Tunable Thermal Expansion Research Articles

Macro-Scale Strength and Microstructure of ZrW₂O₈ Cementitious Composites with Tunable Low Thermal Expansion.

Concretes with engineered thermal expansion coefficients, capable of avoiding failure or irreversible destruction of structures or devices, are important for civil engineering applications, such as dams, bridges, and buildings. In natural materials, thermal expansion usually cannot be easily regulated and an extremely low thermal expansion coefficient (TEC) is still uncommon. Here we propose a novel cementitious composite, doped with ZrW2O8, showing a wide range of tunable thermal expansion coefficients, from 8.65 × 10−6 °C−1 to 2.48 × 10−6 °C−1. Macro-scale experiments are implemented to quantify the evolution of the thermal expansion coefficients, compressive and flexural strength over a wide range of temperature. Scanning Electron Microscope (SEM) imaging was conducted to quantify the specimens’ microstructural characteristics including pores ratio and size. It is shown that the TEC of the proposed composites depends on the proportion of ZrW2O8 and the ambient curing temperature. Macro-scale experimental results and microstructures have a good agreement. The TEC and strength gradually decrease as ZrW2O8 increases from 0% to 20%, subsequently fluctuates until 60%. The findings reported here provide a new routine to design cementitious composites with tunable thermal expansion for a wide range of engineering applications.

Hoberman-sphere-inspired lattice metamaterials with tunable negative thermal expansion

Materials with engineered thermal expansion coefficients, capable of avoiding failure or irreversible destruction of structures and devices, are important for aerospace, civil, biomedical, optics, and semiconductor applications. In natural materials, thermal expansion usually cannot be adjusted easily and a negative thermal expansion coefficient is still uncommon. Here we propose a novel architected lattice bi-material system, inspired by the Hoberman sphere, showing a wide range of tunable thermal expansion coefficient from negative to positive, −1.04 × 10−3 °C−1 to 1.0 × 10−5 °C−1. Numerical simulations and analytical formulations are implemented to quantify the evolution of the thermal expansion coefficients and reveal the underlying mechanisms responsible for this unusual behavior. We show that the thermal expansion coefficient of the proposed metamaterials depends on the thermal expansion coefficient ratio and the axial stiffness ratio of the constituent materials, as well as the bending stiffness and the topological arrangement of the constitutive elements. The finding reported here provides a new routine to design architected metamaterial systems with tunable negative thermal expansion for a wide range of potential applications.

Auxetic and Negative Thermal Expansion Structure Based on Interconnected Array of Rings and Sliding Rods

An exploration by analytical method has been made herein for a mechanism‐based structure that involves a two‐dimensional array of rings and a three‐dimensional array of double‐rings, with short fixed rods and long sliding rods attached at the outer and inner surfaces of the rings, respectively. Based on the theory of thin rings, effective Poisson's ratio and effective coefficient of thermal expansion (CTE) models have been obtained for single‐ring structures, pole‐loaded double‐ring structures, and equator‐loaded double‐ring structures. Results establish a very strong correlation between these effective properties with the ring radius and rod lengths. In addition, the analysis of four of the double‐ring structures reveals that the sign of Poisson's ratio is dependent on the direction of loading. An example application is demonstrated herein in which positive thermal expansion rings, used in conjunction with rigid rods, enable the design of an overall zero thermal expansion structure (i.e., minimal thermal stress) with tunable negative thermal expansion internal microstructure for use as sieve. Finally, it is herein shown that, by judicious positioning of the short fixed rods and/or long sliding rods, one may possibly obtain various combinations of positive and negative CTEs with positive and negative Poisson's ratio.

High pressure Raman spectroscopic study of low thermal expansion AZr2(PO4)3, A=K, Rb and Cs

AZr2(PO4)3 (A=K, Rb, Cs) are a set of flexible framework compounds that exhibit tunable ultralow thermal expansion over the wide temperature range of 293-1273 K. High pressure Raman spectroscopic measurements on AZr2(PO4)3 reveals structural phase transformation above 2 GPa and amorphization above 20 GPa. On decompression from 20 GPa, the amorphous phase remains unchanged indicating irreversible nature of pressure induced amorphization (PIA). Various low frequency Raman modes corresponding to translation of Zr atoms and coupled rotation of PO4 tetrahedra and ZrO6 octahedra soften with increase in pressure which could be the driving force for the observed phase transition. Pressure induced phase transition could be due to collapse of Zr-O-P bond angles, and PIA due to kinetic hindrance of equilibrium decomposition. We have compared the phase transition and amorphization pressures of the various members of AZr2(PO4)3 to account for the stability of the ambient rhombohedral phase.

Structure, Magnetism, and Tunable Negative Thermal Expansion in (Hf,Nb)Fe2 Alloys

Negative thermal expansion (NTE) is one of intriguing properties for solid compounds. Here we report structure and tunable negative thermal expansion in the (Hf1-xNbx)Fe2 magnetic alloys. The NTE mechanism has been investigated by a combined analysis of neutron powder diffraction, synchrotron X-ray diffraction, and macroscopic magnetic measurements. Direct experimental evidence shows that magnetovolume effect is the root of NTE of ferromagnetic phase, while the paramagnetic phase responds to the general positive thermal expansion (PTE). Especially, by adjusting the amount of Nb chemical substitution in (Hf1-xNbx)Fe2, the coexistence of NTE ferromagnetic and PTE paramagnetic phases can tune the large NTE (x = 0.05, αv = -23.13 × 10-6 K-1, 323~398 K) to the relatively low thermal expansion (x = 0.15, αv = -8.28×10-6 K-1, 173~323 K). The present study reveals the direct link between NTE and magnetic structure, and shows that thermal expansion could be tuned by the coexistence of magnetic and paramagnetic phases.

Design methodology for porous composites with tunable thermal expansion produced by multi-material topology optimization and additive manufacturing

Abstract To realize negative thermal expansion (NTE), porous composites made of two materials with different coefficients of thermal expansion are being actively researched. NTE can be realized by taking advantage of the thermal deformation mechanisms of a composite material's internal geometry. However, in addition to negative thermal expansion, materials with anisotropic and large positive thermal expansion are also desirable for various applications. Also, additive manufacturing provides new ways to fabricate composites by layering multiple materials at arbitrary points in three-dimensional space. In this study, we developed a design methodology for porous composites, which showed defined thermal expansion characteristics, including negative and positive thermal expansion as well as isotropic and anisotropic thermal expansion. Our approach was tested based on the fabrication of a multi-material photopolymer by additive manufacturing. The internal geometries required to produce such characteristics were designed by topology optimization, which is the most effective structural optimization method for realizing macroscopic inward deformation and for maintaining stiffness. The designed structures were converted to three-dimensional models and fabricated by multi-material photopolymer additive manufacturing. Using laser scanning dilatometry, we measured the thermal expansion of these specimens, revealing well-ordered thermal expansion, from anisotropic positive thermal expansion to anisotropic negative thermal expansion, over a wide range of about −3 × 10−4 K−1 to 1 × 10−3 K−1.

Tunable thermal expansion in framework materials through redox intercalation

Thermal expansion properties of solids are of fundamental interest and control of thermal expansion is important for practical applications but can be difficult to achieve. Many framework-type materials show negative thermal expansion when internal cages are empty but positive thermal expansion when additional atoms or molecules fill internal voids present. Here we show that redox intercalation offers an effective method to control thermal expansion from positive to zero to negative by insertion of Li ions into the simple negative thermal expansion framework material ScF3, doped with 10% Fe to enable reduction. The small concentration of intercalated Li ions has a strong influence through steric hindrance of transverse fluoride ion vibrations, which directly controls the thermal expansion. Redox intercalation of guest ions is thus likely to be a general and effective method for controlling thermal expansion in the many known framework materials with phonon-driven negative thermal expansion.

Tunable thermal expansion and magnetism in Zr-doped ScF3

The negative thermal expansion (NTE) behavior provides us an opportunity to design materials with controllable coefficient of thermal expansion (CTE). In this letter, we report a tunable isotropic thermal expansion in the cubic (Sc1−xZrx)F3+δ over a wide temperature and CTE range (αl = −4.0 to+ 16.8 × 10−6 K−1, 298–648 K). The thermal expansion can be well adjusted from strong negative to zero, and finally to large positive. Intriguingly, isotropic zero thermal expansion (αl = 2.6 × 10−7 K−1, 298–648 K) has been observed in the composition of (Sc0.8Zr0.2)F3+δ. The controllable thermal expansion in (Sc1−xZrx)F3+δ is correlated to the local structural distortion. Interestingly, the ordered magnetic behavior has been found in the zero thermal expansion compound of (Sc0.8Zr0.2)F3+δ at room temperature, which presumably correlates with the unpaired electron of the lower chemical valence of Zr cation. The present study provides a useful reference to control the thermal expansion and explore the multi-functionalization for NTE materials.

Lightweight Mechanical Metamaterials with Tunable Negative Thermal Expansion.

Ice floating on water is a great manifestation of negative thermal expansion (NTE) in nature. The limited examples of natural materials possessing NTE have stimulated research on engineered structures. Previous studies on NTE structures were mostly focused on theoretical design with limited experimental demonstration in two-dimensional planar geometries. In this work, aided with multimaterial projection microstereolithography, we experimentally fabricate lightweight multimaterial lattices that exhibit significant negative thermal expansion in three directions and over a temperature range of 170degrees. Such NTE is induced by the structural interaction of material components with distinct thermal expansion coefficients. The NTE can be tuned over a large range by varying the thermal expansion coefficient difference between constituent beams and geometrical arrangements. Our experimental results match qualitatively with a simple scaling law and quantitatively with computational models.

Tunable Negative Thermal Expansion in Layered Perovskites from Quasi-Two-Dimensional Vibrations.

We identify a quasi-two-dimensional (quasi-2D) phonon mode in the layered-perovskite Ca_{3}Ti_{2}O_{7}, which exhibits an acoustic branch with quadratic dispersion. Using first-principles methods, we show this mode exhibits atomic displacements perpendicular to the layered [CaTiO_{3}]_{2} blocks comprising the structure and a negative Grüneisen parameter. Owing to these quasi-2D structural and dynamical features, we find that the mode can be utilized to realize unusual membrane effects, including a tunable negative thermal expansion (NTE) and a rare pressure-independent thermal softening of the bulk modulus. Detailed microscopic analysis shows that the NTE relies on strong intralayer Ti-O covalent bonding and weaker interlayer interactions, which is in contrast to conventional NTE mechanisms for perovskites, such as rigid-unit modes, structural transitions, and electronic or magnetic ordering. The general application of the quasi-2D lattice dynamics opens exciting avenues for the control of lattice dynamical and thermodynamic responses of other complex layered compounds through rational chemical substitution, as we show in A_{3}Zr_{2}O_{7} (A=Ca, Sr), and by heterostructuring.

Isotropic Negative Thermal Expansion Metamaterials.

Negative thermal expansion materials are important and desirable in science and engineering applications. However, natural materials with isotropic negative thermal expansion are rare and usually unsatisfied in performance. Here, we propose a novel method to achieve two- and three-dimensional negative thermal expansion metamaterials via antichiral structures. The two-dimensional metamaterial is constructed with unit cells that combine bimaterial strips and antichiral structures, while the three-dimensional metamaterial is fabricated by a multimaterial 3D printing process. Both experimental and simulation results display isotropic negative thermal expansion property of the samples. The effective coefficient of negative thermal expansion of the proposed models is demonstrated to be dependent on the difference between the thermal expansion coefficient of the component materials, as well as on the circular node radius and the ligament length in the antichiral structures. The measured value of the linear negative thermal expansion coefficient of the three-dimensional sample is among the largest achieved in experiments to date. Our findings provide an easy and practical approach to obtaining materials with tunable negative thermal expansion on any scale.

Superelasticity and Tunable Thermal Expansion across a Wide Temperature Range

Materials that undergo a reversible change of crystal structure through martensitic transformation (MT) possess unusual functionalities including shape memory, superelasticity, and low/negative thermal expansion. These properties have many advanced applications, such as actuators, sensors, and energy conversion, but are limited typically in a narrow temperature range of tens of Kelvin. Here we report that, by creating a nano-scale concentration modulation via phase separation, the MT can be rendered continuous by an in-situ elastic confinement mechanism. Through a model titanium alloy, we demonstrate that the elastically confined continuous MT has unprecedented properties, such as superelasticity from below 4.2 K to 500 K, fully tunable and stable thermal expansion, from positive, through zero, to negative, from below 4.2 K to 573 K, and high strength-to-modulus ratio across a wide temperature range. The elastic tuning on the MT, together with a significant extension of the crystal stability limit, provides new opportunities to explore advanced materials.

Hydration and Thermal Expansion in Anatase Nanoparticles.

A tunable thermal expansion is reported in nanosized anatase by taking advantage of surface hydration. The coefficient of thermal expansion of 4 nm TiO2 along a-axis is negative with a hydrated surface and is positive without a hydrated surface. High-energy synchrotron X-ray pair distribution function analysis combined with ab initio calculations on the specific hydrated surface are carried out to reveal the local structure distortion that is responsible for the unusual negative thermal expansion.

An Ag based brazing system with a tunable thermal expansion for the use as sealant for solid oxide cells

An Ag-Al2TiO5 composite braze was developed and successfully tested as seal for solid oxide cells. The thermo-mechanical properties of the Ag-Al2TiO5 system and the chemical compatibility between this composite braze and relevant materials used in stacks were characterized and the leak rates as a function of the operation temperature were measured. The thermal expansion coefficient in the Ag-Al2TiO5 system can be tailored by varying the amount of the ceramic filler. The brazing process can be carried out in air, the joining partners showed a good chemical stability and sufficient low leak rates were demonstrated. Furthermore, the long-term stability of the Ag-Al2TiO5 composite braze was studied under relevant SOFC and SOEC conditions. The stability of brazed Crofer/Ag-Al2TiO5/NiO-YSZ assemblies in reducing atmosphere and in pure oxygen was investigated over 500 h at 850 °C. Additionally, a cell component test was performed to investigate the durability of the Ag-Al2TiO5 seal when exposed to dual atmosphere. The seals performed well over 900 h under electrolysis operation conditions (−0.5 A cm2, 850 °C), and no cell degradation related to the Ag-Al2TiO5 sealing was found, indicating that the developed braze system is applicable for the use in SOFC/SOEC stacks.

Polytope Sector-Based Synthesis and Analysis of Microstructural Architectures With Tunable Thermal Conductivity and Expansion

The aim of this paper is to (1) introduce an approach, called polytope sector-based synthesis (PSS), for synthesizing 2D or 3D microstructural architectures that exhibit a desired bulk-property directionality (e.g., isotropic, cubic, orthotropic, etc.), and (2) provide general analytical methods that can be used to rapidly optimize the geometric parameters of these architectures such that they achieve a desired combination of bulk thermal conductivity and thermal expansion properties. Although the methods introduced can be applied to general beam-based microstructural architectures, we demonstrate their utility in the context of an architecture that can be tuned to achieve a large range of extreme thermal expansion coefficients—positive, zero, and negative. The material-property-combination region that can be achieved by this architecture is determined within an Ashby-material-property plot of thermal expansion versus thermal conductivity using the analytical methods introduced. These methods are verified using finite-element analysis (FEA) and both 2D and 3D versions of the design have been fabricated using projection microstereolithography.

La(Fe, Si, Co)13/Cu conductive composites with tailoring thermal expansion

In this work, metal-matrix composites which possess tunable thermal expansion coefficients in combination with high electrical and thermal conductivities were successfully synthesized by a moderate temperature hot-pressing method. The composites are based on incorporating La(Fe, Si, Co)13, a material with a negative coefficient of thermal expansion, within a continuous Cu matrix. The La(Fe, Si, Co)13 enables us to tune the coefficient of thermal expansion in a predictable manner, while the Cu phase is responsible for the electrical and thermal conductivity properties. The resulting materials exhibit coefficients of thermal expansion which can be tuned between the value of pure Cu and La(Fe, Si, Co)13. Thus, by adjusting the relative amount of the two components, the materials can be designed with high electrical and thermal conductivities and tailoring coefficient of thermal expansion properties. This unique combination of electrical and thermal properties enables these Cu-based metal-matrix composites to be applied in the microelectronic, semiconductor and thermoelectric industries.

Comparative Raman spectroscopic study of phase stability and anharmonic effects in AZr2(PO4)3 (A = K, Rb and Cs)

AZr2(PO4)3 (A=Na, K, Rb, Cs) are a set of framework structured compounds that exhibit tunable ultralow thermal expansion over the wide temperature range of 293–1273K. We report a systematic Raman spectroscopic investigation on AZr2(PO4)3 (A=K, Rb and Cs) compounds as a function of temperature in the range 80–860K and pressures of up to 32GPa. To get insight into the thermal expansion property, phonon anharmonicity has been investigated by studying the temperature and pressure dependence of Raman peak shifts and line widths and computed bulk modulus. We have compared the phase transition and amorphization pressures of the various members of AZr2(PO4)3 to account for the stability of the ambient rhombohedral phase. We find that unlike most of the anomalous thermal expansion materials, in AZr2(PO4)3 (A=K, Rb and Cs), the phonons that are anharmonic with temperature do not necessarily exhibit anharmonicity with pressure.

Cryogenic abnormal thermal expansion properties of carbon-doped La(Fe,Si)13 compounds.

Recently, La(Fe,Si)13-based compounds have attracted much attention due to their isotropic and tunable abnormal thermal expansion (ATE) properties as well as bright prospects for practical applications. In this research, we have prepared cubic NaZn13-type carbon-doped La(Fe,Si)13 compounds by the arc-melting method, and their ATE and magnetic properties were investigated by means of variable-temperature X-ray diffraction, strain gauge and the physical property measurement system (PPMS). The experimental results indicate that both micro and macro negative thermal expansion (NTE) behaviors gradually weaken with the increase of interstitial carbon atoms. Moreover, the temperature region with the most remarkable NTE properties has been broadened and near zero thermal expansion (NZTE) behavior occurs in the bulk carbon-doped La(Fe,Si)13 compounds.

Copper-Based Conductive Composites with Tailored Thermal Expansion

We have devised a moderate temperature hot-pressing route for preparing metal-matrix composites which possess tunable thermal expansion coefficients in combination with high electrical and thermal conductivities. The composites are based on incorporating ZrW2O8, a material with a negative coefficient of thermal expansion (CTE), within a continuous copper matrix. The ZrW2O8 enables us to tune the CTE in a predictable manner, while the copper phase is responsible for the electrical and thermal conductivity properties. An important consideration in the processing of these materials is to avoid the decomposition of the ZrW2O8 phase. This is accomplished by using relatively mild hot-pressing conditions of 500 °C for 1 h at 40 MPa. To ensure that these conditions enable sintering of the copper, we developed a synthesis route for the preparation of Cu nanoparticles (NPs) based on the reduction of a common copper salt in aqueous solution in the presence of a size control agent. Upon hot pressing these nanoparticles at 500 °C, we are able to achieve 92-93% of the theoretical density of copper. The resulting materials exhibit a CTE which can be tuned between the value of pure copper (16.5 ppm/°C) and less than 1 ppm/°C. Thus, by adjusting the relative amount of the two components, the properties of the composite can be designed so that a material with high electrical conductivity and a CTE that matches the relatively low CTE values of semiconductor or thermoelectric materials can be achieved. This unique combination of electrical and thermal properties enables these Cu-based metal-matrix composites to be used as electrical contacts to a variety of semiconductor and thermoelectric devices which offer stable operation under thermal cycling conditions.

Tunable Anisotropic Thermal Expansion of a Porous Zinc(II) Metal–Organic Framework

A novel three-dimensional metal-organic framework (MOF) that displays anisotropic thermal expansion has been prepared and characterized by single-crystal X-ray diffraction (SCD) and thermal analysis. The as-prepared MOF has one-dimensional channels containing guest molecules that can be removed and/or exchanged for other guest molecules in a single-crystal to single-crystal fashion. When the original guest molecules are replaced there is a noticeable effect on the host mechanics, altering the thermal expansion properties of the material. This study of the thermal expansion coefficients of different inclusion complexes of the host MOF involved systematic alteration of guest size, i.e., methanol, ethanol, n-propanol, and isopropanol, showing that fine control over the thermal expansion coefficients can be achieved and that the coefficients can be correlated with the size of the guest. As a proof of concept, this study demonstrates the realizable principle that a single-crystal material with an exchangeable guest component (as opposed to a composite) may be used to achieve a tunable thermal expansion coefficient. In addition, this study demonstrates that greater variance in the absolute dimensions of a crystal can be achieved when one has two variables that affect it, i.e., the host-guest interactions and temperature.