Atomic Linkage Flexibility Tuned Isotropic Negative, Zero, and Positive Thermal Expansion in MZrF₆ (M = Ca, Mn, Fe, Co, Ni, and Zn)

Abstract

The controllable isotropic thermal expansion with a broad coefficient of thermal expansion (CTE) window is intriguing but remains challenge. Herein we report a cubic MZrF series (M = Ca, Mn, Fe, Co, Ni and Zn), which exhibit controllable thermal expansion over a wide temperature range and with a broader CTE window (-6.69 to +18.23 × 10/K). In particular, an isotropic zero thermal expansion (ZTE) is achieved in ZnZrF, which is one of the rarely documented high-temperature isotropic ZTE compounds. By utilizing temperature-dependent high-energy synchrotron X-ray total scattering diffraction, it is found that the flexibility of metal···F atomic linkages in MZrF plays a critical role in distinct thermal expansions. The flexible metal···F atomic linkages induce negative thermal expansion (NTE) for CaZrF, whereas the stiff ones bring positive thermal expansion (PTE) for NiZrF. Thermal expansion could be transformed from striking negative, to zero, and finally to considerable positive though tuning the flexibility of metal···F atomic linkages by substitution with a series of cations on M sites of MZrF. The present study not only extends the scope of NTE families and rare high-temperature isotropic ZTE compounds but also proposes a new method to design systematically controllable isotropic thermal expansion frameworks from the perspective of atomic linkage flexibility.

Switching Between Giant Positive and Negative Thermal Expansions of a YFe(CN)6‐based Prussian Blue Analogue Induced by Guest Species

“…Notably,the presence of guest ions (K + )and molecules (H 2 O) can substantially switch thermal expansion of YFe(CN) 6 from negative (a v = À33.67 10 À6 K À1 )t op ositive (a v =+42.72 10 À6 K À1 )-a range that covers the thermal expansion of most inorganic compounds.T he mechanism of such substantial thermal expansion switching is revealed by joint studies with synchrotron X-ray diffraction, X-rayabsorption fine structure,n eutron powder diffraction, and density functional theory calculations.T he presence of guest ions or molecules plays ac ritical damping effect on transverse vibrations,t hus inhibiting negative thermal expansion. Subsequently,m any more NTE framework materials were found, such as oxides containing MÀOÀMo xygen atom bridges with the general chemical formulae AMO 5 , [7] A 2 M 3 O 12 , [8,9] AO 3 , [10] AM 2 O 7 , [11] and AM 2 O 8 ; [1,12] ReO 3 -type fluorides, [13][14][15][16] cyanides,a nd the Prussian blue analogues formed by double atom M-CN-M bridges in Zn(CN) 2 , [17] Ag 3 Co(CN) 6 , [18] LnCo(CN) 6 , [19] and FeCo(CN) 6 ; [20] and metal-organic frameworks (MOFs) [21][22][23][24] with carboxylate linkages.Thec ontrol of thermal expansion in NTE materials was mainly achieved by chemical substitution, as reported in previous studies. [1][2][3][4][5] Theo ccurrence of negative thermal expansion (NTE) materials offers ap romising possibility.I n 1968, Hummel et al first observed the NTE phenomenon in the framework material ZrW 2 O 8 .…”

“…[1][2][3][4][5] Theo ccurrence of negative thermal expansion (NTE) materials offers ap romising possibility.I n 1968, Hummel et al first observed the NTE phenomenon in the framework material ZrW 2 O 8 . Subsequently,m any more NTE framework materials were found, such as oxides containing MÀOÀMo xygen atom bridges with the general chemical formulae AMO 5 , [7] A 2 M 3 O 12 , [8,9] AO 3 , [10] AM 2 O 7 , [11] and AM 2 O 8 ; [1,12] ReO 3 -type fluorides, [13][14][15][16] cyanides,a nd the Prussian blue analogues formed by double atom M-CN-M bridges in Zn(CN) 2 , [17] Ag 3 Co(CN) 6 , [18] LnCo(CN) 6 , [19] and FeCo(CN) 6 ; [20] and metal-organic frameworks (MOFs) [21][22][23][24] with carboxylate linkages. Subsequently,m any more NTE framework materials were found, such as oxides containing MÀOÀMo xygen atom bridges with the general chemical formulae AMO 5 , [7] A 2 M 3 O 12 , [8,9] AO 3 , [10] AM 2 O 7 , [11] and AM 2 O 8 ; [1,12] ReO 3 -type fluorides, [13][14][15][16] cyanides,a nd the Prussian blue analogues formed by double atom M-CN-M bridges in Zn(CN) 2 , [17] Ag 3 Co(CN) 6 , [18] LnCo(CN) 6 , [19] and FeCo(CN) 6 ; [20] and metal-organic frameworks (MOFs) [21][22][23]…”

Effects of Cr Substitution on Negative Thermal Expansion and Magnetic Properties of Antiperovskite Ga1−xCrxN0.83Mn3 Compounds

“…From the view point of applications, NTE materials can be used as fillers for compensating and controlling the positive thermal expansion (PTE) of normal materials by forming composites (Romao et al, 2003; Chen et al, 2015). NTE has been observed in many materials due to different mechanisms, including flexible framework in crystal structure (Mary et al, 1996; Goodwin et al, 2008; Greve et al, 2010; Ge et al, 2016; Hu et al, 2016; Jiang et al, 2016), ferroelectricity (Xing et al, 2003; Chen et al, 2013), charge transformation (Long et al, 2009; Azuma et al, 2011; Yamada et al, 2011), magnetovolume effect (MVE) (Takenaka and Takagi, 2005; Huang et al, 2013; Li et al, 2015, 2016), and martensitic transformation (Zhao et al, 2015; Lin et al, 2016). Among them, the NTE related with MVE in antiperovskite manganese nitrides ANMn 3 (A: transition metal or semiconducting elements) has been extensively studied because of the large and isotropic NTE with tunable linear coefficient of thermal expansion (α L ), good mechanical properties (large Young's modulus and hardness) and thermal/electrical conductivities (Takenaka and Takagi, 2005; Sun et al, 2007; Huang et al, 2008; Song et al, 2011; Tong et al, 2013a,b; Tan et al, 2014).…”

Negative thermal expansion properties in tetragonal NbPO5 from the first principles studies

“…Ishii et al have shown that thermal expansion can be suppressed in molten aluminum alloy by incorporating with NTE manganese anti-perovskites. 5 Many framework structures, besides metal fluorides [6][7][8][9][10] and metal cyanides, 11 including a large number of metal oxides have been found showing NTE behaviors. Metal oxides showing NTE properties include MO 2 (M = Cu and Ag), 12 ReO 12 have both tetrahedral and octahedral unit connected by corner-sharing oxygen atoms.…”