The components of the frequency-dependent complex refractive index were determined indirectly for the new non-centrosymmetric α-GeO2 crystal using polarized Fourier transform infrared reflectivity spectra measured in the far- and mid-infrared spectral region at room temperature. All the longitudinal- and transverse-optical infrared active modes with E and A2 symmetry, according to the D3 point group, were identified and localized within the 100-1000 cm-1 range in very good agreement with a previous first-principles based calculation. For the A2- and E-type modes, both the longitudinal- and transverse-optical splitting were detected. The refractive indices no ( E⊥c) and ne (E //c) in the infrared domain present considerably higher values than the ones observed in the visible light range, and the high birefringence would find application in many optical devices.

Aim of investigation is to study the possibility of activating a promising Ni(OH)2, prepared using two-step high-temperature synthesis, by adding 3%, 5% and 10% (mol.) Al3+ to Ni2+. For describing the intercalation of Al3+ into hydroxide structure, "Separate-Solid—Liquid—Solid" mechanism, which included the formation of separate Al-containing phase on synthesis stage, and incorporation of Al3+ into Ni(OH)2 or formation of surface compounds during hydrolysis stage, has been proposed. EDX analysis of precursor confirmed the formation of separate Al-containing phases. By means of PXRD, EDX, SEM, TEM revealed realization of both ways of Al3+ incorporation: at high amounts of Al3+ (5% and 10% mol.), predominantly surface compounds are formed with distorted and altered particle shape and appearance of "core–shell" particles. At low amounts of Al3+ (3% mol.), permeably doping occurs, with partial intercalation of Al3+ into the nickel hydroxide structure. Based on CVA and GCDC results, Al3+ acts as a poison upon the formation of surface compounds have been found. Upon doping of hot hydrolysis samples with aluminum, sample activation was observed, which resulted in an increase of specific capacity by 1.99 times, from 569 Fg−1 (pure Ni(OH)2) to 1112 Fg−1.

Soft porous crystals undergo large structural transformations under a variety of physical stimuli. Breathing-like transformations, occurring with a large volume change, have been associated with an existence of bi-stable or multi-stable crystal structures. Here, we provide a detailed, multiscale qualitative and quantitative analysis of the adsorption-induced “breathing” transformations in two metal organic frameworks (MOFs): MIL-53(Al) which is a reference case of our approach, and recently synthetized JUK-8, which does not show any bistability without adsorbate. The proposed approach is based on atomistic simulations and does not require any empirical or adjustable parameters. It allows for a prediction of potential structural transformations in MOF and, in the case of adsorption-induced deformations, a calculation of the adsorption stress. We also show that the quantitative agreement between calculated and experimental results critically depends on the quality of the dispersion energy correction.

The negative thermal expansion material potassium cadmium dicyanoargentate, KCd[Ag(CN) 2 ] 3 , is studied at high pressure using a combination of X-ray single-crystal diffraction, X-ray powder diffraction, infrared and Raman spectroscopy, and density functional theory calculations. In common with the isostructural manganese analogue, KMn[Ag(CN) 2 ] 3 , this material is shown to exhibit very strong negative linear compressibility (NLC) in the crystallographic c direction due to structure hinging. We find increased structural flexibility results in enhanced NLC and NTE properties, but this also leads to two pressure-induced phase transitionsto very large unit cells involving octahedral tilting and shearing of the structurebelow 2 GPa. The presence of potassium cations has an important effect on the mechanical and thermodynamic properties of this family, while the chemical versatility demonstrated here is of considerable interest to tune unusual mechanical properties for application. ■ INTRODUCTION Materials where external stimuli induces an anomalous response, such as expansion upon cooling (negative thermal expansion, NTE 1−3) or on application of hydrostatic pressure (negative linear compressibility, NLC 4,5), have recently received considerable attention. These materials that "break the rules"as a result of specific, and therefore rare, elastic anomalies 6−8 are curious from a fundamental point of view but might also be revolutionary for a range of technologies including interferometric pressure sensors, pressure-controlled or pressure-sensitive electronic devices, and smart actua-tion. 2,4,9−11 The ability to design materials with unusual properties is therefore a key focus of the field: can we understand these elastic anomalies so that we can tune the magnitude and/or range of negative responses? Negative thermal expansion may occur in one, two, or all principal directions without violating thermodynamics. 12,13 Thus, for example, the volume coefficient of thermal expansion (CTE), () V V V T p 1 α = ∂ ∂ , takes large negative values in zirconium tungstate ZrW 2 O 8 and zinc(II) cyanide Zn(CN) 2 over large temperature ranges. 14 Under hydrostatic pressure, however, volume must always reduce and so the volume compressibility (() K V V V p T 1 = − ∂ ∂ , conventionally formulated as the bulk modulus, B = (K V) −1), must be definite and positive. 15 Expansion under pressure can occur in one or two directions, as long as this is coupled to volume reduction. 5,12,16 Therefore, negative linear compressibility (NLC)the expansion in one principal direction of a material under hydrostatic pressureis conceptually and empirically related to linear-NTE. In both cases, anomalous response relies on mechanical anisotropy. The so-called "wine-rack" model is often invoked where mechanical hinging allows linear expansion coupled to volume reduction on increasing pressure or decreasing temperature. 5,8 Attention in this field has focused on a class of materials known as coordination polymers (CPs), in particular due to the very large magnitude of responses found in comparison to conventional oxide-based materials. 7 Examples that show large NTE and NLC include cyanide frameworks such as Ag 3 [Co-(CN) 6 ] (refs 17 and 18), KMn[Ag(CN) 2 ] 3 (refs 19 and 20), Zn[Au(CN) 2 ] 2 (refs 21 and 22), and metal−organic frameworks 23 (MOFs) such as MIL-53 (ref 24), UTSA-16 (ref 25), ZAG-4 (ref 26), and [NH 4 ][Zn(HCOO) 3 ] (ref 27). In many cases, mechanical response can be predicted in these systems by considering the framework as a set of rigid connectors and hinges, sodepending on geometry and topologyNTE or

In this paper, we present the different characterization techniques used to measure the mechanical properties of silica aerogels. The mechanical behaviour of aerogels is generally described in terms of elastic and fragile materials (such as glasses or ceramics) but also in terms of plastic media in compression testing. Because of these very different mechanical behaviors, several types of characterization techniques are proposed in the literature. We first describe the dynamic characterization techniques such as ultrasounds, Brillouin scattering, dynamic mechanical analysis (DMA) to measure the elastic properties: Young's modulus (E) , shear modulus (G), poisson ratio (υ) but also attenuation and internal friction. Thanks to "static" techniques such as three-point bending, uniaxial compression, compression we also access to the elastic modulus (E) and to the rupture strength (σ). The experimental results show that the value of the elastic and fracture moduli measured is several orders of magnitude lower than that of a material without porosity. With regard to the brittleness characteristics, Weibull's analysis is used to show the statistical nature of the fracture resistance. We also present the SENB (single edge notched beam technique) technique to characterize toughness (K1C) and the stress corrosion mechanisms, which are studied in ambient conditions and temperature by the double-cleavage drilled compression experiment (DCDC). In the last part of the paper, we show how, during the isostatic compression test, aerogels behave like plastic materials.The data allow calculating the bulk modulus (K), the amplitude of the plastic deformation and the yield strength (σel), which is the boundary between the elastic and plastic domains. These different techniques allow understanding which parameters influence the overall mechanical behavior of aerogels, such as pore volume, but also pore size, internal connectivity and silanol bounds content. It is shown that pore size plays a very important role; pores can be considered as flaws in the terms of fracture mechanics.

The paper presents a brief review of the recent developments in the field of absorption of atomic and molecular species in carbon cellular structures. Such absorbing objects can be distinctly recognized among a large family of carbon porous materials owing to potential and already observed in experiments very high capacity to soak and to keep inside different substances, which at usual conditions outside the porous matrices may often stay only in a gaseous form. High capacity filling is attained owing to single graphene-like walls separating different cells in the whole structures providing their lightweight. This property of cellular structures makes them very promising for numerous technological applications such as hydrogen storage in fuel cells and molecular sieving in membranes made from such structures or for their usage in microelectronics, photovoltaics and production of Li-ion batteries. Independently of the targeted applications gases are good candidates for probing tests of carbon matrices themselves.

Due to their unique geometry complex, self-assembled nanoporous 2D molecular crystals offer a broad landscape ofpotential applications, ranging from adsorption and catalysis to optoelectronics, substrate processes, and future nanomachineapplications. Here we report and discuss the results of extensive all-atom Molecular Dynamics (MD) investigations of self-assembledorganic monolayers (SAOM) of interdigitated 1,3,5-tristyrilbenzene (TSB) molecules terminated by alkoxy peripheral chains Cncontaining n carbon atoms (TSB3,5-Cn) deposited onto highly ordered pyrolytic graphite (HOPG). In vacuo structural andelectronic properties of the TSB3,5-Cn molecules were initially determined using ab initio second order Møller−Plesset (MP2)calculations. The MD simulations were then used to analyze the behavior of the self-assembled superlattices, including relaxed latticegeometry (in good agreement with experimental results) and stability at ambient temperatures. We show that the intermoleculardisordering of the TSB3,5-Cn monolayers arises from competition between decreased rigidity of the alkoxy chains (loss ofintramolecular order) and increased stabilization with increasing chain length (afforded by interdigitation). We show that theinclusion of guest organic molecules (e.g., benzene, pyrene, coronene, hexabenzocoronene) into the nanopores (voids formed byinterdigitated alkoxy chains) of the TSB3,5-Cn superlattices stabilizes the superstructure, and we highlight the importance of alkoxychain mobility and available pore space in the dynamics of the systems and their potential application in selective adsorption.