Thermochimica Acta 651 (2017) 2233

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

An alternative method to identify critical temperatures for semisolid

materials process applications using differentiation
Gabriela Lujan Brollo, Ceclia Tereza Weishaupt Proni, Leandro Cssio de Paula,
Eugnio Jos Zoqui
Materials and Manufacturing Department, Faculty of Mechanical Engineering, University of Campinas UNICAMP, Campinas, SP 13083-860, Brazil

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

Article history: A novel method is proposed for identifying critical temperatures in thixoformability analysis. The pro-
Received 8 November 2016 posed method applies the principles of differential calculus to semisolid transformation curves. The
Received in revised form 6 February 2017 method is compared with the conventional tangent method for determining the solidus and liquidus
Accepted 9 February 2017
temperatures using DSC curves and with the visual recognition method for identifying the knee, or
Available online 16 February 2017
unstable main eutectic transformation temperature. Numerical simulation is performed with Thermo-

Calc (under the Scheil condition) for A356 alloy, and the same alloy is used to generate experimental
Keywords:
Semisolid processing DSC data for cooling and heating cycles under different kinetic conditions (5, 10, 15, 20 and 25 C/min) in
Thixoformability order to compare the conventional methods for identifying critical temperatures and the novel method
Thermodynamic characterization described here. The ndings indicate that the proposed method, referred to here as the differentiation
method, is an efcient tool for identifying critical points such as the solidus, liquidus and knee tem-
peratures and that the results obtained using the method are in good agreement with results obtained
with traditional methods. The method also proved to be operator-independent, as it uses well-dened
mathematical/graphical criteria to identify critical points. Furthermore, the new method is easy to use,
as after differentiation the critical points become easily recognizable visual and numerical features such
as valleys and peaks (for the knee temperature) and zeros (for the solidus and liquidus) on the curve
being analyzed. The following formal denition for the eutectic knee, the rst of its kind in the literature,
is proposed: the peak/valley in the expected eutectic range of the differentiated DSC curve of the solidica-
tion/melting transformation. Application of the proposed denition yields results that agree well with
results obtained by the traditional visual recognition method, indicating its suitability for identication
of the eutectic knee, especially when a comparative study of different shaped curves is being performed.
A denition that allows suitable lower and upper limits for the SSM processing window to be identied
is also proposed.
2017 Elsevier B.V. All rights reserved.

1. Introduction is to ensure that the solid/liquid mixture can be easily controlled

The term semisolid materials (SSM) processing refers to the
forming of metallic alloys in the semisolid temperature range [1,2].
SSM processing is divided into two main categories: rheocasting, in
which controlled cooling is applied to a liquid alloy so it can reach
the semisolid state with a solid fraction of approximately 0.20.5
[3], and thixoforming (or thixocasting), in which a solid billet is
heated in a controlled manner up to a liquid fraction of approxi-
mately 0.30.6 in the semisolid range [4]. The key to SSM processing
Corresponding author.
E-mail addresses: gbrollo@fem.unicamp.br (G.L. Brollo), wyliah@gmail.com
(C.T.W. Proni), leandrocp@fem.unicamp.br (L.C. de Paula), zoqui@fem.unicamp.br
(E.J. Zoqui).
and that the semisolid alloy microstructure has an spheroidal
rather than a dendritic morphology. This can be achieved using
several techniques, such as stirring during casting or reheating
the alloy after it has been subjected to forming or grain-rened
[49].
A spheroidal microstructure, which is extremely temperature-
and time-dependent [10,11], ensures that the alloy exhibits
semisolid thixotropic behavior when sheared [12,13]. The practical
result of this special rheology is smooth, laminar die lling, avoiding
defects usually found in conventional die casting, such as porosities,
and requiring the use of only a fraction of the force needed in con-
ventional metal forming, with consequent energy savings. Other
advantages include lower processing temperatures, reduced ther-
mal shock to the die, less solidication shrinkage, reduced material
loss and lower process costs [1,2].

http://dx.doi.org/10.1016/j.tca.2017.02.010
0040-6031/ 2017 Elsevier B.V. All rights reserved.
 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233
Most commercial SSM processes use conventional A356 and
A357 aluminum casting alloys [14]. Satisfying the demand for a
wider range of alloys for use in SSM processing represents a chal-
lenge, as candidate alloys must have adequate thixoformability, i.e.,
their thermodynamic properties must allow them to be worked in
the semisolid state. This requirement is closely linked to control of
the SSM process; as rst stated by Tzimas and Zavalianglos [15,16],
the variation in liquid fraction (fl ) with temperature (T) of the candi-
date alloy (a parameter that later came to be known as sensitivity
(S) and is dened as dfl /dT) should be as low as possible so that
temperature variations inherent to the process do not signicantly
affect the formation of solid or liquid, ensuring the reproducibility
of the process.
Alloys used in semisolid applications have a primary phase
followed by a (binary or ternary) eutectic transformation during
solidication. Formation of the second phase usually causes a sharp
change in fl with T, i.e., a high dfl /dT, so the alloy should be processed
only in the primary-phase eld [17]. Another issue when processing
in the eutectic region is the non-thixotropic behavior of the alloy
because of the presence of sharp particles along with primary-
phase spheroids [18].
Since the study by Tzimas and Zavalianglos, several authors have
contributed to the development of thixoformability criteria: Liu
et al. [19] propose the well-known and widely used three rules
based on the fl vs. T semisolid transformation curve: (a) a maxi-
mum solidication interval of 130 C to prevent hot tearing; (b) an
fl range of 0.40.6 in the eutectic transition (known as the knee
in the fl vs. T curve) to prevent the billet collapsing as a result of
processing the material with too much liquid and (c) a maximum
sensitivity of 0.03 C1 at fl = 0.5 to ensure the process is stable when
liquid is being formed in the working window. Uggowitzer and
Uhlenhaut [20] suggest that SSM processing should be performed
at lower and higher values of fl and that forming parameters should
be adjusted to take into account variations in the composition of the
alloy. Finally, Zoqui et al. [21] propose that a much greater range of
alloys can be used in semisolid applications if the working window
is not limited to fl values in the range 0.40.6 and the sensitivity
curve is analyzed in the entire semisolid range to evaluate all pos-
sible regions in which the alloy can be successfully thixoformed,
i.e., all temperatures at which dfl /dT < 0.03 C1 between the unsta-
ble eutectic transformation (knee) and the temperature at which
melting is complete (liquidus).
When analyzing the thixoformability of new alloys for use in
semisolid processing it is essential to identify (a) the solidus and
liquidus temperatures, which are required to plot an accurate
semisolid curve and (b) the knee point, without which the working
window cannot be dened. The following limitations of techniques
used to identify these two points are discussed here:
Fig. 1. Hypothetical endothermic DSC curve (left). Zoom-in on the region at the end of the transformation (right): two different pairs of chosen tangents (pair a continuous
gray lines; pair b dashed gray lines) result in two different points (A and B, respectively) to mark the same transition.
23
a. Determining the solidus and liquidus temperatures. Current
simulation techniques can only precisely predict solidication
phenomena [2224], as the theory governing melting has yet to be
fully elucidated, making selection of new alloys suitable for thixo-
forming processes difcult. When kinetic effects are signicant,
this difculty is aggravated because of the changes in the shape of
the semisolid curve caused by the increase in the cooling/heating
rate. This is an important issue in SSM processing research, par-
ticularly in the case of thixoforming, as heating rates under real
operating conditions are typically 50100 C/min, posing signi-
cant challenges for current simulation techniques.
Differential scanning calorimetry (DSC) is normally performed
to determine experimentally how fl varies with T in semisolid
alloys. The technique can directly measure melting/solidication
heat ow rate during the solid-to-liquid/liquid-to-solid transition
under a broad range of kinetic conditions [25,26]. Flynns tech-
nique, which involves integration of partial areas between the DSC
curves and a chosen baseline, is used to obtain the fl or fs vs. T curve
normally used in thixoformability analysis [27].
Starting with the DSC curves, the liquidus and solidus are usu-
ally identied by what we here call the tangent method, in which
two tangents to the DSC curve are plotted when its slope changes in
relation to a dened baseline, indicating that a phase transforma-
tion is starting or ending. The point at which these two lines meet
is considered an approximation to the point at which the trans-
formation starts or ends [25]. This method is to a certain extent
operator-dependent, as determination of a suitable tangent is based
on common sense and may be subject to measurement errors, as
seen in Fig. 1, where the choice of different pairs of tangents (a and
b) leads to different temperatures (points A and B, respectively) to
mark the same transition in the curve.
b. Determining the knee. Despite its importance in thixoformabil-
ity analysis, there is no formal graphical or mathematical denition
of the eutectic transformation in the literature. In practice it is
determined by visually identifying a knee-like shape in the fl vs.
T curve (a technique we refer to here as the visual recognition
method). This method is highly operator-dependent, increasing the
chances of incorrectly identifying the knee temperature. The lack of
a dened criterion for locating this temperature is especially critical
when a comparative analysis is required. This is illustrated in Fig. 2,
where the hypothetical semisolid curves have different shapes. The
smoother the curve, the less accurately the knee temperature can
be identied, making it difcult to compare this temperature for the
different conditions being analyzed. This situation can occur when,
for example, comparing curves generated under distinct kinetic
conditions.
In light of the issues discussed above, this paper proposes
a method for accurately dening the critical transformation
24 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233
Fig. 2. Hypothetical fl vs. T curves with different shapes. Identication of the knee
becomes less accurate as the curve becomes smoother. The sharpest curve, a, has
a clearly identiable knee (point A), while the knees of the smoother curves, b and
c, cannot be clearly identied. The segments BB and CC , respectively, correspond
to possible positions for these knees.
temperatures in the semisolid state. The proposed method com-
bines principles of differential calculus and features of the DSC
curves as an alternative to the tangent method for identifying
liquidus and solidus temperatures and to the visual recognition
method for determining the knee on the fl vs. T curves of candi-
date alloys for semisolid applications. Criteria for an SSM working
window are proposed, and the new method is used to determine
further semisolid critical points and specify a suitable window.
2. Experimental procedure
To evaluate the applicability of the proposed method, thermo-
dynamic simulation and thermal analysis tests were performed
with grain-rened A356 commercial alloy. The chemical compo-
sition, presented at Table 1, was determined with a BILL OES
optical spectrophotometer. Grain renement was achieved by
adding an Al5.0 wt%Ti1.0 wt%B master alloy. A356 alloy was cho-
sen because of its broad application in semisolid processing and
because extensive information about its phase transformation tem-
peratures is available in the literature, making validation of the
proposed method easier.
Thermal analysis to determine the experimental fl vs. T curve
for the A356 alloy was performed with a NETZSCH STA 409C DSC
system. The DSC sample was heated to 700 C at 5, 10, 15, 20 and
25 C/min and then cooled to room temperature at the same rates.
Heat ow rate (here called HFR) and temperature were monitored
by thermocouples so that heating and cooling HFR vs. T curves could
be generated. All DSC tests were carried out using the same speci-
men to avoid that differences in the chemical composition along the
billet inuenced the results. Prior to data acquisition, the DSC sam-
ple was heated to 700 C and then cooled to room temperature at
the lowest rate (5 C/min) to also guarantee chemical homogeneity
along the specimen. To apply the differentiation method, HFR data
was derived with respect to temperature, originating the variation
of the heat ow rate in relation to temperature along the cooling
and heating process (dHFR/dT vs. T curves). The fl vs. T relation-
ship was determined with NETZSCH Protheus thermal analysis
Table 1
Chemical composition of the A356 alloy (in wt%) at pressure p = 0.1 MPa.a
Si Mg Fe
6.78 0.14 0.42 0.08 0.35 0.07
a
Maximum of 0.23 wt% other residual elements and Aluminum = Balance.
b
Other residual elements such Cr, Ni, Mn etc.
software by applying the Flynn method [27] of integration of partial
areas under the DSC curves, using the tangent and differentiation
methods to determine the solidus and liquidus. The differentiation
method also allowed several critical temperatures to be identi-
ed, such as the knee and the upper and lower limits of the SSM
working window. Origin software was used for further integration
and differentiation operations. Analysis of the heating and cooling
cycles allowed both melting and solidication transformations to
be analyzed. The use of several heating and cooling rates allowed a
comparative study of the kinetic behavior of the alloy to be carried
out.
Thermodynamic simulation was performed with Thermo-Calc
to generate the fl vs. T curve for the A356 alloy under the non-
equilibrium Scheil condition, which is based on the following
assumptions: (a) equilibrium exists at the solidliquid interface;
(b) no back diffusion occurs in solid phase that has already formed;
(c) the composition throughout the entire liquid phase is homo-
geneous and (d) the solid and liquid phases have equal densities
[23]. The results of this simulation were used as a reference in the
analysis of the experimental curves. The percentages of Al, Cu, Mg,
Fe and Ti were taken into account in the simulation.
3. Results and discussion
3.1. The proposed method
This section considers some practical aspects of the proposed
method, which we call the differentiation method (DM). Specif-
ically, it describes steps that should be followed to accurately
identify several critical temperatures in the semisolid range, such
as the solidus, liquidus and eutectic knee, and determine a suit-
able working window for SSM processing. The theory underlying
the proposed method is presented in the Appendixes. Appendix
A contains a complete graphical and mathematical characteriza-
tion of a single phase transformation in the semisolid state and
discusses features of the transformation that allow the knee tem-
perature, which should be avoided in SSM processing, to be formally
dened and determined. Appendix B describes a methodology for
determining the solidus and liquidus temperatures by extending
the reasoning presented in Appendix A to a complete solidica-
tion/melting reaction so that the semisolid range can be accurately
identied. Finally, Appendix C describes how other critical points
used to determine the temperature range for rheocasting and thixo-
forming operations can be identied.
The method proposed here consists of the following steps:
(a) Starting with the HFR (usually in mW/mg) vs. T curves gen-
erated from the results of the DSC experiments (the black
curves in Fig. 3a, cooling, and b, heating), the corresponding
rst derivative with respect to temperature, i.e., the dHFR/dT
(in mW/mg C1 ), can be plotted for the complete temperature
range tested, regardless of whether the experiment was per-
formed to map the solidication (cooling cycle rheocasting)
or melting (heating cycle thixoforming) phenomenon. The
rst derivatives correspond to the blue curves in Fig. 3a and b,
respectively.
(b) By analyzing the behavior of this derivative curve (see
Appendixes A, B and C), the initial and nal temperatures of the
Cu Zn Ti Otherb
0.18 0.04 0.14 0.04 0.23 0.05 < 0.23
 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233 25

Fig. 3. Illustration of the proposed differentiation method. Determination of the solidus, liquidus, eutectic knee and SSM working window using the rst derivative of the
HFR curve for solidication (a) and melting (b) phenomena; partial integration of the HFR curve within the semisolid range for solidication (c) and melting (d) phenomena;
the liquid fraction and its rst derivative, liquid fraction sensitivity, as a function of temperature showing the SSM processing temperature range for both solidication and
melting phenomena (e).

(solidication or melting) reaction, i.e., the liquidus and solidus
temperatures, can be accurately determined. These are high-
lighted in red in Fig. 3a and b and correspond to the closest
points to the semisolid transition at which the derivative is zero.
The derivative curve also allows the knee, which characterizes
the unstable eutectic transformation and should be avoided in
semisolid processing, to be precisely identied. This point cor-
responds to the rst peak (for cooling) or valley (for heating)
on the derivative curve and is indicated in purple in Fig. 3a and
b. The derivative curve also allows a working window for SSM
processing to be dened. This is the region between the tem-
peratures TSSMI (initial) and TSSMF (nal), the two points in green
in Fig. 3a and b where the derivative curve crosses the baseline
above the eutectic knee.
(c) Once the solidus and liquidus temperatures have been deter-
mined, the curve corresponding to the partial integration of the
HFR within the semisolid range (the red curve in Fig. 3c and d),
i.e., the fl vs. T curve, can be drawn. Then, in possession of the
knee and the suggested temperatures (TSSMI and TSSMF ) for the
working window, the corresponding liquid fraction for these
critical points can be determined.
(d) Finally, once the solid-to-liquid transition curve has been
drawn, the derivative of this curve (the green curve in Fig. 3e)
can also be drawn. This is the liquid fraction sensitivity curve
(dfl /dT) and shows the region where semisolid processing can
be adequately controlled, i.e., where dfl /dT < 0.03 C1 . By com-
bining this information with the working window (between
TSSMI and TSSMF ) suggested earlier, the manageable tempera-
ture range in which semisolid processing can be performed is
nally dened. This is shown schematically in Fig. 3e as SSM
process.
3.2. Application of the differentiation method to A356 alloy
3.2.1. Thermodynamic characterization using CALPHAD
simulation
Thermodynamic simulation using Thermo-Calc under the
Scheil condition for A356 alloy yielded the curve shown in Fig. 4.
The arrows indicate the formation of the following phases in liq-
uid during solidication: (1) an FCC aluminum primary phase
(L + Al-fcc), which starts to solidify at Tliquidus = 620.8 C; (2) a Si-
rich main eutectic (L + Al-fcc + Si), marking the knee at 574.0 C
and fl = 0.48; (3) an AlFeSi Fe-rich -phase (L + Al-fcc + Si + ); (4)
an AlFeSi Si-rich phase (L + Al-fcc + Si + + ) and, nally, (5)
tertiary AlFeMgSi-rich particles, such as Al8 FeMg3 Si6 and Mg2 Si
compounds (L + Al-fcc + Si + + + AlFeMgSi particles). Complete
solidication occurs at Tsolidus = 538.8 C.
The eutectic forms within a temperature range rather than at
a well-dened point characteristic of an invariant transformation.
This is because of the presence of residual elements, such as Fe, Cu,
Ti and Mg, which increase the complexity of the eutectic transition,
extending the temperature range in which it occurs.
The formation of tertiary AlFeMgSi compounds in the semisolid
temperature range does not affect semisolid processing, as this is
26 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233
Fig. 4. fl vs. T curve based on the results of the numerical simulation for A356 alloy
(Thermo-Calc under the Scheil condition). The arrows indicate phase transforma-
tions during solidication.
performed above the temperature at which these particles pre-
cipitate. The amount, distribution, size and morphology of these
particles are only relevant because of their impact on the mechan-
ical properties of the nal thixoformed or rheocast component, as
they are present in the solidied microstructure. For this reason,
their effects will not be discussed here.
3.2.2. Identication of critical points by differentiation of the DSC
curve
DSC tests at several cooling and heating rates for A356 alloy
resulted in the curves shown in Fig. 5a and b, respectively. There
are two main transformations in the solidication/melting reac-
tion: one related to the Si-rich eutectic, represented by the rst
valley/peak (at lower temperatures), and another related to the
Al-rich primary phase, represented by the second valley/peak (at
Fig. 5. HFR vs. T curves (a and b) and dHFR/dT vs. T curves (c and d) for A356 alloy at cooling/heating rates of 5, 10, 15, 20 and 25 C/min. Five temperatures of interest for
semisolid processing were determined by the differentiation method: the solidus, liquidus, knee and upper and lower limits of the working window. Examples of these
temperatures for a 20 C/min cooling/heating rate are highlighted in the gure.
higher temperatures). Because of kinetic effects, higher heating
rates result in DSC curves with higher exothermic/endothermic
HFR levels, in agreement with the literature [25]. This is because
transformations that have less time in which to occur (i.e., faster
reactions, corresponding to higher rates) require a larger input of
thermal energy per unit temperature than slower ones, leading to
larger HFR valleys/peaks.
Further tertiary phase transformations previously observed in
the Scheil curve were not detected by the DSC equipment, probably
because of the low HFR generated during the associated pro-
cesses. This in turn is a result of the small mass fraction associated
with these reactions compared with the two main transformations
(Si-eutectic and Al-fcc). As can be seen in Fig. 4, these smaller
reactions represent less than 20% of the total mass transformed
in the semisolid temperature range and are masked by the larger
Si-eutectic peak/valley.
The tangent method was used on the outer edges of the Si-
eutectic and Al-fcc valleys/peaks in the DSC curves in Fig. 5a and b to
determine the solidus and liquidus temperatures. These are shown
in Table 2 in the columns headed Tan for the heating and cooling
cycles and the ve cooling/heating rates. As an example, the results
obtained using this method for the 20 C/min cooling/heating rate
are shown in green for the cooling cycle (Fig. 5a) and light blue for
the heating cycle (Fig. 5b).
The DSC cooling and heating curves differentiated with respect
to temperature (dHFR/dT vs. T) for A356 alloy are shown in Fig. 5c
and d, respectively. These were used to identify ve temperatures
of relevance in semisolid processing: the solidus, liquidus, eutec-
tic knee and upper and lower limits of the working window. The
solidus and liquidus are shown in blue and correspond to the rst
and last points at which the curves are zero; the eutectic knee
is the rst peak or valley; and the upper and lower limits of the
working window, TSSMI and TSSMF , are the rst and second point,
respectively, after the eutectic knee where the curve crosses the
horizontal axis.
 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233 27

Table 2
Critical temperatures on the DSC curve and its derivative determined using the tangent method (tan) and differentiation method (DM) for the A356 alloy. The results of the
numerical simulation (under the Scheil condition) are shown as a reference at pressure p = 0.1 MPa.a

Cycle Rate ( C/min) Tsolidus ( C) TKnee ( C) TSSMI ( C) TSSMF ( C) Tliquidus ( C)

Tan DM DM DM DM Tan DM

Thermo-Calc Scheil 538.8 574.0 574.0 617.0 620.8

5 543.0 536.9 561.9 569.4 601.9 609.4 610.4

10 535.4 527.4 560.9 568.5 597.0 605.9 607.9
Cooling 15 520.0 517.8 560.0 567.3 597.5 607.5 610.4
20 519.8 517.9 557.3 567.3 599.8 617.3 620.4
25 512.9 512.9 557.9 562.9 595.4 607.9 610.4

5 563.0 557.5 582.5 590.0 605.0 625.7 627.5

10 562.0 557.5 587.5 600.0 615.0 630.8 635.0
Heating 15 558.5 555.0 590.0 605.0 615.0 633.5 642.5
20 559.6 555.1 587.5 602.5 617.5 635.8 647.5
25 559.5 555.1 597.5 609.5 614.0 647.5 650.0
a
Standard uncertainties u are u(T) = 0.05 C.

The locations corresponding to these temperatures on the
curves in Fig. 5c and d are indicated by arrows, and the correspond-
ing temperatures for the heating and cooling cycles and the ve
cooling/heating rates are shown in Table 2 in the column headed
DM. Again, as an example, the results for a cooling/heating rate
of 20 C/min are shown on the differentiated curves (Fig. 5c and
d) in dark blue for the cooling cycle and red for the heating cycle.
The solidus and liquidus are also shown on the original DSC curve
(Fig. 5a and b) so that a comparison with the results obtained using
the tangent method can be made.
3.2.3. Identication of the liquidus and solidus
To compare the tangent and differentiation methods in terms of
the liquidus and solidus identied for A356 alloy using each method
and shown in Table 2, these critical temperatures are plotted in the
form of a semisolid range in Fig. 6. Generally, regardless of whether
the tangent or differentiation method is used, the Scheil values (the
dashed lines in the graph) lie between the cooling temperatures
(dark blue/green bars) and heating temperatures (red/light blue
bars) for both the tangent and differentiation methods. Heating
temperatures are higher than cooling ones, and a slight increase
in the semisolid interval is observed as the heating/cooling rate
increases. These trends will be explained later in this section, when
the graph in Fig. 7 is analyzed.
Both methods showed good agreement between their respec-
tive values for each condition, with mean variations (standard
error) of Tsolidus = 4.06 0.72 C and Tliquidus = 4.07 1.09 C. The
solidus and liquidus temperatures determined with the DM are,
respectively, slightly lower and higher than the corresponding
points calculated using the tangent method. Hence, the alternative
method proposed here provides a slightly larger semisolid interval
than the traditional method. This result is easily explained by the
inherent differences in the way the extreme semisolid tempera-
tures are measured in each method. In the differentiation method,
the temperature is determined as soon as the DSC curve changes
its slope, and the start or end of a phase transformation is indicated
by a zero on the differentiation curve (dHFR/dT), while in the tan-
gent method, the temperatures identied by the points at which
the tangents cross over tend to correspond to a delayed start to, or
earlier end of, the transformation, slightly shortening the semisolid
interval. These differences can be clearly observed in Fig. 5a and b.
Fig. 7 shows the fl vs. T curves for solidication/melting of A365
alloy after partial area integration of the DSC curves. The solidus and
liquidus were identied using the tangent (light blue/green curves)
and differentiation (red/dark blue curves) methods and the values
in Table 2. The black curve shows the variation in fl with T under
the Scheil condition, as in Fig. 4. The cooling and heating cycles are
clearly divided into two separate groups in the graph, and the curve
corresponding to the Scheil condition lies between them.
The relative positions of the curves are explained by the fact that
the higher the cooling/heating rate (i.e., the farther from equilib-
rium conditions the process is), the more the phase transformations

Fig. 7. fl vs. T curves produced by integration of partial areas under cooling/heating

DSC curves with respect to temperature for A356 alloy at 5, 10, 15, 20 and 25 C/min
Fig. 6. Solidus and liquidus temperatures for A356 alloy measured using the tangent cooling/heating rates using the tangent and differentiation methods to identify the
and differentiation methods at ve heating/cooling rates. The values predicted by solidus and liquidus points. The curve predicted by numerical simulation (Scheil
numerical simulation (Scheil condition) are shown as a reference. condition) is shown as a reference.
28 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233

are delayed and extended in the temperature range, i.e., at higher Table 3
Knee parameters obtained by the differentiation (DM) and visual recognition (Vis)
cooling/heating rates the imposed heat input is not followed by
methods for A356 alloy at several cooling/heating rates at pressure p = 0.1 MPa. Val-
the diffusion processes responsible for phase transformations, so ues that could not be determined are shown as NI. Values predicted by numerical
these are forced to occur over a wider temperature range than simulation (Scheil condition) are shown as a reference.a
that predicted for equilibrium conditions. This effect is amplied as
Cycle Rate ( C/min) TKnee ( C) fl Knee
the cooling/heating rate increases. The result is that cooling curves
move toward lower temperatures (left) and heating curves toward Vis DM Vis DM
higher temperatures (right) as the cooling/heating rate increases. Thermo-Calc

Scheil 574.0 0.48
Hence, the outer and inner edges of each group are progressively
5 563.9 561.9 0.50 0.45
farther from and closer to equilibrium, respectively. Between the 10 560.5 560.9 0.43 0.43
curves corresponding to the lowest cooling/heating rates (5 C/min) Cooling 15 560.4 560.0 0.47 0.47
lies the Scheil curve, which is nearer equilibrium than any of the 20 558.4 557.3 0.44 0.43
25 556.0 557.9 0.48 0.50
experimental curves. In addition to causing a delay in the semisolid
transformations, higher rates result in a larger driving force (super- 5 582.0 582.5 0.55 0.56
cooling/superheating) for solidication/melting, making them start 10 588.4 587.5 0.54 0.51
Heating 15 NI 590.0 NI 0.51
sooner [23]. Consequently, faster cycles have a larger semisolid
20 NI 587.5 NI 0.43
interval. Faster cooling curves have higher liquidus points than 25 NI 597.5 NI 0.54
slower ones, and a similar trend is observed for heating curves, a
Standard uncertainties u are u(T) = 0.05 C and u(fl ) = 0.01.
with faster heating curves having slightly lower solidus tempera-
tures. This explains the trends shown earlier in Fig. 6. For heating
curves, the decrease in solidus temperature is difcult to see in operator-dependent. For the 15, 20 and 25 C/min heating curves,
Fig. 7 due to the reduced extend of the difference (4 C) compared the knee could not be identied and the corresponding values are
to the magnication of the graph, that has a x-axis scale ranging therefore missing in their respective elds in Table 2 (indicated as
from 520 to 650 C (T = 130 C) in the limited page space. Further- NI, not identiable) and in Fig. 8. This problem does not arise
more, the separation of the lower limit for these specic curves with the differentiation method, as it uses mathematical/graphical
occurs at extremely low liquid fractions, in which the curves are procedures to identify the knee that do not change even when it is
practically horizontal and join together. However, this trend can be imperceptible to the human eye.
clearly seen in Table 1. In Fig. 8, as in Fig. 7, the knee is at a higher temperature in heating
Another feature of the curves in Fig. 7, especially in heating cycles (red points) than in cooling ones (dark blue points), and the
cycles, is that the faster the rate, the softer the knee shape of the values corresponding to the Scheil condition lie in between (dashed
Si-eutectic transformation. This smoothing is a result of the effect lines). The reasons for this have already been discussed. Analysis of
mentioned above whereby the farther the process is from equi- the results where a knee could be identied by the visual recogni-
librium conditions, the greater the temperature range over which tion method, i.e., excluding the 15, 20 and 25 C/min heating curves,
phase transformations occur. revealed that there was good agreement between both methods
Finally, it can be observed that the curves generated using each and that the mean difference (and standard error) in the knee tem-
method for a particular condition are very similar, indicating that perature and knee liquid fraction between the two methods was
the choice of method (differentiation vs. tangent) does not signif- only Tknee = 0.22 0.4 C and fl (knee) = 0.0083 0.008.
icantly affect the shape of the curve. Hence, the results for both Therefore, the differentiation method proved to be (a) suitable
methods are coherent. for accurately identifying the knee point and in good agreement
In summary, the differentiation method proved to be (a) able with the visual recognition method; (b) operator-independent, as
to accurately identify the solidus and liquidus temperatures, as it it uses the same mathematical/graphical procedure to identify the
yielded results that were in good agreement with those obtained by knee and therefore does not require common sense to identify
the tangent method; (b) operator-free, as it uses the same math- a knee-like shape in the curve, as a result of which measure-
ematical/graphical procedure to identify the solidus and liquidus ment inaccuracies are avoided; (c) technically easier to use than
points, eliminating the need for common sense when choosing the the visual recognition method, as the knee is represented by a
most appropriate tangents so that measurement inaccuracies are
avoided and (c) technically easier to use than the tangent method,
as the solidus and liquidus points are represented by points where
the curve being analyzed is equal to zero instead of changes in the
slope of the curve (features that may be barely identiable in some
situations).

3.2.4. Identication of the knee

To analyze the effectiveness of the differentiation method in
identifying the unstable Si-eutectic transformation temperature for
A356 alloy, the standard visual recognition method for identifying
the knee was used with the red and dark blue fl vs. T curves in
Fig. 7. The values of temperature and liquid fraction determined in
this way are shown in the Vis (Visual) columns in Table 3. The
values of knee temperature obtained earlier from the derivatives
of the DSC curves (Tknee column in Table 2) were used with the
integrated fl vs. T curves to obtain the corresponding knee liquid
fraction shown in the last DM column of Table 2. The temperature
and liquid fraction data in Table 3 is shown graphically in Fig. 8.
Fig. 8. Knee temperature and liquid fraction determined by the visual recognition
The knee for the 10 C/min heating curve could only be identied and differentiation methods for A356 alloy at several cooling/heating rates. Values
very imprecisely by the visual recognition method and was highly predicted by numerical simulation (Scheil condition) are shown as a reference.
 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233 29

Fig. 9. Comparative behavior of dHFR/dT vs. T (dark blue), fl vs. T (bright blue) and dfl /dT vs. T (light blue) curves derived from DSC data for semisolid transformation of A356
alloy at cooling rates of 5 (b), 10 (c), 15 (d), 20 (e) and 25 (f) C/min. The values predicted by numerical simulation (Scheil condition) are shown at the top-left as a reference
(a).

valley/peak in the curve being analyzed instead of an unstable knee-
like shape and (d) much better able to identify the knee than the
visual recognition method, as seen for the 15, 20 and 25 C/min
heating curves.
For some authors, identication of the knee becomes less
important for thixoformability analysis as the cooling/heating rate
increases due to the smoothening of the knee-like shape caused
by kinetic effects. As the transformation at these higher rates does
not occur at a specic point but over a progressively broader tem-
perature range, identication can become meaningless in practical
terms. Nevertheless, the method proposed here can still be use-
ful for intermediate cooling/heating rates, for which the knee is
still present although only roughly identiable, as seen for the
10 C/min heating condition in this study. The method can also be
used for further comparative analysis, e.g., to gain a better under-
standing of how kinetic effects inuence knee temperature under
different heating/cooling conditions.
3.2.5. Determining the semisolid processing range
The dHFR/dT vs. T curves and the resulting fl vs. T and dfl /dT vs.
T (sensitivity) curves for A356 alloy for all the conditions analyzed
here are shown in Fig. 9 (cooling) and Fig. 10 (heating) and provide
an overview of the graphical behavior as the semisolid transfor-
mation progresses. The Scheil condition is shown as a reference in
Figs. 9a and 10a (black curve). The ve critical temperatures identi-
ed earlier by differentiating the DSC curves (shown in the solidus,
knee, TSSMI , TSSMF and liquidus columns in Table 1) are indicated on
the curves for all the conditions analyzed.
To establish an adequate working window for SSM processing of
A356 alloy by the differentiation method, as described in Appendix
C of this work, the maximum sensitivity (dfl /dTmax ) in the proposed
interval (between TSSMI and TSSMF ) was read on the graph to assess
the thermodynamic stability. The liquid fractions at the boundaries
of the proposed interval (fl SSMI and fl SSMF ) were also identied so
that the range of liquid fractions during the process was known.
These data are shown in Table 4 for all the conditions analyzed
and are highlighted for illustrative purposes on the curves for the
20 C/min cooling and heating cycles in Figs. 9 and 10.
Apart from the 10 C/min cooling condition, all the sensitiv-
ity values in Table 4 are below the 0.03 C1 limit, so the original
interval suggested by the differentiation method was maintained.
In the case of the 10 C/min cooling cycle, the upper limit of the
working window (the region of maximum sensitivity) was low-
ered to the next temperature in the interval at which the sensitivity
30 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233

Fig. 10. Comparative behavior of dHFR/dT vs. T (dark red), fl vs. T (bright red) and dfl /dT vs. T (light red) curves plotted using DSC data for semisolid transformation of A356
alloy at heating rates of 5 (b), 10 (c), 15 (d), 20 (e) and 25 (f) C/min. The values predicted by numerical simulation (Scheil condition) are shown at the top-left as a reference
(a).

satised the 0.03 C1 criterion. The resulting interval was con-
sidered for SSM processing and had the following corrected
parameters: TSSMF = 596 C, Tcooling = 27.5 C, fl SSMF cooling = 0.83
and fl SSM cooling = 0.32 and dfl /dTmax = 0.029 C1 . The data in
Table 3 were then used to plot the working windows for A356
alloy for all the cooling and heating cycles. The results are shown in
Fig. 11a and b in terms of temperature and liquid fraction, respec-
tively.
Three features related to the temperature range for SSM
processing can be observed in Fig. 11a:

Table 4
Parameters for the working window for SSM processing of A356 alloy determined by the differentiation method for ve cooling/heating rates at pressure p = 0.1 MPa. The
values predicted by numerical simulation (Scheil condition) are shown as a reference.a

Cycle Rate ( C/min) TSSMI ( C) TSSMF ( C) TSSM ( C) fl SSMI fl SSMF fl SSM dfl /dTmax ( C1 )

Thermo-Calc Scheil 574.0 617.0 43.0 0.48 0.92 0.44 0.019

5 569.4 601.9 32.5 0.55 0.92 0.37 0.026

10 568.5 597.0 28.5 0.51 0.86 0.35 0.032
Cooling (rheocasting) 15 567.3 597.5 30.2 0.54 0.87 0.33 0.017
20 567.3 599.8 32.5 0.52 0.88 0.36 0.016
25 562.9 595.4 32.5 0.55 0.91 0.36 0.016

5 590.0 605.0 15.0 0.65 0.84 0.19 0.014

10 600.0 615.0 15.0 0.69 0.88 0.19 0.014
Heating (thixoforming) 15 605.0 615.0 10.0 0.74 0.87 0.13 0.014
20 602.5 617.5 15.0 0.67 0.88 0.21 0.015
25 609.5 614.0 4.5 0.75 0.82 0.07 0.016
a
Standard uncertainties u are u(T) = 0.05 C, u(fl ) = 0.01 and u(dfl /dT) = 0.005 C1 .
 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233
Fig. 11. Working window for SSM processing obtained by the differentiation method for A356 alloy at different cooling (rheocasting) and heating (thixoforming) rates:
temperature range (a) and liquid fraction range (b). The values predicted by numerical simulation (Scheil condition) are shown as a reference.
(a) In cooling cycles the working window temperatures for SSM
processing are lower than the temperatures for heating cycles. This
is a result of the kinetic effects already discussed in Section 3.2.3.
Cooling and heating curves move toward lower and higher temper-
atures, respectively, as the cooling/heating rate increases because
of the delayed semisolid phase transformations and greater tem-
perature range over which the transformations occur. In practical
terms, this result shows that rheocasting operations should be per-
formed at lower temperatures than thixoforming operations to
achieve more controllable processing conditions. In fact the authors
believe that this particular nding is not a unexpected result, since
the solidication phenomena is time dependent due to diffusion
as well as segregation of Silicon and the residual elements into
the liquid, i.e., the solidication of the primary Alfcc and solid solu-
tion depends upon segregation. The melting phenomena is less
time dependent, since all the silicon particles as well as most of the
residual elements are already conned in the secondary (eutectic)
volume of the material, therefore the TSSMI that marks the nal
eutectic melting is expected to be higher when the primary Alfcc
and solid solution starts to melt.
(b) Another feature related to kinetic effects is that the work-
ing window for SSM processing remains almost unaltered as the
cooling rate increases, varying by only 5 C (27.532.5 C) between
the smallest and largest window; however, the window generally
becomes smaller as the heating rate increases, varying by 10.5 C
(4.515.0 C) between the highest and lowest heating rate. This
behavior shows that the melting phenomenon is more affected by
kinetic effects than the solidication one. A practical consequence
of this is that rheocasting processes are more stable than thixoform-
ing ones for processing conditions farther from thermodynamic
equilibrium.
The signicant reduction in the working window for heat-
ing cycles (especially for a heating rate of 25 C/min, for which
TSSM = 4.5 C) indicates that the delayed semisolid transforma-
tions and greater temperature range over which these occur
because of kinetic effects is more marked for eutectic melting than
for -phase melting, i.e., TSSMI is more delayed than TSSMF , making
the interval between them narrower as the heating rate increases.
Thus, the working window for higher heating rates should perhaps
be dened so as to extend over a wider range by raising TSSMF ,
since the progressive smoothing of the transformation curve as
the heating rate increases reduces the importance of identifying
critical points. This issue was discussed earlier for the knee temper-
ature (Section 3.2.4) and arises because the transformations occur
in a progressively wider temperature range as the kinetic effects
intensify.
(c) A further feature of Fig. 11a is that the SSM processing
temperature range for cooling is wider than for heating for all
31
the conditions analyzed: TSSM cooling = 31.0 0.9 C and TSSM
heating = 11.9 2.0 C (mean standard error). This result shows
another thermokinetic advantage of rheocasting over thixoform-
ing: the former is more controllable, as the semisolid material is
stable over a wider temperature range. It also suggests that the
working window for thixoforming processes should be dened to
extend over a wider temperature range when kinetic effects are
signicant.
Two of the three results discussed here related to the SSM
processing temperature range are also reected in the SSM liq-
uid fraction range shown in Fig. 11b. Because the SSM temperature
range for cooling cycles is wider than for heating cycles (Fig. 11a),
the corresponding liquid fraction ranges are also wider, as shown in
Fig. 11b: fl SSM cooling = 0.35 0.01 and fl SSM heating = 0.16 0.026
(mean standard error). Similarly, because the SSM temperature
range remains almost unchanged between cooling cycles (Fig. 11a),
the liquid fraction range for cooling also remains essentially
unchanged (Fig. 11b), varying by only 0.05 among all the cycles
(from 0.32 to 0.37). In contrast, the liquid fraction for heating cycles
varies by 0.12 (from 0.07 to 0.19). As stated for the temperature
range analysis, these results also show that rheocasting operations
are superior to thixoforming operations in terms of process control
parameters.
However, although the SSM working window temperatures are
lower for cooling cycles than for heating cycles, the SSM liquid
fraction ranges overlap. For rheocasting the liquid fraction varies
between 0.55 and 0.92, and for thixoforming it varies within a nar-
rower range (0.650.88) contained within this interval. This result
indicates that because of the thermokinetic behavior of the melt-
ing and solidication phenomena, their critical points are in similar
regions of reacted mass (liquid or solid fraction) even though the
transformations occur in different temperature ranges.
For the purposes of comparison, Table 5 shows the working
windows for A356 alloy for all the cooling and heating condi-
tions analyzed using three different approaches: the differentiation
method and the criteria proposed by Liu et al. [19] and Zoqui et al.
[21], which are described in Section 1 of this work.
The traditional denition of the working window proposed by
Liu et al. does not consider the thermodynamic behavior of individ-
ual alloys in the semisolid state (which is strongly affected by the
composition of the alloy and kinetic factors) and limits the process
to a dened fl of 0.40.6. The result is that for all the conditions
analyzed the unstable eutectic knee lies within the chosen work-
ing window, which is not recommended for various reasons already
discussed in this work (working windows containing the knee are
highlighted in bold in Table 4). Furthermore, some conditions are
discarded merely because the sensitivity is greater than 0.03 C1
at fl = 0.5. Examples of this are the 5 C/min cooling and heating
32 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233

Table 5
SSM working windows obtained by the differentiation method and the criteria proposed by Liu et al. [19] and Zoqui et al. [21] for A356 alloy at several cooling/heating rates
at pressure p = 0.1 MPa. Bold values represent intervals containing the unstable eutectic knee. Empty boxes represent conditions for which dfl /dT(0.5) > 0.03 C1 .a

Cycle Rate ( C/min) SSM working window

TLiu ( C) TZoqui ( C) TDIF ( C) fl Liu fl Zoqui fl DIF

5 565610 569602 0.51.0 0.50.9

10 559581 561595 568597 0.40.8 0.50.9
Cooling (rheocasting) 15 556575 560610 567597 0.51.0 0.50.9
20 556578 557620 567600 0.41.0 0.50.9
25 552570 558610 563595 0.51.0 0.50.9
0.40.6
5 582627 590605 0.51.0 0.60.8
10 584592 587635 600615 0.51.0 0.70.9
Heating (thixoforming) 15 586594 590642 605615 0.51.0 0.70.9
20 586597 587647 602617 0.41.0 0.70.9
25 592601 597650 609614 0.51.0 0.70.8
a
Standard uncertainties u are u(T) = 0.05 C, u(fl ) = 0.01 and u(dfl /dT) = 0.005 C1 .

cycles, for which the processing intervals are not shown in Table 4.
By using this criterion, the entire stable region above the knee for
these two cooling and heating cycles is simply ignored, showing
that this method may not evaluate the full potential of a candidate
alloy or kinetic condition for SSM processing.
The criteria proposed by Zoqui et al. signicantly increase the
number of alloys that could potentially be considered for SSM
processing by using only the position of the eutectic knee as a
constraint (lower limit) on the working window and by analyzing
the sensitivity throughout the entire interval (dfl /dT < 0.03 C1 ).
The processing window with this approach is the widest of the
three windows determined with the approaches considered here
and generally extends from the knee to the liquidus temperature.
However, it allows SSM processing to take place near the region of
the curve where eutectic particles are still present in the semisolid
slurry and the liquid fraction is extremely high, potentially having
an adverse effect on the slurry rheology during processing as well
as on the microstructure of the nal product.
The differentiation method seeks to improve on the approach
proposed by Zoqui et al. by narrowing the working window. It does
this by moving the lower boundary of the window farther from the
unstable eutectic knee and the upper boundary farther from the liq-
uidus, decreasing the likelihood of eutectic particles being present
in the slurry and avoiding an excessive amount of liquid during
SSM processing. Despite these differences, both the differentiation
method and the approach proposed by Zoqui et al. consider the
characteristic thermodynamic behavior of a particular alloy under
specic kinetic conditions and not only are more compatible with
real SSM operations but also allow more commercial alloys to be
used in SSM processing. Finally, although it predicts a small working
window for thixoforming operations, the differentiation method is
suitable for use with both rheocasting and thixoforming operations
as in practice in a commercial environment it is easier to heat billets
for semisolid processing than to cool material in order to rheocast
it.
A remark should be made concerning the use of the suggested
working window (presented in Appendix C) for real forming oper-
ations in the semisolid state. It is known that in addition to
thixoformability, several factors play a determining role in SSM
processing, such as microstructure and rheology of the semisolid
slurry as well as further processing limitations such as hetero-
geneous temperature and chemical composition of the billet.
Furthermore, specic characteristics and issues associated to rheo-
casting and thixoforming operations raise signicant practical
differences between these two operations. The thermodynamic
analysis presented here is only the initial step for the character-
ization of candidate alloys for SSM process and an adaptation of
the suggested working window should be performed in order to
adequate the observed thermodynamic features to these other
inherent aspects of SSM processing. The scope of this work is
limited to a thermodynamic characterization and for this reason
other (but not less important) points concerning the applicability
of new alloys to SSM processing are not discussed and are strongly
suggested as future research.
4. Conclusions
An alternative method for identifying critical points in thixo-
formability analysis and a formal denition for the knee point
have been proposed. The method can be used with solidi-
cation and melting transformations. A new SSM processing
window has been suggested for both rheocasting and thixoforming
operations.
The ndings indicate that the proposed method is an effective
tool for identifying critical points such as the solidus, liquidus and
knee temperatures. The results agree well with those obtained
using traditional methods. The differences between the solidus
and liquidus temperatures measured with the proposed method
and with the tangent method were Tsolidus = 4.06 0.72 C
and Tliquidus = 4.07 1.09 C, and the differences between the
knee temperatures and liquid fractions measured with the pro-
posed method and with the visual recognition method were
Tknee = 0.22 0.4 C and fl knee = 0.0083 000.8. The proposed
method also proved to be operator-independent, as it uses well-
dened mathematical/graphical criteria to identify critical points,
thereby avoiding measurement inaccuracies. Furthermore, it is eas-
ier to use than other methods, as critical points are turned into
easily recognizable visual and numerical features of the curve being
analyzed after second-order differentiation, such as valleys, peaks
and zeros, instead of slight changes in slope or knee-like shapes,
which may be barely identiable in some situations, especially
when kinetic effects are more signicant.
The suggested formal denition for the knee point (the
peak/valley in the expected eutectic range of the differentiated DSC
curve of the solidication/melting transformation) yields results that
agree well with those obtained using traditional approaches, indi-
cating the suitability of this denition for identication of the knee,
particularly when the aim is to compare different shaped curves.
The proposed working window allows suitable lower and upper
limits for SSM processing to be identied.
Acknowledgments
The authors would like to thank the Brazilian research fund-
ing agencies FAPESP (So Paulo Research Foundation Projects
2013/09961-3 and 2015/22143-3), CNPq (National Council for Sci-
entic and Technological Development Project 470572/2011-6)
and CAPES (Federal Agency for the Support and Improvement of
 G.L. Brollo et al. / Thermochimica Acta 651 (2017) 2233
Higher Education) for providing nancial support for this study. The
authors are also indebted to the Faculty of Mechanical Engineering
at the University of Campinas for the practical support very kindly
provided.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tca.2017.02.010.
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