Pyroelectricity
Encyclopedia
Pyroelectricity is the ability of certain materials to generate a temporary voltage
Voltage
Voltage, otherwise known as electrical potential difference or electric tension is the difference in electric potential between two points — or the difference in electric potential energy per unit charge between two points...

  when they are heated or cooled. The change in temperature modifies the positions of the atoms slightly within the crystal structure
Crystal structure
In mineralogy and crystallography, crystal structure is a unique arrangement of atoms or molecules in a crystalline liquid or solid. A crystal structure is composed of a pattern, a set of atoms arranged in a particular way, and a lattice exhibiting long-range order and symmetry...

, such that the polarization of the material changes. This polarization change gives rise to a voltage across the crystal. If the temperature stays constant at its new value, the pyroelectric voltage gradually disappears due to leakage current
Leakage (electronics)
In electronics, leakage may refer to a gradual loss of energy from a charged capacitor. It is primarily caused by electronic devices attached to the capacitors, such as transistors or diodes, which conduct a small amount of current even when they are turned off...

 (the leakage can be due to electrons moving through the crystal, ions moving through the air, current leaking through a voltmeter
Voltmeter
A voltmeter is an instrument used for measuring electrical potential difference between two points in an electric circuit. Analog voltmeters move a pointer across a scale in proportion to the voltage of the circuit; digital voltmeters give a numerical display of voltage by use of an analog to...

 attached across the crystal, etc.).

Pyroelectricity should not be confused with thermoelectricity: In a typical demonstration of pyroelectricity, the whole crystal is changed from one temperature to another, and the result is a temporary voltage across the crystal. In a typical demonstration of thermoelectricity, one side of the material is kept at one temperature and the other side at a different temperature, and the result is a permanent voltage across the crystal.

Explanation

Pyroelectricity can be visualized as one side of a triangle, where each corner represents energy states in the crystal: kinetic
Kinetic energy
The kinetic energy of an object is the energy which it possesses due to its motion.It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acceleration, the body maintains this kinetic energy unless its speed changes...

, electrical and thermal energy
Thermal energy
Thermal energy is the part of the total internal energy of a thermodynamic system or sample of matter that results in the system's temperature....

. The side between electrical and thermal corners represents the pyroelectric effect and produces no kinetic energy
Kinetic energy
The kinetic energy of an object is the energy which it possesses due to its motion.It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acceleration, the body maintains this kinetic energy unless its speed changes...

. The side between kinetic and electrical corners represents the piezoelectric effect and produces no heat
Heat
In physics and thermodynamics, heat is energy transferred from one body, region, or thermodynamic system to another due to thermal contact or thermal radiation when the systems are at different temperatures. It is often described as one of the fundamental processes of energy transfer between...

.

Although artificial pyroelectric materials have been engineered, the effect was first discovered in minerals such as tourmaline
Tourmaline
Tourmaline is a crystal boron silicate mineral compounded with elements such as aluminium, iron, magnesium, sodium, lithium, or potassium. Tourmaline is classified as a semi-precious stone and the gem comes in a wide variety of colors...

. The pyroelectric effect is also present in both bone
Bone
Bones are rigid organs that constitute part of the endoskeleton of vertebrates. They support, and protect the various organs of the body, produce red and white blood cells and store minerals. Bone tissue is a type of dense connective tissue...

 and tendon
Tendon
A tendon is a tough band of fibrous connective tissue that usually connects muscle to bone and is capable of withstanding tension. Tendons are similar to ligaments and fasciae as they are all made of collagen except that ligaments join one bone to another bone, and fasciae connect muscles to other...

.

Pyroelectric charge in mineral
Mineral
A mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition, highly ordered atomic structure, and specific physical properties. By comparison, a rock is an aggregate of minerals and/or mineraloids and does not...

s develops on the opposite faces of asymmetric crystals. The direction in which the propagation of the charge tends toward is usually constant throughout a pyroelectric material, but in some materials this direction can be changed by a nearby electric field. These materials are said to exhibit ferroelectricity
Ferroelectricity
Ferroelectricity is a property of certain materials which possess a spontaneous electric polarization that can be reversed by the application of an external electric field. The term is used in analogy to ferromagnetism, in which a material exhibits a permanent magnetic moment. Ferromagnetism was...

. All pyroelectric materials are also piezoelectric
Piezoelectricity
Piezoelectricity is the charge which accumulates in certain solid materials in response to applied mechanical stress. The word piezoelectricity means electricity resulting from pressure...

, the two properties being closely related. However, note that some piezoelectric materials have a crystal symmetry that does not allow pyroelectricity.

Very small changes in temperature can produce an electric potential due to a materials' pyroelectricity. Passive infrared sensors are often designed around pyroelectric materials, as the heat of a human or animal from several feet away is enough to generate a difference in charge.

History

The first reference to the pyroelectric effect is in writings by Theophrastus
Theophrastus
Theophrastus , a Greek native of Eresos in Lesbos, was the successor to Aristotle in the Peripatetic school. He came to Athens at a young age, and initially studied in Plato's school. After Plato's death he attached himself to Aristotle. Aristotle bequeathed to Theophrastus his writings, and...

 in 314 BC, who noted that tourmaline
Tourmaline
Tourmaline is a crystal boron silicate mineral compounded with elements such as aluminium, iron, magnesium, sodium, lithium, or potassium. Tourmaline is classified as a semi-precious stone and the gem comes in a wide variety of colors...

 attracted bits of straw and ash when heated. Tourmaline
Tourmaline
Tourmaline is a crystal boron silicate mineral compounded with elements such as aluminium, iron, magnesium, sodium, lithium, or potassium. Tourmaline is classified as a semi-precious stone and the gem comes in a wide variety of colors...

's properties were rediscovered in 1707 by Johann Georg Schmidt, who also noted the attractive properties of the mineral when heated. Pyroelectricity was first described—although not named as such—by Louis Lemery in 1717. In 1747 Linnaeus first related the phenomenon to electricity, although this was not proven until 1756 by Franz Ulrich Theodor Aepinus.

Research in pyroelectricity became more sophisticated in the 19th century. In 1824 Sir David Brewster
David Brewster
Sir David Brewster KH PRSE FRS FSA FSSA MICE was a Scottish physicist, mathematician, astronomer, inventor, writer and university principal.-Early life:...

 gave the effect the name it has today. Both William Thomson
William Thomson, 1st Baron Kelvin
William Thomson, 1st Baron Kelvin OM, GCVO, PC, PRS, PRSE, was a mathematical physicist and engineer. At the University of Glasgow he did important work in the mathematical analysis of electricity and formulation of the first and second laws of thermodynamics, and did much to unify the emerging...

 in 1878 and Woldemar Voigt
Woldemar Voigt
Woldemar Voigt was a German physicist, who taught at the Georg August University of Göttingen. Voigt eventually went on to head the Mathematical Physics Department at Göttingen and was succeeded in 1914 by Peter Debye, who took charge of the theoretical department of the Physical Institute...

 in 1897 helped develop a theory for the processes behind pyroelectricity. Pierre Curie
Pierre Curie
Pierre Curie was a French physicist, a pioneer in crystallography, magnetism, piezoelectricity and radioactivity, and Nobel laureate. He was the son of Dr. Eugène Curie and Sophie-Claire Depouilly Curie ...

 and his brother, Jacques Curie
Jacques Curie
Paul-Jacques Curie was a French physicist and professor at the University of Montpellier. He and his brother, Pierre Curie, studied pyroelectricity in the 1880s, leading to their discovery of some of the mechanisms behind piezoelectricity....

, studied pyroelectricity in the 1880s, leading to their discovery of some of the mechanisms behind piezoelectricity.

The pyroelectric crystal classes

Crystal structures can be divided into 32 classes, or point groups, according to the number of rotational axes and reflection planes they exhibit that leave the pyroelectric crystal
Pyroelectric crystal
Pyroelectric crystals are crystals that generate electricity when heated. It is similar to piezoelectricity.-Crystal symmetry:Crystal structures can be divided into 32 classes, or point groups, according to the number of rotational axes and reflection planes they exhibit that leave the crystal...

 structure unchanged. Of the thirty-two crystal classes, twenty-one are non-centrosymmetric (not having a centre of symmetry
Fixed points of isometry groups in Euclidean space
A fixed point of an isometry group is a point that is a fixed point for every isometry in the group. For any isometry group in Euclidean space the set of fixed points is either empty or an affine space....

). Of these twenty-one, twenty exhibit direct piezoelectricity
Piezoelectricity
Piezoelectricity is the charge which accumulates in certain solid materials in response to applied mechanical stress. The word piezoelectricity means electricity resulting from pressure...

, the remaining one being the cubic class 432. Ten of these twenty piezoelectric classes are polar, i.e., they possess a spontaneous polarization, having a dipole in their unit cell, and exhibit pyroelectricity. If this dipole can be reversed by the application of an electric field, the material is said to be ferroelectric. Any dielectric material develops a dielectric polarization (electrostatics) when an electric field is applied, but a substance which has such a natural charge separation even in the absence of a field is called a polar material. Whether or not a material is polar is determined solely by its crystal structure. Only 10 of the 32 point groups are polar. All polar crystals are pyroelectric, so the 10 polar crystal classes are sometimes referred to as the pyroelectric classes.

Piezoelectric crystal classes: 1, 2, m, 222, mm2, 4, -4, 422, 4mm, -42m, 3, 32, 3m, 6, -6, 622, 6mm, -62m, 23, -43m

Pyroelectric: 1, 2, m, mm2, 3, 3m, 4, 4mm, 6, 6mm

The property of pyroelectricity is the measured change in net polarization (a vector) proportional to a change in temperature. The total pyroelectric coefficient measured at constant stress is the sum of the pyroelectric coefficients at constant strain (primary pyroelectric effect) and the piezoelectric contribution from thermal expansion (secondary pyroelectric effect). Under normal circumstances, even polar materials do not display a net dipole moment. As a consequence there are no electric dipole equivalents of bar magnets because the intrinsic dipole moment is neutralized by "free" electric charge that builds up on the surface by internal conduction or from the ambient atmosphere. Polar crystals only reveal their nature when perturbed in some fashion that momentarily upsets the balance with the compensating surface charge.

Recent developments

Progress has been made in creating artificial pyroelectric materials, usually in the form of a thin film, out of gallium nitride (Ga
Gallium
Gallium is a chemical element that has the symbol Ga and atomic number 31. Elemental gallium does not occur in nature, but as the gallium salt in trace amounts in bauxite and zinc ores. A soft silvery metallic poor metal, elemental gallium is a brittle solid at low temperatures. As it liquefies...

N
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

), caesium nitrate
Caesium nitrate
Caesium nitrate is a chemical compound with the chemical formula CsNO3. It is used in pyrotechnic compositions, as a colorant and an oxidizer, e.g. in decoys and illumination flares...

 (Cs
Caesium
Caesium or cesium is the chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-gold alkali metal with a melting point of 28 °C , which makes it one of only five elemental metals that are liquid at room temperature...

N
Nitrogen
Nitrogen is a chemical element that has the symbol N, atomic number of 7 and atomic mass 14.00674 u. Elemental nitrogen is a colorless, odorless, tasteless, and mostly inert diatomic gas at standard conditions, constituting 78.08% by volume of Earth's atmosphere...

O
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

3), polyvinyl fluoride
Polyvinyl fluoride
Polyvinyl fluoride or –n– is a polymer material mainly used in flammability-lowering coating of airplane interiors and photovoltaic module backsheets. It is also used in raincoats and metal sheeting...

s, derivatives of phenylpyrazine, and cobalt
Cobalt
Cobalt is a chemical element with symbol Co and atomic number 27. It is found naturally only in chemically combined form. The free element, produced by reductive smelting, is a hard, lustrous, silver-gray metal....

 phthalocyanine
Phthalocyanine
Phthalocyanine is an intensely blue-green coloured macrocyclic compound that is widely used in dyeing. Phthalocyanines form coordination complexes with most elements of the periodic table...

. (See pyroelectric crystal
Pyroelectric crystal
Pyroelectric crystals are crystals that generate electricity when heated. It is similar to piezoelectricity.-Crystal symmetry:Crystal structures can be divided into 32 classes, or point groups, according to the number of rotational axes and reflection planes they exhibit that leave the crystal...

s.) Lithium tantalate
Lithium tantalate
Lithium tantalate , is a crystalline solid which possesses unique optical, piezoelectric and pyroelectric properties which make it valuable for nonlinear optics, passive infrared sensors such as motion detectors, terahertz generation and detection, surface acoustic wave applications, cell phones...

 (Li
Lithium
Lithium is a soft, silver-white metal that belongs to the alkali metal group of chemical elements. It is represented by the symbol Li, and it has the atomic number 3. Under standard conditions it is the lightest metal and the least dense solid element. Like all alkali metals, lithium is highly...

Ta
Tantalum
Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as tantalium, the name comes from Tantalus, a character in Greek mythology. Tantalum is a rare, hard, blue-gray, lustrous transition metal that is highly corrosion resistant. It is part of the refractory...

O
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

3) is a crystal exhibiting both piezoelectric and pyroelectric properties, which has been used to create small-scale nuclear fusion
Nuclear fusion
Nuclear fusion is the process by which two or more atomic nuclei join together, or "fuse", to form a single heavier nucleus. This is usually accompanied by the release or absorption of large quantities of energy...

 ("pyroelectric fusion
Pyroelectric fusion
Pyroelectric fusion refers to the technique of using pyroelectric crystals to generate high strength electrostatic fields to accelerate deuterium ions into a metal hydride target also containing deuterium with sufficient kinetic energy to cause these ions to undergo nuclear fusion. It was...

"). http://www.nature.com/nature/journal/v434/n7037/suppinfo/nature03575.html

Mathematical description

The pyroelectric coefficient may be described as the change in the spontaneous polarization vector with temperature

where pi (Cm-2K-1)
is the vector for the pyroelectric coefficient.

Power generation

A pyroelectric can be repeatedly heated and cooled (analogously to a heat engine
Heat engine
In thermodynamics, a heat engine is a system that performs the conversion of heat or thermal energy to mechanical work. It does this by bringing a working substance from a high temperature state to a lower temperature state. A heat "source" generates thermal energy that brings the working substance...

) to generate usable electrical power. One group calculated that a pyroelectric in an Ericsson cycle
Ericsson cycle
The Ericsson cycle is named after inventor John Ericsson, who designed and built many unique heat engines based on various thermodynamic cycles. He is credited with inventing two unique heat engine cycles and developing practical engines based on these cycles...

 could reach 50% of Carnot efficiency, while a different study found a material that could in theory reach 84-92% of Carnot efficiency. (These efficiency values are for the pyroelectric itself, ignoring losses from heating and cooling the substrate
Thin film
A thin film is a layer of material ranging from fractions of a nanometer to several micrometers in thickness. Electronic semiconductor devices and optical coatings are the main applications benefiting from thin film construction....

, other heat-transfer losses, and all other losses elsewhere in the system.) Possible advantages of pyroelectric generators for generating electricity (as compared to the conventional heat engine
Heat engine
In thermodynamics, a heat engine is a system that performs the conversion of heat or thermal energy to mechanical work. It does this by bringing a working substance from a high temperature state to a lower temperature state. A heat "source" generates thermal energy that brings the working substance...

 plus electrical generator
Electrical generator
In electricity generation, an electric generator is a device that converts mechanical energy to electrical energy. A generator forces electric charge to flow through an external electrical circuit. It is analogous to a water pump, which causes water to flow...

), include potentially lower operating temperature
Operating temperature
An operating temperature is the temperature at which an electrical or mechanical device operates. The device will operate effectively within a specified temperature range which varies based on the device function and application context, and ranges from the minimum operating temperature to the...

s, less bulky equipment, and fewer moving parts. Although a few patents have been filed for such a device, it does not appear to be anywhere close to commercialization yet.

See also

  • Pyroelectric crystal
    Pyroelectric crystal
    Pyroelectric crystals are crystals that generate electricity when heated. It is similar to piezoelectricity.-Crystal symmetry:Crystal structures can be divided into 32 classes, or point groups, according to the number of rotational axes and reflection planes they exhibit that leave the crystal...

  • Pyroelectric fusion
    Pyroelectric fusion
    Pyroelectric fusion refers to the technique of using pyroelectric crystals to generate high strength electrostatic fields to accelerate deuterium ions into a metal hydride target also containing deuterium with sufficient kinetic energy to cause these ions to undergo nuclear fusion. It was...

  • The opposite effect is called electrocaloric effect
    Electrocaloric effect
    The electrocaloric effect is phenomenon in which a material shows a reversible temperature change under an applied electric field. It is often considered to be the physical inverse of the pyroelectric effect....

  • Thermoelectricity
  • Kelvin probe force microscope
    Kelvin probe force microscope
    Kelvin probe force microscopy , also known as surface potential microscopy, is a noncontact variant of atomic force microscopy that was invented in 1991. With KPFM, the work function of surfaces can be observed at atomic or molecular scales...


External links

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