energies

Article
Thermal Stability and Thermodynamic Performances of Pure
Siloxanes and Their Mixtures in Organic Rankine Cycles
Gioele Di Marcoberardino 1 , Costante Mario Invernizzi 1, * , Paolo Iora 1 , Luca Arosio 2 , Marcello Canavese 2 ,
Angelo Lunghi 2 and Antonella Mazzei 2
1 Department of Mechanical and Industrial Engineering, University of Brescia, Via Branze 38,
25123 Brescia, Italy; [email protected] (G.D.M.); [email protected] (P.I.)
2 NNOVHUB Stazioni Sperimentali per l’Industria, Via Galileo Galilei, 20097 San Donato Milanese, Italy;
[email protected] (L.A.); [email protected] (M.C.);
[email protected] (A.L.); [email protected] (A.M.)
* Correspondence: [email protected]

Abstract: Organic Rankine cycles are often the best solution for the conversion of thermal energy.
The many working fluids include silicon oils. One crucial issue that determines the choice of a
working fluid is its thermochemical stability, as this sets a limit to the maximum temperature at
which the fluid can be used in a power plant. A second subject, much debated today, is the use of
mixtures in ORCs. In the first part of this study, an investigation into the thermal stability of siloxanes
using two different approaches was carried out. The results confirmed a limit working temperature
for the considered siloxanes of about 300 °C, with a degradation that advanced significantly over
time at 350 °C. In the second part of the study, an analysis of the thermodynamic performances
of some siloxane mixtures was carried out. It was found that the efficiencies of the corresponding





 thermodynamic cycles were substantially the same as for the pure fluids used today. By changing
Citation: Di Marcoberardino, G.; the composition of the mixture, it was also possible to vary, within reasonable limits, the values of
Invernizzi, C.M.; Iora, P.; Arosio, L.; the condensation pressure, adapting the thermodynamic cycle to the different situations that can be
Canavese, M.; Lunghi A.; Mazzei A. encountered in current practice.
Thermal Stability and
Thermodynamic Performances of Keywords: organic Rankine cycles (ORC); thermal stability; siloxanes; mixture of fluids
Pure Siloxanes and Their Mixtures in
Organic Rankine Cycles. Energies
2022, 15, 3498. https://doi.org/
10.3390/en15103498 1. Introduction
Academic Editors: Talal Yusaf Rankine cycles with organic working fluids are widely used in numerous industrial
and George Kosmadakis sectors (see, for example, [1–3]). Siloxanes are among the numerous working fluids pro-
Received: 10 March 2022
posed and used. Silicon oils are widely used as heat transfer fluids for high temperature
Accepted: 6 May 2022
applications [4–6]. They are considered nontoxic fluids and are available in many configu-
Published: 10 May 2022
rations, such as linear, cyclic, or with methyl and phenyl groups, which are characterised
by different and specific properties. For example, the introduction of phenyl groups in
Publisher’s Note: MDPI stays neutral
the molecule can increase the thermal stability [7]. Fluorosilicones combine some of the
with regard to jurisdictional claims in
advantages of fluorocarbons and of silicones and are proposed as lubricants for extreme
published maps and institutional affil-
pressure applications [7].
iations.
The viscosity of commercial silicones varies across a wide spectrum, ranging from
0.65 cSt to tens of millions of cSt, Anonymous1 . They are mainly adopted as heat transfer
fluids, but they are also proposed as dielectric, hydraulic fluids, for power transmission
Copyright: © 2022 by the authors.
and as damping fluids [7].
Licensee MDPI, Basel, Switzerland. Regarding their use as heat transfer fluids, some of them are recommended for wide
This article is an open access article temperature ranges. For example, Syltherm HF is recommended for temperatures from
distributed under the terms and −73 °C, Anonymous2 to 260 °C, Anonymous2 ; Syltherm 800 is provided for uses up to
conditions of the Creative Commons 400 °C, Anonymous3 .
Attribution (CC BY) license (https:// Due to their good thermal stability, commercial silicones are also considered as heat
creativecommons.org/licenses/by/ transfer fluids in modern concentrating solar power systems using parabolic trough [8–10].
4.0/). Helisol has been effectively employed in a solar test facility up to 425 °C for 480 h at 27 bar,

Energies 2022, 15, 3498. https://doi.org/10.3390/en15103498 https://www.mdpi.com/journal/energies

Energies 2022, 15, 3498 2 of 20

without any serious problems, except for the formation of some gases, but, according to the
authors, without any serious consequences [6].
Silicon heat transfer fluids are mostly multi-component mixtures of dimethyl poli-
siloxanes with different molecular weights, which implies high boiling points, and, conse-
quently, rather low vapour pressures at moderate temperatures. For example, at 100 °C,
Syltherm HF and Syltherm 800 have a vapour pressure of about 0.03 bar and 0.05 bar,
respectively, [4,5].
In spite of their rather low vapour pressures at temperatures close to environmen-
tal ones, some oligomer siloxanes are used today as working fluids in Rankine cycles,
particularly, hexamethylsiloxane (MM) and octamethyltrisiloxane (MDM).
The use of cyclic siloxanes in organic fluid Rankine cycles (ORC) was first proposed
in [11].
Nowadays, at least 320 biomass plants are operating across the world (about 60 in
Italy) with sizes from 0.2 MWe to 8 MWe. The majority of them are cogenerative and use
siloxanes as the working fluid. Biomass could still be considered a valid option to reduce
the carbon emission footprint, as foreseen, for example, by the recent ambitious European
decarbonisation plans [12].
Moreover, siloxanes, due to their good thermal stability, have recently been proposed
for use in specific plant configurations at high-temperature [13].
Much valuable operational experience has been accumulated over past years and
extensive practical information is available, as documented, for example, in [14,15].
Due to their wide use in organic Rankine cycles, in recent years many authors have
published studies concerning the thermodynamic properties of certain oligomers, with
the aim of improving their thermodynamic modeling by use of equations of state. In [16],
for example, the authors optimised the parameters of a specific equation of state after a
critical evaluation of the experimental thermodynamic properties available at that time for
two linear and two cyclic methyl-siloxanes. In [17], measurements of density and of sound
velocity in the liquid phase were presented for three methyl-siloxanes and the obtained
data, integrating the many results accumulated over the last few years in the literature, and
were used to calibrate a specific volumetric equation of state.
In [18], bubble pressures for three mixtures of linear siloxanes with different composi-
tions over a temperature range of 270 K to 380 K, were reported.
Some transport property measurements are also available in the literature. For exam-
ple, ref. [19] reported the values of the thermal conductivities for some pure linear and
cyclic oligomers and for a mixture of 50% mass of two linear siloxanes in the tempera-
ture range from 290 K to 520 K and pressures from 1 bar to 100 bar. The same paper also
presented some data on the dynamic viscosity at atmospheric pressure. Different and
additional values for transport properties are also available in the technical literature of the
fluid suppliers.
Some papers have presented and discussed measurements of heat transfer coefficients
for pure siloxanes and for some mixtures. For example, in [20], for pure hexamethylsilox-
ane and octamethyltrisiloxane, and for some of their mixtures, the values of heat transfer
coefficients in evaporation in a horizontal tube are presented, while in [21], some measure-
ments of the Nussel Number, in a vertical heated upward tube, are discussed regarding
supercritical pressures for hexamethyldisiloxane.
In conclusion, silicones, as well as their wide use in industrial applications, have also
been effectively adopted as working fluids in organic Rankine cycles and much information
on the thermo-physical properties of the simpler siloxanes is now available. Moreover, in
recent years the use of non-azeotropic mixtures, instead of pure fluids, in organic fluid
Rankine cycles has been proposed; some of the previously cited publications specifically
consider mixtures of siloxanes.
A crucial but still controversial problem in the use of unconventional working flu-
ids in Rankine cycles is their thermal stability. In this study, we compared the results
obtained from two different thermochemical stability approaches for some siloxanes. The
Energies 2022, 15, 3498 3 of 20

presented and discussed experimental procedure can also be applied to all pure candidate
working fluids.
In the second part of the paper, we develop some thermodynamic evaluations of the
performance of mixtures of siloxanes in the case of heat recovery. Currently, there are
numerous proposals to use mixtures as working fluids in Rankine cycles, with contradictory
results [22–24].

2. Thermal Stability of Siloxanes

In addition to the typical characteristics that a working fluid for organic Rankine cycle
must have (e.g., favourable thermodynamic properties, low viscosity, good heat transfer
characteristics, low or no toxicity, low or non-flammability, no negative effects on the
environment and a reasonable cost), its thermal stability is crucial to define the maximum
operating temperatures of the engine.
As the heat resistance of a molecule basically depends on its bond energies, BE
provides a first rough indicator of thermal stability; however, it does not take into account
possible chemical interactions with the environment where the fluid is used. It is calculated
as the value of the standard enthalpy of formation ∆ f Hgas0 (at 25 °C) divided by the number
0 /n ∝ BE and reasonably
n B of the bonds in the molecule. More negative is the ratio ∆ f Hgas B
higher is the mean value of the bond energy BE of the atoms in the molecule.
0 for hexamethyldisiloxane, car-
In Table 1, for example, we report the values of ∆ f Hgas
bon tetrafluoride, sulphur hexafluoride and two hydrocarbons (n-pentane and iso-pentane).
Perfluorocarbons are considered to be among the most thermally stable fluids. In [25],
carbon tetrafluoride in an Inconel bomb, after conditioning of the bomb surface, showed
clear signs of decomposition starting from about 940 °C. Sulphur hexafluoride was used
primarily as an electrical insulator and is considered to be inert. According to [26], it
can be heated to 500 °C in quartz containers without any decomposition effects. The two
hydrocarbons n-pentane and iso-pentane are representative working fluids for organic
Rankine cycles operating at relatively low temperatures, and typically used for geothermal
applications [27]. In [28], a solar power plant is described with an organic Rankine cycle
using n-pentane with an inlet turbine temperature of 240 °C.

0 at 25 °C and the estimated mean energy bond EB for

Table 1. Standard formation enthalpies ∆ f Hgas
0 are from [29].
the atoms in the molecule for some compounds. The values of ∆ f Hgas

Compound 0 (kJ mol−1 )

∆ f Hgas EB (zJ/Bond)
MM (Hexamethyldisiloxane) 778 50
Carbon tetrafluoride 925 380
Sulphur hexafluoride 1209 330
n-Pentane 146 15
iso-Pentane 154 16

From the data in Table 1, hexamethyldisiloxane (and, by extension, the other silox-
anes, linear and cyclic) should have a thermal stability significantly higher than that of
hydrocarbons, without, however, reaching the typical levels of stability of the simpler
perfluoro-carbons.
In real-world conditions, as a result of the presence of different materials and sub-
stances (e.g., different metals and different types of gaskets, lubricants, air, water) the
thermal stability of the fluid can be drastically reduced. Therefore, in general, it is better to
refer to its thermochemical stability [30]. Nevertheless, for sufficiently high temperatures
thermal decomposition is always present, with a rate increasing exponentially with the
temperature; the problem is to identify the degradation rate and to estimate a reasonable
and safe duration of the working fluid.
The degradation usually occurs with breakdown of the molecules into long- and short-
chain compounds. The analysis of the degradation can be evaluated according to different
methods (in static or dynamic tests) and by examination of the different chemical and
Energies 2022, 15, 3498 4 of 20

physical properties of the tested fluid (for example, analysing any carbonaceous residues,
the flash point variation, the total acid number, the viscosity variations of the residual
liquid, the variation in sub-atmospheric vapour pressure) or the composition of the residual
liquid and gas phases by gas-chromatography or by use of mass-spectrometers [30,31].
A recent approach to the analysis of thermal stability involves a molecular dynamics
simulation [32].
For the oligomer siloxanes, some thermal stability results are already provided in
the literature. In [10], results for samples of MD2 M (decamethyltetrasiloxane, with a
boiling temperature of 194 °C), and MD3 M (dodecamethylpentasiloxanes, with a boiling
temperature of 230 °C), in glass and steel ampoules at 400 °C, after 48 h decomposed by
twenty and forty percent, respectively, are presented.
In [33], MM (hexamethyldisiloxane) at 420 °C in a stainless steel tube, appeared to
reach equilibrium after 72 h, but with a significant reduction in MM in the final mixture
(about 50%, on a mass basis) and a large presence of methane (15–20% in the gas phase).
From an analysis of the influence of the temperature (with a fixed time of 72 h), it appears
that a safe temperature for MM would be 300 °C, with an estimated annual degradation
mass rate of about 3.5%.
In [14], the authors examined fluid samples taken from eight different organic Rankine
plants operating with MDM as the working fluid. The plants operated with a source
maximum temperature equal to about 300 °C accumulated over a total of 460,000 working
hours. The degradation of the working fluid (across a very wide range, from 5 to 34%)
resulted in significant contamination of the used lubricants which increased with the
operating time.
Variation in the sub-atmospheric vapour pressure of samples of hexamethyldisilox-
ane (MM) and octamethyltrysiloxane (MDM) after 80 h at different test temperatures are
discussed in [34], according to a procedure previously presented in [35]. In stainless steel
cylinders, the sample of MM after 80 h at 340 °C decomposed, according to chemical
analysis of the liquid phase, by less than one percent, and the sample of MDM appeared
un-decomposed after eighty hours at 350 °C. In spite of this, the sub-atmospheric vapour
pressures, for both the samples, showed significant deviation from the reference curves, due
to the important contribution of the non-condensable gases (mainly methane and carbon
dioxide) produced,albeit in minimal quantities. Therefore, the sub-atmospheric vapour
pressure variations are highly sensitive and could be too restrictive for the evaluation of
the maximum operating temperatures of assumed working fluids.
Finally, according to [36], a sample of MM at 360 °C, in stainless steel, at 25 bar, in 72 h
decomposed by approximately 4.6% (on a molar basis), at 300 °C. At a pressure of 17 bar,
in the same time, the molar decomposition was 3.97%, with a mean degradation rate of
approximately 38 × 10−3 mol/h—a result that does not seem to be consistent with that
reported in [33].
To conclude, for siloxanes, some results relating to their thermal stability are available
in the literature, but some of these seem inconsistent with each other due to the different
approaches used. A chemical analysis of the products is always useful, but there are too
many variables that affect thermochemical stability. A general approach to the problem, that
could at minimum be used for a first selection among different fluids would, in our opinion,
be useful, both for siloxane and all other fluids potentially usable in Rankine engines.
In the following, we describe two different experimental approaches and we present
some results related to some simple siloxanes.

2.1. The Differential Scanning Calorimeter

The general objective of thermal screening of chemicals and mixtures is to identify
whether the sample can undergo an exothermic process and the temperature range of
its occurrence, which provides a preliminary indication of potential chemical reaction
hazards. Calorimeters for thermal screening are available from various producers in
different specifications and with different sensitivity. The same exothermic effect can be
detected at different temperatures depending on the sensibility of the calorimeter used.
 Energies 2022, 15, 3498 5 of 20

DSC directly measures the heat flow and the resulting thermal effect (endo- or exo-thermic)
can be integrated to obtain the enthalpy of the transition. In a typical experiment, a small
amount of a sample (2 mg to 5 mg) is placed in a pressure resistant metal container and
is heated at a constant rate (5 K min−1 ) in the temperature range of 30 °C to 280 °C (for a
stainless steel container, with a viton sealing o-ring) or of 30 °C to 500 °C (for a gold-plated
stainless steel container without an o-ring). The closed high-pressure containers are used
to suppress/limit vaporisation and keep volatile decomposition products contained, which
may contribute to further decomposition.
When the analysed material is closed in the container, the thermal behaviour strongly
depends on the atmosphere present inside the pan; it is not important which gas type
flows in the furnace but the atmosphere inside the crucible is important. Generally samples
are enclosed in the pan, including the air present in the laboratory, inside the crucible.
Exothermic effects in this situation can be generated by oxidation of the sample and not
by thermal decomposition. In these sets of experiments, crucibles (made of stainless steel
and gold-plated stainless steel) were closed and sealed in both air and in an inert (N2 )
atmosphere, using a special apparatus to distinguish the effects due to the reaction of the
sample with the gas (such as oxidation) and decomposition effects due to the thermal
instability of the sample [37].
In Figure 1, as an example, the resulting diagram for MM samples in a gold-plated
stainless steel container in an atmosphere of nitrogen is reported.
The samples were found to be substantially stable in stainless steel (both in air and in
Energies 2022, 1, 0 nitrogen) at least up to 280 °C and in gold up to 500 °C (in nitrogen). Similar results were6 of 22
obtained for MDM and D4.

Figure 1. ResultsFigure Results

of DSC for1.MM ofa DSC
samples in for stainless
gold-plated MM samples in aingold-plated
steel container, stainless
a nitrogen atmosphere. steel container, in a nitrogen
atmosphere.

2.2. Variation in the Normal Boiling Temperature

Following the procedure described in [34,35], a sample of hexamethyldisiloxane was
loaded, after a first conditioning of its internal surface, in a stainless steel cylinder, and,
after an acceptable degassing, varying the thermal bath temperature, a reference vapour
curve was obtained. In Figure 2, the reference vapour pressure for a sample of 29 g of
hexamethyldisiloxane is shown. The estimated uncertainties of the measured pressures
Energies 2022, 15, 3498 6 of 20

and temperatures were about 2 mbar and 1 °C, respectively. In Figure 2, for comparison,
the values of vapour pressures calculated by Aspen Plus© v9.0 are reported.

Figure 2. Vapour pressure of hexamethyldisiloxane (MM) as a function of temperature. The continu-

ous line is from Aspen Plus© v.9.0; the open circles are from our measured values.

The sample was placed repeatedly, for one hundred hours each time, in a muffle
furnace at increasing test temperatures. Between each successive test the vapour pressure
of the sample was measured.
In [35], the values of the sub-atmospheric vapour pressure, after each test, were
compared with reference values (at the same temperatures) and the differences, correlated to
the fraction of decomposed fluid, were assumed to represent an index of decomposition [30].
However, the methods followed in [30,35], appeared to overestimate the actual
decomposition, as minimal degradation of the fluid produced non-condensable gases with
significant over-pressure effects [34].
Therefore, we decided, after every temperature test, to consider only the variations in
the vapour pressure near the atmospheric value, to estimate the variation of the normal
boiling temperature and assume it represented an index of decomposition of the fluid. In
this way, the misleading effects of the non-condensable gases were reduced. Only three
values of vapour pressure were selected to estimate the normal boiling temperature (see
Figure 3), and this, together with a relatively high temperature uncertainty (about one
Celsius degree), unfortunately, introduced high uncertainties u( TB ) in its calculated values
(see Figure 4 and Table 2), due to the high u( B) and u( A) on the coefficients B and A of the
used equation
B
ln P = A + (1)
T
From Equation (1), the normal boiling temperature can be estimated by

B
TB = (2)
ln P − A

with a general uncertainty u( TB ) equal to

q
u( TB ) = (dTB /dB × u( B))2 + (dTB /dA × u( A))2 + (dTB /dP × u( P))2 (3)
Energies 2022, 15, 3498 7 of 20

in which, u( B) and u( A) are the uncertainties of the coefficients B and A, respectively, and
u( P) is the uncertainty of the measured value of the pressure
Table 2 reports the values of the coefficients A and B after each test temperature, while
Figure 3 and 4 show the resulting vapour pressure trends, and the corresponding values of
TB , respectively.
In Figure 3, the variation in the slope of the vapour pressure lines is evident, and,
despite the high uncertainties, in Figure 4, a significant variation in the temperature TB , can
be seen at 450 °C. Figure 5 shows the confidence index of the variations of the coefficient B
in the Equation (1); for the test temperature of 450 °C, the variation ∆B = B − Bre f results
were significantly high, indicating a clear alteration in the fluid sample analysed. The
parameter B has a direct physical meaning because it is also closely related to the heat of
evaporation according to the Clausius–Clapeyron rule.

Table 2. Coefficients A and B of Equation (1) after the keeping of the sample of MM at different test
temperatures, each time for one hundred hours.

Test Temperature (◦ C) A u( A) B u( B)
Reference 10.9653 0.78659 −4125.8982 293.2008
250 10.8103 0.7591 −4053.0637 285.3927
300 11.3394 0.75912 −4253.3055 284.539
350 10.1633 0.69293 −3825.6393 254.3471
400 10.0917 0.71663 −3776.8606 269.722
450 8.2482 0.57604 −3016.8684 215.1247

Figure 3. Vapour pressure for hexamethyldisiloxane (MM) near the ambient pressure after the fluid
sample remained at three different temperatures for one hundred hours each time.
Energies 2022, 15, 3498 8 of 20

Figure 4. Normal boiling temperatures of a sample of hexamethyldisiloxane (MM) after it remained

at different temperatures for one hundred hours each time.

Figure 5. Relative variations in the B coefficient in Equation (1) for a sample of hexamethyldisiloxane
(MM) after its keeping at different temperatures for one hundred hours each time.

In the case considered here, a temperature in the range 350 °C to 400 °C can be consid-
ered to be a limit working temperature value for hexamethyldisiloxane (without significant
contamination, in AISI 304), a result which is in accordance with the conclusion in [34].
Some other papers and publications suggest maximum working temperatures for siloxanes
of 400 °C to 425 °C. On the other hand, according to [38], samples of hexamethyldisiloxane
in low carbon steel with air and probable humidity traces, decomposed substantially after
about 312 h .
It is well known that the presence of contaminants greatly reduces the thermal re-
sistance of working fluids. Clearly, only a chemical analysis can quantify the real degree
of decomposition. However, the approach described here could be useful for a relative
comparison among different pure fluids, and, after appropriate calibration, it could also
provide an indication of the rate of decomposition, which probably is always present, even
at relatively low temperatures.
Energies 2022, 15, 3498 9 of 20

For a fixed temperature, the decomposition could also increase with time in accordance
with the kinetics governing the complex chemical reactions involved in the process. So,
for a rough analysis of the possible effect of time on the decomposition, we considered a
sample of MM at 350 °C for time intervals of 100 h each.
After each time interval, we measured the vapour pressure near the ambient pressure.
In Figure 6, values of the resulting ratio Y = |∆B/u(∆B)| as a function of time are shown.
Despite the high uncertainty in the calculated values, an increase in Y with time is evident,
suggesting an increase in decomposition, occurring significantly after about 300 h, when
Y results were greater than unity. The corresponding variation in the normal boiling
temperature was 1–2 °C, as can be seen in Figure 7.

Figure 6. Relative variations (the confidence index) in the B coefficient in Equation (1) for a sample of
hexamethyldisiloxane (MM) at 350 °C for time intervals of 100 h each.

Figure 7. Vapour pressure for a sample of hexamethyldisiloxane (MM) at 350 °C after time intervals
of 100 h each.
Energies 2022, 15, 3498 10 of 20

The decomposition of the working fluid with time has a generally negative effect on
the thermodynamics of the cycles (see ([39], p. 148) and [40], for example), and, in the worst
situation, it could damage the functioning of key engine components [15]. It is therefore
important to have information on how decomposition proceeds over time.

3. Mixtures of Siloxanes as Working Fluids

In Table 3, there are some thermodynamic properties of the two first simpler methyl-
siloxanes, with a linear molecule (MM, MDM) and with a cyclic structure (D3 and D4 ). Hex-
amethylcyclotrisiloxane (D3 ) has a freezing temperature of 64 °C at atmospheric pressure—
as such, it is not really feasible as a working fluid in Rankine cycles using organic fluids.
The linear methyl-siloxanes with a molecular complexity greater than that of MDM have
a boiling temperature which is excessively high, and, in our opinion, they are also not
attractive as working fluids in Rankine cycles.

Table 3. Some thermodynamic properties of two linear and two cyclic siloxanes.

Compound Tcr a (◦ C) Pcr b (bar) MW c TB d (◦ C) T f e (◦ C) σf

MM (Hexamethyldisiloxane) 245.85 19.2 162.38 100.52 −68.22 29
MDM (Octamethyltrisiloxane) 291.25 14.6 236.53 152.55 −80 43.66
D3 (Hexamethylcyclotrisiloxane) 281.05 17.8 222.46 134 64 33.76
D4 (Octamethylcyclotetrasiloxane) 313.35 13.172 296.62 175 17.58 53.25
a Critical temperature; b Critical pressure; c Molecular weight; d Normal boiling temperature; e Freezing
temperature; f Parameter of molecular complexity: σ = (dS/dT )0.7Tcr × Tcr /R, with the derivative evaluated on
the dew line, [39], p. 109.

Generally speaking, the molecular complexity of methylsiloxanes is very high and

so is the parameter σ, as reported in Table 3. As a consequence, the slope of the saturated
vapour line in a thermodynamic T-S diagram for these fluids is largely positive. On the
other hand, the cooling during the expansion is relatively small, and, consequently, the
thermal power recovered (in the recuperator) has to be high in comparison to the produced
net power.
A second thermodynamic drawback is the typical high normal boiling temperature of
methylsiloxanes, which implies high volumetric expansion ratios that, in turn, require two
or three stage turbines, notwithstanding the low specific expansion work.
Nonetheless, as is well known, MM and MDM, owing to their low toxicity and low
flammability, are frequently used as working fluids in Rankine cycles with an electric power
size of about one MW.
Figure 8 shows the vapour pressure curves for MM, MDM and D4 . At a pressure of
0.05 bar, a practical reasonable minimum limiting value for the condensing pressure, the
corresponding condensation temperatures are reported in Figure: 22 °C for MM; 65 °C and
84 °C for MDM and D4 , respectively. Thus, cycles with MDM or D4 are normally adopted
in cogenerative applications (or CHP plants).
Lately, many papers have investigated the use of non-azeotropic mixtures instead of
pure fluids as working fluids in Rankine cycles. The potential advantages of the use of non-
azeotropic mixtures are well known; the temperature “glides” (a continuous temperature
variation) in evaporation (which is useful when the heat source is of variable temperature
and when the required evaporation thermal power is a sensible fraction of the total input
cycle thermal power) and in condensation.
The condensation “glide” could be useful when, in cogenerative systems, the max-
imum temperature of the cooling water and a minimum internal temperature approach
are fixed.
Among the disadvantages of the use of mixtures are their heat transfer coefficients
during evaporation and condensation that, generally, are lower than that of the pure
fluids [41,42].
Energies 2022, 15, 3498 11 of 20

Figure 8. Vapour pressures curves for some siloxanes. From Aspen Plus© v.9.0.

For example, in [20], the authors analysed the performances of mixtures of MM and
MDM in Rankine cycles and estimated increases of 1 to 14 percent in the required heat
transfer areas of the evaporator, according to the mixture composition, against obtaining
an increase of only 1 to 2 points in the exergetic efficiency in a CHP configuration.
In [43], the authors developed some performance evaluations for a hybrid solar-
biomass plant in Ottana (Italy). Siloxane mixtures of MM and MDM were considered and
compared with the use of pure MM. According to the authors, the net power and the annual
net energy increased by about 1 to 2 percent and between 2 to 5 percent, respectively, but
with an appreciable increase also in the required heat transfer surfaces (18 to 21 percent).
In [44], the authors, taking as a reference case a CHP plant using MDM as the working
fluid, considered many binary (and some ternary) mixtures of linear (from MM to MD6 M)
and cyclic (from D3 to D6 ) methylsiloxane, obtaining, in the best case, an increase in
electrical efficiency from 18.7% to 20.6% (about two points).
From the literature data, in the case of siloxanes, the use of mixtures instead of pure
fluids generally leads to a benefit in the conversion efficiencies, but with limited margins.
On the other hand, the concrete possibility of a significant increase in the overall cost of the
plant must be considered.
However, it is difficult to directly compare the results of the literature data with
each other given the different assumptions for the design parameters and the calculation
hypotheses. After a brief discussion of the approach followed here to evaluate the required
thermodynamic properties, in the next sections, we will develop some further simple cycle
thermodynamic analyses.

3.1. Evaluation of the Thermodynamic Properties of Some Siloxane Mixtures

From the data available in Aspen Plus© v.9.0 (from the NIST data bank), the binary
interaction coefficients k1,2 for the simple Peng–Robinson equation of state were evaluated
for mixtures of MM and MDM, and for mixtures of MM and D4 . The regressed values
and their standard deviation are shown in Figure 9, with some results of the calculated
vapour-liquid equilibria at different pressures. The temperature “glides” were lower for
mixtures of MM and MDM than the corresponding values for mixtures of MM and D4 ,
and, in both cases, the temperature differences significantly reduced with pressure.
Energies 2022, 15, 3498 12 of 20

(a)

(b)
Figure 9. Vapour-liquid equilibrium lines for mixtures of siloxanes. (a) T-xy diagram for MM/MDM
at different pressures. (b) T-xy diagram for MM/D4 mixtures.

In Figure 10, as an indicative example, some P-T envelopes and the critical locus for
MM and D4 mixtures are reported.
Energies 2022, 15, 3498 13 of 20

Figure 10. Pressure-temperature envelopes and critical locus for mixtures of MM/D4 at different
molar composition.

Both the mixtures seem rather “ideal”, with continuous and regular variations of the
critical point with the composition. However, for any mixture, it is possible to obtain a
continuous variation of the condensation pressure, for example, by varying the composi-
tion. This, generally, could itself provide a beneficial degree of freedom in the choice of
the mixture.
In Figure 11, for example, for a dew temperature of 60 °C, the variations in the cor-
responding pressure and in the temperature “glide” with the composition are reported
for the two mixtures considered. The maximum temperature difference between the dew
and the bubble point at a molar composition of 0.5 for both the mixtures and the value for
MM + D4 was about double the corresponding value for the mixture MM + MDM.

(a)

Figure 11. Cont.

Energies 2022, 15, 3498 14 of 20

(b)

Figure 11. (a) Variation in the dew pressure and (b) variation in the temperature “glide” for two
mixtures of siloxanes as a function of their molar composition. The dew temperature is fixed at 60 °C.

Fixing, for example, a functional pressure of 0.05 bar, at a dew temperature of 60 °C,
this may be obtained with a molar composition of about z1 = 0.25 and of about z1 = 0.75
for mixtures of MM(1) + MDM(2) and MM(1) + D4 (2), respectively.
A comparison among bubble points, evaluated with the assumed thermodynamic
model and the experimental values reported in [18], was carried out. Unfortunately, in the
cited reference, the experimental results were reported only in a graphical form and the
comparison can only be qualitative. Nonetheless, the results were completely acceptable.

3.2. The Performances of Siloxane Mixtures in Thermodynamic Cycles

With reference to the mixtures discussed in Section 3.1, we developed a thermody-
namic analysis for Rankine cycles by recovering heat from a hot oil source (Therminol
66, [45]) at 300 °C considering a mass flow rate of one kilogram per second. The calculation
assumptions are in Table 4. The typical cycle scheme assumed is provided in Figure 12.
At the condenser, we assumed cold water was available at 45 °C to be heated up to
55 °C, temperature levels which are compatible with the planned last generation district
heating systems [46].
As constraints, we assumed a minimum condensation pressure of 0.05 bar, in accor-
dance with the design indications of typical commercial available biomass boilers (see, for
example, [15,44]) and a temperature of the thermal oil after cooling equal to 250 °C.

Table 4. Design parameters assumed for the thermodynamic cycle calculations.

Minimum internal temperature approach in the recuperator: 20 °C

Minimum internal temperature approach in the heater: 20 °C
Minimum internal temperature approach in the condenser: 5 °C
Temperature increase in the cooling water: 10 °C
Water inlet temperature: 45 °C
Oil hot temperature: 300 °C
Mass flow rate of the oil: 1 kg s−1
Superheating degree in the heater: 5 °C
Pressure drops: none
(Isentropic) Turbine efficiency: 0.85
Pump efficiency: 0.8
Energies 2022, 15, 3498 15 of 20

Figure 12. The considered thermodynamic cycle scheme. The corresponding T − Q̇ diagrams for two
cases are reported in Figure 14.

From Figure 13a, pure thermodynamic cycles using pure MM tended to excessively
cool the hot source. Only cycles with pure D4 , or with mixtures with a molar fraction of
MM lower than 0.25, guaranteed a minimum oil temperature of 250 °C. On the other hand,
according to Table 5, only a molar composition z1 = 0.25 provided a condensation pressure
equal to about 0.05 bar.
With respect to MM(1) + MDM(2), only a mixture with a molar composition z1 = 0.2
provided the required minimum hot oil temperature and an adequate condensation pres-
sure (see Figure 13b and Table 5).
For the mixtures MM(1) + D4 (2) (z1 = 0.25) and for MM(1) + MDM(2) (z1 = 0.2),
the calculated efficiencies of the corresponding thermodynamic cycles were 0.253 and
Energies 2022, 15, 3498 16 of 20

0.264, respectively (Table 5). The two cycles, in a plane temperature–power, are shown in
Figure 14.
The better efficiency of the mixture MM(1) + MDM(2) (z1 = 0.2) was substantially
due to a lower LMTD at the condenser, about 9.5 °C, sixty percent of the corresponding
value for the mixture MM(1) + D4 (2) (z1 = 0.25) (Table 5). On the other hand, as a
consequence, the corresponding condenser U A results were about 1.73 times greater.
Some results related to the turbine are shown in Table 6, for a reference isentropic
power of one MW. The isentropic enthalpy drops were relatively low in both cases, but the
volumetric expansion ratios results were high, 251 and 344 for the mixture MM(1) + D4 (2)
and for MM(1) + MDM(2), respectively. The difference was substantially due to the higher
evaporation pressure of MM(1) + MDM(2) (12.5 bar) with respect to that of MM(1) + D4 (2)
(9 bar).
These high volumetric expansion ratios require at least two to three axial turbine
stages to obtain high isentropic expansion efficiencies. The lower isentropic enthalpy drop
for MM(1) + D4 (2) was a consequence of the greater molecular weight of D4 compared to
that of MDM (see Table 3).

(a)

(b)

Figure 13. Thermal oil outlet temperature from the heat recovery heat exchanger as a function of the
evaporation temperature and for different mixture compositions, for (a) a mixture of MM and D4 and
(b) a binary mixture of MM and MDM.
Energies 2022, 15, 3498 17 of 20

(a)

(b)

Figure 14. Two siloxane mixtures cycles, in the temperature - power exchanged plane, at optimal
compositions and evaporation pressures. The design cycle parameters are shown in Table 4. In
accordance with the simpler cycle configuration usually adopted, 1–2 represents the liquid compres-
sion, 2–3/5–6 the recuperator, 3–4 the pre-heating and the boiling, 4–5 the expansion in turbine, and
6–1 the condensation process. (a) for a mixture of MM(1) + D4 (2) at z1 = 0.25; (b) for a mixture of
MM(1) + MDM(2) at z1 = 0.2.

Table 5. Some cycle results. Hot oil mass flow rate: one kilo per second.

Working Cycle Condensation Evaporation LMT D a U A/Ẇ b

Fluid Efficiency (%) Pressure (mbar) Pressure (bar) Condenser (◦ C) Condenser (◦ C−1 )
MM(1) + D4 (2)
25.34 49.04 9.0 15.71 0.187
z1 = 0.25 (molar fraction)
MM(1) + MDM(2)
26.42 56.75 12.5 9.46 0.295
z1 = 0.2 (molar fraction)
aAverage logarithmic mean temperature difference for the whole condenser; b Calculated total U × A, the product
of overall heat transfer coefficient U and heat transfer area A for the condenser per unit of useful power.
Energies 2022, 15, 3498 18 of 20

Table 6. Some turbine results. A comparison. Isentropic power one MW.

Working Volumetric Isentropic Isentropic Size

Fluid Expansion Ratio a Enthalpy Drop (kJ kg−1 ) Parameter b (m)
MM(1) + D4 (2)
251.12 79.61 0.3752
z1 = 0.25 (molar fraction)
MM(1) + MDM(2)
344.47 94.65 0.3294
z1 = 0.2 (molar fraction)
√
a V̇out,S V̇out,S
VFR = , [47]; b SP = , [47].
V̇in ∆HS0.25

4. Conclusions
From the previous discussion, regarding thermal stability, it follows that, in an inert
environment, the thermochemical stability of the fluid samples analysed is naturally very
high—at least up to 500 °C for MM in a gold-plated stainless steel container, with a nitrogen
atmosphere. A method such as the differential scanning calorimeter could be a valid
option for a first screening, as long as it is possible to use metal containers in steel even at
high temperatures, with or without suitable sealing o-rings.
The measurement of the vapour pressure, for instance around the atmospheric value,
for pure fluids, provided a good indication of the thermal stability of the working fluid
candidate. However, in order to substantially improve the results, an accuracy in the
measurement of temperatures at least one order of magnitude higher than that of our
measuring system is required.
In any case, the vapour pressure measure was reconfirmed as a valid approach to
analysing the thermo-chemical decomposition. For hexamethyldisiloxane (MM), a limit
temperature of thermal stability of 300 °C to 350 °C was reconfirmed, in the absence of
specific contaminants. However, at 350 °C the decomposition significantly progressed
over time. A detailed analysis was conducted here only for MM, but the results are easily
extendable to MDM as well, given its similar molecular structure.
The approach described here could be applied to any (pure) fluid. For mixtures of
fluids, the measurement of vapour pressure could be replaced by isochore measurements.
With respect to the thermodynamics of the mixtures of polysiloxanes, in the cases
considered, according to the assumptions made and to the selected thermodynamic models,
the results suggest that:
• from a strictly thermodynamic point of view, for the considered mixtures, there
was no significant improvement in the cycle efficiency compared to a pure fluid (for
example, we obtained a value of about 25–26 per cent, the same as for pure MDM),
On the other hand, the modest temperature “glides” obtained in condensation, closely
follows the relatively low heating (10 °C) of the water used for the condensation.
• The isobaric temperature variations during a change of phase (with fixed composition
of the mixture) generally decreased with increase in the bubble temperature. So, if
the temperature “glide” in condensation is low, the corresponding lower “glide” in
evaporation may result in a negligible contribution to the cooling of the heat source.
For the cases considered, good performances were obtained with a condensing pres-
sure of about 50 mbar to 60 mbar. With pure MDM, for example, at the assumed con-
densation temperature, the minimum pressure would be only 37 mbar, which could be
problematic for the design of the engine.
With mixtures, the design of the heat exchangers (in particular of the condenser) can be
critical, both from the point of view of their geometrical configuration, and, in general, because
of the limited knowledge of accurate values of the relevant necessary transport properties.
In the case of the mixture MM(1) + MDM(2), with z1 = 0.2, for example, the values of
the overall U A for the condenser per unit of useful power results were the same as that of
pure MDM, i.e., about 0.3 °C−1 . Therefore, the correct value of U (the overall heat transfer
coefficient) becomes crucial for the correct evaluation of the surface of the heat exchanger.
Energies 2022, 15, 3498 19 of 20

Finally, in the case of mixtures, it is possible by varying their composition to modify,

to some extent, the design pressure, the critical point and the temperature “glide”, which,
in principle, would enable adaptation of the engine to different power sizes.

Author Contributions: Conceptualization, C.M.I.; methodology, C.M.I., G.D.M., P.I., L.A., M.C., A.L.
and A.M.; writing—original draft preparation, C.M.I.; writing—review and editing, G.D.M., P.I. and
A.L.; supervision, C.M.I. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations, Symbols and Subscripts

P pressure (bar)
T temperature (°C or K)
TB normal boiling temperature (°C or K)
UA the product of overall heat transfer coefficient U and the heat transfer area A (W °C−1 )
u( X ) measurement uncertainty for the physical quantity X (dimensions of X)
V̇in inlet volumetric flow rate (m3 s−1 )
V̇out, S outlet isentropic volumetric flow rate (m3 s−1 )
z molar fraction
∆HS specific isentropic enthalpy drop (J kg−1 )

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