High Temperature, Vol. 39, No. 3, 2001, pp. 420–428. Translated from Teplofizika Vysokikh Temperatur, Vol.

39, No. 3, 2001, pp. 450–459.

Original Russian Text Copyright © 2001 by Chekhovskoi, Tarasov, Arseev.

THERMOPHYSICAL PROPERTIES
OF MATERIALS

Experimental Investigation of the Heat Capacity

and Enthalpy of 12Kh18N9T and 12Kh18N10T
(Chrome–Nickel–Titanium) Austenitic Steels
in the Temperature Range from 300 to 1678 K
V. Ya. Chekhovskoi, V. D. Tarasov, and I. V. Arseev
Institute of High Energy Density, IVTAN (Institute of High Temperatures) Scientific Association,
Russian Academy of Sciences, Moscow, 127412 Russia
Received June 20, 2000

Abstract—The results of experimental investigation of the enthalpy and of the true and mean heat capacity of
12Kh18N9T and 12Kh18N10T (chrome–nickel–titanium) austenitic stainless steels are given. The heat capac-
ity is measured with an error of 1% in the temperature range from 300 to 900 K by the method of continuous
adiabatic heating. The enthalpy and mean heat capacity are investigated by the method of mixtures in the tem-
perature range from 1200 to 1678 K with an error of 1%. The experimental results are approximated by an uni-
fied equation for the temperature range from 298.15 to 1678 K using the least-squares method. The errors of
calculated data are estimated.

INTRODUCTION INVESTIGATION OF HEAT CAPACITY

Stainless steels of austenitic type (Grade
12Kh18N9T and 12Kh18N10T: chrome–nickel–tita-
nium) are widely used in thermal power engineering
and other branches of industry owing to their corrosion
and heat resistance. In order to calculate the thermal
processes and design of heat-exchange apparatuses,
one needs reliable data on the thermal properties of
these steels (including the enthalpy and heat capacity)
in a wide range of temperatures. In some studies, it is
suggested to use the thermal properties of such steels as
standard reference data in limited temperature ranges,
namely, for thermal expansion in the temperature range
from 500 to 1650 K [1], for enthalpy and heat capacity
in the range from 400 to 1380 K [2], and for thermal
conductivity, thermal diffusivity, and heat capacity in
the range from 300 to 800 K [3]. This paper gives the
results of many years of investigations of the enthalpy
and heat capacity of 12Kh18N9T and 12Kh18N10T
austenitic steels in the temperature range from 300 K
up to the solidus temperature of 1678 K [4]. The reli-
ability of the results is proved by the internal self-
checking of the data obtained in three experimental
facilities with six steel specimens. The reliability and
high accuracy of the results provided a basis for refin-
ing the recommended reference data on the enthalpy
and heat capacity of 12Kh18N9T and 12Kh18N10T
austenitic steels in the temperature range from 300 to
1650 K.
The heat capacity of 12Kh18N9T and 12Kh18N10T
steels was measured by the method of continuous adia-
batic heating of the specimen to be tested with an error
of 1%. A specimen 40 mm high and 20 mm in diameter
was heated by an electrical heater located in the axial
space of the specimen. It was placed inside a shell with
a low thermal inertia, with the electrical heater being
double-wound around the shell. The latter was placed
inside a furnace surrounded by reflecting screens. The
assembled structure was arranged in a sealed water-
cooled chamber made of stainless steel. The experiments
were carried out either in a vacuum of 10–2–10–3 Pa or in
an atmosphere of highly pure argon.
The temperature of the specimen was measured by
a second class Pt–Pt/Rh thermocouple pressed to the
specimen surface by a molybdenum bandage. Thermal
emf of the Pt–Pt/Rh thermocouple was measured by a
class 0.015 potentiometer. The dependence of the ther-
mal emf on temperature and its temperature coefficient
for the temperature range from 273 to 573 K were
determined in accordance with the recommendations of
[5], as well as from a comparison of the individual cal-
ibration of the employed thermocouple with the stan-
dard calibration table [6].
The adiabatic conditions during the measurement of
heat capacity were controlled by differential Chromel–
Alumel thermocouples with thermoelectrodes 0.2 mm
in diameter, and the temperature difference between the

0018-151X/01/3903-0420$25.00 © 2001 MAIK “Nauka /Interperiodica”

 EXPERIMENTAL INVESTIGATION OF THE HEAT CAPACITY 421

Table 1. Chemical composition of specimens of austenitic steels, in wt % (here and in the text)
Specimen, no.

Chemical composition
Grade Refe-
of steel Ni Cr Mn Ti C Si S P other elements (Ni + Cr) rences

1 12Kh18N9T 8.95 17.00 1.84 0.40 0.10 0.33 0.013 0.0011 25.95 Our data
2 12Kh18N10T 10.83 17.55 1.30 0.54 0.08 0.62 0.080 0.3100 28.38
3, 4 12Kh18N9T 9.10 17.00 1.40 0.66 ≤0.12 ≤0.80 ≤0.020 ≤0.035 26.10
5 12Kh18N9T 9.44 19.45 0.82 1.10 0.08 0.21 0.029 0.130 28.89
6 12Kh18N10T 9.95 18.43 0.58 0.84 0.08 0.20 0.054 0.055 28.38
1 12Kh18N9T 9.10 17.00 1.40 0.66 ≤0.12 ≤0.80 ≤0.020 ≤0.035 26.10 [2]
2 12Kh18N10T 10.48 18.15 1.63 0.57 0.11 0.39 28.63
3 12Kh18N10T 9.90 17.80 1.70 0.60 0.07 0.30 27.70
AISI No. 347 11.10 18.30 1.30 0.08 0.52 0.86 Nb 29.40 [11]
RSM 735 12.00 16.00 1.20 0.10 28.00 [3]
1 EI 481 8.10 11.70 7.70 0.02 0.35 0.37 0.001 0.03 1.22 Mo, 0.33 Nb, 1.32 V 19.80 [12]
2 EI 572 8.96 19.00 0.70 0.42 0.32 0.49 0.29 0.180 1.38 Mo, 0.40 Nb, 1.38 W 27.60
3 EI 612 36.70 14.90 1.00 1.30 0.09 0.38 0.018 0.007 3.38 W 51.60
EYa1T 9.60 18.10 0.88 0.41 0.10 0.74 0.4 Mo 27.70 [13]

specimen and the shell and between the specimen and
the furnace was measured by the differential thermo-
couples. The adiabatic conditions during the continu-
ous heating of the specimen were automatically main-
tained by a temperature regulator. The temperature dif-
ference between the specimen and the shell did not
exceed 0.05 K, and the temperature of the furnace was
maintained several degrees below the specimen temper-
ature. The specimen heating rate was 1–2 deg/min with
its temperature increasing continuously by 4–20 K. In
accordance with the calculation results obtained in
solving the differential equation of thermal conductiv-
ity, with a heating rate of 2 deg/min, the difference
between the temperature measured by a thermocouple
on the specimen surface and its volume average tem-
perature at 600 K is 0.065 K; i.e., it is an order of mag-
nitude less than the measurement error.
The heat capacity was calculated by the formula
∑c
c p = UI/ [ ( dT /dτ ) a M ] – ( pi m i )/M,
where U and I are the voltage drop across the specimen
heater and the current strength in it, respectively;
(dT/dτ)a = (dT/dτ) – (dT/dτ)* = [(dE/dτ) –
(dE/dτ)*]/(dE/dT); (dE/dT) is the temperature coeffi-
cient of the thermal emf of the thermocouple used to
measure the specimen temperature; (dT/dτ) and
(dT/dτ)* are the specimen heating rates with the heater
switched on and off; M is the specimen mass; and
∑ c pi mi is the thermal value of the inactive part of the
calorimetric system made up of the specimen heater,
thermocouple junctions complete with insulation, and a
bandage to fasten the latter on the specimen cylindrical
surface. The latter value was approximately 1% of the
thermal value of the specimen.
The heat-capacity measurement technique and sin-
gular features of the design of the experimental facility
are described in detail in [7]. The operation of the facil-
ity was checked by measuring the heat capacity of cop-
per in the temperature range from 300 to 900 K [7]. The
deviation of the obtained values of the heat capacity of
copper from the reference data of [8–10] did not exceed
0.65%.
The heat capacity of 12Kh18N9T and 12Kh18N10T
steels were measured in four specimens (whose chem-
ical composition is given in Table 1). The results of
measurement of the heat capacity of 12Kh18N9T steel
in specimens nos. 1, 3, and 4 and those of 12Kh18N10T
steel in specimen no. 2 are given in Table 2. The chem-
(1) ical composition of specimens nos. 3 and 4 is identical
to that of the specimens in which the enthalpy was
investigated for the tables of standard reference data
[2], because they were made of the same steel blank. In
measuring the heat capacity of specimens nos. 3 and 4,
we have somewhat improved the measurement tech-
nique: we used an improved automatic system to con-
trol the adiabatic heating; the thermocouple was placed
in the middle of the specimen wall thickness rather than
on its surface and was used to measure its volume aver-
age temperature.

HIGH TEMPERATURE Vol. 39 No. 3 2001

422 CHEKHOVSKOI et al.

Table 2. Results of measurement of the heat capacity of 12Kh18N9T and 12Kh18N10T austenitic steels

No. T, K cp, kJ/(kg K) (cp – c cal cal

p )/ c p , %
No. T, K cp, kJ/(kg K) (cp – c cal cal
p )/ c p , %

Specimen no. 1, 12Kh18N9T steel

1 335.6 0.4799 –0.04 7 566.0 0.5427 +0.92
2 400.5 0.4971 –1.06 8 608.9 0.5422 –0.52
3 416.8 0.5025 –0.86 9 686.6 0.5560 –0.31
4 450.9 0.5100 –1.01 10 716.2 0.5598 –0.49
5 491.2 0.5217 –0.41 11 784.6 0.5732 –0.08
6 546.7 0.5339 –0.08
Specimen no. 2, 12Kh18N10T steel
1 348.3 0.4899 +0.97 6 577.0 0.5456 +1.10
2 397.3 0.5012 +0.53 7 668.2 0.5577 +0.53
3 448.4 0.5192 +0.89 8 723.5 0.5632 –0.09
4 487.7 0.5280 +0.93 9 785.7 0.5728 –0.18
5 517.7 0.5330 +0.76 10 887.1 0.5866 –0.74
Specimen no. 3, 12Kh18N9T steel
1 364.0 0.4916 +0.13 7 562.5 0.5382 +0.20
2 381.0 0.4962 –0.08 8 586.0 0.5435 +0.43
3 425.0 0.5071 –0.37 9 618.8 0.5486 +0.35
4 471.0 0.5201 +0.09 10 680.2 0.5569 +0.03
5 481.0 0.5230 +0.24 11 835.0 0.5824 +0.06
6 522.8 0.5302 +0.04
Specimen no. 4, 12Kh18N9T steel
1 367.0 0.4933 +0.26 8 584.0 0.5410 +0.03
2 386.0 0.4950 –0.63 9 630.0 0.5448 –0.68
3 403.0 0.4996 –0.70 10 662.0 0.5515 –0.41
4 440.0 0.5125 –0.03 11 781.3 0.5716 –0.27
5 473.6 0.5201 –0.02 12 835.3 0.5806 –0.26
6 503.0 0.5243 –0.36 13 855.0 0.5891 +0.62
7 524.0 0.5276 –0.49

INVESTIGATION OF THE ENTHALPY carried out in an atmosphere of high-purity argon

AND MEAN HEAT CAPACITY
The enthalpy and mean heat capacity of
12Kh18N9T and 12Kh18N10T steels were investi-
gated by the method of mixtures in the temperature
range from 1200 to 1678 K in two experimental facili-
ties. The first setup consisted of a furnace with a cylin-
drical electrical tungsten heater, a calorimeter, and a
water-cooled shutter device provided between the fur-
nace and the calorimeter to protect the latter against the
furnace radiation. The massive copper block of the cal-
orimetric system was surrounded by an isothermal shell
whose temperature during the experiment was main-
tained constant within ±10–3 K with the aid of a water
thermostat. The variation in the temperature of the cal-
orimetric system was measured by a quartz thermome-
ter with a sensitivity of 10– 4 K, whose readings were
registered in time by a computer. The experiments were
which filled the hermetically sealed volume of the
experimental facility preevacuated to 5 × 10–2 Pa.
A specimen suspended on a tungsten wire at the center
of the tungsten heater was heated to the required tem-
perature. On the opening of the shutter device, the sus-
pension wire was automatically burned by electric cur-
rent. The specimen dropped through the shutter device
and the automatic shutter which opened for fractions of
a second, and entered the receiver of the massive cop-
per block of the calorimeter. The dropped specimen
triggered the mechanism closing the lids of the copper
block receiver and of the isothermal shell.
An EOP-66 first-class optical monochromatic
pyrometer was used to measure the temperature of the
specimen being investigated through a totally reflecting
prism. The pyrometer was sighted on a blackbody
model such as an axial cylindrical cavity in the speci-

HIGH TEMPERATURE Vol. 39 No. 3 2001

 EXPERIMENTAL INVESTIGATION OF THE HEAT CAPACITY 423

Table 3. Results of measurement of the enthalpy and mean heat capacity of 12Kh18N9T (specimen no. 5) and 12Kh18N10T
(specimen no. 6) austenitic steels
mean mean mean mean
Experiment no. T, K H(T)–H(298.15), kJ/kg cp , kJ/(kg K) ( c pexp – c pcal )/ c pcal , %

1 1235 535.8 0.5719 +0.39

2 1353 612.2 0.5804 –0.20
3* 1385 637.5 0.5866 +0.32
4* 1400 649.8 0.5897 +0.60
5 1401 646.1 0.5858 –0.08
6* 1402 650.3 0.5891 +0.46
7* 1421 662.8 0.5903 +0.39
8 1435 667.1 0.5868 –0.51
9 1441 667.4 0.5840 –1.09
10* 1460 693.1 0.5965 +0.70
11* 1464 695.0 0.5961 +0.56
12 1464 694.8 0.5960 +0.54
13 1474 695.8 0.5917 –0.35
14* 1481 707.0 0.5977 +0.53
15* 1590 781.2 0.6047 –0.25
16 1604 786.2 0.6021 –0.94
17 1644 818.6 0.6082 –0.65
18 1647 826.1 0.6139 +0.23
19 1678 854.5 0.6193 +0.52
* The results are obtained in specimen no. 6 (12Kh18N10T steel).

men. The measured temperature was corrected by
introducing corrections for the absorption of radiation
in the prism and for the difference of the reflectivity of
the blackbody model from unity. The measurement
results were processed by a computer using special
codes. The procedure of measuring the enthalpy and
the components of the experimental facility are
described in detail in [14, 15]. The operation of the
experimental facility was checked by the results of
measurements of the enthalpy of molybdenum in the
temperature range from 1200 to 2400 K [16] and of
tungsten in the range from 1250 to 2550 K [17]. The
deviation from the recommended reference data
[18, 19] did not exceed 1%.
Specimen no. 5 was 18 mm in diameter and 35 mm
high. Its chemical composition is given in Table 1. The
results of measuring the enthalpy and mean heat capac-
ity of this specimen are given in Table 3.
The second experimental facility was used to mea-
sure the enthalpy and mean heat capacity of specimen
no. 6. The specimen to be investigated was suspended
on a molybdenum wire and heated in a cylindrical mul-
titurn inductor energized by a high-frequency generator
at a frequency of 440 kHz. The heat input from the
dropping specimen was measured in a calorimeter. The
latter consisted of a copper block placed in an isother-
mal shell whose temperature was automatically main-
tained constant within ±10–3 K by an oil thermostat.
The variation in the temperature of the calorimetric sys-
tem was measured by a low-inertia copper resistance
thermometer whose voltage drop and current strength
were registered by class 0.005 digital voltmeters and
automatically input to a computer.
Specimen no. 6 was 9 mm in diameter and 16 mm
high. For measuring the temperature by the EOP-66
pyrometer, a cylindrical axial cavity was provided in
the specimen and served as a blackbody model. The
specimen to be investigated was heated in an atmo-
sphere of high-purity argon which filled the hermeti-
cally sealed volume of the facility that was preevacu-
ated to 10–2 Pa. On reaching the preassigned tempera-
ture, a device was triggered to burn the suspension wire
and to close, after 0.3 s, the lid of the copper block with
the specimen that fell into it. The specimen dropping
through the opening in the water-cooled shutter and the
lower second shutter automatically opened and closed
the second shutter. The experimental calorimetric
results were processed by a computer. The obtained
results are given in Table 3.
The enthalpy measurement technique and the
design of the experimental facility are described in
detail in [20]. The working capacity of the facility was
checked in terms of the results of measurement of the
enthalpy of standard calorimetric substances of molyb-

HIGH TEMPERATURE Vol. 39 No. 3 2001

424
denum and corundum [20]. The maximum deviation of
the measured values from the recommended data did
not exceed 1%.
PROCEDURE OF PROCESSING
THE MEASUREMENT RESULTS
The obtained experimental data on the enthalpy and
heat capacity were processed jointly by the least-
squares method using a unified linear (relative to the
coefficients) equation. In this calculation procedure, we
minimized the sum of the squares of deviations of the
measured values of the true and mean heat capacities
from their regressions.
The temperature dependence of heat capacity was
described by the equation
c = ∑a j f j(T )
= a 1 f 1 ( T ) + a 2 f 2 ( T ) + … + a k f k ( T ),
where aj denotes the coefficients of the equation to be
calculated; f j (T) denotes the functions defining the
form of equation and independent of the coefficients; T
is temperature; j = 1, 2, …; and k is the subscript of
equation term. Hence, the enthalpy is determined as
H(T ) – H(T0) =
= a 1 F 1 ( T ) + a 2 F 2 ( T ) + … + a k F k ( T ),
where,
T
F j(T ) = ∫ f ( T ) dT ,
j of the mathematical model. An additional, fourth, term
T0
and the mean heat capacity,
= [ H ( T ) – H ( T 0 ) ]/ ( T – T 0 )
mean
c experimental values from the regression line during
= ∑ a ϕ (T) = a ϕ (T) + a ϕ (T) + … + a ϕ (T), (4)
j j 1 1 2 2
where,
ϕ j ( T ) = F j ( T )/ ( T – T 0 ).
Assuming the true and mean heat capacities to have
been measured with the same accuracy (their disper-
sions are approximately equal, σ true ⯝ σ mean ), we find
2 2
the sum of squares of deviations,
N N
∑ ∑ [ C – αc – ( 1 – α )c
εi
2
R = = i i i
i=1 i=1
Here, α = 1 if Ci is the measured value of heat capac-
ity and α = 0 if Ci is the measured value of mean heat
mean
capacity; ci and c i are the investigated regressions of
respective heat capacities; εi is a deviation of the mea-
sured value from the value of its regression at point i;
and N is the total number of the points being processed.
CHEKHOVSKOI et al.
When measuring the values of properties with different
accuracy, statistical weights are to be introduced in
Eq. (5). However, preliminary estimates of the disper-
sions of the values of heat capacity and enthalpy (mean
heat capacity) showed that the presented data were
measured with the same accuracy. Therefore, the statis-
tical weights were assumed to be unity.
We minimize the sum of squares of deviations rela-
tive to the coefficients of the selected model in view of
Eqs. (2) and (4) to derive the system of equations
∂R/∂a j = ∑ 2 [ C – αc – ( 1 – α )c ]
mean
i i i
(6)
× ∂{ ∑ [ Ci – α ci – ( 1 – α ) ci ] } / ∂ a j = 0,
mean
whose solution enables us to determine the coefficients
of the sought equations and obtain the information for
(2) analyzing the selected model.
In what followed, the statistical and regression anal-
yses were carried out by the classical procedures
described in the literature, for example, [21–26].
APPROXIMATION OF DATA
The experimentally obtained data on the heat capac-
∑ a F (T )
j j ity and mean heat capacity (enthalpy) in the tempera-
ture range from 300 to 1678 K were generalized using
(3) several equations by the aforedescribed procedure. The
first two terms in Eq. (2) were the same: f1(T) = 1,
f2(T) = T; the third term varied as f3(T) = T –1, f3(T) =
T −3/2, or f3(T) = T –2. These three terms formed the basis
had the form of f4(T) = 0, f4(T) = T 2, f4(T) = T 3, or
f4(T) = exp(–k/T)/T 2. The exponent k was calculated by
the minimum of the sum of squares of deviations of the
rotation, or as an angular coefficient of the linear
k k dependence of logarithm of the deviations of high-tem-
perature data on the regression line of low-temperature
values as a function of 1/T. For both methods of the
determination of k, deviations proved to be insignifi-
cant. However, for physical reasons, we had to abandon
the model including the exponent.
ESTIMATION ERRORS OF CALCULATION
OF THE HEAT CAPACITY AND ENTHALPY
As a result of statistical and regression analysis of
mean 2
] .
(5) the treated versions, we selected a model containing the
following functions: f1(T) = 1, f2(T) = T, f3(T) = –1/T 2,
f4(T) = 3(T – T0)2; F1(T) = (T – T0), F2(T) = (T 2 – T 0 )/2,
2
F3(T) = 1/T – 1/T0, F4(T) = (T – T0)3; ϕ1(T) = 1, ϕ2(T) =
(T + T0)/2, ϕ3(T) = –1/(TT0), and ϕ4(T) = (T – T0)2. After
the substitution of the derived coefficients and appro-
priate transformations in Eqs. (2)–(4), we derived the
following equations for the approximation of the
HIGH TEMPERATURE Vol. 39 No. 3 2001
 EXPERIMENTAL INVESTIGATION OF THE HEAT CAPACITY 425

enthalpy and heat capacity of 12Kh18N9T and Table 4. True heat capacity, enthalpy, and mean heat capac-
12Kh18N10T stainless steels: ity, calculated by Eqs. (7)–(9)

c p = 0.53094 + 1.1907 × 10 T – 6864.6T

–6 –2 mean
(7) T, K c p , kJ/(kg K) H(T)–H(298.15), cp ,
kJ/kg kJ/(kg K)
+ 8.6031 × 10 T , kJ/ ( kg K ),
–8 2

298.15 0.4617 0.00000 0.4617

H(T ) – H(298.15) = 0.53094T + 5.9535 × 10 T
–7 2
300 0.4628 0.85515 0.4622
(8)
+ 6864.6T + 2.8677 × 10 T – 182.14, kJ/kg,
–1 –8 3 350 0.4859 24.607 0.4746
400 0.5023 49.331 0.4844
= [ H ( T ) – H ( 298.15 ) ]/ ( T – 298.15 )
mean
cp 450 0.5150 74.774 0.4924
500 0.5256 100.80 0.4994
= 0.53367 + 9.1454 × 10 T – 23.024T
–6 –1
(9) 550 0.5349 127.31 0.5055
600 0.5436 154.28 0.5111
+ 2.8677 × 10 T , kJ/ ( kg K ) .
–8 2
650 0.5518 181.66 0.5163
In this case, the mean-square errors of the coeffi- 700 0.5599 209.46 0.5212
cients were Sa1 = 1.388 × 10–2 kJ/(kg K), Sa2 = 2.092 × 750 0.5680 237.65 0.5260
10–5 kJ/(kg K2), Sa3 = 9.250 × 102 kJ K/kg, and Sa4 = 800 0.5762 266.26 0.5306
4.980 × 10–9 kJ/(kg K3), and their correlation coeffi-
850 0.5846 295.28 0.5351
cients were ρa1, a2 = ρa2, a1 = 0.995, ρa1, a3 = ρa3, a1 =
0.977, ρa1, a4 = ρa4, a1 = 0.964, ρa2, a3 = ρa3, a2 = –0.954, 900 0.5932 324.72 0.5395
ρa2, a4 = ρa4, a2 = –0.984, and ρa3, a4 = ρa4, a3 = 0.903. The 950 0.6021 354.61 0.5440
mean-square random error in the observation of the true 1000 0.6113 384.94 0.5485
and mean heat capacity was S0 = 3.061 × 10–3 kJ/(kg K). 1050 0.6208 415.74 0.5530
The smoothed values of the properties calculated by 1100 0.6307 447.03 0.5575
Eqs. (7)–(9) are given in Table 4 and Fig. 1. The relative 1150 0.6409 478.81 0.5621
deviations of the experimental data on heat capacity 1200 0.6515 511.12 0.5668
and enthalpy from the values determined by Eqs. (7)
and (8) are given in Tables 2 and 3. For the obtained 1250 0.6625 543.97 0.5715
regressions of these properties, we estimated the rela- 1300 0.6738 577.37 0.5763
tive confidence limits δreg = tSreg (where t is Student’s 1350 0.6856 611.35 0.5812
coefficient, and Sreg is the relative mean-square error) at 1400 0.6977 645.94 0.5862
the confidence probability of 0.95 (Fig. 2).
1450 0.7103 681.13 0.5913
In accordance with the recommendations of [26], 1500 0.7232 716.97 0.5966
the confidence limits of nonexcluded systematic errors
of the result of measurement of true heat capacity at the 1550 0.7366 753.47 0.6019
confidence probability of 0.95 are equal to 1600 0.7504 790.64 0.6073
1650 0.7646 828.51 0.6129
∑θ )
2 1/2
δ θ = 1.1 ( i ⯝ 0.41%, (10) 1678 0.7727 850.04 0.6160
where θi denote relative nonexcluded systematic errors,
namely, θ1 = 0.06% of measurements of the electric We use δ c p (Fig. 2) and δθ (10) to estimate the con-
power of the specimen heater; θ2 = 0.005% of measure- fidence limits of the relative total error of calculation of
ments of the specimen mass; θ3 = 0.1% of determina- heat capacity by Eq. (7), including random and nonex-
tion of the temperature coefficient of the thermal emf of cluded systematic errors, at the confidence probability of
thermocouple; θ4 = 0.2% and θ5 = 0.4% of measure- 0.95 for the temperature range from 400 to 1000 K [26],
ments of the rate of variation of thermal emf (smoothed 2 1/2
δΣ = ( δc p + δΘ )
2
values) with the heater in the specimen switched on and ⯝ 0.85%.
off; θ6 = 0.1% of the determination of the heat capacity
with the error of measuring the temperature by the ther- At a temperature of 300 K, the value of δ c p
mocouple of 0.5–1.0 K; θ7 = 0.01% of the difference of increases to 1.4%. In the temperature range from 1100
the temperature being measured from the volume aver- to 1650 K, the total error of determination of heat
age temperature of the specimen; and θ8 = 2% of calcu- capacity increases with temperature from 1 to 2.2%.
lation of the ballast part of the thermal value of the cal- The total error of similar calculation of enthalpy by
orimetric system. Eq. (8) in the temperature range from 400 to 1650 K is

HIGH TEMPERATURE Vol. 39 No. 3 2001

426 CHEKHOVSKOI et al.

cp, c mean
p , kJ/(kg ä) of measurement of the specimen mass θ3 = 0.005%; the
0.8 thermal loss of the dropping specimen θ4 = 0.03%; that
of determination of enthalpy, associated with the error
of temperature measurement θ5 = 0.39–0.45%, which
allows for the inaccuracy of calibration of the pyrome-
0.7 ter, the temperature gradient over the specimen height,
3 the error of determination of pyrometric absorption of
the prism, etc.
1
0.6 DISCUSSION OF THE RESULTS
2 In order to correctly compare the results of measure-
4 ment of the enthalpy and heat capacity of 12Kh18N9T
0.5 and 12Kh18N10T steels with the data of other authors,
we have to assess the influence of the chemical compo-
sition and thermal history of the investigated speci-
300 500 700 900 1100 1300 1500 1700 mens. It is known that GOST (State Standard) [27] pro-
T, ä vides for a variation in the chemical composition of
12Kh18N9T and 12Kh18N10T steels in certain ranges,
Fig. 1. Experimental values of (1) heat capacity cp and mean mainly with respect to the chrome and nickel content.
mean The calculation of the heat capacity according to the
(2) heat capacity c p , and their temperature dependences additivity rule is difficult because of the suppression of
calculated (3) by Eq. (7) (heat capacity) and (4) by Eq. (9) the thermal effects of phase transitions in the main
(mean heat capacity). components of these steels. However, in a first approx-
imation, the effect of the composition may be estimated
if one uses the results of investigation of the mean heat
δcp, δH, (c exp calc calc
p – c p )/c p , (H
exp – H calc)/Hcalc, %
capacity of three austenitic steels in the temperature
2 range from 373 to 1630 K [12], whose chemical com-
3 positions differ substantially by the content of chrome
1 and nickel (see Table 1). It is the use of the data of only
1 one study [12] that allows eliminating the systematic
2
4 measurement errors which may distort the conclusions
made when using the results of different authors. The
results of estimating calculations have showed that a
0 decrease in the content of [Cr + Ni] by 1% leads to an
increase in the mean heat capacity of steel by approxi-
mately 0.25%. For six steel specimens investigated by
–1 us (nos. 1–6), the average content of [Cr + Ni] was
27.30%. The maximum deviation of the content of
[Cr + Ni] from the average value (specimen no. 5) was
–2 1.59%, which may lead to a change in the experimental
300 500 700 900 1100 1300 1500 1700 data on the mean heat capacity by 0.4%, i.e., by a value
T, ä which is less than the measurement error. In accordance
with GOST [27], the content of [Cr + Ni] in the inves-
Fig. 2. Relative confidence limits of the results of calcula- tigated grades of steel is allowed within 25–30%,
tion of heat capacity δ c (curve 3) and enthalpy δH (curve 4) which may lead to a deviation of 0.7% from our data for
p
at the confidence probability of 0.95 and relative deviations the mean heat capacity and enthalpy calculated by
of the experimental data from the calculated values of Eqs. (8) and (9).
exp calc calc
(1) heat capacity ( c p – cp )/ c p and (2) enthalpy The effect of the temperature history of the speci-
(Hexp – Hcalc)/Hcalc.
mens of 12Kh18N9T steel on the results of heat capac-
ity measurement are given in the handbook [28]. The
heat capacity of an annealed specimen exceeds that cp
of the specimen quenched in water at 1323 K by
estimated at δΣ = 0.54–0.76%, while δθ = 0.50–0.57%. approximately 0.8% in the temperature range from 300
To calculate δθ, we used the following nonexcluded to 1073 K. In view of this, Gomel’skii et al. [2] recom-
systematic errors of enthalpy measurement: that of mended performing a preliminary annealing of steel
determination of the thermal value of the calorimetric specimens for one hour at 1073 K. Note, however, that,
system θ1 = 0.07%; that of measurement of the rise of during the process of measuring the enthalpy and heat
temperature of the calorimetric system θ2 = 0.2%; that capacity of the specimens, they are subjected to

HIGH TEMPERATURE Vol. 39 No. 3 2001

 EXPERIMENTAL INVESTIGATION OF THE HEAT CAPACITY
repeated heating and cooling. When measuring the
enthalpy by the method of mixtures, the specimen
dropping from the furnace into the calorimeter is sub-
jected (to some extent) to quenching. Nonetheless, nei-
ther in our experiments nor in those of [2, 11, 12] has it
been noted that such quenching affects the results.
Moreover, the obtained enthalpy values agree with the
measured values of true heat capacity.
Figure 3 gives a comparison of the values of enthalpy
[2, 11] and heat capacity [3, 13, 29] of austenitic steels
with the values calculated by Eqs. (7) and (8) and given
in Table 4. The chemical composition of these steels is
given in Table 1. Direct measurements of the true heat
capacity of 12Kh18N9T austenitic steel were carried
out in [13, 29] by the method of continuous adiabatic
heating. In [13], the heat capacity was measured in the
temperature range from 323 to 1173 K with an error of
1%. The measurement results have been published in
the form of a table of smoothed values which, in accor-
dance with Fig. 3, deviate in the temperature range of
323–900 K from those given in Table 4 by not more
than 1.0–1.5%. At higher temperatures, the divergence
increases to 5.5%. The smoothed values of heat capac-
ity [29], obtained in the temperature range from 300 to
900 K with an error of 1% in a specimen with a chem-
ical composition identical to that of our specimen no. 1
(see Table 1), coincide with those given in Table 4
within 1%.
In [3], the table of smoothed values of heat capacity
in the temperature range from 300 to 800 K is given for
a standard RSM 735 specimen of austenitic stainless
steel, with an error of ±2.5%. These data were obtained
at the US National Bureau of Standards. In the temper-
ature range from 400 to 700 K, the results of [3] coin-
cide with those of Table 4 within ±0.5%; at higher tem-
peratures, a deviation of up to 2.4% is observed.
Tables of standard reference data on enthalpy and
heat capacity for 12Kh18N9T and 12Kh18N10T
austenitic steels in the temperature range from 400 to
1380 K are recommended in [2]. The total error at the
confidence probability of 0.95 for enthalpy is estimated
in [2] at 1%, and for true heat capacity at 1.5%. The
tables of [2] were developed at the Sverdlovsk Branch
of the Mendeleev All-Union Research Institute of
Metrology from the experimental data obtained as a
result of investigation of the enthalpy of steels by the
method of mixtures. The values of enthalpy given in [2]
coincide in the temperature range from 500 to 1380 K
with the enthalpy values given in Table 4 within 1%,
and in the temperature range from 400 to 500 K the
deviation increases to 4.5%. The heat capacity values
obtained in [2] coincide with those given in Table 4 in
the temperature range from 500 to 1200 K within 1.5%;
however, the deviation increases to 6.6% as the temper-
ature rises to 1380 K.
The enthalpy of AISI no. 347 austenitic stainless
steel was investigated with high precision in the tem-
perature range from 273 to 1169 K using a Bunsen ice
HIGH TEMPERATURE Vol. 39 No. 3 2001
427
(c exp calc calc
p – c p )/c p , (H
exp – H calc)/Hcalc, %
4
2
2
0
6 5
4
–2
1 3
7
–4
–6
300 500 700 900 1100 1300
T, ä
Fig. 3. Relative deviations of the published data on heat
capacity and enthalpy from the values calculated by Eqs. (7)
and (8). Enthalpy: curve 2 [2], 5 [11]; heat capacity:
curve 1 [3], 3 [2], 4 [11], 6 [29], 7 [13].
calorimeter [11]. The enthalpy values were measured in
six specimens with the results differing by not more
than 0.25%. Several backup measurements were per-
formed in each specimen at the same temperature in the
furnace, and the divergence of the measurement results
did not exceed 0.05%. In [11], the error of calculation
of true heat capacity by the suggested empirical equa-
tion is estimated at ±2%. The chemical composition of
steel in [11] somewhat differs from that of the speci-
mens investigated by us (see Table 1). However, an ade-
quate agreement is observed between the experimental
results and the data given in Table 4: with regard to
enthalpy, within 0.2–0.7%, and with regard to true heat
capacity, within 1%.
The agreement of the data given in Table 4 with the
investigation results of various laboratories [2, 3, 11,
13, 29], including metrological ones, with respect to the
true heat capacity and enthalpy of austenitic stainless
steels within the estimated errors leads one to the fol-
lowing conclusions: (1) the correctness of the assess-
ment of the effect of the content of [Cr + Ni] on the
caloric properties of austenitic stainless steels is con-
firmed in a first approximation; (2) the values of true
heat capacity and enthalpy of 12Kh18N9T and
12Kh18N10T stainless steels ([Cr + Ni] = 27.3%)
given in Table 4 may be recommended as the most reli-
able data in the temperature range from 300 to 1650 K
at atmospheric pressure (at a temperature above
1000 K, in an inert medium). The estimates of general
errors of heat capacity and enthalpy are given above.
428 CHEKHOVSKOI et al.
ACKNOWLEDGMENTS
We are grateful to G.Z. Gerasina, Yu.A. Klimenko,
and Yu.V. Guseva for their participation in the experi-
ments.
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HIGH TEMPERATURE Vol. 39 No. 3 2001