HEAT CAPACITY OF OXIDE SCALE IN THE RANGE FROM 0 ºC TO 1300 ºC: GENERALIZED ESTIMATES WITH

ACCOUNT FOR MOVABILITY OF PHASE TRANSITIONS

Emmanuil Beygelzimer1, Yan Beygelzimer2

1
OMD-Engineering LLC, Dnipro, Ukraine
2
Donetsk Institute for Physics and Engineering named after A.A. Galkin, National Academy of Sciences of Ukraine, Kyiv, Ukraine

*Corresponding author: [email protected], tel.: +380 (50) 368-63-42, 49000, Volodymyr Monomakh Street, 6 of. 303, Dnipro, Ukraine.

ABSTRACT

The known data on the heat capacity of magnetite (Fe3O4), hematite (Fe2O3) and iron (Fe) at different temperatures are approximated by formulas containing phase
transition temperatures as varying parameters. This allows to take into account the effect of phase transition shifts, for example, due to impurities, lattice defects, grain
sizes or high cooling rates. For this purpose, the entire target temperature range from 0 to 1300 ºC is divided by phase transition temperatures into separate intervals. The
conjugation of the approximating functions between the intervals at the magnetic transition point is performed without a gap, and at the point of polymorphic
transformation (α-Fe ↔ γ-Fe) - with a finite gap of heat capacity values. For wüstite Fe1-хO, which does not experience phase transformations, the temperature dependence
of the heat capacity is approximated by a single smooth function. In combination with previously obtained formulas for the density of iron oxides and iron the proposed
approximations allow us to estimate the specific mass heat capacity of oxide scale depending of its structural composition and temperature. By model calculations it is
shown that at temperatures of 200 °C and 900 °C specific mass heat capacity of oxide scale practically does not depend on the percentage of its individual components
and is approximately 750 and 850 J·kg-1K-1, respectively. At a temperature of about 575 °C, on the contrary, actually possible variations in the composition of oxide scale
can lead to a change in its specific heat capacity from 850 to 1150 J·kg-1 K-1. The obtained dependencies are recommended for use in mathematical modeling of production
and processing of steel products in the presence of oxide scale on their surface.

Keywords: heat capacity; wüstite; magnetite; hematite; oxide scale; Curie point

INTRODUCTION When the data in the primary source are presented only as enthalpy values, the
authors recalculated them into values of specific mass heat capacity c(T)
The authors continues the description of engineering methods proposed by them to [J·kg-1K-1] by the formula:
estimate in the range from 0 to 1300 °C the thermophysical characteristics of oxide 𝐻𝑖+1 − 𝐻𝑖
scale, consisting, in general, of wüstite Fe1-хO (x ≈ 0.05...0.15), magnetite Fe3O4, 𝑐(𝑇) = (2)
hematite Fe2O3, metallic iron, oxides of alloying elements and voids. The thermal 𝑇𝑖+1 − 𝑇𝑖
expansion [1] and density [2] were considered earlier. This report presents results where Ti and Ti+1, Hi and Hi+1 are tabulated values of temperature [K] and enthalpy
on the true isobaric specific mass heat capacity c [J·kg-1K-1], which is defined as [J·kg-1] from the primary source, with T = (Ti + Ti+1) / 2.
the value:
1 𝑑𝑄 RESULTS AND DISCUSSION
𝑐(𝑇) = ∙ (1)
𝑚 𝑑𝑇
Magnetite Fe3O4
where dQ [J] is the small amount of heat needed to change the temperature of a
substance of mass m [kg] by a small amount of degrees dT [K] at constant pressure. Empirical data on the specific mass heat capacity of magnetite (Fig. 1) are
For brevity, the parameter c(T), the meaning of which is defined by expression (1), approximated separately in two temperature intervals: before and after the Curie
will be hereinafter referred to simply as the specific mass heat capacity at point. The proposed formulas are summarized in Table 1 and contain the Curie
temperature T. temperature (T1) as a formal parameter. The graphs in Fig. 2 demonstrate the
response of these formulas to varying the Curie point in the possible range of 823-
METHODS 900 K (550-627 °C) [1]. For example, at 873 K (600 °C), the calculated value of
the specific mass heat capacity of magnetite, is 947, 1024 or 1228 J·kg-1 K-1 for
Known experimental and reference data on the heat capacity of the considered Curie temperature 823, 848 or 900 K, respectively. In other words, for different
substances are approximated by the general methods [1], which allows to obtain values of the Curie point, the specific mass heat capacity of magnetite cFe3O4 at the
mutually consistent temperature dependences of different thermophysical specified design temperature of 873 K may differ by 281 J·kg-1 K-1, i.e., by 27%
parameters. The basis of the methods consists in the use of reference points, relative to its value at the base value of 848 K. The results of similar evaluations
through which the graph of the approximating function should pass. They include for different design temperatures in the range of 150 K (±75 K from the Curie basic
nodal points near the boundaries of the target temperature range (i.e., around 0 °С temperature) are shown in Table 2. According to these evaluations, the thermal
and 1300 °С) and critical points where there is a sharp change in properties. All expansion of magnetite can vary by as much as 45% due to changes in the Curie
coordinates (temperature and properties) of the reference points are set as point over its real range of variation. This example demonstrates the possibility of
constants, except for the temperatures of the critical points, which are included in using critical temperatures (in this case, the Curie point of magnetite) as adaptation
the approximating functions as varying parameters. Accordingly, other parameters parameters in mathematical simulation of processes in the presence of oxide scale
of these functions become dependent on the given values of critical temperatures. on the surface of products.
Such an approach makes it possible to coordinate the values of critical Fig.2 also explains the approach to selecting functions passing through
temperatures when calculating the heat capacity and other thermophysical independently selected nodal points with coordinates (T0, c0) and (T2, c2) and the
parameters, as well as to take into account the influence of a possible shift of critical point with coordinates (T1, c1). The type of the approximating function and
critical points in specific conditions. The ranges of movability of critical values of its constants in each interval are selected based on the location of
temperatures for above mentioned iron oxides and pure iron are summarized in [1]. empirical points in the individual series. At the boundary between the intervals, the
Within each interval bounded by the critical temperatures, the specific mass heat calculated graphs form a sharp peak in accordance with the exponential character
capacity is described by a smooth function c(T). As a reasonable simplification for of the heat capacity change at the magnetic transition point [3-5].
engineering calculations and taking into account the works [3-5], the conjugation
of the functions c(T) at the point of magnetic transition is made without a gap, and
at the point of polymorphous transformation - with a finite gap of heat capacity
values on different sides from the critical temperature.

DOI: 1
Table 2. Calculated effect of the Curie point of magnetite on its heat capacity At the basic value of Curie point for magnetite T1 = 848 K (575 ºC) the formulas
Design cFe3O4 [J·kg-1K-1] at different T1 [K] ([ºC]) Range from Table 1 are converted to a particular form (cFe3O4 in [J·kg-1K-1], T in [K], the
temperature (in % of base corresponding graph is shown in Fig. 1):
[K] ([ºC]) 823 (550) 848 (575) 900 (627) - in italics)  in the range of 273 K ≤ T ≤ 848 K
773 (500) 1151 1093 1017 12%
𝑐Fe3O4 = −76.494 + 75.249 ∙ 𝑇 0.4 + 310𝑒 −0.016(848−𝑇) (3)
848 (575) 1024 1350 1149 24%
 in the range of 848 K < T ≤ 1573 K
873 (600) 947 1024 1228 27%
900 (627) 924 944 1350 45% 𝑐Fe3O4 = 814.84 + 9.0001 ∙ 107 ∙ 𝑇 −2 + 410𝑒 −0.06(𝑇−848) (4)
923 (650) 916 925 1037 13%

Table 1. Formulas for calculating the specific mass heat capacity of Fe 3O4 (T1 [K] is the Curie point of magnetite)
Temperature interval [K] 273 ≤ 𝑇 ≤ 𝑇1

Approximating function [J·kg-1K-1] 𝑐Fe3O4 (𝑇) = 𝑎0 + 𝑎1 𝑇 𝑛 + 𝑎3 𝑒 −𝑎4 (𝑇1 −𝑇)

Constants 𝒏 = 0.4 𝑎3 = 310 𝑎4 = 0.016

Coordinates of the reference points T0 = 200 K c0 = 550 J·kg K -1 -1
c1 = 1350 J·kg-1K-1

𝑐1 − 𝑐0 − 𝑎3 (1 − 𝑒 −𝑎4 (𝑇1−𝑇0 ) )
𝑎1 =
Coefficients to be calculated 𝑇1𝑛 − 𝑇0𝑛

𝑎0 = 𝑐1 − 𝑎1 𝑇1𝑛 − 𝑎3

Temperature interval [K] 𝑇1 < 𝑇 ≤ 1573

Approximating function [J·kg-1K-1] 𝑐Fe3O4 (𝑇) = 𝑏0 + 𝑏1 𝑇 𝑝 + 𝑏3 𝑒 −𝑏4 (𝑇−𝑇1 )

Constants p = -2 b3 = 410 b4 = 0.06

Coordinates of the reference points T2 = 1600 K c2 = 850 J·kg-1K-1

𝑐1 − 𝑐2 − 𝑏3 (1 − 𝑒 −𝑏4 (𝑇2 −𝑇1) )

𝑏1 = 𝑝 𝑝
Coefficients to be calculated 𝑇1 − 𝑇2
𝑝
𝑏0 = 𝑐1 − 𝑏1 𝑇1 − 𝑏3

Fig. 1. Specific mass heat capacity of magnetite according to the empirical data Fig. 2. Graphs of specific mass heat capacity of magnetite Fe 3O4 calculated
of Coughlin [6] (recalculated by the authors of this article by enthalpy values), according to formulas of Table 1 for different values of Curie point T1: 1 – 848 К
Grosu (two methods) [7], Grǿnvold [4], Hemingway [8], Robie [9], Parks [10, p. (575 °C); 2 – 823 К (550 °C); 3 – 900 К (627 °C).
114, set 1], Millar [10, p. 114, set 2] and the generalized recommendations of
Touloukian [11, p. 367]. Approx - graph by formulas (3)-(4).

2
Wüstite Fe1-xO
𝑐Fe2O3 = −31639 + 30499 ∙ 𝑇 0.01 + 145𝑒 −0.02(950−𝑇) (6)
The known data on the specific mass heat capacity of wüstite are shown in Fig. 3.  in the range of 950 K < T ≤ 1573 K
In the entire range from 0 to 1300 °С the true specific heat capacity of wüstite
increases monotonically, therefore, in contrast to approximations of thermal 𝑐Fe2O3 = 779.25 + 3.2687 ∙ 𝑇 0.5 + 290𝑒 −0.04(𝑇−950) (7)
expansion and thermal conductivity, there is no reason to divide this temperature
range by the boundary of thermodynamic stability of Fe 1-xO (Chaudron point). The Table 4. Calculated effect of the Curie point of hematite on its heat capacity
dependence of the specific mass heat capacity [J·kg-1·K-1] of wüstite on the
Design cFe2O3 [J·kg-1K-1] at different T1 [K] ([ºC]) Range
temperature T [K] is described by one formula in the whole range of 273 K ≤ T ≤ temperature (in % of base
1573 K: 943 (670) 950 (677) 998 (725)
[K] ([ºC]) - in italics)
𝑐FeO = 548.17 + 8.7958 ∙ 𝑇 0.5 − 556.96 ∙ 𝑇 −2 (5) 875 (602) 1038 1031 996 4%
943 (670) 1170 1149 1055 10%
950 (677) 1100 1170 1065 9%
998 (725) 915 925 1170 28%
1025 (752) 895 898 980 9%

Fig. 3. Specific mass heat capacity of wüstite according to reference data of Ravdel
[12, p. 77], Samsonov [13, p. 109], Mishchenko [14, p. 14], Li [15], enthalpy
measurements of White [16] and Coughlin [6] (enthalpy values were recalculated
into heat capacity by the authors), experimental data of Todd [10, p. 107, set 1],
Stølen [17], Kant [18] and generalized recommendations by Touloukian [11, p.
361]. The graph calculated by formula (5) is also shown (denoted as “Approx”).
Fig. 4. Specific mass heat capacity of hematite according to reference data of
Hematite Fe2O3 Mishchenko [14, p. 14], Kelley [20, p. 95], Robie [9, p. 166] and the empirical data
of Gronvold [19], Parks [10, p. 110, sets 1 and 5], Coughlin [6] (in the latter case
When describing hematite heat capacity data (see Fig. 4) only one critical state, the authors of this article recalculated enthalpy values into specific heat capacity
namely, magnetic transformation in the region of 950 K (677 ºC), was taken into by (2)) and generalized recommendations of Touloukian [11, p. 366]. For
account. The second anomaly of heat capacity of Fe 2O3 at 1050 K noted in [6, p. comparison, the graph calculated by formulas (6)-(7) is given (denoted as
3893] was not considered, because it was not identified in later studies [19]. “Approx”).
Table 3 shows the approximating formulas in general form with the Curie
temperature T1 as a varying parameter. The sensitivity of the specific mass heat
capacity of hematite to the movability of the Curie point can be estimated from Iron Fe
Table 4, which shows the values of cFe2O3, for some temperatures, calculated
from the formulas of Table 3 at different values of the Curie point T1. It can be Data from different authors on the specific mass heat capacity of iron cFe are shown
seen that at the same design temperature, the value of the specific mass heat in Fig. 5. Approximating formulas to estimate cFe [J·kg-1K-1] are given in Table 5
capacity of hematite can vary by up to 28%, depending on the position of the and contain the following parameters: T [K] is the design temperature; T1 [K] is
Curie point within its mobility range. the Curie point of iron; T2 [K] is the temperature of polymorphic γ↔α
At the basic value for the Curie point of hematite T1 = 950 K (677 ºC), the formulas transformation. A prerequisite for the application of these formulas is the ratio
from Table 3 are reduced to the form (cFe2O3 in [J·kg-1 K-1], T in [K], the graph is T1 < T2.
shown in Fig. 4):
 in the range of 273 K ≤ T ≤ 950 K

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 Table 3: Formulas for calculating the specific mass heat capacity of hematite Fe 2O3 (T1 [K] is the Curie point of hematite)
Temperature interval [K] 273 ≤ 𝑇 ≤ 𝑇1

Approximating function [J·kg-1K-1] 𝑐Fe2O3 = 𝑎0 + 𝑎1 𝑇 𝑛 + 𝑎3 𝑒 −𝑎4 (𝑇1 −𝑇)

Constants n = 0.01 a3 = 145 a4 = 0.02

Coordinates of the reference points T0 = 200 K c0 = 520 J·kg K -1 -1
c1 = 1170 J·kg-1K-1

𝑐1 − 𝑐0 − 𝑎3 (1 − 𝑒 −𝑎4 (𝑇1−𝑇0 ) )
𝑎1 =
Coefficients to be calculated 𝑇1𝑛 − 𝑇0𝑛

𝑎0 = 𝑐1 − 𝑎1 𝑇1𝑛 − 𝑎3

Temperature interval [K] 𝑇1 < 𝑇 ≤ 1573

Approximating function [J·kg-1K-1] 𝑐Fe2O3 = 𝑏0 + 𝑏1 𝑇 𝑝 + 𝑏3 𝑒 −𝑏4(𝑇−𝑇1 )

Constants 𝑝 = 0.5 𝑏3 = 290 𝑏4 = 0.04

Coordinates of the reference points T2 = 1600 K c2 = 910 J·kg-1K-1

𝑐1 − 𝑐2 − 𝑏3 (1 − 𝑒 −𝑏4 (𝑇2 −𝑇1) )

𝑏1 = 𝑝 𝑝
Coefficients to be calculated 𝑇1 − 𝑇2
𝑝
𝑏0 = 𝑐1 − 𝑏1 𝑇1 − 𝑏3

Fig. 5. Specific mass heat capacity of iron cFe according to the experimental data of Pallister [10, p. 102, set 1], McElroy [10, p. 102, set
9], Lehman [10, p. 102, set 6], Lubimov [10, p. 102, set 5], Anderson [10, p. 102, set 12], Awbery [10, p. 102, set 4], Rogace [10, p.
102, set 6], Wallace [10, p. 102, set 8], Rogez [21], Shanks [22], Bendick [23], Ledermann [24], Varchenko [25] and generalized data
from Desai [26, p. 976] and Touloukian [11, p. 292]. “Approx” is the graph of the approximating function (8)-(10).

4
 Table 5. Formulas for calculating the specific mass heat capacity of iron Fe (T1 [K] is the Curie point; T2 [K] is the polymorphic transformation temperature)

Temperature interval [K] 273 ≤ 𝑇 ≤ 𝑇1

Approximating function [J·kg-1K-1] сFe = 𝑎0 + 𝑎1 𝑇 𝑛 + 𝑎2 𝑇 𝑚 + 𝑎3 𝑒 −𝑎4 (𝑇1 −𝑇)

Constants n = 2.7 m = -2.0 a0 = 480 a3 = 580 a4 = 0.045

Coordinates of the reference points T0 = 200 K c0 = 385 J·kg-1K-1 c1 = 1500 J·kg-1K-1

𝑐0 − 𝑣𝑐1 − 𝑎0 (1 − 𝑣) + 𝑎3 (𝑣 − 𝑒 −𝑎4 (𝑇1 −𝑇0) )

𝑎1 =
𝑇1𝑛 (𝑢 − 𝑣)
Coefficients to be calculated
𝑐1 − 𝑎0 − 𝑎1 𝑇1𝑛 − 𝑎3
𝑎2 =
𝑇1𝑚

𝑢 = (𝑇0 ⁄𝑇1 ) 𝑛
Auxiliary parameters
𝑣 = (𝑇0 ⁄𝑇1 )𝑚

Temperature interval [K] 𝑇1 < 𝑇 ≤ 𝑇2

Approximating function [J·kg-1K-1] сFe = 𝑏0 + 𝑏1 𝑇 𝑝 + 𝑏3 𝑒 −𝑏4 (𝑇−𝑇1 )

Constants 𝑝 = 0.12 𝑏0 = 10000 𝑏4 = 0.15

Coordinates of the reference points c2(2) = 716 J·kg K
-1 -1

𝑏0 − 𝑐2(2) − 𝑊(𝑐1 − 𝑏0 )
𝑏1 = 𝑝 𝑝
𝑊𝑇1 − 𝑇2
Coefficients to be calculated
𝑝
𝑏3 = 𝑐1 − 𝑏0 − 𝑏1 𝑇1

Auxiliary parameter 𝑊 = 𝑒 −𝑏4 (𝑇2 −𝑇1)

Temperature interval [K] 𝑇2 < 𝑇 ≤ 1573

Approximating function [J·kg-1K-1] сFe = 𝑑0 + 𝑑1 (𝑇 − 𝑇2 )

Coordinates of the reference points T3 = 1600 K c2(3) = 605 J·kg-1K-1 c3 = 674 J·kg-1K-1
𝑑0 = 𝑐2(3)

Coefficients to be calculated 𝑐3 − 𝑐2(3)

𝑑1 =
𝑇3 − 𝑇2

Fig. 6 and Tables 6 show the data calculated using the formulas from Table 5 to  in the range of 1185 K < T ≤ 1573 K:
estimate the sensitivity of the specific mass heat capacity of iron cFe to variations
in the Curie point T1 and the polymorphic transformation point T2. These data show 𝛼Fe = 23,0 ∙ 10−6 (10)
that at the same design temperature (780 ºC was chosen as an example), the values
of cFe can differ by 20% or more for different combinations of the Curie point and Table 6. Calculated values of specific mass heat capacity of iron cFe [J·kg-1 K-1]
polymorphic transformation temperature within their movability range. In at the design temperature T = 1053 K (780 ºC) for different combinations of the
addition, it should be taken into account that under nonequilibrium conditions, the Curie point T1 and polymorphic transition temperature T2
movability range of the polymorphic transformation temperature can be T1 [K] ([ºC])
significantly greater than that taken into account in the above data. T2 [K] ([ºC])
At basic values T1 = 1043 K (770 ºC) and T2 = 1185 K (912 ºC), the function of the 1032 (759) 1043 (770) 1046 (773)
true CLTE of iron αFe [K-1] versus temperature T [K] is (graph - in Fig. 5): 1183 (910) 872 989 1072
 in the range of 273 K ≤ T ≤ 1043 K:
1185 (912) 874 990 1073
𝛼Fe = (−21 + 14.765 ∙ 𝑇 0,14 − 7.0642 ∙ 𝑒 −0,013(1043−𝑇) ) ∙ 10−6 (8)
1208 (935) 894 1006 1086
 in the range of 1043 K < T ≤ 1185 K:
𝛼Fe = (16.004 − 5.0041 ∙ 𝑒 −0.05(𝑇−1043) ) ∙ 10 −6 (9)

5
 individual components of oxide scale, c1, c2, ... - specific mass heat capacity of the
components; ε1, ε2, ... - mass fraction of the components.
The mass fractions of the components εi are related to their volume fractions ψi by
the following relations (i = 1, 2, ...):
𝜀𝑖 = 𝜁𝑖 𝜓𝑖 (12)
where the volume fractions are understood without taking into account the pores,
i.e.
𝜓1 + 𝜓2 + ⋯ = 1 (13)
and the symbol ζi denotes the relative density of this component as the ratio of its
density ρi to the true (without considering the pores) density of the oxide scale ρsc:
𝜌𝑖
𝜁𝑖 = (14)
𝜌𝑠𝑐
Taking into account (12) and the adopted notations of the scale components,
expression (11) can be written in the form:
𝑐𝑠𝑐 = (𝑐𝜁𝜓) FeO + (𝑐𝜁𝜓) Fe3O4 + (𝑐𝜁𝜓) Fe2O3 + (𝑐𝜁𝜓) Fe + (𝑐𝜁𝜓) 𝑥O (15)
where each summand is the product of the specific mass heat capacity of a given
component by its relative density and volume fraction in the scale (the index xO
stands for the oxide of the alloying element).
The specific mass heat capacity of iron oxides and metallic iron can be calculated
Fig. 6. Graphs for specific mass heat capacity of iron calculated by the formulas by the formulas described above, and the density by the formulas given in [2].
from Table 6 with two different combinations of the Curie point T1 and the
As an example, Fig. 8 shows graphs csc , which are computed by the formula (15)
polymorphic transformation temperature T2: 1 - T1 = 1046 K (773 ºC) and T2 = for four different compositions of oxide scale listed in Tables 7-8. The first three
1183 K (910 ºC); 2 - T1 = 1032 K (759 ºC) and T2 = 1208 K (935 ºC). cases conventionally assume the same component content over the entire
temperature range (which can be considered in the first approximation as
Oxide scale as a whole corresponding to the conditions of rapid cooling), and the fourth case has a variable
content depending on temperature (modeling the conditions of slow cooling with
Fig. 7 compares the temperature dependences of the specific mass heat capacity decomposition of wüstite into an eutectoid mixture of magnetite and metallic iron).
for different structural components of the scale, calculated using the above In all cases of calculation, the oxides of alloying elements in the composition of
formulas for the basic values of critical temperatures. the oxide scale are not taken into account.

Fig. 8. Graphs of temperature dependence of specific mass heat capacity of scale

Fig. 7. Comparison of calculated graphs of specific mass heat capacity of wustite calculated by formula (15) through the corresponding properties of its structural
(Fe1-xO), magnetite (Fe3O4), hematite (Fe2O3) and iron (Fe) as a function of components. Numbers in the curves are numbers of calculated compositions of
temperature. The calculations were performed according to formulas (5), (3)-(4), scale according to Tables 4-5.
(6)-(7) and (8)-(10) respectively
Performed results show that there are two temperature regions in which the value
The specific mass heat capacity of scale as a multicomponent material can be of the specific mass heat capacity of oxide scale practically does not depend on its
defined as: structural composition (in the real range of its change): csc ≈ 750 J·kg-1·K-1 at
∆𝐻 𝑚1 𝑐1 + 𝑚2 𝑐2 + ⋯ 200 °C, and csc ≈ 850 J·kg-1·K-1 at 900 °C. On the other hand, at temperatures
𝑐s𝑐 = = = 𝜀1 𝑐1 + 𝜀2 𝑐2 + ⋯ (11) around 575 °C (the basic value of the Curie temperature of magnetite), the specific
𝑚sc 𝑚sc
mass heat capacity of oxide scale is unstable and can vary from 850 J·kg-1·K-1 to
where msc - mass of a given amount of oxide scale, ∆H - change in heat content of 1150 J·kg-1·K-1, depending on the percentage of its structural components.
this mass when its temperature changes by one degree, m1, m2, ... - masses of

6
In the end, we note that the porosity of the scale has no effect on its specific mass https://arxiv.org/ftp/arxiv/papers/2110/2110.08528.pdf
heat capacity (this is obvious from formula (11), if we consider the pores as a 2. E. Beygelzimer, Y. Beygelzimer. Generalized estimates for the density of
component with zero mass). oxide scale in the range from 0 °C to 1300 °C, 2021, 9 p.
https://arxiv.org/ftp/arxiv/papers/2110/2110.09791.pdf
Table 7. Constant compositions of scale No. 1-3, adopted in the calculations of the 3. F. Grønvold. Heat Capacities in Critical Regions: Pure & Appl. Chem., 47,
graphs in Fig. 10. 1976, 251—266. http://dx.doi.org/10.1351/pac197647040251
Component volume fraction ψ 4. F. Grønvold, A. Sveen. Heat capacity and thermodynamic properties of
Composition synthetic magnetite (Fe3O4) from 300 to 1050 K. Ferrimagnetic transition and zero-
FeO Fe3O4 Fe2O3 Fe point entropy: J. Chem. Thermodynamics, 6, 1974, 859-872.
https://doi.org/10.1016/0021-9614(74)90230-4
1 0,8 0,15 0,05 0
5. F. J. Cook. Analysis of Specific Heat Data in the Critical Region of Magnetic
2 0,5 0,35 0,1 0,05 Solids: J. Phys. Chem. Ref. Data, 2 (1), 1973, 11-24.
https://doi.org/10.1063/1.3253111
3 0,2 0,55 0,15 0,1 6. J. P. Coughlin, E. G. King, K. R. Bonnickson. High-Temperature Heat
Contents of Ferrous Oxide, Magnetite and Ferric Oxide: J. Am. Chem. Soc., 73,
Table 8. Variable composition of scale No. 4, adopted in the calculations of the 1951, 3891-3893. https://doi.org/10.1021/ja01152a098
graph in Fig. 10 (more details - in [1]) 7. Y. Grosu, A. Faik, I. Ortega-Fernández, B. D'Aguanno. Natural Magnetite for
Component volume fraction ψ thermal energy storage: Excellent thermophysical properties, reversible latent heat
Temperature,
transition and controlled thermal conductivity: Solar Energy Materials & Solar
°С FeO Fe3O4 Fe2O3 Fe Cells, 161, 2017, 170-176. https://doi.org/10.1016/j.solmat.2016.12.006
8. B. S. Hemingway. Thermodynamic properties for bunsenite, NiO, magnetite,
1300 0,880 0,100 0,020 0
Fe3O4, and hematite, Fe2O3, with comments on selected oxygen buffer reactions.
1000 0,880 0,100 0,020 0 American Mineralogist, 75, 1990, 781-790.
9. R. A. Robie, B. S. Hemingway, J. R. Fisher. Thermodynamic Properties of
900 0,880 0,100 0,020 0 Minerals and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and
800 0,875 0,100 0,025 0 at Higher Temperatures: Washington, U. S. Govt. Print. U.S. Geological Survey
Bulletin 1452, 1978, 456 p. https://doi.org/10.3133/b1452
700 0,779 0,166 0,055 0 10. Y. S. Touloukian, E. H. Buyco. Thermophysical Properties of Matter. Vol. 5.
Specific Heat. Nonmetallic Solids, New York-Washington: IFI/Plenum., 1970,
600 0,416 0,489 0,095 0
1730 p.
570 0,286 0,596 0,118 0 11. Y. S. Touloukian (Ed.). Recommended Values of the Thermophysical
Properties of Eight Alloys, Major Constituents and Their Oxides. NBS Sub-
500 0,068 0,749 0,090 0,093 Contract No. CST-7590, NASA Order R-45. Purdue University. Lafayette, Ind.,
400 0 0,788 0,090 0,122 1966, 549 p.
12. Ravdel A. A., Ponomareva A. M. (Ed.): A short reference book of physical
300 0 0,788 0,090 0,122 and chemical quantities, St. Petersburg: Ivan Fedorov Publishing House, 2003. 240
100 0 0,788 0,090 0,122 p. (in Russian).
13. G. V. Samsonov (Ed.): Physico-chemical properties of the oxides: Reference
book, Moscow: Metallurgiya, 1978, 472 p. (in Russian).
CONCLUSION 14. K. P. Mischenko, A. A. Ravdel (Ed.): A short reference book of physical and
chemical quantities, Leningrad: Himiya, 1974, 200 p. (in Russian).
Known from technical literature data on the specific mass heat capacity of 15. M. Li, R. Endo, M. Akoshima, M. Susa. Temperature Dependence of Thermal
magnetite Fe3O4, hematite Fe2O3 and pure iron Fe are approximated by analytical Diffusivity and Conductivity of FeO Scale Produced on Iron by Thermal
functions containing the temperatures of magnetic and polymorphic Oxidation: ISIJ International, 57 (12), 2017, 2097–2106.
transformations as varying parameters. Accordingly, the entire target temperature http://dx.doi.org/10.2355/isijinternational.ISIJINT-2017-301
range from 0 to 1300 °C for each of the above components of oxide scale is divided 16. W. P. White. Extra Specific Heat in Cuprous Sulfide; Specific Heat of Ferrous
into separate intervals with moving boundaries. In each of these intervals, the Oxide: J. Am. Chem. Soc., 55, 1933, 1047-1053.
specific mass heat capacity was described by a smooth function that takes into https://doi.org/10.1021/ja01330a026
account the exponential growth of this parameter to the Curie point. The 17. S. Stølen, R. Glöckner, F. Grønvold, T. Atake, S. Izumisawa. Heat capacity
conjugation of functions for adjacent intervals at the Curie point was performed and thermodynamic properties of nearly stoichiometric wustite from 13 to 450 K:
without a break in the heat capacity, and at the point of polymorphic transformation American Mineralogist, 81, 1996, 973-981.
(for Fe) with a finite break in the heat capacity. For the wüstite Fe1-xO, which does https://doi.org/10.2138/am-1996-7-819
not undergo phase transformations throughout the indicated temperature range, the 18. Ch. Kant [et al.]. Spin-phonon coupling in highly correlated transition-metal
generalized temperature dependence of the specific mass heat capacity was monoxides: Eur. Phys. J. Special Topics, 180, 2010, 43-59.
described by a single smooth function. https://doi.org/10.1140/epjst/e2010-01211-6
The data obtained allow us to calculate the specific mass heat capacity of scale csc 19. F. Grǿnvold, E. J. Samuelsen. Heat capacity and thermodynamic properties of
as a multicomponent mixture. The results of model calculations presented in the α-Fe2O3 in the region 300–1050 K. Antiferromagnetic transition: Journal of
paper show that at temperatures of 200 °С and 900 °С the oxide scale specific heat Physics and Chemistry of Solids, 36 (4), 1975, 249-256.
capacity practically does not depend on the structural components content and is 20. K. K. Kelley (Ed.) Contributions to the Data on Theoretical Metallurgy. XIII.
approximately 750 J·kg-1·K-1 and 850 J·kg-1·K-1 respectively. In the region of 575 High-Temperature Heat-Content, Heat-Capacity, and Entropy Data for the
°С, on the contrary, it depends strongly on its percentage composition, varying Elements and Inorganic Compounds. Washington, U. S. Govt. Print. Off. Bureau
from 850 J·kg-1·K-1 to 1150 J·kg-1·K-1. of Mines. Bull. 584,1960, 248 p.
The proposed formulas are recommended for use in mathematical simulation of 21. J. Rogez, J. Le Coze. Description et étalonnage d’un calorimètre adiabatique
production and processing of steel products in the presence of surface scale. à balayage (800 K -1 800 K): Revue Phys. Appl, 15, 1980, 341-351 (in French).
http://dx.doi.org/10.1051/rphysap:01980001502034100
REFERENCES 22. H. R. Shanks, A. H. Klein, G. C. Danielson. Thermal Properties of Armco
Iron: Journal of Applied Physics, 38 (7), 1967, 2885-2892.
1. E. Beygelzimer, Y. Beygelzimer. Generalized estimates for thermal expansion https://doi.org/10.1063/1.1710018
of oxide scale in the range from 0 ºC to 1300 ºC with account for movability of 23. W. Bendick, W. Pepperhoff. On The α/γ Phase Stability of Iron: Acta metall.,
phase transitions in its component, 2021, 10 p. 30, 1982, 679-684. https://doi.org/10.1016/0001-6160(82)90117-1

7
24. F. L. Lederman, M. B. Salamon. Experimental verification of scaling and test 26. P. D. Desai. Thermodynamic Properties of Iron and Silicon: Journal of
of the universality hypothesis from specific-heat data. Physical Review B, 9 (7), Physical and Chemical Reference Data, 15, 1986, 967-983
1974, 2981-2988. https://doi.org/10.1103/PhysRevB.9.2981 https://doi.org/10.1063/1.555761
25. A. A. Varchenko, Ya. A. Kraftmakher, T. Yu. Pinegina. The use of electronic
heating in the modulation method for measuring the heat capacity: Thermal physics
of high temperatures, 16 (4), 1978, 844-847 (in Russian).