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Scripta Materialia 65 (2011) 664667 www.elsevier.com/locate/scriptamat

Origin of negative thermal expansion phenomenon in solids

Zi-Kui Liu, Yi Wang and Shun-Li Shang
Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA 16802, USA
Received 6 June 2011; revised 7 June 2011; accepted 1 July 2011 Available online 13 July 2011

We show that the negative thermal expansion (NTE) phenomenon originates from the existence of high pressure, small volume phases with higher entropy, with their congurations present in the stable phase matrix through thermal uctuations, thus exists. Consequently, it extends the platform for designing structures with desired thermal expansion properties whether positive, negative, or zero. The theory is validated for a range of pure elements and compounds and utilized to provide insights to the NTE phenomenon in Fe3Pt and ZrW2O8. 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Thermodynamics; Metastable phases; Continuous ordering; Polyphase microstructure

Solids with negative thermal expansion (NTE), i.e. volume reduction upon heating, have been discovered serendipitously throughout the history [14]. It is commonly believed that they are rare incidences [57] due to the lack of a full understanding of the origin of the NTE phenomenon. For instance, after the discovery of NTE in Fe65Ni35 by Guillaume [1,2] more than 100 years ago, its theoretical origin is still being discussed [8,9]. Furthermore, NTE in ZrW2O8 between 0.3 and 1050 K [4,10] spurred a renewed interest in this phenomenon [1113]. The discussions in the literature have been largely focused on specics in individual NTE solids and are mostly phenomenological, and there is a lack of fundamental understanding why some solids possess this property while others do not. In the present work, we aim to solve the enigma of the NTE phenomenon by examining a solid from one more dimension in addition to temperature (T), i.e. the pressure (P), and demonstrate that the NTE phenomenon exists in many solids in nature and can be predicted systematically. It is universally true that with increasing pressure at a constant temperature, the volume of a solid decreases. At higher pressures, the solid may experience a symmetry change to form a new phase with a smaller volume. The symmetry change can be related to atomic structures, spin polarizations, or both, and is dictated by electronic structures of the solid as a function of pressure. The relation of the two-phase equilibrium as a function of temperature and pressure is obtained from the

combined rst and second law of thermodynamics [14] as follows, commonly known as ClausiusClapeyron equation, dT DV m dP DS m 1

Corresponding author. E-mail: yuw3@psu.edu

where DVm and DSm are the molar volume and molar entropy dierences of two phases and dened as DV m V c V b and DS m S c S b where c is the m m m m phase stable at higher pressure with smaller molar volume, and b is the phase stable at lower pressure with larger molar volume. Since DVm < 0, the sign of Eq. (1), i.e. the slope of the two-phase equilibrium line, is dictated by the sign of DSm. When DSm = 0, the slope is innite, and the two-phase equilibrium line is vertical in the TP potential phase diagram. When DSm < 0, the larger volume b phase has the higher entropy and becomes more stable at higher temperatures, resulting in a positive slope for the two-phase equilibrium line. When DSm > 0, the smaller volume b phase has higher entropy and becomes more stable at higher temperatures, and the slope of the two-phase equilibrium line is negative. The above analysis depicts a well-known, yet extraordinary observation as it indicates that any systems with DVm < 0 and DSm > 0 will experience a volume decrease upon heating at a constant pressure when the two-phase equilibrium line is crossed. At temperatures higher or lower than the transition temperature, the phase with higher Gibbs energy is no longer stable and transforms to the more stable phase with lower Gibbs energy. Systems with this type of two-phase equilibrium lines are indeed ubiquitous in nature, such as the phase

1359-6462/$ - see front matter 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.scriptamat.2011.07.001

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transformation between ice and water [15,16]. However, systems exhibiting volume reduction involving this type of rst-order transition is usually not classied as NTE solids because their volume change is measured across two dierent phases as opposed to the volume change occurring in one phase when NTE is discussed. Now let us have a closer look when the system is approaching the two-phase equilibrium line from the low temperature, large volume b single phase eld. It is self evident that the b phase has lower Gibbs energy than the c phase. However, from the viewpoint of statistical mechanics, it is possible to observe the conguration of c in the b phase though with a Gibbs energy penalty of DG. Such a probability is proportional to exp(DG/RT) with R being the gas constant. This penalty reects the Gibbs energy dierence between c and b and other contributions such as the strain energy in tting the c conguration in the b matrix. The volume of such a solid with DVm < 0 and DSm > 0 thus contains contributions from both stable b phase and the metastable c conguration due to thermal uctuation. The thermal expansion of such a solid can thus be approximated as follows using the rule of mixture: @V m @ f c V c 1 f c V b m m aV m @T @T c c @f c 2 ab V b f cc a V m ab V b DV m m m @T b c where a, a , and a are the thermal expansion coecients of the system, the b phase, and the c conguration in the b matrix, respectively, Vm, is the molar volume of the system, and fc is the probability of observing the c conguration in the b matrix, proportional to exp(DG/ RT). For a solid with NTE, i.e. a < 0, Eq. (2) becomes     V c ac 1 V c @f c >1 3 fc 1 m b b 1 m a Vb a V b @T m m Therefore, the necessary condition to observe the NTE c phenomenon is V c < V b and @f > 0, which is consistent m m @T with the conditions of DVm < 0 and DSm > 0 discussed above. Eq. (3) demonstrates that, for a material to have NTE, the value of DG/RT must be small and decreases with the increase in temperature so a sucient amount of c conguration with smaller volume than that of c the b matrix can be observed and @f > 0. The limit of @T NTE is given when the left side of Eq. (3) equals unity, i.e. zero thermal expansion of the solid. Based on the above analyses, the criterion for the NTE phenomenon is DVm < 0 and DSm > 0, such that dT/dP < 0. As a result, a NTE material must have a schematic TP phase diagram shown in Figure 1. In this phase diagram, the solidsolid (b/c, c/amorphous) and solidliquid (b/Liquid, c/Liquid) two-phase equilibrium lines are drawn with negative slopes. Based on our criterion, NTE is expected in the b phase in a wide temperature range due to the contributions from the c conguration at low temperatures and the liquid conguration at high temperatures. By the same token, NTE is also expected in the c phase due to the contributions from the amorphous conguration at low temperatures and the liquid conguration at high temperatures, in the stable c single phase eld at pressures higher than ambient pressure.

Figure 1. A schematic TP phase diagram satisfying the criterion for the NTE phenomenon in b and c phases.

To validate the criterion on NTE solids, let us examine the available TP phase diagrams of pure elements [17] and compounds [18,19] compiled by Tonkov and his colleagues and in the literature [57]. The systems with dT/dP < 0 for one or more two-phase equilibrium lines are listed in Tables S1 and S2 in the Supplementary Information. It is observed that solids with their NTE observed experimentally show one or more two-phase equilibrium lines with dT/dP < 0, consistent with our criterion. In the Tables S1 and S2, a range of pure elements and compounds with dT/dP < 0 is predicted to have NTE which are not reported yet in the literature. There could be a number of reasons such as that attentions in terms of NTE phenomenon have not been paid to those solids, the temperature range for NTE is small, and solids may not show the NTE phenomenon under ambient conditions because DG/RT is not low enough to generate signicant probability of observing the lower volume congurations in the higher volume matrix phase. Recently through rst-principles calculations based on density functional theory, Wang et al. [9] predicted the Gibbs energy functions of ferromagnetic (FM) conguration and a range of spin-ipping congurations in Fe3Pt. By considering the sum of the spin-ipping congurations as the paramagnetic (PM) phase, they calculated the phase diagram as shown in Figure 2. It can be seen that and the TP phase diagram has DVm < 0, and DSm > 0, giving dT/dP < 0. The values of DG/RT at P = 0 for various spin-ipping congurations are evaluated in the present work and plotted in Figure 3. With the molar volumes of the PM conguration being about 1.8% smaller than that of the FM matrix phase and assuming similar thermal expansion for all congurations and the FM matrix, it can be shown that the left side of Eq. (3) becomes larger than unity at 272 K, which is in agreement with the experimental observation of NTE starting from 300 K [9]. More detailed theoretic predictions by Wang et al. [9] showed that the NTE phenomenon ends around 450 K near the two-phase equilibrium line, where the positive thermal expansions of the PM and FM congurations overweigh the dierence of their individual thermal expansions.

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Figure 2. Calculated TP phase diagram of Fe3Pt of ferromagnetic (FM) and paramagnetic (PM) phases by Wang et al. [9] with the solid and dotted lines for rst- and second-order transformations, respectively, and the circle marking the critical point between the two.

high temperatures show negative slopes. Based on the criterion developed in the present work, the lower volume c conguration does not contribute to the NTE phenomenon of b due to the lower entropy in c. On the other hand, the lower volume amorphous phase has higher entropy than c and b. It can thus be concluded that both c and b possess NTE due to the presence of the amorphous phase [4,11]. The b/amorphous two-phase equilibrium line with negative slope at high temperatures causes the NTE of b to extend to its decomposition temperature at 1050 K [4,10]. Furthermore, the properties of the amorphous phase are isotropic, enabling the NTE of ZrW2O8 to be isotropic too. In summary, we present a fundamental criterion to determine whether or not a material possesses NTE characteristics, i.e. DVm < 0 and DSm > 0. Our criterion is validated for existing NTE materials reported in the literature and is used to predict a range of NTE materials based on available TP phase diagrams for the community to test. Furthermore, advanced computational methodologies enable us to predict new NTE materials through the calculations of properties of high pressure phases and slopes of two-phase equilibrium lines. This work is funded by Oce of Naval Research under the Contract number of N0014-07-1-0638 and National Science Foundation through Grant DMR-1006557. We greatly appreciate the program managers David Shier and Alan J. Ardell for their support and encouragement. We would like to thank Brian Vanleeuwen and Chelsey Zacherl for their comments of the manuscript.

Figure 3. DG/RT for various spin-ipping phases (SFs) with respect to the ferromagnetic phase (FM) by Wang et al. [9] as a function of temperature at P = 0.

It can be argued that the NTE phenomenon should thus exist in many magnetic solids as a magnetic solid typically loses its magnetic ordering at high pressures and high temperatures with DVm < 0 and DSm > 0, resulting in dT/dP < 0 though Ce is an exception [20,21]. Similarly, our criterion predicts that ferroelectric materials also possess the NTE characteristics as the cubic phase is stabilized at high pressures with smaller volume and at high temperatures with higher entropy [5]. Some solids exhibit pressure-induced amorphorization such ice [15,16], plutonium and bismuth [17]. With the understanding that an amorphous phase can be viewed as a supercooled liquid thus with higher entropy than that of the solid crystalline phase, the two-phase equilibrium line between the amorphous and crystal phases has DVm < 0, DSm > 0, and dT/dP < 0. The NTE phenomenon is expected as schematically shown in Figure 1 for the b/amorphous two-phase equilibrium line. Let us examine the ZrW2O8 system. The TP phase diagram was proposed by Arora et al. [22] showing the pressure-induced phase transition from the cubic b-ZrW2O8 to the orthorhombic c-ZrW2O8 phase and its subsequent amorphization [11,23]. The two-phase equilibrium line between b and c has a slightly positive slope, while the two-phase equilibrium lines between c/amorphous at low temperatures and b/amorphous at

Supplementary data associated with this article can be found, in the online version, at doi:10.1016/ j.scriptamat.2011.07.001.
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