Crystallization and second harmonic generation in thermally poled niobium borophosphate glasses

Crystallization of glasses with compositions (1−x)(0.95 NaPO₃+0.05 Na₂B₄O₇)+xNb₂O₅, x=0.4, 0.43, 0.45, 0.48 was investigated by differential scanning calorimetry and X-ray powder diffraction. Crystallization of two phases was observed in the glasses with x=0.43-0.48. First phase is a sodium niobate with the structure of tetragonal tungsten bronze () and second phase is Na₄Nb₈P₄O₃₂ (). The crystallization of sodium niobate is correlated with increasing of nonlinear optical efficiency reported for thermally poled glasses with x>0.4. The results of Raman spectroscopy show the formation of three-dimensional (3D) niobium oxide framework in the glasses with increase of niobium concentration. This framework is supposed to have tetragonal tungsten bronze structure and to be responsible for nonlinear optical properties of the glass. Second harmonic generation signals of as prepared and crystallized glass after thermal poling are compared. The nucleation and crystallization do not improve the NLO properties of the glasses under study.     

Optical characterization of Eu3+ and Tb3+ ions doped cadmium lithium alumino fluoro boro tellurite glasses

This article reports on the development and spectral results of Eu(3+) and Tb(3+) ions doped cadmium lithium alumino fluoro boro tellurite (CLiAFBT) glasses in the following composition. 40TeO2-30B2O3-10CdO-10Li2O-10AlF3 (Hostglass) (40-x)TeO2-30B2O3-10CdO-10Li2O-10AlF3-xEu2O3 (40-x)TeO2-30B2O3-10CdO-10Li2O-10AlF3-xTb4O7 where x=0.25, 0.50, 0.75, 1.0, 1.25 mol%. Glass amorphous nature and thermal properties have been studied using the XRD and DSC profiles. From the emission spectra of Eu(3+):glasses, five emission transitions have been observed at 578 nm, 592 nm, 612 nm, 653 nm, 701 nm and are assigned to the transitions (5)D(0)→(7)F(0), (7)F(1,)(7)F(2), (7)F(3) and (7)F(4), respectively, with λ(exci)=392 nm ((7)F(0)→(5)L(6)). In case of Tb(3+):glasses, four emission transitions ((5)D(4)→(7)F(6,)(7)F(5), (7)F(4) and (7)F(3)) are observed at 488 nm, 543 nm, 584 nm and 614 nm, respectively, with λ(exci)=376 nm. Decay curves and energy level diagrams have been plotted to evaluate the life times and to analyze the emission mechanism.     

Crystallization kinetic of fluoro- zirconate glasses by non-isothermal analysis

Fluoride glasses have been extensively studied due to their high transparency in the infrared wavelength. The crystallization kinetics of these systems has been studied using DTA and DSC techniques. Most of the experimental data is frequently investigated in terms of the Johnson-Mehl-Avrami (JMA) model in order to obtain kinetic parameters. In this work, DSC technique has been used to study the crystallization of fluorozirconate glass under non-isothermal conditions. It was found that JMA model was not fit to be applied directly to these systems, therefore, the method proposed by Málek has been applied and the Šesták-Berggren (SB) model seems to be adequate to describe the crystallization process. This revised version was published online in July 2006 with corrections to the Cover Date.     

Na-Gd phosphate glasses

Summary The present paper deals with preparation, thermal properties and radioluminescence of Ce-doped Na-Gd phosphate glasses. Thanks to their high radioluminescence intensity, three times greater than that of BGO, these glasses are promising materials for the detection of neutrons, - and X-rays. The glasses with a Gd concentration up to 89 mol% were prepared by a rapid quenching technique in air. Their thermal properties were determined using DSC and temperatures of glass transition were measured in addition using TMA. Temperatures of glass transition, crystallization and melting depend on Gd concentration and they follow the liquidus line in a phase diagram of binary system in which two eutectics and a congruently melting compound exist. High glass-forming ability of this glass system was found evidenced. The glasses containing at least 30 mol% Gd were moisture resistant.     

Synthesis and second harmonic generation studies of nlo-functionalized polyimides

Several NLO-functionalized polyimides were synthesized through novel synthetic pathways and their NLO properties were characterized. For preventing the disadvantage in poly(amic acid) precursor route, the Mitsunobu reaction and alternative synthetic route for NLO polyimides were chosen. The second-order NLO coefficients (χ⁽²⁾) of the synthesized polyimides were between 48pm/V and 122pm/V. The thermal stability of nonlinearity characterized showed that all polyimide films retain their NLO activities at temperatures below 100°C.     

高分子结晶和熔融行为的Flash DSC研究进展

近年来,作为常规示差扫描量热仪(DSC)技术的发展,商业化的快速扫描芯片量热技术(fast-scan chip-calorimeter,FSC)对推动高分子结晶学研究进展发挥了重要的作用.本文首先介绍了闪速示差扫描量热仪Flash DSC的研发历程及其对高分子结晶样品的测试技术,然后举例介绍了其在高分子结晶和熔融行为研究中的一些应用,包括总结晶动力学、晶体成核动力学、成核剂和填料对结晶的影响、共聚单元对结晶的影响、多重熔融峰的鉴定、折叠链片晶的不可逆和可逆熔化、以及极性大分子晶体的熔融等.Flash DSC极大地扩展了扫描温度速率范围,使得其研究的时间窗口能与实际高分子材料加工过程和计算机分子模拟的时间窗口相互匹配,所提供的综合信息有助于我们更好地理解高分子结晶、退火和熔融行为的微观机理.     

Thermal properties and stability of lithium titanophosphate glasses

DTA was used to study thermal properties and thermal stability of (50-x)Li₂O-xTiO₂-50P₂O₅ (x=0–10 mol%) and 45Li₂Ot-yTiO₂-(55-y)P₂O₅ (y=5–20 mol%) glasses. The addition of TiO₂ to lithium phosphate glasses results in a non-linear increase of glass transition temperature. All prepared glasses crystallize under heating within the temperature range of 400–540°C. The lowest tendency towards crystallization have the glasses with x=7.5 and y=10 mol% TiO₂. X-ray diffraction analysis showed that major compounds formed by annealing of the glasses were LiPO₃, Li₄ P₂O₇, TiP₂O₇ and NASICON-type LiTi₂(PO₄)₃. DTA results also indicated that the maximum of nucleation rate for 45Li₂O-5TiO₂-50P₂O₅ glass is close to the glass transition temperature.     

Up-conversion luminescence analysis in ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses

Ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses have been synthesized by conventional melting method. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions 2H11/2-->4I15/2, 4S3/2-->4I15/2 and 4F9/2-->4I15/2, respectively, were simultaneously observed at room temperature in these glasses. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. Tellurite glass showed a weaker up-conversion emission than germanate-niobic-lead glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate-niobic-lead glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. Our results reveal that the phonon density and the maximum phonon energy of host glasses are both important factors in determining the up-conversion efficiency.     

Crystallization kinetics,morphology, and mechanical properties of novel poly(ethylene succinate-co-octamethylene succinate)

The crystallization kinetics, morphology and mechanical properties of a novel poly(ethylene succinate-co-octamethylene succinate) (PEOS) copolyester with 82 mol% ethylene succinate (ES) units and 18 mol% octamethylene succinate (OS) units, and its homopolymer poly(ethylene succinate) (PES) were extensively investigated. The glass transition temperature, cold crystallization peak temperature and melting point of PEOS are around −24, 47.5, and 80.5 °C, respectively. The Avrami equation was used to analyze the isothermal melt crystallization kinetics of PEOS and PES. They display the same crystallization mechanism, and PEOS crystallizes slower than PES at the same degree of supercooling. The spherulitic growth rates of PEOS and PES exhibit a bell shape within the investigated crystallization temperature range, with the crystallization regime transition temperature of PEOS being lower than that of PES. In addition, PEOS has high thermal stability and good mechanical properties.     

Enhancement of second harmonic generation in helical Sc liquid crystals

In a ferroelectric liquid crystal, a special type of phase-matching for optical second harmonic generation (SHG) is possible, where two counter-propagating fundamental waves create second harmonic waves at the edge of the selective reflection band. We compute the SHG intensity in such a situation and show that, at slight detuning from exact phase-matching, useful resonance enhancement can be obtained. A considerable amount of SHG also appears when the second harmonic frequency is in the reflection band, where the SHG wave is non-propagating.     

Cation Effects in some series of mixed alkali fluoride glasses

An investigation of electrical properties of two series of fluoride glasses containing simultaneously LiF and NaF has been undertaken. The alkali fluoride contents are respectively x_AF = 0.10 and x_AF = 0.30 : (ZrF₄)_0.58(BaF₂)_0.25(LaF₃)_0.07(LiF)_0.10-x(NaF)_x and (ZrF₄)_0.50(BaF₂)_0.15(LaF₃)_0.05(LiF)_0.30-x(NaF)_x. In both series, a mixed alkali effect revealed by the existence of a conductivity minimum is apparently observed. It is shown, however, that the minima have a quite different nature and none of them is actually compatible with the classical ?mixed alkali effect”? of mobile cations. In the series x_AF = 0.10, where charge transport is essentially assured by the F^?-ions, this effect results from the presence of non mobile alkali ions of different nature in the vicinity of the F^?-ions. In the series x_AF = 0.30, the electrical properties of the extreme compositions x_LiF = 0.30 and x_NaF = 0.30 are due respectively either to Li⁺-ions only or to mobile F^?-ions only. The variation of the ratio r = Na/(Li + Na) from 0 to 1 corresponds to progressive cross over from a cationic conducting glass to an anionic conducting one. The presence of a minimum of conductivity for 0.50 < r < 0.75 has been explained.     

Preparation and second harmonic generation of nanosized Sb<Subscript>2</Subscript>S<Subscript>3</Subscript> doped silica glasses by the sol-gel process

The nanosized Sb₂S₃ doped silica glasses were prepared by the sol-gel method and the maximum dopant of Sb₂S₃ dissolvable in the silica is 7wt.%. XRD, HRTEM and FTFIR measurements indicated that the nanocrystal was formed in the matrix. The red shift with the increasing of the annealing time and temperature was observed by the transmission spectra measurements of the bulk, which was due to the quantum size effect. Second harmonic generation was also observed in the glasses irradiated by electron beam. The SH intensity of the sample was about four times larger than that of quartz as a reference.     

Influence of SiO2 on the structure and optical properties of lithium bismuth silicate glasses

Bismuth silicate glasses containing lithium oxide with composition 20Li₂O·(80 − x)Bi₂O₃·xSiO₂ (5 ? x ? 70 mol%) have been prepared by melt-quench technique. Density (D), molar volume (V_M) and glass transition temperature (T_g) for all the glass samples have been measured. FTIR spectroscopy has been employed to investigate the structure of these glasses in order to obtain information about the competitive role of Bi₂O₃ and SiO₂ in the formation of glass network. The increase of SiO₂ content in the glass matrix results in increasing the Si-O-Si bond angle and hence the ionicity of Si-O bond increases with decrease in Bi₂O₃/SiO₂ ratio. The optical transmittance spectra of all the glasses have been recorded in the wavelength range 200-3300 nm. The values of optical band gap (E_g) have been determined from the cutoff wavelength of these glasses. The average electronic polarizability of oxide ion () and the optical basicity (Λ_th) have been estimated from the calculated values of the E_g and were found to be dependent directly on Bi₂O₃/SiO₂ ratio. The variation in different physical parameters such as D, V_M and T_g and optical parameters; viz., E_g, , Λ_th with Bi₂O₃/SiO₂ ratio have been analyzed and discussed in terms of change in the glass structure.     

Optical second harmonic generation in ferroelectric liquid crystals under oblique incidence

The second harmonic generation (SHG) in ferroelectric liquid crystals under oblique incidence was studied by using a numerical band matrix method that uses boundary conditions directly. No approximations were used except for the nondepleted fundamental wave. By matching the edge of the full-pitch band with that of the half-pitch band, the SH intensity increased significantly. The thickness (L) dependence of the SH intensity showed L ^6.93–L ^7.09 dependence without the limitation of the thickness.     

Crystallization,mechanical, thermal and rheological properties of polypropylene composites reinforced by magnesium oxysulfate whisker

Polypropylene(PP) composites containing magnesium oxysulfate whisker(MOSw) or lauric acid(LA) modified MOSw(LAMOSw) were prepared via melt mixing in a torque rheometer. The heterogeneous nucleating effect of LAMOSw was clearly observed in polarized light microscopy(PLM) pictures with the presence of an abundance of small spherulites. MOSw exhibited no nucleation effect and formed a few spherulites with large size. Compared with PP/MOSw composites, PP/LAMOSw exhibited better impact strength, tensile strength and nominal strain at break, ascribing to three possible reasons:(i) more β-crystal PP formed,(ii) better dispersity of LAMOSw in PP matrix and(iii) the plasticizing effect of LA. The results of dynamic mechanical thermal analysis(DMTA) indicated that brittleness of the PP matrix at low temperature was improved by the addition of LAMOSw, while the interfacial interactions between MOSw and PP matrix were actually weakened by LA, as evidenced by the higher tanδ values over the entire range of test temperatures. In terms of the rheological properties of the composites, both the η* and G′ at low frequencies increase with the addition of MOSw or LAMOSw, indicating that the PP matrix was transformed from liquid-like to solid-like. However, a network of whiskers did not form because no plateau was found in the G′ at low frequencies. With low filler content, LAMOSw produced a stronger solid-like behavior than MOSw mainly due to the better dispersion of the LAMOSw in PP matrix. However, for highly-filled composites, the η* of PP/LAMOSw at low frequencies was smaller than that of PP/MOSw composite, since the particleparticle contact effect played a major role.     

Phase transition of lipid-like monolayer characterized by second harmonic generation

Phase transition of a lipid-like hemicyanine compound characterized by second harmonic generation is studied carefully. The phase transition is assigned as the first order transition between solid state and liquid state. The transition temperature increases with an increase in the surface molecular concentration. A monolayer structure parameter a which is very sensitive to the phase transition is introduced.     

High-temperature dielectric switch and second harmonic generation integrated in a stimulus responsive material

Stimulus re s ponsive materials can provide a variety of desirable properties in one equipment unit,such as optoelectronic devices,data communications,actuators,memories,sensors and capacitors.However,it remains a large challenge to design such stimulus responsive materials,especially functional materials having both dielectric switch and second harmonic generation(SHG).Here,a new stimuli-responsive switchable material [(CH₃)₃N(CH₂)₂Cl]₂]Mn(SCN)₄(H₂O)₂] was discovered as a potential secondharmonic generation(SHG) dielectric switch.It is worth noting that it has SHG characteristics before and after undergoing reversible high-temperature phase transitions.In this work,we successfully refined the tetramethylammonium cation to obtain a quasi-spherical cation,which is tetramethylchloroethylamine(TMCEM) cation.By substituting H with a halogen,the increased steric hindrance of the molecular makes energy barrier increased,resulting in the reversible high-temperature phase transition.At the same time,the interactions of quasi-spherical cations and [Mn(SCN)₄(H₂O)₂]^2- anions affect a noncentrosymmetric structure to induce the SHG effect.These findings provide a new approach to design novel functional switch materials.     

尼龙6/氯化钾复合材料的结晶与性能

通过熔融共混法制备了不同KCl含量下的尼龙6(PA6)/KCl复合材料,采用示差扫描量热仪(DSC)、流变仪、红外光谱(IR)、电子拉伸机等研究了KCl含量对PA6/KCl复合材料结晶行为、流变性能及力学性能的影响,并研究了其受限机制.力学性能研究结果表明,随着KCl含量的增加,PA6/KCl复合材料拉伸强度和冲击强度呈现出先增大后减小的趋势,在KCl含量为3 phr时,复合材料拉伸强度和冲击强度分别达到最大值82.67 MPa和7.34 k J/m~2,较纯PA6分别增加了10.8%和34.68%,动态力学性能测量结果表明,在测量温度范围内,复合材料的储能模量均高于纯PA6,在25℃体系储能模量(G')随KCl含量的增加而增大,复合体系抵抗弯曲变形能力增加,而结晶行为研究结果表明,增加KCl的含量,PA6/KCl复合材料的成核温度、晶体生长温度、熔融温度及玻璃化转变温度均向低温方向移动,成核密度和成核速率也逐渐减小,结晶能力下降,结晶度减小,结晶度由原来25.30%变为19.34%,而结晶诱导时间逐渐增加.流变性能研究结果表明,随着KCl含量的增加,复合体系的零剪切黏度逐渐增加,且所有的体系均呈现出假塑性流体行为,剪切变稀现象越来越明显,特征松弛时间τ_1、τ_2和τ_3逐渐增加,复合体系的松弛机制发生变化.     

Anharmonicity and fragility in lithium borate glasses

Since the physical properties of lithium borate glasses xLi₂O-(1-x)B₂O₃ (0<x< 0.28) vary over a wide range with the composition, this binary system is particularly suitable for studying the relationship between vibrational anharmonicity and fragility. The density, the linear expansion coefficient, the longitudinal and transverse ultrasonic velocities and their respective temperature coefficients of the velocities are measured, from which the vibrational anharmonicity in lithium borate glasses is evaluated with the help of the Grüneisen parameter at the Debye cut-off frequency and the Anderson-Grüneisen parameter: these two parameters plotted vs. composition have the same characteristics with minima at x≈0.08. The fragility is evaluated from the temperature width of the glass transition; the fragility also shows a minimum at x≈0.08. The presence of minima at x≈0.08 is ascribable to the fact that the crosslinking density between six-membered rings in the glass reaches a maximum at this composition. We show that the anharmonic parameters strongly correlate with the fragility metrics. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electrical field induced phase-matched second harmonic generation in low Tg polymer waveguides

Second-harmonic generation in the guided waveguide configuration is very attractive because a high fundamental power density can be coupled over long propagation length therefore remarkably high conversion efficiencies can be expected compared to bulk materials.¹ Organic SHG devices in optical waveguides have not been developed extensively because of the difficulty encountered in phase-matching. To avoid this problem, the use of an artificial periodic structure, Cerenkov radiation, and non-colinear light path geometry have already been demonstrated. Recently, we reported an electric field-induced dynamic phase-matching in a guided wave configuration using a main-chain polymer in which the effective phase-matching thickness can be controlled by an applied electric field.² This technique is able to increase the waveguide dimension tolerances of phase-matching condition. In the case of a main-chain polymer, the thermal optic effects due to the heating prevent to satisfy the optimum phase-matching conditions, which causes a reduction in the conversion efficiency of devices. In order to overcome this problem, we have synthesized novel low glass transition temperature (Tg) nonlinear optical (NLO) polymers. In this presentation, we will discuss an electric field-induced dynamic phase-matching of a multilayer waveguide at room temperature using a low Tg NLO polymer which can increase both the waveguide dimension tolerances and overlap integral. Using this technique, efficient phase-matched SHG was generated from p-nitroaniline grafted NLO materials. The dimension tolerance of waveguides under an electric field will be described.