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DOE OSTI2025

Enhancing Thermal Transport in Polymeric Composites Via Engineered Noncovalent Filler–Polymer Interactions

Understanding thermal transport mechanisms in polymeric composites allows us to expand the boundaries of thermal conductivity in them, either increasing it for more efficient heat dissipation or decreasing it for better thermal insulation. But, these mechanisms are not fully understood. Systematic experimental investigations remain limited. Practical strategies to tune the interfacial thermal resistance (ITR) between fillers and polymers and the thermal conductivity of composites remain elusive. Here, we studied the thermal transport in representative polymer composites, using polyethylene (PE) or polyaniline (PANI) as matrices and graphite as fillers. PANI, with aromatic rings in its backbone, interacts with graphite through strong noncovalent π–π stacking interactions, whereas PE lacks such interactions. We can then quantify how π–π stacking interactions between graphite and polymers enhance thermal transport in composites. PE/graphite and PANI/graphite composites with the same 1.5% filler volume fractions show a ∼22.82% and ∼34.85% enhancement in thermal conductivity compared to pure polymers, respectively. Calculated ITRs in PE/graphite and PANI/graphite are ~6 x 10 -8 m 2 KW -1 and ~1 x 10 -8 m 2 KW -1 , respectively, highlighting how π–π stacking interactions reduce ITR. Molecular dynamics (MD) simulations suggest that π–π stacking interactions between PANI chains and graphite surfaces enhance alignment of PANI's aromatic rings with graphite surfaces. This allows more carbon atoms from PANI chains to interact with graphite surfaces at a shorter distance compared to PE chains. Finally, our work indicates that tuning the π–π stacking interactions between polymers and fillers is an effective approach to reduce the ITR and enhance the thermal conductivity of composites.

atoms↗

DOE OSTI2020

MESOSCALE THERMAL TRANSPORT MEASUREMENTS OF MULTI-PHASE AND POROUS NUCLEAR FUELS USING A SQUARE-WAVE PULSE THERMOREFLECTANCE TECHNIQUE

The safe and efficient operation of nuclear reactors require accurate knowledge of peak temperatures in the fuel assemblies. The temperature profiles are governed by the thermal transport properties of the fuel, namely the thermal conductivities (k) and thermal diffusivities (D). These values can be very difficult to measure as they are known to vary considerably from the measured bulk values of the fresh fuel, and quickly degrade with increasing burnup [1 -3] . Laser-based techniques have been effectively used for non-destructive and non-contact thermal transport measurements of a wide variety of materials, including nuclear materials [4-6] that would otherwise prove too hazardous or difficult to measure otherwise. In this study, a new thermoreflectance technique known as square-pulse transient thermoreflectance (SPTR) is described and used to determine the mesoscale thermal diffusivity of both uranium sesquisilicide (U3Si2) and uranium nitride (UN) phases in a composite fuel with micron level spatial resolution [7]. This technique employs a rapid train of square-wave pulses from an excitation laser to create a periodic heat flux on a gold coated sample surface. Surface adsorption results in transient film temperatures and hence rapid fluctuations in thermoreflectance that can be measured via a detection laser coupled with a digital oscilloscope. The lasers are coaxially focused on the sample surface, allowing for a sample measurement area of a single convolved laser spot size (~2 µm). A sensitivity analysis was conducted to identify key measurement parameters of this technique using reference materials with a range of thermal conductivities comparable to those of both ceramic, composite, and metal nuclear fuel types (1.4 – 27.2 W/m-K). The reference materials were measured using the new technique as well as a spatial-domain thermoreflectance technique (SDTR) previously reported for a comparison [8]. Additionally, measurements of several U3Si2 and UN phase regions of a polished UN/U3Si2 (70/30 vol.%) sample were taken, and the resulting calculated D values are reported, with both techniques showing excellent agreement between samples. This technique was used to scan a multiphase region at 5 micron increments to generate a local diffusivity map, demonstrating the utility of the techniques for measuring thermal transport properties in specimens with precipitates and secondary phases. Furthermore, the technique is currently being applied to measure thermal properties of Fast Flux Test Reactor (FFTR) irradiated metal fuel specimens whose porous microstructure make it very difficult to measure using other techniques. Comparison of the local scale measurements are compared with the pre-irradiated fuel samples to show the degradation of thermal transport in fuels due to pores from fission gas bubbles and other irradiation induced defects.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2010

Reduced order models for thermal analysis : final report : LDRD Project No. 137807.

This LDRD Senior's Council Project is focused on the development, implementation and evaluation of Reduced Order Models (ROM) for application in the thermal analysis of complex engineering problems. Two basic approaches to developing a ROM for combined thermal conduction and enclosure radiation problems are considered. As a prerequisite to a ROM a fully coupled solution method for conduction/radiation models is required; a parallel implementation is explored for this class of problems. High-fidelity models of large, complex systems are now used routinely to verify design and performance. However, there are applications where the high-fidelity model is too large to be used repetitively in a design mode. One such application is the design of a control system that oversees the functioning of the complex, high-fidelity model. Examples include control systems for manufacturing processes such as brazing and annealing furnaces as well as control systems for the thermal management of optical systems. A reduced order model (ROM) seeks to reduce the number of degrees of freedom needed to represent the overall behavior of the large system without a significant loss in accuracy. The reduction in the number of degrees of freedom of the ROM leads to immediate increases in computational efficiency and allows many design parameters and perturbations to be quickly and effectively evaluated. Reduced order models are routinely used in solid mechanics where techniques such as modal analysis have reached a high state of refinement. Similar techniques have recently been applied in standard thermal conduction problems e.g. though the general use of ROM for heat transfer is not yet widespread. One major difficulty with the development of ROM for general thermal analysis is the need to include the very nonlinear effects of enclosure radiation in many applications. Many ROM methods have considered only linear or mildly nonlinear problems. In the present study a reduced order model is considered for application to the combined problem of thermal conduction and enclosure radiation. The main objective is to develop a procedure that can be implemented in an existing thermal analysis code. The main analysis objective is to allow thermal controller software to be used in the design of a control system for a large optical system that resides with a complex radiation dominated enclosure. In the remainder of this section a brief outline of ROM methods is provided. The following chapter describes the fully coupled conduction/radiation method that is required prior to considering a ROM approach. Considerable effort was expended to implement and test the combined solution method; the ROM project ended shortly after the completion of this milestone and thus the ROM results are incomplete. The report concludes with some observations and recommendations.

42 ENGINEERING↗

DOE OSTI2015

Discrete Modeling of Early-Life Thermal Fracture in Ceramic Nuclear Fuel

Fracturing of ceramic fuel pellets heavily influences performance of light water reactor (LWR) fuel. Early in the life of fuel, starting with the initial power ramp, large thermal gradients cause high tensile hoop and axial stresses in the outer region of the fuel pellets, resulting in the formation of radial and axial cracks. Circumferential cracks form due to thermal gradients that occur when the power is ramped down. These thermal cracks cause the fuel to expand radially, closing the pellet/cladding gap and enhancing the thermal conductance across that gap, while decreasing the effective conductivity of the fuel in directions normal to the cracking. At lower length scales, formation of microcracks is an important contributor to the decrease in bulk thermal conductivity that occurs over the life of the fuel as the burnup increases. Because of the important effects that fracture has on fuel performance, a realistic, physically based fracture modeling capability is essential to predict fuel behavior in a wide variety of normal and abnormal conditions. Modeling fracture within the context of the finite element method, which is based on continuous interpolations of solution variables, has always been challenging because fracture is an inherently discontinuous phenomenon. Work is underway at Idaho National Laboratory to apply two modeling techniques model fracture as a discrete displacement discontinuity to nuclear fuel: The extended finite element method (XFEM), and discrete element method (DEM). XFEM is based on the standard finite element method, but with enhancements to represent discontinuous behavior. DEM represents a solid as a network of particles connected by bonds, which can arbitrarily fail if a fracture criterion is reached. This paper presents initial results applying the aforementioned techniques to model fuel fracturing. This work has initially focused on early life behavior of ceramic LWR fuel. A coupled thermal-mechanical XFEM method that includes discontinuities in both temperature and displacement fields at crack locations has been developed and is being applied to thermal fracture of LWR fuel. A DEM model of coupled heat conduction and solid mechanics has been developed and used to simulate random initiation and propagation of thermally driven cracks during initial power cycles. This DEM model predicts the formation of realistic radial cracking patterns during power rise and circumferential cracks as power is ramped down. These initial results are very encouraging, and these techniques are expected to provide improved understanding of fuel behavior in a wide variety of conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2019

Anomalous Defect Dependence of Thermal Conductivity in Epitaxial WO 3 Thin Films

Lattice defects typically reduce lattice thermal conductivity, which has been widely exploited in applications such as thermoelectric energy conversion. Here, an anomalous dependence of the lattice thermal conductivity on point defects is demonstrated in epitaxial WO 3 thin films. Depending on the substrate, the lattice of epitaxial WO 3 expands or contracts as protons are intercalated by electrolyte gating or oxygen vacancies are introduced by adjusting growth conditions. Surprisingly, the observed lattice volume, instead of the defect concentration, plays the dominant role in determining the thermal conductivity. In particular, the thermal conductivity increases significantly with proton intercalation, which is contrary to the expectation that point defects typically lower the lattice thermal conductivity. The thermal conductivity can be dynamically varied by a factor of ≈1.7 via electrolyte gating, and tuned over a larger range, from 7.8 to 1.1 W m -1 K -1 , by adjusting the oxygen pressure during film growth. The electrolyte-gating-induced changes in thermal conductivity and lattice dimensions are reversible through multiple cycles. These findings not only expand the basic understanding of thermal transport in complex oxides, but also provide a path to dynamically control the thermal conductivity.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Saturation of SERCA's lipid annulus may protect against its thermal inactivation

The sarco(endo)plasmic reticulum Ca{sup 2+}-ATPase (SERCA) pumps are integral membrane proteins that catalyze the active transport of Ca{sup 2+} into the sarcoplasmic reticulum, thereby eliciting muscle relaxation. SERCA pumps are highly susceptible to oxidative damage, and cytoprotection of SERCA dampens thermal inactivation and is a viable therapeutic strategy in combating diseases where SERCA activity is impaired, such as muscular dystrophy. Here, we sought to determine whether increasing the percent of saturated fatty acids (SFA) within SERCA's lipid annulus through diet could protect SERCA pumps from thermal inactivation. Female Wistar rats were fed either a semi-purified control diet (AIN93G, 7% soybean oil by weight) or a modified AIN93G diet containing high SFA (20% lard by weight) for 17 weeks. Soleus muscles were extracted and SERCA lipid annulus and activity under thermal stress were analyzed. Our results show that SERCA's lipid annulus is abundant with short-chain (12–14 carbon) fatty acids, which corresponds well with SERCA's predicted bilayer thickness of 21 Å. Under control-fed conditions, SERCA's lipid annulus was already highly saturated (79%), and high-fat feeding did not increase this any further. High-fat feeding did not mitigate the reductions in SERCA activity seen with thermal stress; however, correlational analyses revealed significant and strong associations between % SFA and thermal stability of SERCA activity with greater %SFA being associated with lower thermal inactivation and greater % polyunsaturation and unsaturation index being associated with increased thermal inactivation. Altogether, these findings show that SERCA's lipid annulus may influence its susceptibility to oxidative damage, which could have implications in muscular dystrophy and age-related muscle wasting. - Highlights: • SERCA's lipid annulus in rat soleus was measured after immunoconcentration. • Short fatty acid chains surround SERCA and may ensure optimal hydrophobic matching. • SERCA's annulus is highly saturated in control-fed and high-fat fed rats. • Greater saturation associates with small levels of thermal inactivation. • Greater unsaturation associates with large levels of thermal inactivation.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2022

Processing of phase change materials by fused deposition modeling: Toward efficient thermal energy storage designs

We report that recently, several efforts have emerged that employ additive manufacturing techniques to integrate phase change material (PCM) thermal energy storage into geometrically complex designs for advanced thermal management. In this work, we contribute to this emerging research by reporting on the production of a composite nylon-based filament for fused deposition modeling incorporating encapsulated PCMs for 3D printing heat sink geometries. Microencapsulated PCM (MEPCM) with a 6 degrees C transition temperature was selected as the material for thermal energy storage. This transition temperature was selected due to its suitability to provide thermal energy storage to target air-conditioning applications in buildings. In an attempt to improve the thermal conductivity of the composite, fine boron nitride fillers were added, although the effect on improvement was found to be negligible in the overall composite mixture. The nylon-MEPCM ratio in the filaments was optimized, and filaments containing up to 40 wt% MEPCM were successfully synthesized, which were found optimal for 3D printing complex heat sink and other geometries. Thermal and mechanical properties of the filaments were characterized, including latent heat of fusion, thermal conductivity, phase change temperature, tensile strength, and more. Thermal infrared imaging of heat sink geometries printed using the MEPCM filaments undergoing thermal discharging was also conducted. This work presents the most promising result to date in the open literature for a 3D-printed PCM composite in the combination of size, energy density, and geometric complexity of printed parts.

25 ENERGY STORAGE↗

DOE OSTI2025

Mechanically induced thermal runaway severity analysis of Li-ion batteries and continuous energy release monitoring

The large-scale deployment of Li-ion batteries in stationary energy storage and electrical vehicle applications demands a strong focus on safety, particularly on the thermal runaway risk and severity evaluation. A standardized single-side mechanical indentation test protocol was developed to induce an internal short-circuit (ISC) and evaluate cells' thermal runaway severity at different state of charge (SOC). The observed hazard severity (OHS in five categories) and evaluated scores in this work have a comprehensive consideration of each cell's capacity, initial voltage, SOC, temperature and voltage change, allowing a better evaluation of the cells' thermal runaway potential. This method was applied to about 200 Li-ion batteries in order to build an extensive thermal runaway database covering various SOCs, capacities and chemistries. In this study, we monitored the transitions of stored electrochemical energy and applied mechanical energy into both thermal energy and acoustic emissions (AE). The surface temperature and mechanical failures were monitored by infrared imaging and AE to capture critical events within battery cells throughout the mechanical indentation tests. Furthermore, the initial temperature maps can predict two types of follow-up events: thermal runaway or gradual heat release via conduction. Analyzing each cell's severity, AEs, and leveraging the evolving database offer insights into predicting occurrences of thermal runaway. The test method, thermal runaway severity evaluation and prediction, and the corresponding database provide battery designers, manufacturers, and end-users a clear overview of Li-ion batteries' thermal runaway potential under mechanical abuse, advancing the safety design of Li-ion batteries.

Acoustic emission↗

DOE OSTI2020

Thermal coupling-decoupling mechanism of heat transfer across van der Waals interfaces in n-eicosane

Progress toward improving thermal transport properties of n-eicosane, a promising phase change material for thermal energy storage near human body temperature, is hindered by lack of a general theoretical framework to model thermal interfacial conductance (TIC) of the van der Waals (vdW) force bonded molecular interfaces, which have little compositional/structural mismatch. Combining molecular dynamics simulations at temperatures up to the melting point and a time-domain analysis of interfacial heat currents in individual molecules, we unveil that (1) the heat flux across a molecular vdW interface has an alternating coupling-decoupling pattern at the single molecule level due to thermal fluctuations, and (2) the net heat transfer during the thermally coupled periods is orders of magnitude larger than that during the thermally decoupled periods. Furthermore, we demonstrate that a vdW interface's TIC correlates almost linearly with two atomistic-scale coupling-decoupling parameters: αc and σc, that represent the duration and strength of the thermal coupling, respectively. This thermal coupling-decoupling mechanism proposes a new paradigm that explicitly accounts for the effects of structural flexibility and dynamical fluctuation on heat transfer across molecular interfaces, and will likely provide new insights into modeling thermal transport properties in a wide-ranging soft materials, including self-assembled monolayers, paraffins or lipids.

42 ENGINEERING↗

DOE OSTI2024

Thermal conductivity of 3D-printed block-copolymer-inspired structures

This study primarily focuses on examining the impact that geometric structure has on thermal conductivity of multi-phase constructs in different 3D-printed poly(lactic acid), PLA, samples. The investigated structures are inspired by morphologies formed by diblock copolymers: lamellae, hexagonally packed cylinders, and gyroid. This research also investigates how volume percentage and material combination influence the thermal conductivity of these structures. Further, the samples can be tailored to simulate various thermal management structures observed in practical applications, such as thermal interface materials in electronic devices. Thermal conductivity ratio is controlled using air, the least conductive material at 0.026 W/(m K), PLA at 0.136 W/(m K), and thermal paste at 5.11 W/(m K). Different models were tested against thermal conductivity measurements in order to capture the effect of material type (PLA-Air versus PLA-Thermal Paste), volume percentage, structure, and orientation. Simple, effective medium models were good predictions of thermal conductivity in lamellar structures, but it was necessary to develop models for conduction through cylindrical and gyroid structures. Finally, all results were normalized to find a universal model that is independent of structure and material. This approach provides a simple method to predict how to reduce or enhance transport properties and heat management capabilities of 3D printed objects.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Thermal conductivity suppression in uranium-doped thorium dioxide due to phonon-spin interactions

In this work, impact of low level of uranium (U) atom substitution on thermal conductivity of thorium dioxide (ThO 2 ) is investigated. ThO 2 is an electronic insulator with a wide optical band-gap and no unpaired electrons whose thermal transport is governed by phonons. U-substitution introduces unpaired f-electrons resulting in paramagnetic behavior of U-ThO 2 at room temperature, which significantly suppresses its thermal conductivity. A single crystal of U-ThO 2 with graded composition of U is grown using a hydrothermal synthesis method, and thermal conductivity measurements are performed in regions with uniform composition of U at levels of 0%, 6%, 9% and 16%. Measured thermal conductivity profiles over 77–300 K temperature range are analyzed using an analytical expression for phonon-mediated thermal transport based on Klemens-Callaway model. Temperature dependent thermal conductivity is found to deviate significantly from the Rayleigh scattering trend expected for a simple substitutional point defect with a small perturbation to mass and interatomic forces. With the resonant scattering term, observed large suppression of thermal conductivity at low temperatures can be closely reproduced. Additionally, the extracted phonon-spin coupling constants imply a nonlinear relation of phonon-spin interaction intensity with respect to U doping percentage. Our study reveals how phonon-spin scattering contributed by unpaired f-electrons in U atoms influences thermal transport in the U-ThO 2 system.

36 MATERIALS SCIENCE↗

DOE OSTI2020

High spatial resolution thermal conductivity mapping of SiC/SiC composites

Herein, silicon carbide (SiC) ceramic matrix composites are being investigated as a new generation of fuel cladding materials due to its higher accident tolerance compared to Zircaloy. Characterization of the thermal conductivity of SiC constituents and their interfaces and interphases in SiC/SiC composites is needed as inputs to models of cladding performance. We used time-domain thermoreflectance (TDTR) to map the thermal conductivity with a spatial resolution of 2 µm. The SiC/SiC composite is comprised of Hi-Nicalon Type S fibers in a matrix made by chemical vapor infiltration (CVI matrix). The interphase material is a pyrolytic carbon/SiC multilayer. We report thermal conductivity maps of the SiC fiber and SiC matrix at temperatures of 25 °C, 90 °C, 164 °C, and 250 °C. The fiber has a uniform and isotropic thermal conductivity of 22 W m -1 K -1 at 25 °C; the thermal conductivity of fiber is approximately independent of temperature. The matrix thermal conductivity is not uniform and varies from 50 to 120 W m -1 K -1 at 25 °C; the thermal conductivity of the matrix scales approximately with the inverse of the square root of temperature, i.e., ∝ 1/T 1/2 . The thermal conductivity of the interphase at room temperature is 6 W m -1 K -1 . The calculated spatially averaged thermal conductivity of this SiC/SiC composite at 1000°C is 29 W m -1 K -1 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2022

Hydrogen effects on thermal diffusivity and electrical resistivity of zircaloy cladding

Thermal diffusivity measurements on Zirconium-based cladding materials have historically been a challenge due to the difficulty to measure on specimens with curved geometries, including nuclear grade Zircaloy cladding materials. Here, in this work, we first used laser flash analysis method and four-probe configuration method to measure the thermal diffusivity and electrical resistivity of Zircaloy tubes respectively, which show good agreement with Zircaloy plates in this work, as well as previously published data. The consistent results proved the applicability of the laser flash analysis setup and four-probe configuration method for investigating thermal diffusivity and electrical resistivity of Zircaloy tubes. We further investigated the hydrogen effect on thermal diffusivity and electrical resistivity of Zircaloy. Hydrogen plays significant roles in the thermal diffusivity of Zircaloy, which depends on the hydrogen concentration. For higher hydrogen contents (1130 and 1820 wppm in this work), where phase transformation (α-Zr + δ-hydride → α-Zr + β-Zr) occurs at 567 °C, thermal diffusivity decreases as a function of temperature at the α-Zr + δ-hydride phase regime, while increase at higher temperature at the α-Zr + β-Zr phase regime. For low hydrogen concentration, where hydride dissolved into α-Zr matrix phase at higher temperature, the thermal diffusivity is lower than non-hydrided Zircaloy-4 with similar temperature-dependent trends. Such observation demonstrates the hydrogen effects on reducing thermal diffusivity of α-Zr phase. Hydrogen increases the electrical resistivity of Zircaloy. Similar to thermal diffusivity results, the phase transformation causes a reversal of temperature-dependent trends in electrical resistivity results in Zircaloy-4 with higher hydrogen contents.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Implications of point defect accumulation on UO 2 thermal conductivity and fission gas release under accelerated fuel irradiation

Evaluation of thermal properties is a crucial factor for nuclear fuel performance. During reactor operation, the accumulation of fission products and irradiation-induced lattice defects are responsible for degradation in thermal conductivity. Consequently, it affects fuel temperature and fission gas release (FGR) among other Multiphysics processes important for economics and safety analysis. We analyze the implications of point defects (PD) accumulation described using a rate theory (RT) Model on lattice thermal conductivity of UO 2 . Here, we demonstrate that fission rate-dependent point defect concentrations have the largest impact on in-pile thermal conductivity in the periphery of light water reactor fuels below a temperature threshold governed by the migration barrier of defects. Our analysis provides a mechanistic description of this phenomena which current fuel performance codes treat empirically. The reduction of thermal conductivity in the low -temperature rim region acts as additional thermal resistance and leads to a temperature notably larger than suggested by Lucuta thermal conductivity correlation. These effects are anticipated to have notable impacts when fuels are exposed to accelerated radiation. The impact of such point defect-informed treatment of thermal conductivity on fuel performance is evaluated by a detailed analysis of fission gas behavior and its release. We consider several models capturing different stages of fission gas bubble evolution and fission gas release (FGR). Finally, a new fission rate-dependent correction to the Lucuta correlation is proposed. The results show a significant reduction in thermal conductivity at the fuels’ periphery and an increase in fuel centerline temperature specifically at low burnups. Ultimately a modified LC shows a higher FGR compared to the original LC, while the acceleration process results in a reduction in overall FGR.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Computational design of isotropic and anisotropic ultralow thermal conductivity polymer foams

Current state-of-the-art commercial polymer thermal insulation foam exhibits a thermal conductivity of 24 mW·m -1 ·K -1 (equivalently thermal resistivity of R-6/in.), similar to that of static air. To further optimize building energy efficiency, achieving even lower thermal conductivity is needed, which is, however, highly challenging. This paper presents computational evidence that demonstrates the feasibility of achieving an ultra-low thermal conductivity of less than 14.4 mW·m -1 ·K -1 (equivalently R-10/in.) using isotropic and anisotropic foam cell designs. For the isotropic design, we have identified analytical effective medium approximation (EMA) models within the accuracy of ±5% as finite element analysis (FEA) in predicting the effective thermal conductivity of foams with various porosities and filler gases. For the anisotropic design, we have developed and validated new EMA models against FEA in predicting the effective thermal conductivity of general anisotropic cuboids and Voronoi foams. For both isotropic and anisotropic designs, the design spaces for 18, 16, and 14.4 mW·m -1 ·K -1 (equivalently R-8, R-9 and R-10/in.) using various filler gases are obtained. It is found that polymer foams can be improved to achieve ultralow thermal conductivity by reducing CO 2 concentration, reducing radiation, increasing porosity, and using anisotropic pore geometry. In conclusion, these findings contribute to the development of highly efficient thermal insulation materials, enhancing building energy efficiency and promoting sustainable construction practices.

42 ENGINEERING↗

DOE OSTI2011

Thermal expansion in 3d-metal Prussian Blue Analogs-A survey study

We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions M{sup II}{sub 3}[(M'){sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O and M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O, where M{sup II}=Mn, Fe, Co, Ni, Cu and Zn, (M'){sup III}=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150 deg. C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3-bar m, F4-bar 3m and Pm3-bar m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7x{sup 1}0{sup -6} K{sup -1} for Co{sub 3}[Co(CN){sub 6}]{sub 2}.12H{sub 2}O. All of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O compounds show negative thermal expansion behavior, which correlates with the Irving-Williams series for metal complex stability. The thermal expansion behavior for the PBAs of the M{sup II}{sub 3}[Fe{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O compounds show positive thermal expansion behavior. - Graphical Abstract: The structure of Prussian Blue analogs (PBAs) consists of two types of metal centered octahedral units connected by cyanide ligand. Lattice and interstitial water molecules are present in these framework structures. All the PBAs of the M{sub 3}[Co(CN){sub 6}]{sub 2}.nH{sub 2}O family show negative thermal expansion (NTE) behavior. The lattice parameters and magnitude of NTE correlates inversely with the Irving-Williams series of metal complex stability. Highlights: > Thermal expansion behavior of 17 Prussian Blue Analogs has been studied via XRD. > Nine compounds display negative thermal expansion (NTE) behavior. > All compounds of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} family exhibit NTE behavior. > Magnitude of the NTE in M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} follows the order Mn>Fe>Co>Ni>Cu<Zn. > NTE materials show correlations with lattice parameters and Irving-Williams series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

Thermal expansion of Ba{sub 2}ZnSi{sub 2}O{sub 7}, BaZnSiO{sub 4} and the solid solution series BaZn{sub 2-x}Mg{sub x}Si{sub 2}O{sub 7} (0{<=}x{<=}2) studied by high-temperature X-ray diffraction and dilatometry

The thermal expansion behavior of Ba{sub 2}ZnSi{sub 2}O{sub 7}, BaZnSiO{sub 4} and BaZn{sub 2}Si{sub 2}O{sub 7} is characterized by both high-temperature X-ray diffraction (HT-XRD) and dilatometry. Ba{sub 2}ZnSi{sub 2}O{sub 7} and BaZnSiO{sub 4} show a thermal expansion (100-800 Degree-Sign C) in the range from 8.9 to 10.4 Multiplication-Sign 10{sup -6} K{sup -1}. By contrast, BaZn{sub 2}Si{sub 2}O{sub 7} has a much higher thermal expansion in the low-temperature modification and shows a phase transition at 280 Degree-Sign C which runs parallel with a steep increase in cell volume. This phase transition is also observed in the solid solution series BaZn{sub 2-x}Mg{sub x}Si{sub 2}O{sub 7}, but it is shifted to higher temperatures and to a smaller volume change with increasing Mg{sup 2+} concentration. This solid solution series is characterized by dilatometry, X-ray diffraction and differential scanning calorimetry. An adjustment of the MgO/ZnO-ratio enables the preparation of materials with a large variety of thermal expansions. - Graphical abstract: XRD-patterns of Ba{sub 2}ZnSi{sub 2}O{sub 7} were recorded at different temperatures (left). For each XRD-pattern a Rietveld-refinement was performed, the image in the middle shows the XRD-pattern measured at room temperature (circles), the Rietveld calculation (red line) and the difference between them (blue line). The lattice parameters derived hereof were plottet against the temperature and fitted to a polynomial (right picture). From those polynomials the lattice expansion was calculated. Highlights: Black-Right-Pointing-Pointer We examined the thermal expansion of Ba{sub 2}ZnSi{sub 2}O{sub 7}, BaZnSiO{sub 4} and BaZn{sub 2-x}Mg{sub x}Si{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Thermal expansions were determined by dilatometry and high-temperature X-ray diffraction. Black-Right-Pointing-Pointer High-temperature X-ray diffraction enabled to determine anisotropic thermal expansion. Black-Right-Pointing-Pointer BaZn{sub 2}Si{sub 2}O{sub 7} exhibits the highest thermal expansion due to a phase transition. Black-Right-Pointing-Pointer Substitution of small amounts of Zn{sup 2+} for Mg{sup 2+} leads to a decrease in thermal expansion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Anisotropic thermal expansion of a 3D metal–organic framework with hydrophilic and hydrophobic pores

A 3D flexible metal–organic framework (MOF) with 1D hydrophilic and hydrophobic pores shows anisotropic thermal expansion with relatively large thermal expansion coefficient (α{sub a}=−21×10{sup −6} K{sup −1} and α{sub c}=79×10{sup −6} K{sup −1}) between 133 K and 383 K. Temperature change gives deformation of both pores, which expand in diameter and elongate in length on cooling and vice versa. The thermally induced structural change should be derived from a unique framework topology like “lattice fence”. Silica accommodation changes not only the nature of the MOF but also thermal responsiveness of the MOF. Since the hydrophobic pores in the material are selectively blocked by the silica, the MOF with the silica is considered as a hydrophilic microporous material. Furthermore, inclusion of silica resulted in a drastic pore contraction in diameter and anisotropically changed the thermal responsiveness of the MOF. - Graphical abstract: A 3D metal–organic framework with hydrophilic and hydrophobic pores shows anisotropic thermal expansion behavior. The influence of silica filler in the hydrophobic pore was investigated. - Highlights: • Thermally induced structural change of a 3D MOF with a lattice fence topology was investigated. • The structural change was analyzed by synchrotron X-ray diffraction patterns. • Temperature change induces anisotropic thermal expansion/contraction of the MOF. • Silica inclusion anisotropically changes the thermal responsiveness of the MOF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗