Effect of triboelectricity: styrofoam peanuts clinging to a cat's fur due to static electricity. This effect is also the cause of static cling in clothes.

The triboelectric effect (also known as triboelectricity, triboelectric charging, triboelectrification, or tribocharging) describes electric charge transfer between two objects when they contact or slide against each other. It can occur with different materials, such as the sole of a shoe on a carpet, or between two pieces of the same material. It occurs with differing amounts of charge transfer (tribocharge) for all solid materials and all contacts and sliding. There is evidence that tribocharging can also occur between combinations of solids, liquids and gases.

Often static electricity is a consequence of the triboelectric effect when the charge stays on one or both of the objects and is not conducted away. The term triboelectricity has been used to refer to the field of study or the general phenomenon of the triboelectric effect,[1][2][3][4] or to the static electricity that results from it.[5][6] When there is no sliding, tribocharging is sometimes called contact electrification, and any static electricity generated is sometimes called contact electricity. The terms are often used interchangeably, and may be confused.

Triboelectric charge plays a major role in industries ranging from xerography[7] to packaging of pharmaceutical powders,[3][8] and in many processes such as dust storms[9] and planetary formation.[10] It can also increase friction and adhesion. While many aspects of the triboelectric effect are now understood and extensively documented, significant disagreements remain in the current literature about the underlying details.

History

See also: Timeline of electromagnetism and classical optics, History of electromagnetic theory, and Electric charge § History

The historical development of triboelectricity is interwoven with work on static electricity and electrons themselves. Experiments involving triboelectricity and static electricity occurred before the discovery of the electron. The name ēlektron comes from the Greek word for amber,[11][12] which in turn is connected to the recording of electrostatic charging by Thales of Miletus around 585 BCE,[13] and possibly others even earlier.[13][14] The prefix tribo- (Greek for ‘rub’) refers to sliding, friction and related processes, as in tribology.

From the earliest days the attraction of materials due to static electricity by rubbing amber and the attraction of magnetic materials were considered to be very similar or the same.[12] There are indications that it was known both in Europe and outside, for instance China and other places.[12] Syrian women used amber whorls in weaving and exploited the triboelectric properties, as noted by Pliny the Elder.[12][15]

The effect was mentioned in various records from the medieval period. Archbishop Eustathius of Thessalonica, Greek scholar and writer of the 12th century, records that Woliver, king of the Goths, was able to draw sparks from his body. The same writer states that a certain philosopher was able, while dressing, to draw sparks from his clothes, a result seemingly akin to that obtained by Robert Symmer in his silk stocking experiments, an account of which may be found in the 1759 Philosophical Transactions.[16]

Generator built by Francis Hauksbee.[17]

It is generally considered[14] that the first major scientific analysis was by William Gilbert in his publication De Magnete in 1600.[16][18] He discovered that many more materials than amber such as sulphur, wax, glass could produce static electricity when rubbed, and that moisture prevented electrification. Others such as Sir Thomas Browne made important contributions slightly later, both in terms of materials and the first use of the word electricity in Pseudodoxia Epidemica.[19] He noted that metals did not show triboelectric charging, perhaps because the charge was conducted away. An important step was in 1660 when Otto von Guericke invented a machine that could automate triboelectric charge generation, making it much easier to produce more tribocharge; other electrostatic generators followed.[16] For instance, shown in the Figure is an electrostatic generator built by Francis Hauksbee the Younger. Another key development was in the 1730s when C.F. du Fay pointed out that there were two types of charge which he named vitreous and resinous.[20][21] These names corresponded to the glass (vitreous) rods and bituminous coal, amber, or sealing wax (resinous) used in du Fay's experiments.[22]: I:44  These names were used through out the 19th century. The use of the terms positive and negative for types of electricity grew out of the independent work of Benjamin Franklin around 1747 where he ascribed electricity to an over- or under- abundance of an electrical fluid.[22]: 47 

At about the same time Johan Carl Wilcke published in a 1757 paper a triboelectric series.[23][24] In this work materials were listed in order of the polarity of charge separation when they are touched or slide against another. A material towards the bottom of the series, when touched to a material near the top of the series, will acquire a more negative charge.

The first systematic analysis of triboelectricity is considered to be the work of Jean Claude Eugène Péclet in 1834.[25] He studied triboelectric charging for a range of conditions such as the material, pressure and rubbing of surfaces. It was some time before there were further quantitative works by Owen in 1909[26] and Jones in 1915.[27] The most extensive early set of experimental analyses was from 1914–1930 by the group of Professor Shaw, who laid much of the foundation of experimental knowledge. In a series of papers he: was one of the first to mention some of the failings of the triboelectric series, also showing that heat had a major effect on tribocharging;[28] analyzed in detail where different materials would fall in a triboelectric series, at the same time pointing out anomalies;[1] separately analyzed glass and solid elements[29] and solid elements and textiles,[30] carefully measuring both tribocharging and friction; analyzed charging due to air-blown particles;[31] demonstrated that surface strain and relaxation played a critical role for a range of materials,[32][33] and examined the tribocharging of many different elements with silica.[34]

Much of this work predates an understanding of solid state variations of energies levels with position, and also band bending.[35] It was in the early 1950s in the work of authors such as Vick[36] that these were taken into account along with concepts such as quantum tunnelling and behavior such as Schottky barrier effects, as well as including models such as asperities for contacts based upon the work of Frank Philip Bowden and David Tabor.[37]

Basic characteristics

Triboelectric charging occurs when two materials are brought into contact then separated, or slide against each other. An example is rubbing a plastic pen on a shirt sleeve made of cotton, wool, polyester, or the blended fabrics used in modern clothing. An electrified pen will attract and pick up pieces of paper less than a square centimeter, and will repel a similarly electrified pen. This repulsion is detectable by hanging both pens on threads and setting them near one another. Such experiments led to the theory of two types of electric charge, one being the negative of the other, with a simple sum respecting signs giving the total charge. The electrostatic attraction of the charged plastic pen to neutral uncharged pieces of paper (for example) is due to induced dipoles (polarization) in the paper.[35]

The triboelectric effect can be very unpredictable because many details are often not controlled.[38] Different, and at times apparently contradictory phenomena have been known for many years. For instance, as early as 1910, Jaimeson observed that for a piece of cellulose, the sign of the charge was dependent upon whether the it was bent concave or convex during rubbing.[39] The same behavior with curvature was reported in 1917 by Shaw,[1] who noted that the effect of curvature with different materials made them either more positive or negative. In 1920, Richards pointed out that for colliding particles the velocity and mass played a role.[40] In 1926, Shaw pointed out that the sign of the charge transfer could change with time.[41]

There are other more recent experimental results which also do not have a simple explanation. For instance the work of Burgo and Erdemir,[42] which showed that the sign of charge transfer reverses between when a tip is pushing into a substrate versus when it pulls out; the detailed work of Lee et al[43] and Forward, Lacks and Sankaran[44] and others measuring the charge transfer during collisions between particles of zirconia of different sizes, with one size charging positive, the other negative; the observations using sliding[44] or using Kelvin probe force microscope of inhomogeneous charge variations.[45]

Illustration of triboelectric charging from contacting asperities

The details of how and why tribocharging occurs are not as yet established science. One component is the difference in the work function (also called the electron affinity) between the two materials.[46] This can lead to charge transfer as, for instance, analyzed by Harper.[47][48] As has been known for some time,[36][49][50][51] the contact potential is part of the process but does not explain many results, such as the apparently contradictory ones mentioned above.[39][41][42][45] Many studies have pointed out issues with the work function difference as a complete explanation.[52][53][54][4] There is also the question of why sliding is often important. Surfaces have many nanoscale asperities where the contact is taking place,[37] which has been taken into account in many approaches to triboelectrification.[47] Volta and Helmholtz suggested that the role of sliding was to produce more contacts per second.[48] In modern terms, the idea is that electrons move many times faster than atoms, so the electrons are always in equilibrium when atoms move (the Born–Oppenheimer approximation). With this approximation, each asperity contact during sliding is equivalent to a stationary one; there is no direct coupling between the sliding velocity and electron motion.[55] An alternative view (beyond the Born–Oppenheimer approximation) is that sliding acts as a quantum mechanical pump which can excite electrons to go from one material to another.[56] A different suggestion is that local heating during sliding matters,[57] an idea first suggested by Frenkel in 1941.[58] Other papers have considered that local bending at the nanoscale produces voltages which help drive charge transfer via the flexoelectric effect.[59][60] There are also suggestions that surface or trapped charges are important.[61][62] More recently there have been attempts to include a full solid state description.[63][64][65][56]

Explanations and mechanisms

From early work starting around the end of the 19th century a large amount of information is available about what, empirically, causes triboelectricity. While there is extensive experimental data on triboelectricity there is not as yet full scientific consensus on the source,[66][67] or perhaps more probably the sources. Some aspects are established, and will be part of the full picture:

Triboelectric series

A simple triboelectric series

An empirical approach to triboelectricity is via a triboelectric series. This is a list of materials ordered by how they develop a charge relative to other materials on the list. Johan Carl Wilcke published the first one in a 1757 paper.[23][24] The series was expanded by Shaw[1] and Henniker[69] by including natural and synthetic polymers, and included alterations in the sequence depending on surface and environmental conditions. Lists vary somewhat as to the order of some materials.[1][69]

Another triboelectric series based on measuring the triboelectric charge density of materials was proposed by the group of Zhong Lin Wang. The triboelectric charge density of the tested materials was measured with respect to liquid mercury in a glove box under well-defined conditions, with fixed temperature, pressure and humidity.[70]

Cyclic triboelectric series example, illustrating that the approach does not work in practice.

It is known that this approach is too simple and unreliable.[36][47][71] There are many cases where there are triangles: material A is positive when rubbed against B, B is positive when rubbed against C, and C is positive when rubbed against A, an issue mentioned by Shaw in 1914.[28] This cannot be explained by a linear series, cyclic series are inconsistent with the empirical triboelectric series.[72] Furthermore, there are many cases where charging occurs with contacts between two pieces of the same material.[73][74][45] This has been modelled as a consequence of the electric fields from local bending (flexoelectricity).[59][60][75]

Work function differences

When the two metals depicted here are in thermodynamic equilibrium with each other as shown (equal Fermi levels), the vacuum electrostatic potential ϕ is not flat due to a difference in work function.

In all materials there is a positive electrostatic potential from the positive atomic nuclei, partially balanced by a negative electrostatic potential of what can be described as a sea of electrons.[35] The average potential is positive, what is called the mean inner potential (MIP). Different materials have different MIPs, depending upon the types of atoms and how close they are. At a surface the electrons also spill out a little into the vacuum, as analyzed in detail by Kohn and Liang.[35][76] This leads to a dipole at the surface. Combined, the dipole and the MIP lead to a potential barrier for electrons to leave a material which is called the work function.[35]

A rationalization of the triboelectric series is that different members have different work functions, so electrons can go from the material with a small work function to one with a large.[36] The potential difference between the two materials is called the Volta potential, also called the contact potential. Experiments have validated the importance of this for metals and other materials.[46] However, because the surface dipoles vary for different surfaces of any solid[35][76] the contact potential is not a universal parameter. By itself it cannot explain many of the results which were established in the early 20th century.[40][41][39]

Electromechanical contributions

Whenever a solid is strained, electric fields can be generated. One process is due to linear strains, and is called piezoelectricity, the second depends upon how rapidly strains are changing with distance (derivative) and is called flexoelectricity. Both are established science, and can be both measured and calculated using density functional theory methods. Because flexoelectricity depends upon a gradient it can be much larger at the nanoscale during sliding or contact of asperity between two objects.[37]

There has been considerable work on the connection between piezoelectricity and triboelectricity.[77][78] While it can be important, piezoelectricity only occurs in the small number of materials which do not have inversion symmetry,[35] so it is not a general explanation. It has recently been suggested that flexoelectricity may be very important[59] in triboelectricity as it occurs in all insulators and semiconductors.[79][80] Quite a few of the experimental results such as the effect of curvature can be explained by this approach, although full details have not as yet been determined.[60] There is also early work from Shaw and Hanstock,[81] and from the group of Daniel Lacks demonstrating that strain matters.[82][83][68]

A different type of model has been proposed by Alicki and Jenkins.[56] They suggest that the electrons in the two materials when they are sliding against each other have different velocities, and quantum mechanics cause this imbalance to pump electrons from one material to the other.[56]

Capacitor charge compensation model

Capacitor schematic with dielectric.

An explanation that has appeared in different forms is analogous to charge on a capacitor. If there is a potential difference between two materials due to the difference in their work functions (contact potential), this can be thought of as equivalent to the potential difference across a capacitor. The charge to compensate this is that which cancels the electric field. If an insulating dielectric is in between the two materials, then this will lead to a polarization density and a bound surface charge of , where is the surface normal.[84][85] The total charge in the capacitor is then the combination of the bound surface charge from the polarization and that from the potential.

The triboelectric charge from this compensation model has been frequently considered as a key component.[86][87][88][89] If the additional polarization due to strain (piezoelectricity) or bending of samples (flexoelectricity) is included[59][60] this can explain observations such as the effect of curvature[39] or inhomogeneous charging.[75]

Electron and/or ion transfer

There is debate about whether electrons or ions are transferred in triboelectricity. For instance Harper[47] discusses both possibilities, whereas Vick[36] was more in favor of electron transfer. The debate remains to this day with, for instance, George M. Whitesides advocating for ions,[90] while others support electrons.[91][92]

Humidity

Generally, increased humidity (water in the air) leads to a decrease in the magnitude of triboelectric charging.[93] The size of this effect varies greatly depending on the contacting materials; the decrease in charging ranges from up to a factor of 10 or more to very little humidity dependence.[94] Some experiments find increased charging at moderate humidity compared to extremely dry conditions before a subsequent decrease at higher humidity.[95] The most widespread explanation is that higher humidity leads to more water adsorbed at the surface of contacting materials, leading to a higher surface conductivity.[96][97] The higher conductivity allows for greater charge recombination as contacts separate, resulting in a smaller transfer of charge.[96][98][99] Another proposed explanation for humidity effects considers the case when charge transfer is observed to increase with humidity in dry conditions. Increasing humidity may lead to the formation of water bridges between contacting materials that promote the transfer of ions.[95]

Examples

Friction and adhesion from tribocharging

Friction[100] is a retarding force due to different energy dissipation process such as elastic and plastic deformation, phonon and electron excitation, and also adhesion.[101] As an example, in a car or any other vehicle the wheels elastic deform as they go over roughness in the road. Part of the energy needed for this deformation is recovered (elastic deformation), some is not and goes into heating the tires. The energy which is not recovered contributes to the back force, a process called rolling friction.

Similar to rolling friction there are energy terms in charge transfer, which contribute to friction. In static friction there is coupling between elastic strains, polarization and surface charge which contributes to the frictional force.[79] In sliding friction,[102] when asperities contact[37] and there is charge transfer, some of the charge returns as the contacts are released, some does not[103] and will contribute to the macroscopically observed friction. There is evidence for a retarding Coulomb force between asperities of different charges,[104] and an increase in the adhesion from contact electrification when geckos walk on water.[105] There is also evidence of connections between jerky (stick–slip) processes during sliding with charge transfer,[42] electrical discharge[106] and x-ray emission.[107] How large the triboelectric contribution is to friction has been debated. It has been suggested by some[104] that it may dominate for polymers, whereas Harper[108] has argued that it is small.

Liquids and gases

Illustration of tribocharge generated from a sliding drop

The generation of static electricity from the relative motion of liquids or gases is well established, with one of the first analyses in 1886 by Lord Kelvin in his water dropper which used falling drops to create an electric generator.[109] Liquid mercury is a special case as it typically acts as a simple metal, so has been used as a reference electrode.[2] More common is water, and electricity due to water droplets hitting surfaces has been documented since the discovery by Philipp Lenard in 1892 of the spray electrification or waterfall effect.[110][111] This is when falling water generates static electricity either by collisions between water drops or with the ground, leading to the finer mist in updrafts being mainly negatively charged, with positive near the lower surface. It can also occur for sliding drops.[112]

Another type of charge can be produced during rapid solidification of water containing ions, which is called the Workman–Reynolds effect.[113] During the solidification the positive and negative ions may not be equally distributed between the liquid and solid.[114] For instance, in thunderstorms this can contribute (together with the waterfall effect) to separation of positive hydrogen ions and negative hydroxide ions, leading to static charge.

A third class is associated with contact potential differences between liquids or gases and other materials, similar to the work function differences for solids. It has been suggested that a triboelectric series for liquids is useful.[115] One difference from solids is that often liquids have charged double layers, and most of the work to date supports that ion transfer (rather than electron) dominates for liquids[116] as first suggested by Irving Langmuir in 1938.[117]

Finally, with liquids there can be flow-rate gradients at interfaces, and also viscosity gradients. These can produce electric fields and also polarization of the liquid, a field called electrohydrodynamics.[118] These are analogous to the electromechanical terms for solids where electric fields can occur due to elastic strains as described earlier.

Powders

During commercial powder processing[3][119][120] or in natural processes such as dust storms,[121][122][9] triboelectric charge transfer can occur. There can be electric fields of up to 160kV/m with moderate wind conditions, which leads to Coulomb forces of about the same magnitude as gravity.[123] There does not need to be air present, significant charging can occur, for instance, on airless planetary bodies.[124] With pharmaceutic powders and other commercial powders the tribocharging needs to be controlled for quality control of the materials and doses. Static discharge is also a particular hazard in grain elevators owing to the danger of a dust explosion,[125] in places that store explosive powders,[126] and in many other cases.[127]

Other examples

Contact with the slide has left this child's hair positively charged so that the individual hairs repel one another. The hair can also be attracted to the negatively charged slide surface.

While the simple case of stroking a cat is familiar to many, there are other areas in modern technological civilization where triboelectricity is exploited or is a concern:

See also

References

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