Negative thermal expansion - Wikipedia https://en.wikipedia.

org/wiki/Negative_thermal_expansion

Negative thermal expansion

Negative thermal expansion (NTE) is an unusual physicochemical process in which some materials contract upon heating, rather than expand as
most other materials do. The most well-known material with NTE is water at 0~4 °C. Materials which undergo NTE have a range of potential
engineering, photonic, electronic, and structural applications. For example, if one were to mix a negative thermal expansion material with a "normal"
material which expands on heating, it could be possible to use it as a thermal expansion compensator what might allow for forming composites with
tailored or even close to zero thermal expansion.

Contents
Origin of negative thermal expansion
Negative thermal expansion in close-packed systems
Materials
Applications
References
Further reading

Origin of negative thermal expansion

There are a number of physical processes which may cause contraction with increasing temperature, including transverse vibrational modes, Rigid Unit
Modes and phase transitions.

Recently, Liu et al.[1] showed that the NTE phenomenon originates from the existence of high pressure, small volume configurations with higher entropy,
with their configurations present in the stable phase matrix through thermal fluctuations. They were able to predict both the colossal positive thermal
expansion (In cerium) and zero and infinite negative thermal expansion (in Fe3Pt).[2] Alternatively, large negative and positive thermal expansion may
result from the design of internal microstructure.[3]

Negative thermal expansion in close-packed systems

Negative thermal expansion is usually observed in non-close-packed systems with directional interactions (e.g. ice, graphene, etc.) and complex
compounds (e.g. Cu2O, ZrW2O8, beta-quartz, some zeolites, etc.). However, in a paper,[4] it was shown that negative thermal expansion (NTE) is also
realized in single-component close-packed lattices with pair central force interactions. The following sufficient condition for potential giving rise to NTE
behavior is proposed for the interatomic potential, , at the equilibrium distance :

Where is shorthand for the third derivative of the interatomic potential at the equilibrium point:

This condition is (i) necessary and sufficient in 1D and (ii) sufficient, but not necessary in 2D and 3D. An approximate necessary and sufficient condition
is derived in a paper[5]

where is the space dimensionality. Thus in 2D and 3D negative thermal expansion in close-packed systems with pair interactions is realized even when
the third derivative of the potential is zero or even negative. Note that one-dimensional and multidimensional cases are qualitatively different. In 1D
thermal expansion is caused by anharmonicity of interatomic potential only. Therefore, the sign of thermal expansion coefficient is determined by the
sign of the third derivative of the potential. In multidimensional case the geometrical nonlinearity is also present, i.e. lattice vibrations are nonlinear even
in the case of harmonic interatomic potential. This nonlinearity contributes to thermal expansion. Therefore, in multidimensional case both and
are present in the condition for negative thermal expansion.

Materials
Perhaps one of the most studied materials to exhibit negative thermal expansion is zirconium tungstate (ZrW2O8). This compound contracts
continuously over a temperature range of 0.3 to 1050 K (at higher temperatures the material decomposes).[6] Other materials that exhibit NTE
behaviour include other members of the AM2O8 family of materials (where A = Zr or Hf, M = Mo or W) and HfV2O7 and ZrV2O7, though HfV2O7 and
ZrV2O7 only in their high temperature phase starting at 350 to 400 K.[7] A2(MO4)3 also is an example of controllable negative thermal expansion. Cubic
materials like ZrW2O8 and also HfV2O7 and ZrV2O7 are especially precious for applications in engineering because they exhibit isotropic NTE i.e. the
NTE is the same in all three dimensions making it easier to apply them as thermal expansion compensators.[8]

Ordinary ice shows NTE in its hexagonal and cubic phases at very low temperatures (below –200 °C).[9] In its liquid form, pure water also displays
negative thermal expansivity below 3.984 °C.

ALLVAR, a titanium-based alloy, shows NTE over a wide temperature range, with a -30 ppm/°C instantaneous coefficient of thermal expansion at

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20 °C.[10]

Rubber elasticity shows NTE at normal temperatures, but the reason for the effect is rather different from that in most other materials. Put simply, as the
long polymer chains absorb energy, they adopt a more contorted configuration, reducing the volume of the material.[11]

Carbon fibers shows NTE between 20°C and 500°C. [12] This property is utilized in tight-tolerance aerospace applications to tailor the CTE of carbon
fiber reinforced plastic components for specific applications/conditions, by adjusting the ratio of carbon fiber to plastic and by adjusting the orientation
of the carbon fibers within the part.

Quartz (SiO2) and a number of zeolites also show NTE over certain temperature ranges.[13][14] Fairly pure silicon (Si) has a negative coefficient of
thermal expansion for temperatures between about 18 K and 120 K.[15] Cubic Scandium trifluoride has this property which is explained by the quartic
oscillation of the fluoride ions. The energy stored in the bending strain of the fluoride ion is proportional to the fourth power of the displacement angle,
unlike most other materials where it is proportional to the square of the displacement. A fluorine atom is bound to two scandium atoms, and as
temperature increases the fluorine oscillates more perpendicularly to its bonds. This draws the scandium atoms together throughout the material and it
contracts.[16] ScF3 exhibits this property from 10 to 1100 K above which it shows the normal positive thermal expansion.[17] Shape memory alloys such as
NiTi are a nascent class of materials that exhibit zero and negative thermal expansion.[18][19]

Applications
Forming a composite of a material with (ordinary) positive thermal expansion with a material with (anomalous) negative thermal expansion could allow
for tailoring the thermal expansion of the composites or even having composites with a thermal expansion close to zero. Negative and positive thermal
expansion hereby compensate each other to a certain amount if the temperature is changed. Tailoring the overall thermal expansion coefficient (CTE) to
a certain value can be achieved by varying the volume fractions of the different materials contributing to the thermal expansion of the composite.[8][20]

Especially in engineering there is a need for having materials with a CTE close to zero i.e. with constant performance over a large temperature range e.g.
for application in precision instruments. But also in everyday life materials with a CTE close to zero are required. Glass-ceramic cooktops like Ceran
cooktops need to withstand large temperature gradients and rapid changes in temperature while cooking because only certain parts of the cooktops will
be heated while other parts stay close to ambient temperature. In general, due to its brittleness temperature gradients in glass might cause cracks.
However, the glass-ceramics used in cooktops consist of multiple different phases, some exhibiting positive and some others exhibiting negative thermal
expansion. The expansion of the different phases compensate each other so that there is not much change in volume of the glass-ceramic with
temperature and crack formation is avoided.

An everyday life example for the need for materials with tailored thermal expansion are dental fillings. If the fillings tend to expand by an amount
different from the teeth, for example when drinking a hot or cold drink, it might cause a toothache. If dental fillings are, however, made of a composite
material containing a mixture of materials with positive and negative thermal expansion then the overall expansion could be precisely tailored to that of
tooth enamel.

References
1. Liu, Zi-Kui; Wang, Yi; Shang, Shun-Li (2011). "Origin of negative
thermal expansion phenomenon in solids". Scripta Materialia. 65 (8):
664–667. doi:10.1016/j.scriptamat.2011.07.001 (https://doi.org
/10.1016%2Fj.scriptamat.2011.07.001).
2. Liu, Zi-Kui; Wang, Yi; Shang, Shunli (2014). "Thermal Expansion
Anomaly Regulated by Entropy" (https://www.ncbi.nlm.nih.gov
/pmc/articles/PMC4229665). Scientific Reports. 4: 7043.
Bibcode:2014NatSR...4E7043L (https://ui.adsabs.harvard.edu
/abs/2014NatSR...4E7043L). doi:10.1038/srep07043 (https://doi.org
/10.1038%2Fsrep07043). PMC 4229665 (https://www.ncbi.nlm.nih.gov
/pmc/articles/PMC4229665). PMID 25391631
(https://pubmed.ncbi.nlm.nih.gov/25391631).
3. Cabras, Luigi; Brun, Michele; Misseroni, Diego (2019). "Micro-
structured medium with large isotropic negative thermal expansion"
(https://doi.org/10.1098/rspa.2019.0468). Proceedings of the Royal
Society A: Mathematical, Physical and Engineering Sciences. 475:
7043. doi:10.1098/rspa.2019.0468 (https://doi.org
/10.1098%2Frspa.2019.0468).
4. Rechtsman, M.C.; Stillinger, F.H.; Torquato, S. (2007), "Negative
thermal expansion in single-component systems with isotropic
interactions", The Journal of Physical Chemistry A, 111 (49):
12816–12821, arXiv:0807.3559 (https://arxiv.org/abs/0807.3559),
Bibcode:2007JPCA..11112816R (https://ui.adsabs.harvard.edu
/abs/2007JPCA..11112816R), doi:10.1021/jp076859l (https://doi.org
/10.1021%2Fjp076859l), PMID 17988108
(https://pubmed.ncbi.nlm.nih.gov/17988108)
10. Monroe, James A. (10 July 2018). Navarro, Ramón; Geyl, Roland
5. Kuzkin, Vitaly A. (2014), "Comment on 'Negative Thermal Expansion in
Single-Component Systems with Isotropic Interactions' ", The Journal
of Physical Chemistry A, 118 (41): 9793–4,
Bibcode:2014JPCA..118.9793K (https://ui.adsabs.harvard.edu
/abs/2014JPCA..118.9793K), doi:10.1021/jp509140n (https://doi.org
11. "Heating a rubber band: negative coefficient of thermal expansion |
/10.1021%2Fjp509140n), PMID 25245826
(https://pubmed.ncbi.nlm.nih.gov/25245826)
6. Mary, T. A.; Evans, J. S. O.; Vogt, T.; Sleight, A. W. (1996). "Negative
Thermal Expansion from 0.3 to 1050 Kelvin in ZrW2O8". Science. 272
(5258): 90–92. Bibcode:1996Sci...272...90M
(https://ui.adsabs.harvard.edu/abs/1996Sci...272...90M).
doi:10.1126/science.272.5258.90 (https://doi.org
/10.1126%2Fscience.272.5258.90).
7. Hisashige, Tetsuo; Yamaguchi, Teppei; Tsuji, Toshihide; Yamamura,
Yasuhisa (2006). "Phase Transition of Zr1-xHfxV2O7 Solid Solutions
Having Negative Thermal Expansion" (https://doi.org/10.2109
/jcersj.114.607). Journal of the Ceramic Society of Japan. 114 (1331):
607–611. doi:10.2109/jcersj.114.607 (https://doi.org
/10.2109%2Fjcersj.114.607). ISSN 0914-5400
(https://www.worldcat.org/issn/0914-5400).
8. Dove, Martin T; Fang, Hong (2016-06-01). "Negative thermal expansion
and associated anomalous physical properties: review of the lattice
dynamics theoretical foundation". Reports on Progress in Physics. 79
(6): 066503. doi:10.1088/0034-4885/79/6/066503 (https://doi.org
/10.1088%2F0034-4885%2F79%2F6%2F066503). ISSN 0034-4885
(https://www.worldcat.org/issn/0034-4885). PMID 27177210
(https://pubmed.ncbi.nlm.nih.gov/27177210).
9. Röttger, K.; Endriss, A.; Ihringer, J.; Doyle, S.; Kuhs, W. F. (1994).
"Lattice constants and thermal expansion of H2O and D2O ice Ih
between 10 and 265 K". Acta Crystallographica Section B. 50 (6):
644–648. doi:10.1107/S0108768194004933 (https://doi.org
/10.1107%2FS0108768194004933).
(eds.). "Negative thermal expansion ALLVAR alloys for telescopes".
Advances in Optical and Mechanical Technologies for Telescopes and
Instrumentation II. III: 26. doi:10.1117/12.2314657 (https://doi.org
/10.1117%2F12.2314657). ISBN 9781510619654.
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Berkeleyphysicsdemos.net. Retrieved 2015-05-10.

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12. Kude, Y.; Sohda, Y. (1997). "Thermal management of carbon-carbon
composites by functionally graded fiber arrangement technique". In
Shiota, Ichiro; Miyamoto, Yoshinari (eds.). Functionally Graded
Materials 1996 (https://doi.org/10.1016/B978-044482548-3/50040-8).
Elsevier Science B.V. pp. 239–244. ISBN 9780444825483. Retrieved
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13. Lightfoot, Philip; Woodcock, David A.; Maple, Martin J.; Villaescusa,
Luis A.; Wright, Paul A. (2001). "The widespread occurrence of
negative thermal expansion in zeolites". Journal of Materials
Chemistry. 11: 212–216. doi:10.1039/b002950p (https://doi.org
/10.1039%2Fb002950p).
14. Attfield, Martin P. (1998). "Strong negative thermal expansion in
siliceous faujasite". Chemical Communications (5): 601–602.
doi:10.1039/A707141H (https://doi.org/10.1039%2FA707141H).
15. Bullis, W. Murray (1990). "Chapter 6" (https://books.google.com
/books?id=COcVgAtqeKkC&pg=PA431&
dq=silicon+negative+%22coefficient+of+thermal+expansion%22#v=one
page&q=silicon%20negative
%20%22coefficient%20of%20thermal%20expansion%22&f=false). In
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of semiconductor silicon technology. Park Ridge, New Jersey: Noyes
Publications. p. 431. ISBN 978-0-8155-1237-0. Retrieved 2010-07-11.
16. Woo, Marcus (7 November 2011). "An incredible shrinking material:
Engineers reveal how scandium trifluoride contracts with heat"
(http://www.physorg.com/news/2011-11-incredible-material-reveal-
scandium-trifluoride.html). Physorg. Retrieved 8 November 2011.
17. Greve, Benjamin K.; Kenneth L. Martin; Peter L. Lee; Peter J. Chupas;
Karena W. Chapman; Angus P. Wilkinson (19 October 2010).
"Pronounced negative thermal expansion from a simple structure:
cubic ScF3". Journal of the American Chemical Society. 132 (44):
15496–15498. doi:10.1021/ja106711v (https://doi.org
/10.1021%2Fja106711v). PMID 20958035
(https://pubmed.ncbi.nlm.nih.gov/20958035).
18. Röttger, K.; Endriss, A.; Ihringer, J.; Doyle, S.; Kuhs, W. F. (1994).
"Lattice constants and thermal expansion of H2O and D2O ice
Ihbetween 10 and 265 K". Acta Crystallographica Section B. 50 (6):
644–648. doi:10.1107/S0108768194004933 (https://doi.org
/10.1107%2FS0108768194004933).
19. Ahadi, A.; Matsushita, Y.; Sawaguchi, T.; Sun, Q.P.; Tsuchiya, K.
(2017). "Origin of zero and negative thermal expansion in severely-
deformed superelastic Ni Ti alloy". Acta Materialia. 124: 79–92.
doi:10.1016/j.actamat.2016.10.054 (https://doi.org
/10.1016%2Fj.actamat.2016.10.054).
20. Takenaka, Koshi (February 2012). "Negative thermal expansion
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(https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5090290). Science and
Technology of Advanced Materials. 13 (1): 013001.
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/10.1088%2F1468-6996%2F13%2F1%2F013001). ISSN 1468-6996
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(https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5090290).
PMID 27877465 (https://pubmed.ncbi.nlm.nih.gov/27877465).

Further reading
Miller, W.; Smith, C. W.; MacKenzie, D. S.; Evans, K. E. (2009). "Negative thermal expansion: a review". Journal of Materials Science. 44 (20):
5441–5451. Bibcode:2009JMatS..44.5441M (https://ui.adsabs.harvard.edu/abs/2009JMatS..44.5441M). doi:10.1007/s10853-009-3692-4
(https://doi.org/10.1007%2Fs10853-009-3692-4).
Li, J.; Yokochi, A.; Amos, T. G.; Sleight, A. W. (2002). "Strong Negative Thermal Expansion along the O−Cu−O Linkage in CuScO2". Chemistry of
Materials. 14 (6): 2602–2606. doi:10.1021/cm011633v (https://doi.org/10.1021%2Fcm011633v).
Noailles, L. D.; Peng, H.-h.; Starkovich, J.; Dunn, B. (2004). "Thermal Expansion and Phase Formation of ZrW2O8 Aerogels". Chemistry of
Materials. 16 (7): 1252–1259. doi:10.1021/cm034791q (https://doi.org/10.1021%2Fcm034791q).
Grzechnik, A.; Crichton, W. A.; Syassen, K.; Adler, P.; Mezouar, M. (2001). "A New Polymorph of ZrW2O8 Synthesized at High Pressures and High
Temperatures". Chemistry of Materials. 13 (11): 4255–4259. doi:10.1021/cm011126d (https://doi.org/10.1021%2Fcm011126d).
Sanson, A.; Rocca, F.; Dalba, G.; Fornasini, P.; Grisenti, R.; Dapiaggi, M.; Artioli, G. (2006). "Negative thermal expansion and local dynamics in
Cu 2O and Ag2O". Physical Review B. 73 (21): 214305. Bibcode:2006PhRvB..73u4305S (https://ui.adsabs.harvard.edu/abs/2006PhRvB..73u4305S).
doi:10.1103/PhysRevB.73.214305 (https://doi.org/10.1103%2FPhysRevB.73.214305).
Bhange, D. S.; Ramaswamy, Veda (2006). "Negative thermal expansion in silicalite-1 and zirconium silicalite-1 having MFI structure". Materials
Research Bulletin. 41 (7): 1392–1402. CiteSeerX 10.1.1.561.4881 (https://citeseerx.ist.psu.edu/viewdoc/summary?doi=10.1.1.561.4881).
doi:10.1016/j.materresbull.2005.12.002 (https://doi.org/10.1016%2Fj.materresbull.2005.12.002).
Liu, Z.-K.; Wang, Yi; Shang, S.-L. (2011). "Origin of negative thermal expansion in solids". Scripta Materialia. 65 (8): 664–667.
doi:10.1016/j.scriptamat.2011.07.001 (https://doi.org/10.1016%2Fj.scriptamat.2011.07.001).

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