From Wikipedia, the free encyclopedia
Thermal
conductivity (often denoted
k,
λ, or
κ) is the
property of a material to
conduct heat. It is evaluated primarily in terms of the
Fourier's Law for
heat conduction. In general, thermal conductivity is a
tensor property, expressing the
anisotropy of the property.
Heat transfer occurs at a lower rate in materials of low thermal
conductivity than in materials of high thermal conductivity.
Correspondingly, materials of high thermal conductivity are widely used
in
heat sink applications and materials of low thermal conductivity are used as
thermal insulation. The thermal conductivity of a material may depend on temperature. The reciprocal of thermal conductivity is called
thermal resistivity.
Units of thermal conductivity
In the
International System of Units (SI), thermal conductivity is measured in watts per meter-kelvin (
W/(
m⋅
K)). The
dimension of thermal conductivity is M
1L
1T
−3Θ
−1, expressed in terms of the dimensions mass (M), length (L), time (T), and temperature (Θ). In
Imperial units, thermal conductivity is measured in
BTU/(
hr⋅
ft⋅
°F).
[note 1][1]
Other units which are closely related to the thermal conductivity are
in common use in the construction and textile industries. The
construction industry makes use of units such as the
R-value (resistance) and the
U-value
(transmittance). Although related to the thermal conductivity of a
material used in an insulation product, R- and U-values are dependent on
the thickness of the product.
[note 2]
Likewise the textile industry has several units including the
tog and the
clo which express thermal resistance of a material in a way analogous to the R-values used in the construction industry.
Measurement
There are a number of ways to measure thermal conductivity. Each of
these is suitable for a limited range of materials, depending on the
thermal properties and the medium temperature. There is a distinction
between steady-state and transient techniques.
In general, steady-state techniques are useful when the temperature
of the material does not change with time. This makes the signal
analysis straightforward (steady state implies constant signals). The
disadvantage is that a well-engineered experimental setup is usually
needed. The Divided Bar (various types) is the most common device used
for consolidated rock solids.
Experimental values
Experimental values of thermal conductivity.
Thermal conductivity is important in material science, research, electronics,
building insulation and related fields, especially where high operating temperatures are achieved. Several materials are shown in the
list of thermal conductivities. These should be considered approximate due to the uncertainties related to material definitions.
High energy generation rates within
electronics or
turbines require the use of materials with high thermal conductivity such as
copper (see: Copper in heat exchangers),
aluminium, and
silver. On the other hand, materials with low thermal conductance, such as
polystyrene and
alumina, are used in building
construction or in
furnaces in an effort to slow the flow of heat, i.e. for insulation purposes.
Definitions
The reciprocal of thermal conductivity is
thermal resistivity, usually expressed in kelvin-meters per watt (K⋅m⋅W
−1). For a given thickness of a material, that particular construction's
thermal resistance and the reciprocal property,
thermal conductance, can be calculated. Unfortunately, there are differing definitions for these terms.
Thermal conductivity,
k, often depends on temperature.
Therefore, the definitions listed below make sense when the thermal
conductivity is temperature independent. Otherwise a representative mean
value has to be considered; for more, see the
equations section below.
Conductance
For general scientific use,
thermal conductance is the quantity of heat that passes in unit time through a plate of
particular area and thickness when its opposite faces differ in temperature by one kelvin. For a plate of thermal conductivity
k, area
A and thickness
L, the conductance calculated is
kA/
L, measured in W⋅K
−1
(equivalent to: W/°C). ASTM C168-15, however, defines thermal
conductance as "time rate of steady state heat flow through a unit area
of a material or construction induced by a unit temperature difference
between the body surfaces" and defines the units as W/(m
2⋅K) (Btu/(h⋅ft
2⋅°F))
[2]
The thermal conductance of that particular construction is the
inverse of the thermal resistance. Thermal conductivity and conductance
are
analogous to
electrical conductivity (A⋅m
−1⋅V
−1) and
electrical conductance (A⋅V
−1).
There is also a measure known as
heat transfer coefficient: the quantity of heat that passes in unit time through a
unit area of a plate of particular thickness when its opposite faces differ in temperature by one kelvin. The reciprocal is
thermal insulance. In summary:
- thermal conductance = kA/L, measured in W⋅K−1 or in ASTM C168-15 as W/(m2⋅K)[2]
- thermal resistance = L/(kA), measured in K⋅W−1 (equivalent to: °C/W)
- heat transfer coefficient = k/L, measured in W⋅K−1⋅m−2
- thermal insulance = L/k, measured in K⋅m2⋅W−1.
The heat transfer coefficient is also known as
thermal admittance in the sense that the material may be seen as admitting heat to flow.
Resistance
Thermal resistance is the ability of a material to resist the flow of heat.
Thermal resistance is the reciprocal of thermal conductance, i.e.,
lowering its value will raise the heat conduction and vice versa.
When thermal resistances occur in
series, they are
additive.
Thus, when heat flows consecutively through two components each with a
resistance of 3 °C/W, the total resistance is 3 °C/W + 3 °C/W = 6 °C/W.
A common engineering design problem involves the selection of an appropriate sized
heat sink
for a given heat source. Working in units of thermal resistance greatly
simplifies the design calculation. The following formula can be used to
estimate the performance:
where:
- Rhs is the maximum thermal resistance of the heat sink to ambient, in °C/W (equivalent to K/W)
- ΔT is the required temperature difference (temperature drop), in °C
- Pth is the thermal power (heat flow), in watts
- Rs is the thermal resistance of the heat source, in °C/W
For example, if a component produces 100 W of heat, and has a thermal
resistance of 0.5 °C/W, what is the maximum thermal resistance of the
heat sink? Suppose the maximum temperature is 125 °C, and the ambient
temperature is 25 °C; then Δ
T is 100 °C. The heat sink's thermal
resistance to ambient must then be 0.5 °C/W or less (total resistance
component and heat sink is then 1.0 °C/W).
Transmittance
A third term,
thermal transmittance, sub way the thermal conductance of a structure along with heat transfer due to
convection and
radiation. It is measured in the same units as thermal conductance and is sometimes known as the
composite thermal conductance. The term
U-value is often used.
Admittance
The
thermal admittance of a material, such as a building fabric, is a
measure of the ability of a material to transfer heat in the presence of
a temperature difference on opposite sides of the material. Thermal
admittance is measured in the same units as a heat transfer coefficient,
power (watts) per unit area (square meters) per temperature change
(kelvins). Thermal admittance of a building fabric affects a building's
thermal response to variation in outside temperature.
[3]
Co-efficient of thermal conductivity: The co-efficient of thermal
conductivity of the material of a substance is numerically equal to the
quantity of heat that conducts in one second normally through a slab of
unit length and unit area, the difference of temperature between its end
faces being one degree.
Influencing factors
Effect of temperature on thermal conductivity
The
effect of temperature on thermal conductivity is different for metals
and nonmetals. In metals, heat conductivity is primarily due to free
electrons. Following the
Wiedemann–Franz law, thermal conductivity of metals is approximately proportional to the absolute temperature (in
kelvins)
times electrical conductivity. In pure metals the electrical
conductivity decreases with increasing temperature and thus the product
of the two, the thermal conductivity, stays approximately constant. However, as temperatures approach absolute zero, the thermal
conductivity decreases sharply.
[4]
In alloys the change in electrical conductivity is usually smaller and
thus thermal conductivity increases with temperature, often
proportionally to temperature. Many pure metals have a peak thermal
conductivity between 2 K and 10 K.
On the other hand, heat conductivity in nonmetals is mainly due to lattice vibrations (
phonons). Except for high quality crystals at low temperatures, the phonon mean
free path is not reduced significantly at higher temperatures. Thus, the
thermal conductivity of nonmetals is approximately constant at high
temperatures. At low temperatures well below the
Debye temperature, thermal conductivity decreases, as does the heat capacity, due to
carrier scattering from defects at very low temperatures.
[4]
Chemical phase
When
a material undergoes a phase change from solid to liquid or from liquid
to gas the thermal conductivity may change. An example of this would be
the change in thermal conductivity that occurs when ice (thermal
conductivity of 2.18 W/(m⋅K) at 0 °C) melts to form liquid water
(thermal conductivity of 0.56 W/(m⋅K) at 0 °C).
[5]
Thermal anisotropy
Some substances, such as non-
cubic crystals, can exhibit different thermal conductivities along different crystal axes, due to differences in
phonon coupling along a given crystal axis.
Sapphire
is a notable example of variable thermal conductivity based on
orientation and temperature, with 35 W/(m⋅K) along the C-axis and
32 W/(m⋅K) along the A-axis.
[6] Wood
generally conducts better along the grain than across it. Other
examples of materials where the thermal conductivity varies with
direction are metals that have undergone
heavy cold pressing,
laminated materials, cables, the materials used for the
Space Shuttle thermal protection system, and
fiber-reinforced composite structures.
[7]
When anisotropy is present, the direction of heat flow may not be exactly the same as the direction of the thermal gradient.
Electrical conductivity
In metals, thermal conductivity approximately tracks electrical conductivity according to the
Wiedemann–Franz law, as freely moving
valence electrons
transfer not only electric current but also heat energy. However, the
general correlation between electrical and thermal conductance does not
hold for other materials, due to the increased importance of
phonon carriers for heat in non-metals. Highly electrically conductive
silver is less thermally conductive than
diamond, which is an
electrical insulator, but due to its orderly array of atoms it is conductive of heat via phonons.
Magnetic field
The influence of magnetic fields on thermal conductivity is known as the
Righi-Leduc effect.
Convection
Exhaust system components with ceramic coatings having a low thermal conductivity reduce heating of nearby sensitive components
Air and other gases are generally good insulators, in the absence of
convection. Therefore, many insulating materials function simply by
having a large number of gas-filled pockets which prevent large-scale
convection. Examples of these include expanded and extruded
polystyrene (popularly referred to as "styrofoam") and silica
aerogel, as well as warm clothes. Natural, biological insulators such as fur and
feathers achieve similar effects by dramatically inhibiting convection of air or water near an animal's skin.
Light gases, such as
hydrogen and
helium typically have high thermal conductivity. Dense gases such as
xenon and
dichlorodifluoromethane have low thermal conductivity. An exception,
sulfur hexafluoride, a dense gas, has a relatively high thermal conductivity due to its high
heat capacity.
Argon and
krypton, gases denser than air, are often used in
insulated glazing (double paned windows) to improve their insulation characteristics.
Isotopic purity
Isotopically pure diamond can have a significantly higher thermal conductivity.
[8] eg. 41,000
W·
m−1·
K−1 [9] (99.999%
12C calc.200,000
[9])
Physical origins
At
the atomic level, there are no simple, correct expressions for thermal
conductivity. Atomically, the thermal conductivity of a system is
determined by how atoms composing the system interact. There are two
different approaches for calculating the thermal conductivity of a
system.
- The first approach employs the Green–Kubo relations.
Although this employs analytic expressions, which, in principle, can be
solved, calculating the thermal conductivity of a dense fluid or solid
using this relation requires the use of molecular dynamics computer simulation.
- The second approach is based on the relaxation time approach. Due to
the anharmonicity within the crystal potential, the phonons in the
system are known to scatter. There are three main mechanisms for
scattering:
- Boundary scattering, a phonon hitting the boundary of a system;
- Mass defect scattering, a phonon hitting an impurity within the system and scattering;
- Phonon-phonon scattering, a phonon breaking into two lower energy
phonons or a phonon colliding with another phonon and merging into one
higher-energy phonon.
Lattice waves
Heat transport in both amorphous and crystalline
dielectric solids is by way of elastic vibrations of the lattice (
phonons).
This transport mode is limited by the elastic scattering of acoustic
phonons at lattice defects. These predictions were confirmed by the
experiments of Chang and Jones on commercial glasses and glass ceramics,
where the mean free paths were limited by "internal boundary
scattering" to length scales of 10
−2 cm to 10
−3 cm.
[10][11]
The phonon mean free path has been associated directly with the
effective relaxation length for processes without directional
correlation. If V
g is the group velocity of a phonon wave packet, then the relaxation length
is defined as:
where
t is the characteristic relaxation time. Since longitudinal waves have a much greater phase velocity than transverse waves,
Vlong is much greater than
Vtrans,
and the relaxation length or mean free path of longitudinal phonons
will be much greater. Thus, thermal conductivity will be largely
determined by the speed of longitudinal phonons.
[10][12]
Regarding the dependence of wave velocity on wavelength or frequency (
dispersion), low-frequency phonons of long wavelength will be limited in relaxation length by elastic
Rayleigh scattering.
This type of light scattering from small particles is proportional to
the fourth power of the frequency. For higher frequencies, the power of
the frequency will decrease until at highest frequencies scattering is
almost frequency independent. Similar arguments were subsequently
generalized to many glass forming substances using
Brillouin scattering.
[13][14][15][16]
Phonons in the acoustical branch dominate the phonon heat conduction
as they have greater energy dispersion and therefore a greater
distribution of phonon velocities. Additional optical modes could also
be caused by the presence of internal structure (i.e., charge or mass)
at a lattice point; it is implied that the group velocity of these modes
is low and therefore their contribution to the lattice thermal
conductivity
λL (
L) is small.
[17]
Each phonon mode can be split into one longitudinal and two
transverse polarization branches. By extrapolating the phenomenology of
lattice points to the unit cells it is seen that the total number of
degrees of freedom is 3
pq when
p is the number of primitive cells with
q atoms/unit cell. From these only 3p are associated with the acoustic modes, the remaining 3
p(
q − 1) are accommodated through the optical branches. This implies that structures with larger
p and
q contain a greater number of optical modes and a reduced
λL.
From these ideas, it can be concluded that increasing crystal
complexity, which is described by a complexity factor CF (defined as the
number of atoms/primitive unit cell), decreases λ
L.
Micheline Roufosse and P.G. Klemens derived the exact proportionality in
their article Thermal Conductivity of Complex Dielectric Crystals at
Phys. Rev. B 7, 5379–5386 (1973). This was done by assuming that the
relaxation time
τ decreases with increasing number of atoms in
the unit cell and then scaling the parameters of the expression for
thermal conductivity in high temperatures accordingly.
[17]
Describing of anharmonic effects is complicated because exact
treatment as in the harmonic case is not possible and phonons are no
longer exact eigensolutions to the equations of motion. Even if the
state of motion of the crystal could be described with a plane wave at a
particular time, its accuracy would deteriorate progressively with
time. Time development would have to be described by introducing a
spectrum of other phonons, which is known as the phonon decay. The two
most important anharmonic effects are the thermal expansion and the
phonon thermal conductivity.
Only when the phonon number ‹n› deviates from the equilibrium value ‹n›
0, can a thermal current arise as stated in the following expression
where
v is the energy transport velocity of phonons. Only two mechanisms exist that can cause time variation of ‹
n›
in a particular region. The number of phonons that diffuse into the
region from neighboring regions differs from those that diffuse out, or
phonons decay inside the same region into other phonons. A special form
of the
Boltzmann equation
states this. When steady state conditions are assumed the total time
derivate of phonon number is zero, because the temperature is constant
in time and therefore the phonon number stays also constant. Time
variation due to phonon decay is described with a relaxation time (
τ) approximation
which states that the more the phonon number deviates from its
equilibrium value, the more its time variation increases. At steady
state conditions and local thermal equilibrium are assumed we get the
following equation
Using the relaxation time approximation for the Boltzmann equation
and assuming steady-state conditions, the phonon thermal conductivity
λL can be determined. The temperature dependence for
λL originates from the variety of processes, whose significance for
λL depends on the temperature range of interest. Mean free path is one factor that determines the temperature dependence for
λL, as stated in the following equation
where Λ is the mean free path for phonon and
denotes the
heat capacity. This equation is a result of combining the four previous equations with each other and knowing that
for cubic or isotropic systems and
.
[18]
At low temperatures (< 10 K) the anharmonic interaction does not
influence the mean free path and therefore, the thermal resistivity is
determined only from processes for which q-conservation does not hold.
These processes include the scattering of phonons by crystal defects, or
the scattering from the surface of the crystal in case of high quality
single crystal. Therefore, thermal conductance depends on the external
dimensions of the crystal and the quality of the surface. Thus,
temperature dependence of λ
L is determined by the specific heat and is therefore proportional to T
3.
[18]
Phonon quasimomentum is defined as ℏq and differs from normal
momentum because it is only defined within an arbitrary reciprocal
lattice vector. At higher temperatures (10 K <
T <
Θ), the conservation of energy
and quasimomentum
, where
q1 is wave vector of the incident phonon and
q2,
q3 are wave vectors of the resultant phonons, may also involve a reciprocal lattice vector
G complicating the energy transport process. These processes can also reverse the direction of energy transport.
Therefore, these processes are also known as Umklapp (U) processes and can only occur when phonons with sufficiently large
q-vectors are excited, because unless the sum of
q2 and
q3
points outside of the Brillouin zone the momentum is conserved and the
process is normal scattering (N-process). The probability of a phonon to
have energy
E is given by the Boltzmann distribution
. To U-process to occur the decaying phonon to have a wave vector
q1 that is roughly half of the diameter of the Brillouin zone, because otherwise quasimomentum would not be conserved.
Therefore, these phonons have to possess energy of
,
which is a significant fraction of Debye energy that is needed to
generate new phonons. The probability for this is proportional to
, with
. Temperature dependence of the mean free path has an exponential form
.
The presence of the reciprocal lattice wave vector implies a net phonon
backscattering and a resistance to phonon and thermal transport
resulting finite
λL,
[17] as it means that momentum is not conserved. Only momentum non-conserving processes can cause thermal resistance.
[18]
At high temperatures (
T > Θ), the mean free path and therefore
λL has a temperature dependence
T−1, to which one arrives from formula
by making the following approximation
[clarification needed] and writing
.
This dependency is known as Eucken's law and originates from the
temperature dependency of the probability for the U-process to occur.
[17][18]
Thermal conductivity is usually described by the Boltzmann equation
with the relaxation time approximation in which phonon scattering is a
limiting factor. Another approach is to use analytic models or molecular
dynamics or Monte Carlo based methods to describe thermal conductivity
in solids.
Short wavelength phonons are strongly scattered by impurity atoms if
an alloyed phase is present, but mid and long wavelength phonons are
less affected. Mid and long wavelength phonons carry significant
fraction of heat, so to further reduce lattice thermal conductivity one
has to introduce structures to scatter these phonons. This is achieved
by introducing interface scattering mechanism, which requires structures
whose characteristic length is longer than that of impurity atom. Some
possible ways to realize these interfaces are nanocomposites and
embedded nanoparticles/structures.
[19]
Electronic thermal conductivity
Hot
electrons from higher energy states carry more thermal energy than cold
electrons, while electrical conductivity is rather insensitive to the
energy distribution of carriers because the amount of charge that
electrons carry, does not depend on their energy. This is a physical
reason for the greater sensitivity of electronic thermal conductivity to
energy dependence of density of states and relaxation time,
respectively.
[17]
Mahan and Sofo (
PNAS 1996 93 (15) 7436-7439) showed that
materials with a certain electron structure have reduced electron
thermal conductivity. Based on their analysis one can demonstrate that
if the electron density of states in the material is close to the
delta-function, the electronic thermal conductivity drops to zero. By
taking the following equation
, where λ
0
is the electronic thermal conductivity when the electrochemical
potential gradient inside the sample is zero, as a starting point. As
next step the transport coefficients are written as following
- ,
- ,
where
and
a0 the Bohr radius. The dimensionless integrals
In are defined as
- ,
where
s(
x) is the dimensionless transport distribution function. The integrals
In are the moments of the function
- ,
where
x is the energy of carriers. By substituting the previous formulas for the transport coefficient to the equation for
λE we get the following equation
- .
From the previous equation we see that
λE to be zero the bracketed term containing
In terms have to be zero. Now if we assume that
- ,
where
δ is the
Dirac delta function,
In terms get the following expressions
- ,
- ,
- .
By substituting these expressions to the equation for
λE, we see that it goes to zero. Therefore,
P(
x) has to be delta function.
[19]
Equations
In an isotropic medium the thermal conductivity is the parameter
k in the Fourier expression for the heat flux
where
is the heat flux (amount of heat flowing per second and per unit area) and
the temperature
gradient. The sign in the expression is chosen so that always
k
> 0 as heat always flows from a high temperature to a low
temperature. This is a direct consequence of the second law of
thermodynamics.
In the one-dimensional case
q =
H/
A with
H the amount of heat flowing per second through a surface with area
A and the temperature gradient is d
T/d
x so
In case of a thermally insulated bar (except at the ends) in the steady state
H is constant. If
A is constant as well the expression can be integrated with the result
where
TH and
TL are the temperatures at the hot end and the cold end respectively, and
L is the length of the bar. It is convenient to introduce the thermal-conductivity integral
The heat flow rate is then given by
If the temperature difference is small
k can be taken as constant. In that case
Simple kinetic picture
Gas atoms moving randomly through a surface.
In this section we will motivate an expression for the thermal conductivity in terms of microscopic parameters.
Consider a gas of particles of negligible volume governed hard-core
interactions and within a vertical temperature gradient. The upper side
is hot and the lower side cold. There is a downward energy flow because
the gas atoms, going down, have a higher energy than the atoms going up.
The net flow of energy per second is the heat flow
H, which is proportional to the number of particles that cross the area
A per second. In fact,
H should also be proportional to the particle density
n, the mean particle velocity
v, the amount of energy transported per particle so with the heat capacity per particle
c and some characteristic temperature difference Δ
T. So far, in our model,
The unit of
H is J/s and of the right-hand side it is (particle/m
3) × (m/s) × (J/(K × particle)) × (m
2) × (K) = J/s, so this is already of the right dimension. Only a numerical factor is missing. For Δ
T we take the temperature difference of the gas between two collisions
where
l is the mean free path.
Detailed kinetic calculations
[20] show that the numerical factor is -1/3, so, all in all,
Comparison with the one-dimension expression for the heat flow, given above, gives an expression for the factor
k
The particle density and the heat capacity per particle can be combined as the heat capacity per unit volume so
where
CV is the molar heat capacity at constant volume and
Vm the molar volume.
More rigorously, the mean free path of a molecule in a gas is given by
where
σ is the collision cross section. So
The heat capacity per particle
c and the cross section
σ both are temperature independent so the temperature dependence of
k is determined by the
T dependence of
v. For a monatomic gas, with atomic mass
M,
v is given by
So
This expression also shows why gases with a low mass (hydrogen, helium) have a high thermal conductivity.
For
metals at low temperatures the heat is carried mainly by
the free electrons. In this case the mean velocity is the Fermi velocity
which is temperature independent. The mean free path is determined by
the impurities and the crystal imperfections which are temperature
independent as well. So the only temperature-dependent quantity is the
heat capacity
c, which, in this case, is proportional to
T. So
with
k0 a constant. For pure metals such as copper, silver, etc.
l
is large, so the thermal conductivity is high. At higher temperatures
the mean free path is limited by the phonons, so the thermal
conductivity tends to decrease with temperature. In alloys the density
of the impurities is very high, so
l and, consequently
k, are small. Therefore, alloys, such as stainless steel, can be used for thermal insulation.