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METROLOGIA-2003 – Metrologia para a Vida

Sociedade Brasileira de Metrologia (SBM)


Setembro 01−05, 2003, Recife, Pernambuco - BRASIL

FLASH METHOD STANDARDIZATION IN BRAZIL FOR THE


MEASURMENT OF SOLID THERMOPHYSICAL PROPERTIES
Paulo Couto1, Helcio R. B. Orlande1, Renato M. Cotta1, Sérgio P. Oliveira2,
Jorge A. Cruz2, Paulo R. F. Santos2, Cláudio S. Pinto Costa1 and Henrique Massard1.
1
Federal University of Rio de Janeiro - EE/COPPE, Rio de Janeiro, RJ, 21945-970, Brazil
2
National Institute of Metrology, Standardization and Industrial Quality – INMETRO, Xerém, Brazil

Abstract: The flash method, proposed by Parker, Butler, samples imposed intolerable limitations, usually tied to heat
Jenkins, and Abbott from the U.S. Navy Radiological losses and contact resistance between the specimen, and its
Defense Laboratory in 1960, is the most popular method of associated heat sources, heat sinks and measurement
measuring the thermal diffusivity of solids. In this method devices. The Flash Method, first proposed by Parker et al.
the front surface of a small sample is subjected to a very [2], eliminated the problem of contact resistance of the
short burst of radiant thermal energy. The resulting classical methods, and minimized the heat losses by making
temperature rise on the opposite surface of the sample is the measurement time short enough so that very little
measured, and the thermal diffusivity is computed from the cooling can take place. This method consists of heating the
temperature rise vs. time data. Also, the heat capacity can be front surface of a thermally insulated specimen with a high-
computed from the temperature vs. time data, for the intensity short-duration radiative heat pulse and measuring
calculation of the thermal conductivity. Several theoretical the temperature evolution on the back surface by the use of
models are available for the the flash method, which include an infrared (IR) detector. The non-intrusive backside
adiabatic boundary conditions, heat losses, surface coating measurement method eliminates the concern and issues with
effects, among many other aspects. In this paper, these sensor attachment to the sample, and removes all
models are briefly discussed. This paper also describes the uncertainties associated with contact resistance and sensor
implementation of the flash method in Brazil as a standard measurement accuracy.
method for the identification of thermal diffusivity. This
Although different industries and research institutes are
work is undertaken in the context of a joint project between
already using the Flash Method for thermal properties
the Graduate School in Engineering of the Federal
measurements in Brazil, the lack of a national standardized
University of Rio de Janeiro (COPPE-UFRJ) and the
procedure does not allow the inter-laboratory comparison of
National Institute of Metrology, Standardization and
thermal properties, which reduces the measurement
Industrial Quality (INMETRO).
traceability. Therefore, the National Institute of Metrology,
Keywords: flash method standardization, thermal Standardization and Industrial Quality (INMETRO) in a
diffusivity measurement, and thermal conductivity. joint project with the Federal University of Rio de Janeiro
(COPPE/UFRJ), funded by the National Council for
1. INTRODUCTION Scientific and Technological Development (CNPq), is
working towards the implementation of a primary method
The second half of the twentieth century has seen the subject for the measurement of the thermal diffusivity of solids
of thermal properties measurement change from an exercise materials based on the Flash Method, according to the
mostly of academic interest to a complex issue employing ASTM standard E1461-0 [3]. This standardized primary
the attention of a large number of people in different sectors method will stimulate the development of new techniques
of industry, government and universities. The explosion in for thermophysical properties identifications, which is of
materials development for many emerging technologies has main interest of several Brazilian industries, decreasing its
produced very substantial quantities of improved materials external dependence of qualified materials testing and
and composites in different forms. This has led to a thermal characterization.
corresponding requirement for evaluation of their
thermophysical properties more rapidly and often, under This paper describes the actions performed by INMETRO
conditions that cannot be satisfied using the appropriate and COPPE/UFRJ within the scope of this joint project, as
classical methods [1]. These classical methods, which well as a description of the method itself. A brief literature
involved the fitting of steady state and non-steady-state review about the Flash Method is summarized and a
experimental temperature data to theoretical models, were discussion of the traditional theoretical models considered
usually time expendable. Additionally, the large size of the for this method is performed.
2. FLASH METHOD STANDARDIZATION IN well as for determining reference values of materials
BRAZIL properties. Another field of application of reference
materials is testing, measurement or analysis as a basis for
The objective of the work presented here is performing and
important decisions, e.g. for authoritative evidence. The
assessing thermophysical tests of materials and systems
definition of a “reference procedure” presumes the existence
including the provision of reference procedures and
of several procedures for a specified task or of different
reference materials.
realizations of the same methodology. Therefore, a reference
Reference materials and standards are essential tools to procedure is qualified by the uncertainty of results, proven
validate techniques and apparatus based on primary methods to fit for a given purpose. Moreover it has to be accepted as
of measurement and for use in the calibration of techniques such by the relevant target groups. In the case of quantitative
based on secondary or indirect methods. In order to cover results the uncertainty comprises trueness and precision
the wide ranges of material types and their overall combined in the sense of measurement uncertainty. In the
conductivity and temperature ranges of use it is seen that a case of qualitative results the uncertainty is an estimate of
broad variety of materials and specimens are required to the probability of erroneous results.
satisfy the total needs.
Accordingly, the developed procedures and techniques
During the last years there has been a huge increase in the within the scope of this project are implementations of
development and use of new and modified materials for a public standard methods. It will not be include test methods
very broad range of engineering, physical, chemical, for which special legal regulations apply, e.g. in the field of
biological and medical applications. In a majority of cases dangerous goods and substances, nor healthy and
involving heat transfer, the thermal properties (p.ex., environmental rules. Provision of reference procedures at
thermal conductivity, thermal diffusivity and specific heat) metrological level will be oriented towards current needs
are necessary to model, design and safely operate the and tasks; the reference procedures will be reviewed on a
system. The levels of accuracy and precision required can regular basis and an updated list will be published at an
vary depending upon the application. Reliability and Internet site and in every new edition of a booklet catalogue.
confidence in the measured value is the primary intention
In addition to the development of standard procedures in
and use of reference materials is an essential ingredient
Brazil for the identification of thermophysical properties,
towards attaining this goal. It has been found that values,
the present project will also permit the validation and
particularly of thermal conductivity for a material, vary
advancement of new techniques for the identification of
significantly many times by amounts well outside the
thermophysical properties, developed within the framework
required precision levels. In addition, some concern has
of research projects conducted by the group of the
been expressed by the occurrence of cases where significant
Laboratory of Heat Transmission and Technology at
discrepancies appear to exist between directly measured
COPPE/UFRJ. Such novel techniques have been under
thermal conductivities and values derived from
development by using inverse analysis and design of
measurements of thermal diffusivity and specific heat for
optimum experiments approaches [4]. Among the
certain well-known isotropic materials. Clearly such
techniques already available, we can find those for the
differences and uncertainties create serious problems for the
identification of the thermal conductivity components of
scientists and engineers requiring reliable data for whatever
orthotropic materials [5-9], of thermophysical properties of
material and/or application of concern to them.
ablating materials [10], of the heat capacity and thermal
The final goal is the development, certification and conductivity of solids [11,12] and of the heat and mass
provision of reference materials, both in Brazil and abroad, transfer properties of drying bodies [13,14].
designed to meet the increasing scientific and commercial
requirements. Reference materials (RM) are materials or
3. LITERATURE REVIEW
substances with sufficiently well established properties,
which can be used for calibrating instruments, assessing The thermal diffusivity, α, of a medium is the
measurement methods or assigning values to materials. thermophysical property that is associated with the
Reference Materials are the key to guarantee reliability and propagation of heat into a medium during changes of
accuracy for technical measurement data. temperature in time. The higher the thermal diffusivity, the
In addition to reference materials we can refer to reference faster is the propagation of heat. The thermal diffusivity is
procedures (RP). We define reference procedures as those related to the thermal conductivity, k, specific heat, Cp, and
that have been designed to deliver results, which can be used density, ρ, as follows:
as a reference. The term “reference procedure” applies to α = k /( ρC p ) (1)
testing, measurement and analysis, i.e. all procedures for
determining characteristics of materials, products and The thermal diffusivity has the dimension length2/time and it
processes. These characteristics can be of quantitative or is usually expressed in the unit m2/s. The most popular
qualitative form, and they can be defined independently or method used for measuring thermal diffusivity is the flash
by the procedure itself. method. It has the advantage of being fast while providing
Reference procedures are used to validate other procedures, values with excellent accuracy and reproducibility. After the
to characterize reference materials or reference objects, as sample has been stabilized at a desired uniform temperature,
T0, a nearly instantaneous pulse of energy (usually laser,
Xenon lamp, or other discharge source) is imposed on its depends only on the shape of the temperature vs. time curve
front surface, and the temperature increase on the rear (Fig. 2) and thickness of the solid.
surface of the sample is recorded as a function of time (Fig.
1). The thermal diffusivity is then determined by comparing IR detector
this thermogram with theoretical models that describe this
transient heat conduction phenomenon. These models are Signal
discussed next. amplifier
Data
aquisition
3.1. The Parker Analysis

Furnace
Furnace
Parker et al [2] developed the earliest method of analysis in Test sample power
1961. The authors modeled the heat pulse diffusion by supply
conduction in a perfectly insulated solid of thickness L,
using a one-dimensional transient formulation. Parker et al
[2] assumed that all the light energy Q was absorbed Heat pulse
power
instantaneously in a very thin layer g of the sample material source Computer, and
supply
facing the heat pulse source (zero pulse width), and that the (Flash) software
material properties were constant over the small temperature
range of the measurement. Under these conditions, the Figure 1. Schematic of Flash Method
temperature at the rear face (x = L) of the solid at any time thermal diffusivity measurement
can be written as [15]: We note the interesting fact that the time corresponding to



half of the maximum temperature, which is the selected time


αt


Q to compute the thermal diffusivity with equation (6), results


T ( L, t ) = 1 + 2 ( −1) n exp − n 2π 2 2

 

(2)
ρC p L


in a large sensitivity coefficient [16]. Therefore, the use of




n =1 L
such time results in an accurate estimated value for thermal
where ρ, Cp and α are the density, the specific heat, and the conductivity, if the experimental implementation of the
thermal diffusivity of the solid, respectively. Equation (2) method is in accordance with the proposed theoretical
can be written in a dimensionless format, by using the model.
following non-dimensional parameters:
Parker et al. [2] compared data obtained from Eq. (6) with
Θ = T ( L, t ) / Tm (3) several other sources, obtaining good agreement and
maximum deviations on the order of ± 5%. However, this
τ = αt / L2 (4) model is somewhat limited in applicability because it
neglected the heat loss effect from the material surfaces
where Tm is the maximum temperature rise at the rear (adiabatic condition), and it assumed instantaneous pulse
surface [Tm = T(L, t → )]. By substituting Eq. (3) and (4)

heating in the front surface of the solid. These effects


into Eq. (2) we obtain: become more evident at high temperatures.

Θ(τ ) = 1 + 2 ( −1) n exp( −n 2π 2τ )


(5) 3.2. Analyses Accounting for Heat Losses


n =1
Cowan [17] derived in 1963 equations for the temperature
Equation (5) is a function of the non-dimensional time τ distribution within a thin slab of solid material, which has
only. Figure 2 shows the variation of the non-dimensional received a short pulse of energy on one surface, for the case
temperature Θ as a function of τ. According to Parker et al. in which energy losses at the surfaces by radiation or
[2], the thermal diffusivity α can be determined from Eq. (5) convection to surroundings at T0 are not negligible. When
and Fig. 2, at the point where the non-dimensional heat is lost from the sample surface, the temperature vs. time
temperature Θ is equal to 0.5. At this point, the non- curve reaches its maximum at a lower temperature when
compared to the adiabatic case. After the peak, the solid
dimensional time τ is equal to 0.1388, and from Eq. (5) it
temperature drops off due to the cooling effect provided by
follows that:
the heat loss. Additionally, it was also assumed that the
0.1388L2 energy pulse was rectangular in shape and of relatively short
α= (6) duration (pulse time tpulse << t0.5). The expression for the rear
t0.5
surface temperature derived by Cowan [17] is:
where t0.5 is the time required for the back surface ∞


Q
temperature to reach half of the maximum temperature rise. Θ(τ ) = exp( −aτ ) + 2 (−1) n exp( −n 2π 2τ )
 

(7)
Therefore, the thermal diffusivity α can be directly ρC p L


 

n =1
determined from Eq. (6) by measuring the time where the
non-dimensional temperature Θ equals 0.5 (t0.5). It is where τ is defined by Eq. (4) and Θ(τ) = T(L, τ) – T0. The
important to observe that it is not necessary to know the non-dimensional parameter a in the first term on the right
amount of energy absorbed in the front surface in order to hand side of Eq. (7) accounts for the heat losses at the solid,
determine the thermal diffusivity with this method, which and it is given by:
1,0 determining thermal diffusivity based on analysis of the
heating part of the curve (i.e., before the back surface
0,9
temperature reaches its maximum). Clark and Taylor [18]
0,8 determined five points on the time scale corresponding to
five different dimensionless temperatures as measured on

0,7 the temperature rise curve. These times were t0.2, t0.3, t0.4, t0.7
and t0.8. They developed a theoretical relationship between
0,6
the dimensionless time τ in Eq. (4) and the following three
Θ(τ)

0,5 sets of time ratios:

0,4
1,0
0,3
0,9
0,2
0,8
0,1
0,7
0,0

Cp Θ( )L/Q
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0 0,6
τ
0,5
Figure 2. Thermal diffusivity measurement
according to Parker et al. [2]. 0,4 a=0
0,3 a = 0.01
 
 a = 0.1
1 dW 1 dW 0,2 a = 0.5
a=L +


  

(8)
a=1
 

k dT x = 0 k dT x = L


0,1
where W is the heat flux lost to the ambient at the surfaces at 0,0
x = 0 and x = L. It is clear that if there are no heat losses 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
from the solid surfaces, a = 0 and Eq. (7) turns into Eq. (5),
which represents the case modeled by Parker et al. [2]. = t/L2
Figure 3. Thermal diffusivity measurement
This method requires the knowledge of the value of a at according to Cowan [5].
least approximately, for maximum accuracy. In the case of
radiation losses only, a rough knowledge of the sample
emissivity ε may give a with sufficient accuracy from [17]:
Θ(t0.7)/Θ(t0.3), Θ(t0.8)/Θ(t0.4), and Θ(t0.8)/Θ(t0.2) (11)
a ≈ 2.3 × 10 {[1 + (TL / T0 ) ](T / 1000) (εL / k )}
5 3 3 (9) The three values resulting from these ratios are very close
and are averaged to compute the thermal diffusivity value.
Since Equation (8) correlate Θ and τ as a function of a, an
alternative approach for the thermal diffusivity estimation is Koski [18] presented a two-dimensional transient analysis of
to experimentally measure the ratios: the heat transfer problem, including a dimensionless heat
loss factor to characterize the radiative losses form the
Θ(5t0.5)/Θ(t0.5) or Θ(10t0.5)/Θ(t0.5) (10) sample.
and then find the value of τ for a given heat loss estimation. ∞
Q γ n2 (γ n2 + Bi 2 ) cos(γ n )
Θ( L,τ ) = 2 exp( −γ n2τ )

When there is no heat loss from the sample (a = 0), the rear (12)
surface temperature remains constant after reaching its ρC p n =1 γ n2 + Bi 2 + 2Bi
maximum and the ratio Θ(5t0.5)/Θ(t0.5) [or Θ(10t0.5)/Θ(t0.5)]
where γn are the roots of:
becomes 2. The non-dimensional time τ in equation (7) then
becomes 0.1388 as in Parker’s [2] analysis. Although this 2γ n Bi
method accounts for the heat losses, two aspects of this tan γ n = (13)
γ n2 − Bi 2
model may be considered as source of errors: 1) the derived
equations require estimation of parameters, such as the The radiative losses parameter is written in a Biot number
amount of heat loss per square meter; 2) the use of Eq. (9) is format, and it is given by:
tied to the solid thermal conductivity k, which must be
known a priori. 4σεT 3 L
Rloss ≡ Bi = (14)
Clark and Taylor [18] proposed in 1975 another method for k
the thermal diffusivity measurement based on Cowan’s [17] where σ is the Stefan-Boltzmann constant, ε is the surface
procedure. However, instead of analyzing the cooling part of emissivity, T is the average absolute temperature of sample
the temperature rise curve, they proposed a method for front and back faces, L is the sample thickness, and k is the
sample thermal conductivity. The radiative Biot number is curve. Degiovanni and Laurent [20] assumed that the laser
determined in the Koski [17] analysis and provides a pulse width is small compared to the half-rise time t0.5 (i.e.,
measure of the heat loss during the measurement. When there is no finite pulse width correction). The analysis
Bi = 0, there is no heat loss from the sample. Equation (14) allows for heat loss from all sides of the sample, and it
is useful in that it shows how the various variables influence should yield accurate results on thick samples of low
the loss factor. Koski's [17] analysis also allows the laser thermal diffusivity.
pulse width, tpulse to be relatively long, as compared to the
characteristic heating time. 3.3. Heat Capacity Estimations
Koski [17] uses five time and temperature ratios including The specific heat of a material is defined as the amount of
those four indicated in Eqs. (10) and (11), and an additional energy required to raise a unit mass of material by one unit
ratio: of temperature at constant pressure:
Θ(tpulse)/Θ(t0.5) (15) Q
Cp = (19)
Koski [17] generated a series of coefficients that can be used m∆T
in conjunction with various combinations of the five
temperature ratios and temperature ratios to calculate three where Cp is the specific heat, Q is the energy, m is the
values of the dimensionless time τ parameter in Eq. (4) materials mass, and ∆T is the change in temperature.
based on Clark and Taylor's time ratios, and one value of the Specific heat can be measured with the flash method by
τ parameter based on Cowan's temperature ratio. The three comparing the temperature rise of the sample to the
Clark and Taylor results are then averaged. Loss factors (Eq. temperature rise of a reference sample of known specific
14) are also computed for each case. The results of the heat tested under the same conditions [2]. This temperature
Koski [17] analysis are limited to cases where the loss factor rise is recorded during the diffusivity measurement, so the
Bi is less than 1.2 and the pulse time is less than t0.5. Flash specific heat can be calculated from the same data with a
method measurements based on a Xenon Lamp usually have suitable calibration. Assuming that the light pulse energy
a minimum pulse width of 100µs. This means that t0.5 must and its coupling to the sample remain essentially unchanged
be greater than 100µs in all cases. Even when testing thin between samples, Eq. (19) can be rewritten as follows:
samples of high diffusivity material, t0.5 is likely to be
greater than 100µs. The Koski [17] method thus produces Q = Absorbed energy = (∆T m Cp)sample = (∆T m Cp)ref (20)
two values of thermal diffusivity and loss factor for each Or, simply:
test. The results are typically very close. Koski [17]
recommends that the results based on the Clark and Taylor (m∆TC p ) ref
[16] ratios be selected for most conventional tests. (C p ) sample = (21)
(m∆T ) sample
Degiovanni and Laurent [18] developed a different method
of analyzing the experimentally obtained temperature rise A reference sample is measured at each temperature of
curve in 1986. Degiovanni and Laurent [18] used the time interest to calibrate the change in output voltage of the IR
integral of the temperature rise curve, Θ vs. t, which detector ( V) resulting from the absorbed laser energy. The


represent the area under the curve, to describe its shape. In measured V divided by the detector amplifier gain (G) will


addition, a second time integral is calculated representing be proportional to the temperature rise ( T), as long as the


the area under the curve Θ/t vs. t, which can easily be temperature rise is small. This calibration gives the absorbed
derived from the temperature history curve. The integration energy or calibration factor in terms of the mass, specific
is carried out between the limits t0.1 and t0.8: heat, V and G for the reference sample measurement.


When a sample of unknown specific heat is measured, the


t0.8
absorbed energy divided by the product of the mass and
m0 = Θdt (16)
t0.1  V/G of the test sample, Equation (21), gives the test sample
specific heat.
and 

The measured V will be affected by heat loss during the


Θ


t0.8 measurement, so in order to use ratios of the measured V in


m−1 = dt (17)


t0.1 t Equation (21), the heat loss factors (see section the Koski
[19] analysis) of the reference and test sample should be
Between certain limits of the value of m–1, a unique similar. Tests have shown that the light pulse energy is
relationship exists between m0 and m–1 that can be expressed stable from pulse to pulse within about ±2%, so the average
as: of several laser pulses at each temperature are used in the
calculations. The absorptive efficiency of the front surface
m0 = ( L2 / α )[ F (m−1 )] (18) of the samples to the light pulse and the radiative efficiency
of the back surface to the IR detector are controlled by
where F(m–1) is a polynomial function of m–1, whose coating the reference and test samples with a thin layer of
coefficients were derived by Degiovanni and Laurent [18]. graphite.
The thermal diffusivity can be computed from Eq. (18) once
the two integrals have been calculated from the experimental 3.4. Thermal Conductivity Estimations
The thermal conductivity of a sample can be calculated from REFERENCES
Eq. (1) using the diffusivity and specific heat data obtained
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[19] Koski, J. A. Improved Data Reduction Methods for Laser Graças 50, Xerém, RJ, 25250-020, Brazil.
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[20] Degiovanni, A. and Laurent, M., Une Nouvelle Technique Cláudio S. P. Costa, M.Sc.: Researcher, Department of
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Henrique Massard: Undergraduate Student, Department of
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