Type Crystal Structure Research Articles

Spectroscopic studies of methyl paraoxon decomposition over mesoporous Ce-doped titanias for toxic chemical filtration

The ever-constant threat of chemical warfare agents (CWA) motivates the design of materials to provide better protection to warfighters and civilians. Cerium and titanium oxide are known to react with organophosphorus compounds such Sarin and Soman. To study the decomposition of methyl paraoxon (CWA simulant) on such materials, we synthesized ordered mesoporous metal oxides (MMO) TiO2, CexTi1−xO2 (x = 0.005, 0.5, 0.10, 0.15) and CeO2. We fully characterized TiO2 and Ce-doped TiO2 and found phase-pure oxides with cylindrical hexagonally packed pores and high surface areas (176–252 m2/g). Methyl paraoxon decomposition was tracked through UV/Vis and found Ce0.15Ti0.85O2 to decompose the most methyl paraoxon, but CeO2 to be the most reactive when normalized to surface area. The surface area normalized rate constant (kSA) for CeO2 was 3–4.6 times larger than that of TiO2 and the CexTi1−xO2 series. While TiO2 and CexTi1−xO2 for 0.05 ≤ x ≤ 0.10 displayed no significant differences in the kinetics, the mostly amorphous Ce0.15Ti0.85O2 displayed a slight increase in reactivity. Our findings indicate that the nature of the cation, Ce4+ vs Ti4+, is less important to methyl paraoxon reactivity on these MMOs compared to other factors such as crystal structure type.

Synthesis and electrochemical properties of Co-free P2/O3 biphasic Na1-xLixNi0.33Mn0.67O2 cathode material for sodium-ion batteries

• Li x Na 1-x Ni 0.33 Mn 0.67 O 2 material with excellent electrochemical reversibility is obtained. • Synthesis of P 2/O3 biphasic cathode material by high temperature solid state method. • After the introduction of Li + , t the stability of the high voltage region is improved. Co-free cathode material is an ideal material for developing low-cost sodium ion batteries. Both O3 and P 2 single-phases suffer structural degradation, resulting in irreversible structural collapse and rapid capacity decline. Compared with the single-phase crystal structure type O or P, the composite phase crystal structure has attracted the attention of researchers due to its superior performance advantages. Referring to the element composition and crystal structure of Li-rich cathode material, the novel biphasic P 2/O3-Na 1-x Li x Ni 0.33 Mn 0.67 O 2 cathode material was synthesized by solid state method. The introduction of Li + makes more Na + in the material remain in the triangular prism position at high charging voltage, which will not destroy the biphasic structure and improve the stability of high rate during the cycle. At 0.1C and 20C rates, Li 0.2 Na 0.8 Ni 0.33 Mn 0.67 O 2 released 132.5 and 70.1 mAh g −1 discharge specific capacities, respectively. In the deep charging and discharging status, the superior capacity retention of 80.1 % is measured even after 120 cycles of sodium ion extraction and insertion.

Phase Equilibria in the Ti-Rich Part of the Ti-Al-Nb System—Part I: Low-Temperature Phase Equilibria Between 700 and 900 °C

Precise knowledge of the phase equilibria in the Ti-Al-Nb system between 700 and 900 °C is of crucial importance for the urgently needed improvement of TiAl-based turbine materials already in industrial use to achieve further energy savings. As a result of the occurrence of the two ternary intermetallic phases ωo (“Ti4NbAl3”) and O (“Ti2NbAl”), which form in the solid state just in the range of the application-relevant temperatures, the phase relations are very complex and not well studied. In the present investigation, isothermal sections of the Ti-rich part of the Ti-Al-Nb system at 700, 800, and 900 °C were determined by a systematic study of 15 ternary alloys, one solid-solid diffusion couple, and three liquid-solid diffusion couples. Using scanning electron microscopy, electron probe microanalysis (EPMA), x-ray diffraction (XRD), high-energy XRD (HEXRD), differential thermal analysis (DTA), and transmission electron microscopy (TEM) investigations, type and composition of phases as well as phase transitions were determined. With these results, the phase equilibria were established. A focus of the investigations is on the homogeneity ranges of the two ternary phases ωo and O, which both are stable up to temperatures above 900 °C. Based on the compositions measured for the ωo phase and its crystal structure type, a new formula (Ti,Nb)2Al is suggested. The results also indicate that the phase field of the ωo phase is split into two parts at 900 °C because of the growing phase field of the ordered (βTi,Nb)o phase.

Crystal structure and magnetic properties of some compounds with GdNi2Ga3In type structure

Abstract The GdNi2Ga3In type crystal structures (Pnma) of the quaternary intermetallic compounds TbNi2Ga3.03(1)In0.97(1) (a = 2.41554(2), b = 0.41614(4), c = 0.92220(10) nm, wR2 = 0.0512, 2006 F 2 values, 90 parameters) and HoNi2Ga3.03(2)In0.97(2) (a = 2.41822(7), b = 0.41400(15), c = 0.9199(3) nm, wR2 = 0.0588, 1980 F 2 values, 89 parameters) were refined from the single crystal X-ray diffraction data. Single crystals were obtained by high-frequency annealing of the samples in sealed tantalum ampoules. The compounds with RE = Y, Dy and Ho are isotypic and were characterized by powder X-ray diffraction. The magnetic behaviour of the compounds RENi2Ga3In (RE = Y, Dy, Ho) was characterized by means of magnetization and dc magnetic susceptibility measurements, carried out in the temperature range 1.72–400 K in external magnetic fields up to 5 T. YNi2Ga3In was found to be a Pauli paramagnet with a molar magnetic susceptibility of about 4⋅10−5 emu mol−1 at room temperature. DyNi2Ga3In and HoNi2Ga3In are Curie-Weiss paramagnets which order antiferromagnetically below T N = 10.5 K (DyNi2Ga3In) and 4.4 K (HoNi2Ga3In).

Crystal structure evolution in the van der Waals vanadium trihalides

Most transition-metal trihalides are dimorphic. The representative chromium-based triad, CrCl3, CrBr3, CrI3, is characterized by the low-temperature (LT) phase adopting the trigonal BiI3-type while the structure of the high-temperature (HT) phase is monoclinic of AlCl3 type (C2/m). The structural transition between the two crystallographic phases is of the first-order type with large thermal hysteresis in CrCl3 and CrI3. We studied crystal structures and structural phase transitions of vanadium-based counterparts VCl3, VBr3, and VI3 by measuring specific heat, magnetization, and x-ray diffraction as functions of temperature and observed an inverse situation. In these cases, the HT phase has a higher symmetry while the LT structure reveals a lower symmetry. The structural phase transition between them shows no measurable hysteresis in contrast to CrX3. Possible relations of the evolution of the ratio c/a of the unit cell parameters, types of crystal structures, and nature of the structural transitions in V and Cr trihalides are discussed.

Orthorhombic charge density wave on the tetragonal lattice of EuAl4.

EuAl4 possesses the BaAl4 crystal structure type with tetragonal symmetry I4/mmm. It undergoes a charge density wave (CDW) transition at T CDW= 145 K and features four consecutive antiferromagnetic phase transitions below 16 K. Here we use single-crystal X-ray diffraction to determine the incommensurately modulated crystal structure of EuAl4 in its CDW state. The CDW is shown to be incommensurate with modulation wave vector q= (0,0,0.1781 (3)) at 70 K. The symmetry of the incommensurately modulated crystal structure is orthorhombic with superspace group Fmmm(00σ)s00, where Fmmm is a subgroup of I4/mmm of index 2. Both the lattice and the atomic coordinates of the basic structure remain tetragonal. Symmetry breaking is entirely due to the modulation wave, where atoms Eu and Al1 have displacements exclusively along a, while the fourfold rotation would require equal displacement amplitudes along a and b. The calculated band structure of the basic structure and interatomic distances in the modulated crystal structure both indicate the Al atoms as the location of the CDW. The tem-per-ature dependence of the specific heat reveals an anomaly at T CDW= 145 K of a magnitude similar to canonical CDW systems. The present discovery of orthorhombic symmetry for the CDW state of EuAl4 leads to the suggestion of monoclinic instead of orthorhombic symmetry for the third AFM state.

Interrelationship of bonding strength with structural stability of ternary oxide phases of MgSnO3: A first-principles study

We have studied the Ilmenite, Perovskite and LiNbO3 type crystal structures of ternary oxide MgSnO3 by first-principles methods using density functional theory (DFT) and beyond. We conclude that MgSnO3 in LiNbO3 type is both mechanically and dynamically stable, whereas Ilmenite and Perovskite crystal structures are mechanically stable but dynamically unstable. Vibrational stability in MgSnO3 warrants some distortion in the octahedra caused due to the strength of bonding between the atom pairs Sn–O in LiNbO3 type crystal structure. Similarly, Ilmenite and Perovskite crystal structures require a higher number of Mg–Sn and (Mg–Mg, Sn–Sn, O–O and Mg–O) bonds respectively. Ilmenite and LiNbO3 type crystal structures can be used as window layers featuring a large bandgap of 5.22 eV and 3.88 eV respectively, along with a lower absorption coefficient and reflectivity. Likewise, Perovskite crystal structure with a bandgap of 2.55 eV can be deployed as an absorber layer that traps green light of the solar irradiation in tandem solar cells. Perovskite crystal structure has the lowest charge carrier effective masses among all the structures in MgSnO3. LiNbO3 type crystal structure shows a high hardness of 56.5 GPa. It should be tested experimentally in applications requiring super-hard materials.

Vanadium-based cathodes for aqueous zinc ion batteries: Structure, mechanism and prospects

As an emerging energy storage device with high-safety aqueous electrolytes, low-cost, environmental benignity and large-reserves, the rechargeable aqueous zinc-ion batteries (AZIBs) have attracted more and more attention. Vanadium-based compounds are also supposed as the potential candidate cathode materials for AZIBs due to their wide variety of phases, variable crystal structures and high theoretical capacity. In this review, the recent progress in the development of vanadium-based materials was summarized, and the relationship between the crystal structure types of active materials and Zn-ion transport mechanism was highlighted. During the charge-discharge process, the different electrostatic repulsion between the cations of vanadium-based compounds with different crystal structures and Zn2+ results in a variety of the Zn-ion storage mechanisms, which can be significant guidance for designing the advanced battery-electrode materials for AZIBs. Furthermore, other factors associated with the storage mechanisms, such as electrolyte components and electrode morphology, are discussed. Finally, the strategies to improve the electrical conductivity, inhibit the dissolution and stabilize the crystal structure of vanadium-based compounds are proposed and the future prospects for developing high-energy-density AZIBs are presented.

Structural analysis and oxygen defects in the partially oxygen-reduced T′-Pr2-xCexCuO4+δ with x = 0 and 0.15 powders at the normal state

Structural analysis and observation of the oxygen migration of Pr2-xCexCuO4+δ (PCCO) with Ce-doping concentration, x, of 0 and 0.15 powders are briefly studied through neutron diffraction (ND) patterns and x-ray absorption spectroscopy (XAS) spectrum in the extended x-ray absorption fine structure (EXAFS) range. The PCCO powders are synthesized using the chemical dissolved technique and time-dependent oxygen-reduction annealing in flowing Ar atmosphere. All powders show a stable PCCO phase with tetragonal T′-type crystal structure (space group of I4/mmm) for both the as-prepared and partially oxygen-reduced PCCO powders at room temperature. Occupancy of the apical oxygen, O(3), is detected higher in the doped powders due to Ce-doping effect and generally increases after the shorter-time oxygen-reduction annealing. The decrease of O(3) occupancy is observed for the longer-time reduction annealing process indicating a trace of oxygen migration and recovery of oxygen defect on CuO2 plane in the T′-structure. This study is essential to elucidate the mechanism of oxygen removal in the electron-doped cuprates.

Syntheses, crystallographic characterization, and structural relations of Rb[SCN

Abstract Colorless rubidium thiocyanate was synthesized by three different approaches. DCS-TGA measurements allowed for extraction of phase transition, melting, and decomposition temperatures. Single-crystal X-ray diffraction showed Rb[SCN] to crystallize in the low-temperature LT-K[SCN] crystal structure type (Pbcm, oP16). Above its phase-transition temperature (432.1 K) the title compound crystallizes with the high-temperature HT-K[SCN] crystal structure type (I4/mcm, tI28) with head-to-tail disordered thiocyanate anions. Both modifications are related to one another and to the LT/HT-Cs[SCN] structure types, and the relation has been studied in detail employing the Bärnighausen formalism. Phase purity and bulk phase transition were confirmed by temperature-dependent PXRD.

A Microstructural and Compositional Study of ε-Fe2O3 Crystals in the Hare’s Fur Jian Ware

The Jian kilns in the present-day Jianyang County of Fujian Province are well known for their thick and lustrous black-glazed porcelain production. The hare’s fur (HF) glazed Jian wares characterized by radial fur-like strips, as one of the most typical representatives of black-glazed tea bowls, originate from phase separation of glaze melt and crystallization of iron oxides. In this study, various techniques were performed on the yellowish-brown HF samples, including portable energy-dispersive X-ray fluorescence (PXRF), synchrotron X-ray absorption near-edge spectroscopy (XANES), optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy (RS). The objective of this study was to well understand the microstructure characteristics and chemical compositions of glaze patterns. Results showed that the main constituents of the ceramic glaze were alumina (10.61–16.43 wt.%), silica (62.20–77.07 wt.%), calcium (3.85–6.97 wt.%), and iron oxide (4.10–8.35 wt.%). The studies provided evidence that metastable epsilon-iron oxide crystals (ε-Fe2O3) formed on the brownish-yellow glazed surface. Microstructural analysis revealed that there were three types of crystal structures in the glaze surface: One consisted of well-grown leaf-like or dendritic-like structure with highly ordered branches at micrometers scales; another comprised flower-like clusters accompanied by branches radiating from the center, petals growing along the branches, and needles on both sides of the petals; the last type involved a honeycomb structure tightly packed with plentiful spherical or irregular-shaped particles. In addition, ε-Fe2O3 crystals in the cross-section of the glaze showed a gradient distribution.

Large magnetocaloric effect in Ho2Pd2Pb

We report the magnetocaloric effect (MCE) in a polycrystalline plumbide sample of Ho2Pd2Pb. Arc-melted Ho2Pd2Pb crystallizes in Mo2B2Fe type of tetragonal crystal structure and shows an antiferromagnetic behaviour with Néel temperature of 4.5 K. The Arrott plots indicate that Ho2Pd2Pb undergoes a second order antiferromagnetic phase transition. The calculated isothermal magnetic entropy change (ΔSm), and relative power cooling (refrigeration capacity) for a change of field 0–8 T are 17.8 J kg−1 K−1, and 680(497) J kg−1 respectively. The obtained results revealed that Ho2Pd2Pb belongs to a family of large MCE magnetic materials.

Study of the optical properties of Sb2(Se1-xSx)3 (x = 0–1) solid solutions

This study presents a detailed analysis of the optical properties of the Sb2(Se1-xSx)3 (x = 0–1) polycrystals. Four antimony selenosulfide solid solutions Sb2(Se1-xSx)3 together with Sb2Se3 and Sb2S3 were synthesized from elemental precursors at the same synthesis conditions, only varying the x = S/(Se + S) value with a step of Δx = 0.2. Successful formation of the Sb2(Se1-xSx)3 solid solutions was determined by Raman spectroscopy and X-ray diffraction. As expected for the same type of crystal structure of Sb2Se3 and Sb2S3, the bimodal behavior of Ag Raman mode in Sb2(Se1-xSx)3 was detected. Temperature and excitation power dependent photoluminescence (PL) analysis of Sb2(Se1-xSx)3 was performed in order to look into the electronic and defect structure of these promising semiconductor materials for optoelectronic applications. The shift of the near band edge PL emission in Sb2(Se1-xSx)3 towards higher energies from 1.309 eV to 1.728 eV with increasing sulfur content was detected at T = 3 K. A change in the radiative recombination mechanism was detected being of excitonic origin in samples with x ≤ 0.2 and resulting from deep donor-deep acceptor pair recombination in samples with x > 0.2.

Calculation of Tc of Superconducting Elements with the Roeser–Huber Formalism

The superconducting transition temperature, Tc, can be calculated for practically all superconducting elements using the Roeser–Huber formalism. Superconductivity is treated as a resonance effect between the charge carrier wave, i.e., the Cooper pairs, and a characteristic distance, x, in the crystal structure. To calculate Tc for element superconductors, only x and information on the electronic configuration is required. Here, we lay out the principles to find the characteristic lengths, which may require us to sum up the results stemming from several possible paths in the case of more complicated crystal structures. In this way, we establish a non-trivial relation between superconductivity and the respective crystal structure. The model enables a detailed study of polymorphic elements showing superconductivity in different types of crystal structures like Hg or La, or the calculation of Tc under applied pressure. Using the Roeser–Huber approach, the structure-dependent different Tc’s of practically all superconducting elements can nicely be reproduced, demonstrating the usefulness of this approach offering an easy and relatively simple calculation procedure, which can be straightforwardly incorporated in machine-learning approaches.

Theoretical investigation of structural, energetic and magnetic properties of B2 type MnM alloys, DFT and data mining approach

We present crystal structure, energetic stability, magnetic properties and charge transfer of MnM (M: Li, Mg, Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Sr, Y, Rh, Pd, Cd, In, Sn, La, Hf, Ta, W, Re, Os, Ir, Au, Hg, Tl and Bi) equiatomic alloys in the B2 type crystal structure, carried out using density functional theory (DFT) within the generalized gradient approximation framework. The calculated lattice parameters of the studied compounds are in correlation with the M metallic radius rM. The formation energy calculations revealed the energetic stability of MnTa and MnHf alloys for the first time. The studied compounds exhibit different magnetic behavior with magnetic moments ranging between 0 μB and 4 μB per formula unit. The energy difference between the ferri/ferromagnetic and anti-ferri/ferromagnetic coupling of the spins has also been calculated in order to obtain better insight into the ground state magnetic exchange coupling. Finally, the previously calculated properties were studied using the data mining tool principal component analyses PCA to gain more insight into the trends and the correlations between the properties of these different alloys.

Cubic Crystal Structure Formation and Optical Properties within the Ag-BII-MIV-X (BII = Sr, Pb; MIV = Si, Ge, Sn; X = S, Se) Family of Semiconductors.

Quaternary chalcogenide semiconductors are promising materials for energy conversion and nonlinear optical applications, with properties tunable primarily by varying the elemental composition and crystal structure. Here, we first analyze the connections among several cubic crystal structure types, as well as the orthorhombic Ag2PbGeS4-type structure, reported for select members within the Ag-BII-MIV-X (BII = Sr, Pb; MIV = Si, Ge, Sn; X = S, Se) compositional space. Focusing on the Ag-Pb-Si-S and Ag-Sr-Sn-S systems, we show that one structure type, with the formulas Ag2Pb3Si2S8 and Ag2Sr3Sn2S8, is favored. We have prepared powder and single-crystal samples of Ag2Pb3Si2S8 and Ag2Sr3Sn2S8, showing that each takes on the noncentrosymmetric cubic space group I4̅3d and is isostructural to the previously reported compound Ag2Sr3Ge2Se8. Through hybrid density functional theory calculations, these cubic compounds are demonstrated to be (quasi-)direct band gap semiconductors with high densities of states at the band maxima. The band-gap energies are measured by reflectance spectroscopy as 1.95(3) and 2.66(4) eV for Ag2Pb3Si2S8 and Ag2Sr3Sn2S8, respectively. We further measure the optical properties and show the electronic band structures of three other isostructural AI-BII-MIV-X-type materials, i.e., Ag2Sr3Si2S8, Ag2Sr3Ge2S8, and Ag2Sr3Ge2Se8, showing that the band gaps can be predictably tuned by element substitution. Detailed visual analyses of the different structures and of their relationships with other members of the Ag-BII-MIV-X compositional family provide a basis for a broader understanding of the structure formation and optoelectronic properties within the quaternary chalcogenide semiconductor family.

Magnetocaloric effect in La0.70Ag0.25MnO[formula omitted] magnetic nanoparticles

Experimental study of magnetocaloric effect (MCE) was performed by direct and indirect methods on La0.70Ag0.25MnO3+δ nanoparticles with rhombohedral LaAlO3 – type crystal structure (R3¯c space group – No. 167, hP30). The content of oxygen was modified by annealing at 800 °C/48h in different atmosphere (air, O2 and Ar). The Curie temperature TC increases from 250 K to 319.5 K and to 322.9 K with the content of oxygen. The adiabatic temperature change ΔT(4T) = 1.52 K, the change of magnetic entropy −ΔSmax(4T) = 3.96 Jkg−1K−1 and the relative cooling power RCT(4T) = 172 J/kg are maximal for sample treated in Ar and decrease with oxygen content. The frequency dependence of ΔT (f) and the shape of maximum in ΔT (T) and −ΔSmax (T) indicate relaxation processes and presence of magnetic inhomogeneities which are present mostly in sample treated in Ar. The samples demonstrate the stability of the MCE up to 1000 cycles of switching on and off the magnetic field without any signs of degradation.

Soft matter crystallography—Complex, diverse, and new crystal structures in condensed materials on the mesoscale

An increasing variety of crystal structures has been observed in soft condensed matter over the past two decades, surpassing most expectations for the diversity of arrangements accessible through classical driving forces. Here, we survey the structural breadth of mesoscopic crystals—formed by micellar systems, nanoparticles, colloids, etc.—that have been observed in both soft matter experiments and coarse-grained self-assembly simulations. We review structure types that were found to mimic crystals on the atomic scale, as well as those that do not correspond to known geometries and seem to only occur on the mesoscale. While the number of crystal structure types observed in soft condensed matter still lags behind what is known from hard condensed matter, we hypothesize that the high tunability and diversity of building blocks that can be created on the nano- and microscale will render a structural variety that far exceeds that of atomic compounds, which are inevitably restricted by the “limitations” imposed by the periodic table of elements and by the properties of the chemical bond. An infusion of expertise in structural analysis from the field of crystallography into the soft condensed matter community will establish the common language necessary to report, compare, and organize the rapidly accruing structural knowledge gathered from simulations and experiments. The prospect of new materials created in soft matter and new, length-scale-spanning insights into the formation of ordered structures in both hard and soft condensed matter promise exciting new developments in the area of self-assembled mesoscale materials.

Enhanced Production of Formic Acid in Electrochemical CO2 Reduction over Pd-Doped BiOCl Nanosheets.

Bismuth oxyhalides (BiOX, X = F, Cl, Br, I) are emerging energy materials because of their remarkable catalytic activity. The BiOX compounds usually have a tetragonal type crystal structure with unique layered morphology consisting of [X-Bi-O-Bi-X] sheets. Although the BiOX nanosheets exposed with {001} facets perform superior photoactivity, there is lack of understanding about their capability in the electrochemical CO2 reduction reaction (CO2RR). Herein, we adopt wet-chemical syntheses to make 2D BiOCl and Pd-doped BiOCl nanosheets for CO2RR. In the results, formic acid is the only one kind of product converted from CO2 along with H2 gas from water reduction over both BiOCl and Pd-doped BiOCl nanosheets. By thorough analyses with ex situ and in situ spectroscopy, the results reflect that (1) metallic Bi0 atoms generated by the applied negative potentials serve as the catalytic sites for the hydrogen evolution reaction (HER) and CO2RR and (2) the existence of doped Pd ions in the BiOCl structure reduces the barrier of charge transfer over the nanosheets, which enhances HER and CO2RR activities. We believe that the observations are important references for making catalysts toward CO2RR performance.

Effect of elongational rheology on plasticization and properties of thermoplastic starch prepared by biaxial eccentric rotor extruder

Large amounts of plasticizers were added into natural starch for thermoplastic to make it processable due to the high crystallinity and large amount of intermolecular hydrogen bonds of starch. However, the traditional screw extruders based on shear deformation cannot disperse the plasticizer evenly and plasticize the starch well, which affects the comprehensive mechanical properties. In this paper, a self-developed biaxial eccentric rotor extruder (BERE) based on elongational rheology was introduced to prepare thermoplastic starch (TPS) sheets with glycerol as plasticizer at different speeds. The TPS sheets extruded by BERE all have excellent mechanical properties and optical transparency. Scanning electron microscopy, Fourier transformation infrared spectroscopy, X-ray diffraction, dynamic rheometer and universal mechanical tester were used to reveal the morphology, type and strength of hydrogen bonds, crystal structure, dynamic rheological and mechanical properties of TPS to research the effect of elongational rheology on its plasticization and properties. The results showed that the elongational rheology produced during processing process of BERE could obviously promote the dispersion of glycerol in starch and improve the melt-plasticizing effect of TPS, and the comprehensive mechanical properties of the TPS prepared by BERE is excellent with the elongation at break of 226.1%.