Thermal paper

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A receipt printed on thermal paper. A heat source near the paper will color the paper.

Paper roll for thermal fax machine.

Thermal paper is a special fine paper that is coated with a chemical (previously often
containing BPA) that changes color when exposed to heat. It is used in thermal printers and
particularly in inexpensive or lightweight devices such as adding machines, cash registers, and
credit card terminals.

The surface of the paper is coated with a solid-state mixture of a dye and a suitable matrix; a
combination of a fluoran leuco dye as an example. When the matrix is heated above its melting
point, the dye reacts with the acid, shifts to its colored form, and the changed form is then
conserved in a metastable state when the matrix solidifies back quickly enough. The reactant
acid in thermal paper is often bisphenol A (BPA).

Usually, the coating will turn black when heated, but coatings that turn blue or red are sometimes
used. While an open heat source, such as a flame, can discolor the paper, a fingernail swiped
quickly across the paper will also generate enough heat from friction to produce a mark.
Multicolor thermal paper first became available in the early 1990s with the introduction of the
Fuji Thermo-Autochrome (TA) system.[1] This was followed in the early 2000s by the
development of the Polaroid Zink ("zero-ink") system.[2] Both of these methods rely on multi-
layer coatings with three separate colorizing layers, but different methods are used for
independent activation of each layer.

Contents
[hide]

1 History
2 Chemistry
o 2.1 Leuco Dyes
o 2.2 Developers
o 2.3 Sensitizers
o 2.4 Stabilizers
3 Multicolored papers
o 3.1 Zink
4 Protective coating
5 Health and environmental concerns
6 See also
7 References
8 External links

History[edit]
The earliest direct thermal papers were developed by NCR Corporation (using dye chemistry)
and 3M (using metallic salts). The NCR technology became the market leader over time,
although the image would fade rather rapidly compared with the much more expensive, but
durable 3M technology.

Texas Instruments invented the thermal print head in 1965, and the Silent 700, a computer
terminal with a thermal printer, was released in the market in 1969. The Silent 700 was the first
thermal print system that printed on thermal paper. During the 1970s, Hewlett-Packard integrated
thermal paper printers into the design of its HP9800 series desktop computers, and integrated it
into the top of the 2600-series CRT terminals as well as in plotters.

In the 1970s and early 1980s, Japanese producers (such as Ricoh, Jujo, and Kanzaki), using
similar dye-based chemistry, formed partnerships with barcode printer manufacturers (such as
TEC, Sato, and others) and entered the emerging global bar code industry, primarily in
supermarkets. U.S. producers such as Appleton (NCR's licensee), Nashua Corporation, Graphic
Controls, and others fought to gain market share. Leading pressure-sensitive label producers such
as Avery Dennison became major consumers of direct thermal paper for label applications.
In the late 1980s and early 1990s, thermal transfer, laser printing, electrophotography, and, to a
lesser extent, ink jet printing began to take away industrial and warehouse barcode applications
due to better durability. Direct thermal made a strong comeback with point of sale receipts
(gasoline pumps, cash registers, rental car receipts, etc.).

During 1998, Nintendo used thermal paper technology for their Game Boy Printer.

In 2006, NCR Corporation's Systemedia division introduced two-sided thermal printing

technology, called "2ST".

Chemistry[edit]
Four different types of imaging chemicals are used in thermally sensitive papers: leuco dyes,
developers, sensitizers and stabilizers.[3]

Leuco Dyes[edit]

The leuco dyes used in direct thermal paper are usually triaryl methane phthalide dyes, such as
Yamamoto Blue 4450, or fluoran dyes, such as Pergascript Black 2C. A third widely used leuco
dye is Crystal violet lactone. Red or magenta color can be achieved with dyes such as Yamamoto
Red 40. Yellow can be produced by the protonation of a triaryl pyridine, such as Copikem
Yellow 37. These dyes have a colorless leuco form when crystalline or when in a pH neutral
environment, but become colored when dissolved in a melt and exposed to an acidic
environment.

Developers[edit]

Leuco dyes, in general, provide little color when melted unless they are melted in conjunction
with one or more organic acids. Examples of organic acids suitable for thermochromic papers are
phenols such as Bisphenol A (BPA) and Bisphenol S (BPS). Other suitable acidic materials are
sulfonyl ureas such as BTUM and Pergafast 201. Zinc salts of substituted salicylic acids, such as
zinc di-tert-butylsalicylate have also been commercially used as developers.

Sensitizers[edit]

A leuco dye and a developer, when melted together, are enough to produce color. However, the
thermal threshold of the coated layer containing the colorizing components is determined by the
lowest melting component of the layer. Furthermore, developers and leuco dyes often mix poorly
upon melting. To optimize the colorization temperature and to facilitate mixing, a third chemical
called a sensitizer is commonly added to the imaging layer. Sensitizers are commonly simple
ether molecules such as 1,2-bis-(3-methylphenoxy)ethane or 2-benzyloxynapthalene. These two
materials melt at approximately 100C, which is a practical lower limit for thermal coloration.
These low-cost ethers are excellent low viscosity solvents for leuco dyes and developers, and this
facilitates color formation at a well-defined temperature and with minimum energy input.
Stabilizers[edit]

Dyes in thermally sensitive paper are often unstable and return to their original colorless,
crystalline forms when stored in hot or humid conditions.[4] To stabilize the metastable glass
formed by the leuco dye, developer and sensitizer, a fourth type of material called a stabilizer is
often added to thermal papers. Stabilizers often share similarities with developers and are often
complex multifunctional phenols that inhibit recrystallization of the dye and developer, thereby
stabilizing the printed image.

Multicolored papers[edit]
Zink[edit]

In the early 2000s, Polaroid developed the Zink "zero-ink" technology.[2] The paper is used in
compact photo printers. It has several layers: a backing layer with optional pressure sensitive
adhesive, heat-sensitive layers with cyan, magenta and yellow pigments in colorless form, and
overcoat. Zink technology allows the printing of full-color images in a single pass without
requiring ink cartridges.

The color addressing is achieved by controlling the heat pulse length and intensity.[5]

The color-forming layers contain colorless crystals of amorphochromic dyes. These dyes form
microcrystals of their colorless tautomers, which convert to the colored form by melting and
retain color after resolidification.[6]

The yellow layer is the topmost one, sensitive to short heat pulses of high temperature. The
magenta layer is in the middle, sensitive to longer pulses of moderate temperature. The cyan
layer is at the bottom, sensitive to long pulses of low temperature. The layers are separated by
thin interlayers, acting as heat insulation, moderating the heat throughput.[7]

Protective coating[edit]
Most direct thermal papers require a protective top-coating to:

reduce fading of the thermal image caused by exposure to UV light, water, oils, grease,
lard, fats, plasticizers, and similar causes
reduce print head wear
reduce or eliminate residue from the thermal coating on the thermal print heads
provide better anchorage of flexographic printing inks applied to the thermal paper
focus the heat from the thermal print head on the active coating.

Health and environmental concerns[edit]

Some thermal papers are coated with BPA, a chemical considered to be an endocrine
disruptor.[8][9] This material can contaminate recycled paper.[10][11] BPA can transfer readily to the
skin in small amounts:

When taking hold of a receipt consisting of thermal printing paper for five seconds, roughly 1 g
BPA (0.20.6 g) was transferred to the forefinger and the middle finger if the skin was rather
dry, and about ten times more than this if these fingers were wet or very greasy. Exposure to a
person who repeatedly touches thermal printer paper for about ten hours per day, such as at a
cash register, could reach 71 micrograms per day, which is 42 times less than the present
tolerable daily intake (TDI).[12]

The chemical bisphenol A (BPA) is used for thermal paper coatings because of its stability and
heat-resistance. This allows inkless printing for receipts from cash registers. People who often
get in contact with BPA coated receipts do have a higher level of BPA in their bodies than
people with average contact. Therefore, the New York Suffolk County signed a resolution to ban
BPA in thermal receipt papers. Violation of this new law, the "Safer Sales Slip Act", involves a
500 USD penalty. The law became effective beginning January 3, 2014.[13]

Recently, bisphenol S (BPS), an analog of BPA that has been shown to have similar in vitro
estrogenic activity to BPA,[14][15] has been used in thermal paper coatings. The recycling of
thermal paper coated with BPS can introduce BPS into the cycle of paper production and cause
BPS contamination of other types of paper products.[11]
Thermochromism
From Wikipedia, the free encyclopedia

Jump to: navigation, search

A mood ring shown face front. Note the band of color change.

Thermochromism is the property of substances to change color due to a change in temperature.

A mood ring is an excellent example of this phenomenon, but thermochromism also has more
practical uses, e.g. in baby bottles (changes to a different color when cool enough to drink) or
kettles (changes when water is at or near boiling point). Thermochromism is one of several types
of chromism.

Play media

Demonstration of the phenomenon of continuous thermochromism.

Play media

Demonstration of the phenomenon of discontinuous thermochromism.

Contents
[hide]
 1 Organic materials
o 1.1 Thermochromatic liquid crystals
o 1.2 Leuco dyes
1.2.1 Papers
1.2.2 Polymers
1.2.3 Inks
2 Inorganic materials
3 References

Organic materials[edit]
Thermochromatic liquid crystals[edit]

The two common approaches are based on liquid crystals and leuco dyes. Liquid crystals are
used in precision applications, as their responses can be engineered to accurate temperatures, but
their color range is limited by their principle of operation. Leuco dyes allow wider range of
colors to be used, but their response temperatures are more difficult to set with accuracy.

Some liquid crystals are capable of displaying different colors at different temperatures. This
change is dependent on selective reflection of certain wavelengths by the crystallic structure of
the material, as it changes between the low-temperature crystallic phase, through anisotropic
chiral or twisted nematic phase, to the high-temperature isotropic liquid phase. Only the nematic
mesophase has thermochromic properties; this restricts the effective temperature range of the
material.

The twisted nematic phase has the molecules oriented in layers with regularly changing
orientation, which gives them periodic spacing. The light passing through the crystal undergoes
Bragg diffraction on these layers, and the wavelength with the greatest constructive interference
is reflected back, which is perceived as a spectral color. A change in the crystal temperature can
result in a change of spacing between the layers and therefore in the reflected wavelength. The
color of the thermochromic liquid crystal can therefore continuously range from non-reflective
(black) through the spectral colors to black again, depending on the temperature. Typically, the
high temperature state will reflect blue-violet, while the low-temperature state will reflect red-
orange. Since blue is a shorter wavelength than red, this indicates that the distance of layer
spacing is reduced by heating through the liquid-crystal state.

Some such materials are cholesteryl nonanoate or cyanobiphenyls.

Mixtures with 35 C span of temperatures and ranges from about 1723 C to about 3740 C
can be composed from varying proportions of cholesteryl oleyl carbonate, cholesteryl nonanoate,
and cholesteryl benzoate. For example, the mass ratio of 65:25:10 yields range of 1723 C, and
30:60:10 yields range of 3740 C.[1]

Liquid crystals used in dyes and inks often come microencapsulated, in the form of suspension.
Liquid crystals are used in applications where the color change has to be accurately defined.
They find applications in thermometers for room, refrigerator, aquarium, and medical use, and in
indicators of level of propane in tanks. A popular application for thermochromid liquid crystals
are the mood rings.

Liquid crystals are difficult to work with and require specialized printing equipment. The
material itself is also typically more expensive than alternative technologies. High temperatures,
ultraviolet radiation, some chemicals and/or solvents have a negative impact on their lifespan.

Leuco dyes[edit]

Main article: Leuco dye

Example of a thermochromic T-shirt. A hairdryer was used to change the blue to turquoise.

Another example of a thermochromic T-shirt.

Thermochromic dyes are based on mixtures of leuco dyes with suitable other chemicals,
displaying a color change (usually between the colorless leuco form and the colored form) in
dependence on temperature. The dyes are rarely applied on materials directly; they are usually in
the form of microcapsules with the mixture sealed inside. An illustrative example is the
Hypercolor fashion, where microcapsules with crystal violet lactone, weak acid, and a
dissociable salt dissolved in dodecanol are applied to the fabric; when the solvent is solid, the
dye exists in its lactone leuco form, while when the solvent melts, the salt dissociates, the pH
inside the microcapsule lowers, the dye becomes protonated, its lactone ring opens, and its
absorption spectrum shifts drastically, therefore it becomes deeply violet. In this case the
apparent thermochromism is in fact halochromism.
The dyes most commonly used are spirolactones, fluorans, spiropyrans, and fulgides. The acids
include bisphenol A, parabens, 1,2,3-triazole derivates, and 4-hydroxycoumarin and act as proton
donors, changing the dye molecule between its leuco form and its protonated colored form;
stronger acids would make the change irreversible.

Leuco dyes have less accurate temperature response than liquid crystals. They are suitable for
general indicators of approximate temperature ("too cool", "too hot", "about OK"), or for various
novelty items. They are usually used in combination with some other pigment, producing a color
change between the color of the base pigment and the color of the pigment combined with the
color of the non-leuco form of the leuco dye. Organic leuco dyes are available for temperature
ranges between about 5 C (23 F) and 60 C (140 F), in wide range of colors. The color
change usually happens in a 3 C (5.4 F) interval.

Leuco dyes are used in applications where temperature response accuracy is not critical: e.g.
novelties, bath toys, flying discs, and approximate temperature indicators for microwave-heated
foods. Microencapsulation allows their use in wide range of materials and products. The size of
the microcapsules typically ranges between 35 m (over 10 times larger than regular pigment
particles), which requires some adjustments to printing and manufacturing processes.

An application of leuco dyes is in the Duracell battery state indicators. A layer of a leuco dye is
applied on a resistive strip to indicate its heating, thus gauging the amount of current the battery
is able to supply. The strip is triangular-shaped, changing its resistance along its length, therefore
heating up a proportionally long segment with the amount of current flowing through it. The
length of the segment above the threshold temperature for the leuco dye then becomes colored.

Exposure to ultraviolet radiation, solvents and high temperatures reduce the lifespan of leuco
dyes. Temperatures above about 200230 C (392446 F) typically cause irreversible damage
to leuco dyes; a time-limited exposure of some types to about 250 C (482 F) is allowed during
manufacturing.

Thermochromic paints use of liquid crystals or leuco dye technology. After absorbing a certain
amount of light or heat, the crystallic or molecular structure of the pigment reversibly changes in
such a way that it absorbs and emits light at a different wavelength than at lower temperatures.
Thermochromic paints are seen quite often as a coating on coffee mugs, whereby once hot coffee
is poured into the mugs, the thermochromic paint absorbs the heat and becomes colored or
transparent, therefore changing the appearance of the mug.

Papers[edit]

Thermochromic papers are used for thermal printers. One example is the paper impregnated with
the solid mixture of a fluoran dye with octadecylphosphonic acid. This mixture is stable in solid
phase; however, when the octadecylphosphonic acid is melted, the dye undergoes a chemical
reaction in the liquid phase, and assumes the protonated colored form. This state is then
conserved when the matrix solidifies again, if the cooling process is fast enough. As the leuco
form is more stable in lower temperatures and solid phase, the records on thermochromic papers
slowly fade out over years; this may lead to interesting effects in combination with accounting
records, receipts from a thermal printer, and a tax audit.

Polymers[edit]

Thermochromism can appear in thermoplastics, duroplastics, gels or any kind of coatings. The
polymer itself, an embedded thermochromic additive or a high ordered structure built by the
interaction of the polymer with an incorporated non-thermochromic additive can be the origin of
the thermochromic effect. Furthermore, from the physical point of view, the origin of the
thermochromic effect can be multifarious. So it can come from changes of light reflection,
absorption and/or scattering properties with temperature.[2] The application of thermochromic
polymers for adaptive solar protection is of great interest.[3] A function by design strategy,[4] e.g.
applied for the development of non-toxic thermochromic polymers has come into the focus in the
last decade.[5]

Inks[edit]
Main article: Thermochromic ink

Thermochromic inks or dyes are temperature sensitive compounds, developed in the 1970s, that
temporarily change color with exposure to heat. They come in two forms, liquid crystals and
leuco dyes. Leuco dyes are easier to work with and allow for a greater range of applications.
These applications include: flat thermometers, battery testers, clothing, and the indicator on
bottles of maple syrup that change color when the syrup is warm. The thermometers are often
used on the exterior of aquariums, or to obtain a body temperature via the forehead. Coors Light
uses thermochromic ink on its cans now, changing from white to blue to indicate the can is cold.

Inorganic materials[edit]
Virtually all inorganic compounds are thermochromic to some extent. Most examples however
involve only subtle changes in color. For example, titanium dioxide and zinc oxide are white at
room temperature but when heated change to yellow. Similarly indium(III) oxide is yellow and
darkens to yellow-brown when heated. Lead(II) oxide exhibits a similar color change on heating.
The color change is linked to changes in the electronic properties (energy levels, populations) of
these materials.

More dramatic examples of thermochromism are found in materials that undergo phase transition
or exhibit charge-transfer bands near the visible region. Examples include

Cuprous mercury iodide (Cu2HgI4) undergoes a phase transition at 67 C, reversibly changing

from a bright red solid material at low temperature to a dark brown solid at high temperature,
with intermediate red-purple states. The colors are intense and seem to be caused by Cu(I)-
Hg(II) charge-transfer complexes.[6]
Silver mercury iodide (Ag2HgI4) is yellow at low temperatures and orange above 4751 C, with
intermediate yellow-orange states. The colors are intense and seem to be caused by Ag(I)-Hg(II)
charge-transfer complexes.[6]
 Mercury(II) iodide is a crystalline material which at 126 C undergoes reversible phase transition
from red alpha phase to pale yellow beta phase.
Bis(dimethylammonium) tetrachloronickelate is a raspberry-red compound, which becomes
blue at about 110 C. On cooling, the compound becomes a light yellow metastable phase,
which over 23 weeks turns back into original red.[7] Many other tetrachloronickelates are also
thermochromic.
Bis(diethylammonium) tetrachlorocuprate is a bright green solid material, which at 5253 C
reversibly changes color to yellow. The color change is caused by relaxation of the hydrogen
bonds and subsequent change of geometry of the copper-chlorine complex from planar to
deformed tetrahedral, with appropriate change of arrangement of the copper atom's d-orbitals.
There is no stable intermediate, the crystals are either green or yellow.[6]
Chromium(III) oxide:aluminium(III) oxide in 1:9 ratio is red at room temperature and grey at
400 C, due to changes in its crystal field.[8]
Vanadium dioxide has been investigated for use as a "spectrally-selective" window coating to
block infrared transmission and reduce the loss of building interior heat through windows. This
material behaves like a semiconductor at lower temperatures, allowing more transmission, and
like a conductor at higher temperatures, providing much greater reflectivity.[9][10] The phase
change between transparent semiconductive and reflective conductive phase occurs at 68 C;
doping the material with 1.9% of tungsten lowers the transition temperature to 29 C.

Other thermochromic solid semiconductor materials include

CdxZn1xSySe1y (x = 0.51, y = 0.51),

ZnxCdyHg1xyOaSbSecTe1abc (x = 00.5, y = 0.51, a = 00.5, b = 0.51, c = 00.5),
HgxCdyZn1xySbSe1b (x=01, y=01, b=0.51).[11]

Some minerals are thermochromic as well; for example some chromium-rich pyropes, normally
reddish-purplish, become green when heated to about 80 C.[12]