so that the
conducted using a horizontal dilatometer NETZSCH DIL402 DC. resin polymerization is completed and the strength can reach its
Cylindrical specimens with a 20 mm length and 5 mm in diame- optimum. An important parameter which may drastically affect
ter were used. Measurements were done under Argon atmosphere the material properties is moisture since the hardener in the resin
within a temperature range of 25450 C at different heating rates. may react with water to produce CO2 and inhibit polymerization.
The samples are then kept in a dry atmosphere with controlled
2.2.4. Dynamic mechanical analysis (DMA) humidity.
This technique enables to study the viscoelastic properties, Standard rectangular specimens are used. The dimensions and
namely the storage elastic modulus E , the loss modulus E , the the loading conguration are given in Fig. 4. The specimen is loaded
dynamic elastic modulus E and the phase lag between stress at room temperature with a constant mass of 164 g, then heated
and strain dened by tan =E /E . Tensile DMA analysis was con- up to the reference temperature using a resistive furnace. The
ducted on solid polyurethane samples whose dimensions are
20 mm 4 mm 1.5 mm. A METRAVIB VA 4000 setup was used.
The specimens were heated up to 200 C at a heating rate of 2 C/min
and tested at a frequency of 5 Hz.

2.2.5. Tensile tests


Tensile tests were carried out at different temperatures on
standard tensile specimens shown in Fig. 3. An Instron machine
with a 1 kN cell load was used. It is equipped with an Advanced
Video Extensometer system which enables to measure the local
displacement and strain elds, a resistive furnace and a tempera-
ture controller with a type K thermocouple. The effect of several Fig. 4. Four-point bending specimen geometry and loading.
H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041 33

additional crosslinking. The second one is an irreversible chemi-


cal reaction corresponding to urethane bond breakage.
Phase 3: Second exothermic reaction denoted (R3) corresponding
to the breakdown into polymer aromatics.

Upon this temperature range, the polymer exhibits only chem-


ical reactions. The polyurethane resin used in the cold-box process
was identied as a thermosetting resin which undergoes a ther-
mal decomposition process and mass loss starting approximately
at 60 C with solvents evaporation.

3.1.2. TG analysis on resin


Resin mass variation during heating was evaluated through
TGA analysis. The thermogravimetric curve in Fig. 6a shows that
polyurethane decomposition at low heating rates begins with sol-
vent release up to 150 C. It is followed by two main reactions
Fig. 5. Thermal analysis on polyurethane at heating rates of 2 C/min, 5 C/min and
which correspond to two peaks in the DTG curve given in Fig. 6b.
10 C/min.
The rst peak takes place between 150 C and 250 C. The sec-
ond peak starts at 250 C up to 400 C. The critical temperature
temperature control is made using a type K thermocouple placed for each step is shifted with increasing heating rate. A nal char
inside the specimen. The samples were tested at temperatures up residue is obtained. It represents approximately 30% of the initial
to 300 C with low heating rates to ensure a homogeneous tem- mass. Recently, Jomaa et al. (2015) studied the pyrolysis of the
perature inside the specimen. The deection evolution during the same commercial polyurethane resin using non isothermal ther-
bending test which is the maximum displacement at the center of mogravimetric analysis in nitrogen atmosphere. The specimens
the neutral axis was measured using an optical extensometer with were heated at higher temperature rates (20 C/min, 60 C/min and
a camera and digital image correlation technique. 80 C/min). Our results are in agreement with theirs where the resin
Different parameters that may have an impact on the sand core was also found to go through a two-stage decomposition. Since the
behavior were examined, namely: the isothermal reference tem- analysis was made at higher heating rates, the evaporation stage of
perature, the heating rate, complex thermomechanical histories, the solvents could not be detected and the critical temperatures of
the applied load and the binder volume fraction. the two decompositon stages were shifted to higher values com-
pared to our results. The rst step was found to take place up to
3. Results and discussions 250 C while in Jomaa et al. (2015) it extends until 300 C.
The decomposition of polyurethane is particularly complex,
3.1. Resin and core thermophysical characterization since it is governed by several physical and chemical phenomena,
with the formation of various gases. It depends on the chemi-
3.1.1. DSC analysis on resin cal components, nature and complexity of the chemical structure,
The results of the thermal analysis carried out on resin are given type of bonds and their nature. At high temperature, the cova-
in Fig. 5. The curves show a rst endothermic reaction followed lent bonds breakdown to form new fragments or small molecules
by two exothermic reactions. The corresponding temperatures for which may go through further fragmentation or recombine and
each reaction and the peak amplitudes are dependent on heating it ends with the formation of a nal char residue (Navarro-Baena
rate. One can distinguish, mainly, three phases during resin cure as et al., 2015). Some authors (Giese et al., 2009) studied the differ-
discussed in Giese et al. (2009): ent decomposition stages in the polyurethane and its inuence
on the polymer strength evolution at high temperature. They
Phase 1: An endothermic reaction denoted (R1), related to the found that in the rst step, urethane bond (called Hard segments
evaporation of solvents having low boiling temperatures (gener- HS) breakage leads to a modication of the chemical structure
ally between 60 C and 110 C) along with glass transition. of the polymer. This causes a decrease of the bonding strength.
Phase 2: First exothermic reaction denoted (R2). There are two Nevertheless, the polymer strength remains, since aromatic com-
overlapping peaks. The rst one corresponds to polyurethane pounds are still present in the complex three dimensional bonding

Fig. 6. TG analysis on polyurethane at heating rates of 2 C/min and 10 C/min (a) TG curve and (b) DTG curve.
34 H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041

Fig. 7. Dilatometry analysis (a) on sand core at heating rates of 2 C/min, 10 C/min and 20 C/min (b) on resin sample at 2 C/min.

network. From DSC and FTIR analyses, they concluded that the resin showing a good reproducibility. Once the heating rate is switched to
extensive bond network provides a resistance to thermal degra- 20 C/min, the sand core collapses and the resulting gap is between
dation and moderate temperature strength even with urethane those obtained for the two reference curves. It shows that the con-
bond breakdown. In the second step, the phenolic urethane rapidly traction of the specimen depends on the current temperature rate,
decomposes into aromatic compounds and therefore there is a but on temperature history as well.
rapid strength loss. Similarly, Chattopadhyay and Webster (2009) The irreversibility of the observed phenomena was then inves-
and Navarro-Baena et al. (2015) reported that polyisocianate is rigid tigated through the following test:
and exhibits high and complex inter-chain interaction. The uret-
hane bonds are rst broken leading to the degradation of the HS
cycle 1: the specimen was heated up to 450 C at 2 C/min and
during the rst stage, while polyol (referred to as the Soft Segment
SS), which breaks down during the second stage, is exible. Dur- cooled down at 2 C/min.
cycle 2: the same specimen is reheated again up to 450 C at
ing this step, random polymer chain scissions, chain-end scission
and cross linking mechanisms take place. In contrast, other authors, 20 C/min and cooled down at 20 C/min.
looking at polyurethane pyrolysis, supposed that the polyol decom-
position takes place at a rst stage followed by the polyisocianate
The results in Fig. 9b show that the slope of the curve is the same
decomposition in a second stage (Jomaa et al., 2015).
in cycle 1 and in cycle 2 above 350 C. The material response dur-
ing cycle 2 becomes reversible. It means that the microstructure
3.1.3. Dilatometry
inherited from cycle 1 is now frozen, and does not depend on tem-
The dilatometry curve of the sand core is given in Fig. 7a. The
perature history anymore. The analysis of the results in Fig. 9a and
material exhibits a thermal expansion/contraction behavior. A lin-
b suggest the following deformation mechanisms:
ear expansion is observed between room temperature and 220 C.
A contraction is obtained afterwards within two steps. They corre-
spond to the two decomposition stages identied in Section 2.2.2.
A linear expansion regime is recovered at higher temperatures. The
different thresholds as well as the contraction amplitude depend
on heating rate.
The dilatometry analysis on pure solid polyurethane under the
same experimental conditions (Fig. 7b) shows an expansion of the
resin up to 150 C with a rst contraction corresponding to solvent
evaporation, denoted Ev, and a second contraction corresponding
to the glass transition, denoted Tg , while a signicant contraction
and swelling of the resin are obtained afterwards along with the
additional crosslinking and thermal degradation at point D. These
observations can be seen through the nal aspect of the tested
specimens in Fig. 8.
Due to this combination of expansion and contraction effects,
the sand core exhibits a structural modication and granular
rearrangement up to 400 C approximately when the thermal
decomposition in reaction R2 stopped (Fig. 5). The silica sand
expansion occurs afterwards.
The dependence upon heating rate was investigated further-
more under a cycle with heating up to 250 C at 2 C/min and
then switching the temperature rate to 20 C/min from 250 C up
to 450 C. The corresponding dilatometry curve is given in Fig. 9a
and compared to the dilatometry curves obtainted with a contin-
uous heating up to 450 C at 2 C/min and 20 C/min. For the test
at two temperature rates, the part between room temperature and Fig. 8. Dilatometry specimens (a) sand core specimen heated up to 450 C (b) resin
250 C is in good agreement with the reference test at 2 C/min specimen heated up to 200 C and (c) resin specimen heated up to 350 C.
H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041 35

Fig. 9. Dilatometry analysis on sand core specimen between room temperature and 450 C (a) reference tests with a continuous heating at 2 C/min and at 20 C/min and
two level temperature rate test at 2 C/min up to 250 C and 20 C/min up to 450 C (b) cycle 1 at heating rates of 2 C/min and cycle 2 at 20 C/min up to 450 C.

Fig. 10. DMA analysis on Polyurethane. (a) Loss modulus and storage modulus evolution. (b) Elastic modulus and tan evolution at different strain rates of 103 s1 and
102 s1 .

For low temperature rates, the slow heating allows the binder to However, the elastic modulus values and glass transition temper-
become stronger, due to crosslinking of the chains, so that the ature are dependent on polyurethane type and composition.
link between the sand particles remains rather stable.
For high temperature rates, a degradation of the biner takes place,
accompanied by a rearrangement of the particles, and the sand
3.2.2. Tensile tests on resin
core becomes more compact.
The temperature effect on the monotonic behavior of the
Polyuethane resin for a strain rate of 103 s1 is shown in Fig. 11 for
3.2. Resin and core thermomechanical characterization ve different temperatures, 25 C, 70 C, 135 C, 150 C and 200 C.

3.2.1. DMA analysis on resin


DMA analysis was conducted on resin to evaluate the viscoelas-
tic properties evolution during heating. The variation of E and E
as a function of temperature is shown in Fig. 10a, meanwhile E and
tan are in Fig. 10b. The main observations are the following:

There is an important decrease of the storage modulus E due to


the evaporation of the volatile elements and solvents. The values
of the loss modulus E are lower than those of E .
The peak of tan around 100 C is linked to the glass transition.
In Fig. 10b, it can be seen that with increasing strain rate (fre-
quency), the values of the elastic modulus are higher at room
temperature and the difference becomes less important with
increasing temperature, while the peak tan is shifted to a higher
value.
The elastic modulus stabilizes at low values above the glass tran-
sition. There is a stability at intermediate temperatures. These Fig. 11. Tensile tests at a strain rate of 103 s1 at room temperature, 70 C, 135 C,
results are in agreement with the litterature (Trovati et al., 2014). 150 C and 200 C.
36 H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041

Fig. 12. Tensile tests at a strain rate of 103 s1 and 102 s1 (a) at room temperature (b) at 150 C.

A large temperature dependence is observed below the chem- Shaw et al. (2005) worked on elastomers response subjected to
ical decomposition temperature at 150 C, due to the physical nite deformation in a temperature range between 90 and 150 C.
aging and softening process linked to the glass transition between The authors present a model for stress relaxation (viscoelasticity)
90 C and 110 C and the evaporation of solvents. The resin softens and chemical relaxation (chain scission mechanism) under com-
when increasing temperature, which explains the loss of mechan- plex temperature histories and uniaxial loads. A method was also
ical properties in tests from room temperature up to 150 C. The developed to further account for scission process and oxygen deple-
material hardening is observed at 200 C due to crosslinking which tion. In Wineman and Shaw (2007) and Wineman and Shaw (2008),
prevents the thermosetting resin meltdown. The resulting behav- the authors study both deformation, thermal induced scission and
ior is then stronger for 200 C than for 135 C and 150 C. Due to crosslinking in the macromolecular chains. They describe these
thermal decomposition and degassing, the specimen exhibits many mechanisms as time and temperature dependent chemical changes
defects with apparent gas cavities. It was then impossible to per- occuring above a critical temperature in elastomers. However, the
form a mechanical characterization of the polyurethane at high few existing studies were focused on the rubbery stage at tem-
temperature. peratures slightly above the glass transition temperature. We can
Tensile tests at a strain rate of 102 s1 at room temperature safely consider that the chemical aging subject is not as mature as
and 150 C were done in comparison to 103 s1 tests in order to physical aging. Most importantly, at higher temperatures (above
investigate the viscosity effect. The corresponding curves are given the temperature of thermal degradation onset which is 150 C in
in Fig. 12. At room temperature, viscosity is well pronounced in our case), chemical aging (pyrolysis) and its effect on the material
comparison to the test at 150 C. These results are in agreement properties evolution is still an important topic that has not been
with the DMA analysis shown in Section 2.2.4 where the viscos- fully investigated (Brinson and Brinson, 2015).
ity effect vanishes at high temperatures above the glass transition
temperature.
Rodriguez et al. (2014) studied the softening and hardening 3.2.3. Creep tests on resin
phenomena in polymers. The authors describe the softening pro- Fig. 13a shows the results of creep tests conducted on resin.
cess in polymers as caused by chain scission mechanism and the Primary and secondary creep stages were observed in all tests.
hardening (embrittlement) processes as due to the crosslinking At 70 C, a creep saturation is observed. At 200 C, the creep
process at higher temperatures. Tobolsky (1960) discusses further strain is much larger, while the total strain observed at 210 C is
in his study the creep behavior and related cleavage mechanism smaller than for 200 C. It is worth noting that during tests above
(chain scission) and crosslinking for rubbers. In a more recent study, 200 C, the material presents defects due to degassing and its color

Fig. 13. Total strain evolution as a function of time in creep tests (a) at 70 C, 200 C and 210 C with a loading strain rate =10
3 1
s and an applied stress  creep = 1.1 MPa (b)
at 200 C under different applied stresses and loading strain rates.
H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041 37

Fig. 14. Bending test on sand core (a) under self weight at 300 C (b) under a mass of 164 g at different target temperatures.

Fig. 15. SEM image of resin bridges in a sand core (a) at room temperature (b) tested at 200 C (c) tested at 300 C.

changes indicating material degradation such that the test had to done on the tested specimens. The SEM samples were extracted
be interrupted. at the center of the specimen in the region of maximum deection.
In order to obtain information on the inuence of loading his- SEM micrographs of a reference specimen at room temperature
tory on creep response, the resin creep behavior was investigated and specimens tested at 200 C and 300 C are shown in Fig. 15ac
at 200 C under loading strain rates of 103 s1 and 104 s1 and respectively. In Fig. 15a, the surface of a specimen, before the test,
applied stresses 1.1 MPa and 0.85 MPa. The samples loaded under at room temperature, shows a relatively smooth aspect with few
a strain rate of 103 s1 show primary and secondary creep stages cavities at the center of the resin bridge. In contrast, Fig. 15b and c
as seen in Fig. 13b, while only primary creep was obtained with show a signicant development of cavities in the resin bridges at
a loading strain rate of 104 s1 .This is a clear demonstration that high temperatures with more pores towards the center due to mass
time allows the material to become stronger due to the resin retic- loss. Most importantly, these microscopic observations at high tem-
ulation. For a given loading strain rate, the accumulated strain was peratures (Fig. 15b and c) show the presence of resin linking bridges
found to increase with increasing stress. between sand particles. The resin is not completely destroyed. The
overall material deformation is possibly due to internal damage
occuring in the resin as seen through these SEM images. The ther-
3.2.4. Isothermal tests on sand core mal degradation (mass loss, irreversible macromolecular changes)
Four-point bending tests were conducted at different tempera- leads to a strength loss in the bonding resin which has an impact
tures. In Fig. 14a and b, we compare the evolution of the measured on the overall material response. We believe that these observa-
deection at a heating rate of 2 C/min under respectively self tions may explain further the microstructure changes discussed in
weight up to 300 C and with an applied mass of 164 g at different Section 3.1.3.
reference temperatures.
Under both types of loading, there is a deection variation only
during heating. A displacement is observed above 50 C, the tem- 3.2.5. Effect of heating rate
perature for which solvents start boiling, as discussed in section Specimens were tested with four-point bending trials at dif-
2.2.1. When temperature becomes constant, there is a quick sat- ferent heating rates (typically 0.5 C/min, 2 C/min, 10 C/min and
uration of the deformation process. The maximum value reached 20 C/min). Fig. 16, illustrates the evolution of the deection as a
seems to depend on temperature and probably on the resin decom- function of temperature. The maximum deection decreases dras-
position stage. tically with increasing heating rate. In case of temperature rates
This dependence upon temperature was further investigated of 10 C/min and 20 C/min, the specimens lost their strength and
using Scanning Electron Microscopy (SEM). Observations were broke down slightly above 200 C.
38 H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041

heating cycles were performed as described in Fig. 17a and b where


T1= 200 C, t1 = 2 h, T2= 250 C and t2 = 1.5 hour at a heating rate of
2 C/min. The results are given in Fig. 17c and d respectively. The
main observations are the following:

The maximum measured deection at T2 with a hold time at the


intermediate temperature T1 in the test in Fig. 17c is lower than
the reference deection reached with a continuous heating until
T2 in 17d.
During cooling from T2 to T1, the deection remained constant,
demonstrating that the material structure is frozen.

The material state shows a dependence on the maximum tem-


perature reached and the dwell period during the isothermal.
In fact, the present study (see Section 3.1.3), revealed that the
Fig. 16. Four-point bending tests at heating rates of 0.5 C/min, 2 C/min, 10 C/min sand core exhibit a microstructure change (expansion/contraction
and 20 C/min.
behavior) which is dependent on temperature, thermal history and
heating rate. Moreover, we discussed in Section 2.2.5 the differ-
3.2.6. Effect of thermomechanical history ent phenomena which govern the resin thermal degradation (an
The strong dependence of the material behavior upon time, irreversible macromolecular change in the polymer structure and
heating rate and temperature suggests a further investigation with an additional crosslinking mechanism which induces hardening).
more complex thermomechanical histories. Two congurations We believe that the latter may be reponsible for resin hardening
were tested: during the isothermal tests.
Conguration 1: Heating until different temperatures with The inuence of the test parameters like the heating rate (typi-
different hold time cally 0.5 C/min, 2 C/min and 10 C/min) and the hold time t1 at T1
A complex heating cycle was programmed with various heat- (typically t1 = 30 min and t1 = 2 h) were further investigated. Results
ing rates, hold time and isothermal temperatures. Tests with two are given in Fig. 18. During heating from T1 to T2, a longer hold time

Fig. 17. Four-point bending test (a) under heating cycle with a hold time t1 at T1 and then up to T2 and a hold time t2 (b) with direct heating up to T2 and hold time t1 and
cooling down to T1 and a hold time t2 . Deection evolution (c) with a dwell time t1 = 2 h at T1 = 200 C and then up to T2 = 250 C (d) with direct heating up to T2 = 250 C and
dwell time t2 = 1.5 h and cooling down to T1 = 200 C.
H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041 39

Fig. 18. Four-point bending test with hold times of t1 = 30 min and t1 = 2 h at an intermediate temperature T1 = 200 C (a) at 0.5 C/min and (b) at 2 C/min and T1= 150 C (c)
at 10 C/min.

at T1 slows down the deection variation (additional crosslinking This type of material is characterized by its asymmetric behavior
and heardening). Meanwhile, with a higher heating rate (Fig. 18c), in tension and compression. Since performing tensile tests on the
whatever the hold time at T1, the nal state is close to the value sand core is not possible, tests were designed to apply a cyclic load-
obtained with a direct heating up to T2, and the specimen broke ing by turning upside down the specimen during the test. To the
down. These results show an aging effect that is dependent essen- best of our knowledge, such congurations have not been tested
tially on resin degradation kinetics. Particularly, a higher heating yet.
rate was found to cause collapse of the sand core structure and As shown in Fig. 19a, a specimen is heated up to 200 C at
hinder resin additional crosslinking (see Section 3.1.3). 2 C/min and held during 45 min, a sufcient time to reach a station-
Conguration 2: Cyclic mechanical loading by turning upside ary stage. At the point denoted a, the specimen is turned upside
down the specimen: asymmetric tension/compression behavior down without any temperature change.

Fig. 19. Four-point bending tests at a heating rate of 2 C/min with turning upside down the specimen (a) at 200 C at the stage denoted a (b) with heating, cooling and
turning upside down the specimen at stages denoted a and b.
40 H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041

thermal degradation process. The same results are obtained in step


3 where the deection varies above 200 C.
These cyclic loading tests enabled to trigger the compression
and tension areas. The results conrm that the sand core deforms
only during an active thermal decomposition process which is gov-
erned by irreversible chemical reactions.

3.2.7. Effect of applied load


The sand core was tested under four-point bending tests with
two different constant loads (100 g, 164 g) during heating up to
200 C. Fig. 20 shows the evolution of the deection as a function of
the temperature. The deformation under a mass of 164 g is larger
compared to the one observed under a mass of 100 g.

3.2.8. Effect of resin proportion


The effect of the resin decomposition on material behavior raises
Fig. 20. Four-point bending tests at a heating rate of 2 C/min at different applied the question of the inuence of the resin percentage present in
loads.
the sand core. An investigation was then made with total binder
percentages of 0.8 wt%, 1 wt% and 1.3 wt%. The specimens were
The results show that once the specimen is turned, a reverse tested under four-point bending at heating rates of 0.5 C/min and
deformation takes place and tends, again, towards a sationnary 2 C/min up to 200 C.
stage due to resin crosslinking. This evolution may be related to The results given in Fig. 21 show that the sand core is stronger for
the fact that the resin bridges initially loaded in compression are the case of high resin contents. While the specimens broke down at
now loaded in tension with temperature conditions such that the approximately 180 C with the lowest resin percentage of 0.8 wt%.
thermal decomposition and crossslinking are still active. For a nal Based on these results, a higher resin percentage seems to
stage with heating up to 250 C, the deection varies again follow- procure better mechanical properties. But in contrast, this causes
ing a non isothermal resin decomposition path. difculties when extracting the core from the cooled metallic part,
A second specimen (Fig. 19b) was cooled down before being and more gases are emitted during casting due to the resin decom-
turned upside down. The test includes the following steps: position. These gases could be trapped inside the cast part, and may
cause defects in the nal product.
Step 1: The sample is heated at 150 C. The temperature is kept
constant during 45 min, then the specimen is cooled down; 4. Conclusions
Step 2: At stage denoted a, the cooled sample is turned upside
down, heated up one more time and held up at 200 C and then The results shown in the present study allowed us to make a
cooled down; link between the evolution of the properties of the resin and those
Step 3: At stage denoted b, the cooled sample is turned upside of the sand core. The main obervations were made.
down, heated up one more time and held up at 250 C and then
cooled down. Polyurethane resin properties fall drastically during both physi-
cal and chemical aging. Nevertheless, crosslinking was found to
As seen in step 2, in Fig. 19b, once the specimen is turned operate at low temperature rates, so that the bridges between
over and reheated, the deection remains constant until 150 C. sand grains may become stronger.
The deformation obtained in step 1 is irreversible. This is possibly The core deformation was clearly linked to the resin thermal
related to the irreversible chemical reactions as discussed in Sec- degradation and properties evolution. Understanding high tem-
tion 2.2.1. Even when turning upside down the specimen, there is perature properties of the used binder system is the key then for
no deformation of the material if the decomposition process is no controlling sand core behavior and casting quality.
longer active and the resin structure becomes highly crosslinked. Having in hand the physical phenomena that control the defor-
Above 150 C, the deection varies again with the activation of the mation process, a model is going to be developped. It will account

Fig. 21. Four-point bending tests on sand core samples with binder percentages of 0.8 wt%, 1 wt% and 1.3 wt% (a) with a heating ate of 0.5 C/min (b) with a heating rate of
2 C/min.
H. Bargaoui et al. / Journal of Materials Processing Technology 246 (2017) 3041 41

for the two material phases and will depend on the initial porosity Direct and Inverse Problems for Micropolar Elasto-Plasticity. Springer Berlin
of the core. Heidelberg, pp. 175196.
Motoyama, Y., Takahashi, H., Inoue, Y., Shinji, K., Yoshida, M., 2012. Development
of a device for dynamical measurement of the load on casting and the
Acknowledgement contraction of the casting in a sand mold during cooling. J. Mater. Process.
Technol. 212, 13991405.
Navarro-Baena, I., Arrieta, M., Mujica-Garcia, A., Sessini, V., Lopez, D., Kenny, J.,
This work was supported by Montupet group under grant (NO. Peponi, L., 2015. Thermal degradation effects on polyurethanes and their
0911/2014). nanocomposites. In: Reactions and Mechanisms in Thermal Analysis of
Advanced Materials. John Wiley & Sons, Inc., pp. 165189.
Pielichowski, K., Njuguna, J., 2005. Thermal Degradation of Polymeric Materials.
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