Synthesis and optical properties of photochromic perinaphthothioindigo

(1,2-naphtho)(1,8-naphtho)thioindigo (PNT) has been synthesized following a simple Friedel–Crafts route and its photochemical properties in toluene and polymethylmethacrylate (PMMA) have been characterized. PNT is a photochromic molecule capable of reversible photoisomerization between a yellow form (cis-PNT, λ_max = 484 nm) and a purple form (trans-PNT, λ_max = 595 nm). The stable purple form converts to the yellow form with a trans-PNT to cis-PNT conversion quantum yield of 0.027 in toluene and 0.062 in PMMA. The unstable yellow form exhibits a cis-PNT to trans-PNT quantum efficiency of conversion of 0.27–0.85 in toluene and 0.17–0.68 PMMA, with highest conversion efficiency occurring in the vicinity of its λ_max of 484 nm. trans-PNT has a strong fluorescence quantum yield, 0.14 (toluene) and 0.16 (PMMA). For samples prepared photochemically in the cis-PNT form, slow thermal relaxation to the trans form occurs in the dark, with a half life of about 17 h in toluene (25 °C) and even slower, 168 h, in PMMA. The property of photoswitching between fluorescent and non-fluorescent forms makes this material a candidate for many applications in imaging and data storage.     

Effect of growth rate on microstructure parameters and microhardness in directionally solidified Ti–49Al alloy

Intermetallics Ti–49Al (at.%) alloy was directionally solidified with different growth rates (V = 5 μm/s–30 μm/s) at a constant temperature gradient (G = 12.1 K/mm) by using a Bridgman type directional solidification furnace. The primary dendritic spacing (λ), interlamellar spacing (λ_L), and microhardness (HV) were measured. Effect of V on HV, λ and λ_L was experimental investigated. The dependencies of λ, λ_L and HV on the growth rate were determined by using linear regressing analysis. According to the result, the values of λ and λ_L decrease with the increasing of V, and the values of HV increase with the increasing of V and with the decreasing of λ and λ_L. The results were compared with previous similar experimental results for TiAl-based alloys.     

Graphene/MoS2 organic glasses: Fabrication and enhanced reverse saturable absorption properties

Graphene/MoS₂ (G/MoS₂) composites were synthesized for the first time by a hydrothermal method, and then were dispersed in methyl methacrylate (MMA) to fabricate organic glass by a casting method. Here, the poly(methylmethacrylate) (PMMA) host can be obtained by the polymerization of MMA. The nonlinear absorption (NLA) properties of the G/MoS₂/PMMA organic glasses were investigated by using an open-aperture Z-scan technique. The experimental results showed that the G/MoS₂/PMMA organic glasses (the NLA coefficient β, was up to 2110 cm/GW) exhibited enhanced reverse saturable absorption (RSA) properties compared to G/PMMA (β = 242 cm/GW) and MoS₂/PMMA (β = 365 cm/GW) organic glasses. The enhanced mechanism of RSA was analyzed in terms of the energy-level diagram of graphene and MoS₂. The G/MoS₂/PMMA organic glasses have very promising applications in optical devices such as optical limiters and optical shutters.     

Plastic deformation behaviors and mechanical properties of rolled rings of 20CrMnTi alloy in combined radial and axial ring rolling

In this paper, a new combined radial and axial ring rolling process is proposed, in which a large increase in both the ring diameter and height can be achieved. Using the finite element (FE) method, the plastic deformation behaviors and mechanical properties of the rolled rings of 20CrMnTi alloy in combined radial and axial ring rolling are numerically investigated. It is found that under different axial rolling ratio λ_a and radial rolling ratio λ_r, there are three kinds of plastic deformation behaviors during the process. The first one is that when λ_a = 1 and λ_r > 1, the ring produces the deformation of thickness reduction and diameter expansion and its height basically remains unchanged. The second one is that when λ_a > 1 and λ_r > 1, the ring produces the deformation of thickness reduction, diameter expansion and height increase. The third one is that when λ_a > 1 and λ_r = 1, the ring produces the deformation of thickness reduction, outer diameter constancy and height increase. Owing to these plastic deformation behaviors, the axial and circumferential strain distribution of the rolled rings with the same final geometry is different. To evaluate the mechanical properties of these rolled rings, the compression and tensile tests have been carried out numerically and it is found that the rolled rings with the same final geometry may have different mechanical properties due to the different axial and circumferential strain distribution and the proposed combined radial and axial ring rolling process can thus be adopted to manufacture the rings with the same final geometry but different mechanical properties.     

Effect of polymer modifier chain length on thermal conductive property of polyamide 6/graphene nanocomposites

The influence of polymer modifier chain length on the thermal conductivity of polyamide 6/graphene (GA) nanocomposites, including through-plane (λ_z) and in-plane (λ_x) directions were investigated. Here, three chain lengths of double amino-terminated polyethylene glycol (NH₂–PEG–NH₂) were used to covalently functionalize graphene with graphene content of 5.0 wt%. Results showed that λ_z was enhanced with the chain length of NH₂–PEG–NH₂ increased, but λ_x reached a maximum value at a certain chain length of NH₂–PEG–NH₂. The maximum λ_z and λ_x of GA are 0.406 W m⁻¹ K⁻¹ and 9.710 W m⁻¹ K⁻¹, respectively. This study serves as a foundation for further research on the thermal conductive property of graphene nanocomposites using different chain lengths of polymer modifier to improve the λ_z and λ_x of the thermal conductive materials.     

Laser stimulated piezoelectricity in Er3+ doped GeO2–Bi2O3 glasses containing silicon nanocrystals

We report the first observation of the laser stimulated piezoelectricity in Er³⁺ doped GeO₂–Bi₂O₃ glasses containing silicon nanocrystals, prepared using the simple well known melt quenching technique. Two split beams originated from the same nanosecond lasers were used for the performance of the bicolor laser treatment.The fundamental (λ = 1064 nm) and the doubled frequency (λ = 532 nm) signal of a pulsed nanosecond Nd:YAG laser, as the fundamental (λ = 1540 nm) and the doubled frequency (λ = 770 nm) signal of an Er:glass laser were used.The ratio of power densities between the fundamental and the doubled frequency beams has been varied from 4:1 to 8:1. This value was chosen to achieve the maximum output photoinduced piezoelectric response. The present photoinduced piezoelectricity effect opens a new road for obtaining optically operated piezoelectric devices in germanate composites doped with rare-earth ions.     

Effect of solidification parameters on the microstructure of Sn-3.7Ag-0.9Zn solder

In this work, Sn–Ag–Zn alloy of eutectic composition (Sn-3.7wt.%Ag-0.9wt.%Zn) was directionally solidified upward at a constant temperature gradient (G = 4.33 K/mm) in a wide range of growth rates (V = 3.38–220.12 μm/s) and a constant growth rate (V = 11.52 μm/s) with different temperature gradients (G = 4.33–12.41 K/mm) using a Bridgman type directional solidification furnace. The microstructure was observed to be a rod Ag₃Sn structure in the matrix of β–Sn from the directionally solidified Sn-3.7wt.%Ag-0.9wt.%Zn samples. The values of eutectic spacing (λ) were measured from transverse section of samples. The dependency of eutectic spacing on the growth rate (V) and temperature gradient (G) were determined with linear regression analysis. The dependency of λ on the values of V and G were found to be λ = 10.42V ^? 0.53 and λ = 0.27G ^? 0.48, respectively. The values of bulk growth were also determined to be λ²V = 86.39 μm³/s by using the measured values of λ and V. The results obtained in present work were compared with the previous similar experimental results obtained for binary and ternary alloys.     

Synthesis and structure determination of new open-framework chromium carboxylate MIL-105 or CrIII(OH)·{O2C–C6(CH3)4–CO2}·nH2O

Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or Cr^III(OH)·{O₂C-C₆(CH₃)₄-CO₂}·nH₂O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate compound (MIL-53). Both contain trans corner-sharing CrO₄(OH)₂ octahedral chains connected by tetramethylterephthalate di-anions. Each chain is linked by the ligands to four other chains to form a three-dimensional framework with an array of 1D pores channels. The pores of the high temperature form of the solid, MIL-105ht, are empty. However, MIL-105ht re-hydrates at room temperature to finally give MIL-105lt with pores channels filled with free water molecules (lt: low temperature form; ht: high temperature form). The thermal behaviour of the two solids has been investigated using TGA. Crystal data for MIL-105ht: monoclinic space group C2/c with a = 19.653(1) Å, b = 9.984(1) Å, c = 6.970(1) Å, β = 110.67(1)° and Z = 4. Crystal data for MIL-105lt: orthorhombic space group Pnam with a = 17.892(1) Å, b = 11.165(1) Å, c = 6.916(1) Å and Z = 4.     

Threshold crack growth behavior of shear and tensile cracks

Crack-face interference-free mode I and mode II crack-growth data was combined with smooth axial (λ = ε_xy/ε_xx = 0) and torsional (λ = ∞) endurance limit data to develop unified crack growth models that incorporate both shear and tensile cracking. The crack growth models incorporated growth from a slip band (including short crack behavior) size crack until the final failure of a long crack, and the ability to switch between crack growth on shear planes to growth on tensile planes. The models successfully predicted smooth specimen crack-face interference-free fatigue lives and gave reasonable estimates of the smooth specimen endurance limits of crack-face interference free tubular tests run at intermediate strain ratios (λ = 3/4, 3/2, and 3). The series of Kitigawa–Takahashi (threshold fatigue) diagrams developed from the models help illustrate the competition between shear and tensile cracking at the fatigue limit under crack-face interference-free crack growth.     

Preparation and optical characterization of e-beam deposited cerium oxide films

Cerium oxide films, of 0.3–1 μm thickness, were reactively deposited in the oxygen atmosphere onto quartz plates by the PVD method. An electron gun was used as an evaporation source. Films were characterized with the AFM method, Raman spectroscopy and spectrophotometrically. Optical properties of these films were examined for the wavelength range 0.2–2.5 μm. Films were characterized by high transparency, between 0.38 and 2.5 μm. The complex refractive index, n^*=n − jk, was evaluated. The dispersion characteristics for n(λ) and k(λ) were presented. We found that the refractive index strongly depends on the temperature of substrates (300 K ⩽ T_s ⩽ 673 K) during film deposition. Estimated values of the refractive index (at λ = 0.55 μm) were in the range 1.91–2.34.     

Evaluation of thermal conductivity in air permeable concrete for dynamic breathing wall construction

Air permeable concrete (APC) is potentially useful as a dynamic insulator. The dynamic function is achieved by passing air through the material in the direction of heat flow to facilitate heat recovery. An APC sample of 200 mm length with 60% cement filling of large voids (between 0.5 and 5 mm), was tested between 5 and 10 Pa differential pressures; permeabilities were 0.28–0.32 m²/Pa h, confirming its suitability as a dynamic insulator. To characterise properties it is necessary to determine the static thermal conductivity, i.e., no air flow. A one-dimensional heat flow model for predicting the effective thermal conductivity (λ_e) of APC is developed using as variables the fractions of voids, aggregate and cement paste comprising the material. Measured values of λ_e were 0.7–1.4 W/m K. A theoretical model predicts and further improves the performance and formulation of APC. The water/cement ratio (w/c) also controls the λ_e. Increasing w/c increases the volume of micropores, adding resistance to heat flow.     

Compositional variation of photoluminescence from Mn doped MgAl2O4 spinel

Spinel (MgAl₂O₄) crystals doped with 1.0% Mn have been grown by floating zone (FZ) technique with various Mg compositions, x = MgO/Al₂O₃, from 0.2 to 1.0. Compositional variations of photoluminescence are evaluated for a fluorescence thermometer application using crystals grown. Strong photoluminescence (PL) peak is observed at λ from 512 to 520 nm from the crystals grown from compositions, x, from 0.3 to 1.0. Peak wavelength of PL increases linearly from 512 to 520 nm with x. Weak PL peaking at λ = 750 nm is also observed from the specimens. Compositional variations of PL are considered to be due to the variation of crystal field surrounding the Mn²⁺ ions. The variation of crystal field strength agrees with the compositional variation of lattice constant.     

Comparative failure analysis of allograft constructs stabilized with compression plates utilizing unicortical versus bicortical screws with or without PMMA

Orthopaedic internal fixation is subject to high stress concentration around screw holes leading to screw loosening. We compared the screw pullout strength (n = 8), and bending and torsional stiffness (n = 6) for cadaveric (young adult donors age 45 years or less) diaphyseal bone constructs with a gap and stabilized with Zimmer 4.5 narrow stainless steel dynamic compression plates with 4.5 mm cortical stainless steel screws placed in a unicortical or bicortical manner with and without intramedullary PMMA. The pullout strength for unicortical fixation with PMMA (4.3 ± .6 kN) was not significantly different with bicortical fixation with PMMA (5.3 ± 1.5 kN), n = 8, P > .5; and for the group with bicortical fixation without PMMA (4.3 ± 1.1 kN), n = 8, P > .5. The difference in bending stiffness for the group with two unicortical screws fixation with PMMA (324.1 ± 59.7 kN/m) was also not statistically significant when compared with the groups with four bicortical screws fixation without PMMA (278.7 ± 89.6 kN/m) and two bicortical screws fixation with PMMA (347.9 ± 66.7 kN/m), n = 6, P > .1. The difference in torsional stiffness for the group with two unicortical screws fixation with PMMA (173 ± 44 N m/deg) was not statistically significant when compared with the groups with four bicortical screws fixation without PMMA (190 ± 22 N m/deg), two bicortical screws fixation with PMMA (179 ± 36 N m/deg), and two bicortical screws fixation with PMMA (193 ± 31 N m/deg), n = 6, P > .5. The use of PMMA in allograft fixation appears to allow the use of fewer screws, and perhaps unicortical fixation without significant compromise of strength. Clinically, two unicortical screws with PMMA may replace the use of two bicortical screws without PMMA, or two bicortical screws with PMMA may replace four bicortical screws. The clinical relevance would be the ability to use fewer screws and reduce violation of the far cortex of the allograft.     

Optical constants and crystal chemical parameters of Sc2W3O12

The refractive indices of Sc₂W₃O₁₂, measured at wavelengths of 435.8–643.8 nm, were used to calculate n_a = 1.7331, n_b = 1.7510, n_c = 1.7586 at λ = 589.3 nm and n_∞ values at λ = ∞ from a one-term Sellmeier equation. Mean refractive indices, 〈n_D〉, and mean dispersion values, 〈A〉, are, respectively, 1.7475 and 110 × 10^?16 m². Total electronic polarizabilities, α_obs, were calculated from n_∞ and the Lorenz–Lorentz equation. The unusually large difference between the observed polarizability of 28.415 Å³ and the calculated total polarizability α_T of 26.74 Å³ (Δ = +6.3%) is attributed to (1) a large M–O–W angle, and (2) a high degree of W 5d–O 2p and Sc nd–O 2p hybridization, where n signifies unspecified Sc d orbitals.     

Reprint of “Multiaxial fatigue property of Ti–6Al–4V using hollow cylinder specimen under push-pull and cyclic inner pressure loading”

This paper studies a multiaxial fatigue crack mode and a fatigue life of Ti–6Al–4V. Load controlled fatigue tests at room temperature were carried out using a hollow cylinder specimen under multiaxial loading with principal stress ratio λ equal to 0, 0.4, 0.5 and 1.0 and loading ratio R kept constant and equal to 0. λ is defined as λ = σ₂/σ₁, where σ₁ and σ₂ are maximum and intermediate/minimum principal stresses, respectively. Here, the test at λ = 0 is a uniaxial loading test and that at λ = 1.0 an equi-biaxial loading test. A testing machine employed was a newly developed multiaxial fatigue testing machine which can apply push-pull and reversed torsion loading with inner pressure into the hollow cylinder specimen. Based on the obtained results in this study, multiaxial fatigue properties are examined, where the fatigue life evaluation and the crack mode are discussed. The fatigue life is reduced with an increase of λ, due to cyclic ratcheting and crack mode in multiaxial loading. The crack mode is also affected by the surface condition resulting from cut-machining.     

UV-laser-assisted fluorination of polymers

PMMA (Polymethylmethacrylate) substrate was covered with 1,2,3,5-tetrafluorobenzene by spin-coating. Then the sample was irradiated by a KrF-excimer laser (λ = 248 nm). After drying out the polymeric substrate, the sample surface was investigated by SEM and EDX indicating some fluorine content at the top of the sample layer. A UV-photochemical fluorination mechanism is proposed.     

Multiaxial fatigue property of Ti–6Al–4V using hollow cylinder specimen under push-pull and cyclic inner pressure loading

This paper studies a multiaxial fatigue crack mode and a fatigue life of Ti–6Al–4V. Load controlled fatigue tests at room temperature were carried out using a hollow cylinder specimen under multiaxial loading with principal stress ratio λ equal to 0, 0.4, 0.5 and 1.0 and loading ratio R kept constant and equal to 0. λ is defined as λ = σ₂/σ₁, where σ₁ and σ₂ are maximum and intermediate/minimum principal stresses, respectively. Here, the test at λ = 0 is a uniaxial loading test and that at λ = 1.0 an equi-biaxial loading test. A testing machine employed was a newly developed multiaxial fatigue testing machine which can apply push-pull and reversed torsion loading with inner pressure into the hollow cylinder specimen. Based on the obtained results in this study, multiaxial fatigue properties are examined, where the fatigue life evaluation and the crack mode are discussed. The fatigue life is reduced with an increase of λ, due to cyclic ratcheting and crack mode in multiaxial loading. The crack mode is also affected by the surface condition resulting from cut-machining.     

High piezoelectric response in the new coexistent phase boundary of 0.87BaTiO3–(0.13-x)BaZrO3–xCaTiO3

An investigation of the coexistent ferroelectric phase was carried out on the ternary system of 0.87BaTiO₃–(0.13-x)BaZrO₃–xCaTiO₃ [abbreviated as BT–BZ–xCT (where 0.00 ≤ x ≤ 0.13)]. Temperature-, frequency-dependent dielectric data, electric field-dependent strain and polarization as a function of composition are presented in order to understand the relationships of structure-properties and find the high piezoelectric response in this system. Results showed that ceramics in the composition range of 0.00 ≤ x < 0.04 were of a rhombohedral structure and transformed into a tetragonal structure at x > 0.06. The multiphase coexistence of the rhombohedral and tetragonal phase in this system was identified at x = 0.06. A large, virtually hysteresis-free electric field induced strain of 0.23% was achieved with the composition, x = 0.06, at 40 kV/cm on the boundary between rhombohedral and tetragonal phase. This relates to an extraordinarily high and normalized piezoelectric coefficient (S_max/E_max) of 1280 pm/V, which was reached at a low electric field applied at 10 kV/mm. These results indicated that a high piezoelectric response may stem primarily from the rhombohedral-tetragonal phase boundary, due to greater lattice softening and reduced energy barriers for polarized rotation.     

Synthesis,strong room-temperature PL and photocatalytic activity of ZnO/ZnWO4 rod-like nanoparticles

Zinc oxide (ZnO)/zinc tungstate (ZnWO₄) rod-like nanoparticles with diameters in the range of 6–11 nm and length of about 30 nm were synthesized by a low temperature soft solution method at 95 °C in the presence of non-ionic copolymer surfactant. It was found that their crystallinity was enhanced with the increase of heating time from 1 h up to 120 h. The photoluminescence (PL) measurements showed very strong, narrow UV band peaked at 3.30 eV and a broad visible band peaking at 2.71 eV with a shoulder at about 2.53 eV, for λ_exc < 300 nm. Quite large variations in the intensities of the two PL bands were observed for different excitation wavelengths. The intensity of the main visible band decreases with decreasing excitation energy and disappears when samples are excited λ = 320 nm (E_exc = 3.875 eV). We found that observed optical properties originate from ZnO phase. UV band gap PL had high intensity for all applied excitations, probably induced by ZnWO₄ phase presence on the surface. In addition, two values were found for direct band-gap energy of ZnO/ZnWO₄ rod-like nanoparticles 3.62 and 3.21 eV, determined from reflectance spectrum. The photocatalytic behaviour of ZnO is strongly dependent on the formation of ZnWO₄ phase, of the obtained rod-like nanoparticles.     

The luminescent properties of Er3+–Yb3+-doped fluorophosphate fiber glass preforms at high temperatures

Optical properties of fluorophosphate Er³⁺–Yb³⁺ fiber preforms with different concentrations of ErF₃ and YbF₃ are investigated in the temperature interval 25–300 °C. The temperature-dependent absorption spectra and luminescence at 1535 nm (under the λ = 970 nm excitation) spectra as well as the ⁴I_13/2 → ⁴I_15/2 luminescence decay times are used to compute the luminescence cross-section σ_e(λ). Our results show that in the range of the temperature investigated the quenching effect due to the temperature increase weakly affects the luminescence cross-section and decay time, which make these materials promising for fiber-optics applications.