Ultraweak spectrally resolved thermoluminescence in polymers

Spectrally resolved thermoluminescence (TL) measurements provide a lot of information concerning trapping and recombination states in various dielectric materials. As long-lived luminescence is typically weak, this technique requires a very sensitive apparatus. This paper describes the measurement system that is used for studying spectrally resolved TL and phosphorescence decay in polymers. Exemplary investigations are presented for poly(N-vinylcarbazole) (PVK) thin films. The obtained spectra clearly indicate the influence of solvents (dioxane, chlorobenzene) and excitation wavelengths on TL in PVK samples.     

Characteristics of kenaf fibre/epoxy composites subjected to thermal degradation

Kenaf fibres are receiving much attention in the natural fibre composite industry due to its potential as polymer reinforcements. However, like all natural fibres, kenaf fibres have lower thermal resistance as compared to synthetic fibres. In this current work, the characteristics of kenaf fibre/epoxy composites, both treated and untreated using alkalization process, exposed to high temperature were studied. Thermogravimetric analysis (TGA) was used to study the thermal decomposition behaviour of treated and untreated kenaf/epoxy composites as well as their components, kenaf fibre and neat epoxy from room temperature up to 600 °C. The weight loss and physical changes of these samples were observed through furnace pyrolysis. Surface morphology of the composites after degradation was observed using scanning electron microscopy (SEM). The results from the TGA showed that the addition of kenaf fibres into the epoxy slightly improves both the charring and thermal stability of the samples. However, it was observed that alkalization causes reduction in these behaviours for the kenaf/epoxy composite. Generally, increased exposure time causes higher weight loss of the composites only up to 150 °C. At higher temperature, duration of exposure has little influence on the weight loss. Fibre-matrix debondings were observed on degraded samples implying mechanical degradation of the composites had occurred.     

Polymeric nanofilm-coated optical fibre sensor for speciation of aromatic compounds

An optical fibre sensor has been shown to be suitable for monitoring of benzene, toluene and o-xylene (BTX) with both high selectivity and sensitivity. The sensing principle underlying this experimental device is based on the changes of the reflected optical power when BTX vapours are present in the analytical tube containing an optical fibre coated with a thin film of poly[methyl(3, 3, 3-trifluoropropyl)siloxane]. The interaction of organic vapour with the sensitive surface promotes a variation of the light power, proportional to the amount of adsorbed BTX vapour. A set of experiments concerning different operational conditions was performed in order to promote a higher analytical performance and the newly developed BTX sensor showed higher sensitivity and shorter analytical time than a method based on gas chromatography–flame ionisation detector. Furthermore, the proposed sensor also provides the basis for an inexpensive analytical technique with adequate specificity for measurements of BTX at trace levels with appropriate reversibility, repeatability, and reproducibility. Finally, the analytical performance of the developed sensor was also evaluated and found adequate for industrial air samples.     

Experimental and numerical investigation of aramid fibre reinforced laminates subjected to low velocity impact

The low velocity impact performance of domestic aramid fibre reinforced laminates is investigated experimentally and numerically. Laminates with different thicknesses are impacted by drop-weight test machine under different impact energies. The time histories of impact force are recorded and ultrasonic C-scan technology is used to inspect the internal damage of the laminates. Numerical simulation is conducted using finite element method (FEM), taking into account both intralaminar and interlaminar damage. The intralaminar damage model is based on the continuum damage mechanics (CDM) approach, which consists of the strain-based Hashin failure criteria and the exponential damage evolution law, and considers the nonlinear shear behaviour of the material. The interlaminar damage is simulated by interface elements with cohesive zone model. The numerical results show good agreements with the experiments, thus verifying the validity of the presented numerical model.     

利用AFM和SNOM对淋巴细胞膜表面超微结构及其光学性质的初步研究

利用原子力显微镜(Atomic Force Microscopy，AFM)对淋巴细胞表面形貌进行了形态学的初步研究，观察到了其膜表面其他显微技术所不能发现的超微结构．同时也运用扫描近场光学显微镜(Scanning Near field Optical Microscopy，SNOM)对淋巴细胞进行成像，观察了其对光的透射、吸收等光学性质，并对两种成像方法进行了比较．研究发现：淋巴细胞膜表面凹凸不平，分布着大量直径几十到几百纳米不等的小颗粒；淋巴细胞中央部位有自发荧光现象．结果表明，AFM和SNOM可作为进一步探讨淋巴细胞的结构与功能关系的有力工具．     

The use of optical microscopy to follow the degradation of isotactic polypropylene (iPP) subjected to natural and accelerated ageing

Microscopy and mechanical properties are commonly used to follow the changes in morphology and mechanical resistance, respectively, of materials before and after any type of treatment. In this work, we used light microscopy (LM), scanning electron microscopy (SEM) and measurement of the mechanical properties to assess the natural ageing of samples of isotactic polypropylene (iPP) in Campinas and after exposure to Weather-Ometer type accelerated ageing equipment. The results obtained for the mechanical properties and by light microscopy (LM) allowed us to identify the ageing time based on the amount of radiation, for a 50% loss of elongation at break. The results were similar for samples subjected to the two types of ageing processes. Although a simple technique, LM was considered efficient when compared with SEM and the measurement of mechanical properties.     

Homogeneous liquid crystal alignment on poly(vinylidene fluoride-trifluoroethylene) films subjected to ion-beam irradiation

We demonstrate homogeneous and uniform liquid crystal (LC) alignment on poly(vinylidene fluoride-trifluoroethylene) [PVDF-TrFE] films using ion-beam (IB) irradiation and a performance improvement of twisted nematic (TN) cells using IB-irradiated PVDF-TrFE films. Spontaneous ferroelectricity of the PVDF-TrFE films was modified by IB irradiation, which affected the LC alignment properties. The variation in the pre-tilt angles of the LC molecules on the IB-irradiated PVDF films is attributed to surface reformation, including defluorination and oxidation because the pre-tilt angles of LC molecules can be controlled by adjusting the fluorine content. The results of contact angle measurements supported this phenomenon. A 58% reduction in the switching voltage was observed for TN cells, indicating that the IB-irradiated PVDF-TrFE films are a promising candidate for use as an alignment layer.     

Biodegradability of poly(butylene succinate) (PBS) composite reinforced with jute fibre

Poly(butylene succinate) (PBS)/jute composites were prepared, and the effects of fibre content, diameter, surface modification and arrangement forms on the biodegradability were evaluated by compost-soil burial test. The weight losses of PBS/jute composites are higher than that of pure PBS film and bulk jute fibre, and decreased with increasing fibre content. The weight loss of PBS/10% jute composite after 180 days is 62.5%. In the case of the effect of fibre diameter, the weight loss is found to decrease with decreasing fibre diameter. For the effect of fibre surface modification, the order of higher weight loss is PBS/untreated jute > PBS/alkali treated jute > PBS/coupling agent treated jute. Furthermore, the composite of PBS/woven fabric has the highest weigh loss, followed by that of PBS/nonwoven fabric and PBS/bulk jute fibre, respectively.     

New preparation of gold–silver complexes and optical fibre environmental sensors based on vapochromic [Au2Ag2(C6F5)4(phen)2]n

Complexes [Au₂Ag₂(C₆F₅)₄L₂]_n, where L = 1,10‐phenanthroline (phen), 2,2′‐bipyridine (bipy) or tetrahydrothiophene (tht), have been synthesized by reaction of NBu₄[Au(C₆F₅)₂] with Ag(SO₃CF₃), and the addition of phen or bipy thereafter, or with [Ag(SO₃CF₃)(tht)]. The organometallic vapochromic material [Au₂Ag₂(C₆F₅)₄(phen)₂]_n is isolated as a powder that is able to detect volatile organic compounds such as acetone even in an aqueous solution. The colour of this vapochromic material changes from bright yellow to white in the presence of different donor solvents such as acetone, methanol or ethanol. For the practical construction of an optical fibre sensor, a sol‐gel doped with the vapochromic complex was deposited onto one end of a monomode fibre connected to a coupler. The behaviour of the material was studied at different wavelengths and concentrations of acetone vapours and acetone–water solutions. Changes were detected up to 4 dB in the reflected optical power. Copyright © 2005 John Wiley & Sons, Ltd.     

The etching and optical response of Tuffak polycarbonate nuclear track detector to gamma irradiation

The effects of gamma irradiation in the dose range of 1.0–20.0 Mrad on the etching and optical characteristics of Tuffak polycarbonate (C₁₆H₁₄O₃)_n nuclear track detector have been studied by using etching and UV–visible spectroscopic techniques. The bulk etch rates increase and the activation energies for bulk etching decrease with the increase in gamma dose. The optical band gaps determined from the UV–visible spectra were found to decrease with the increase in gamma dose. These results have been explained on the basis of scission of the detector due to gamma irradiation.     

Online SAXS investigations of polymeric hollow fibre membranes

Polymeric membranes are used in industrial and analytical separation techniques. In this study small-angle X-ray scattering (SAXS) with synchrotron radiation has been applied for in-situ characterisation during formation of polymeric membranes. The spinning of a polyetherimide (PEI) hollow fibre membrane was chosen for investigation of dynamic aggregation processes during membrane formation, because it allows the measurement of the dynamic equilibrium at different distances from the spinning nozzle. With this system it is possible to resolve structural changes in the nm-size range which occur during membrane formation on the time-scale of milliseconds. Integral structural parameters, like radius of gyration and pair-distance distribution, were determined. Depending on the chosen spinning parameters, e.g. the flow ratio between polymer solution and coagulant water, significant changes in the scattering curves have been observed. The data are correlated with the distance from the spinning nozzle in order to get information about the kinetics of membrane formation which has fundamental influence on structure and properties of the membrane.     

Effect of proton irradiation on structure and optical property of PTFE film

Effects of protons on chemical structure and optical properties of polytetrafluoroethylene (PTFE) film were investigated in the energy range of 60 to 170 keV to simulate the effects of space proton irradiation environment. The results show that for PTFE film irradiated with protons, the change in C_1s spectrum, along with those in F_1s and the FT‐IR spectrum after irradiation, demonstrates that two processes take place simultaneously. One is substitution in which carbon to fluorine bonds can be broken by the protons and some positions of fluorine are occupied by active protons; the other is the carbonification, which results in the change of surface color and an increase of carbon percentage on the irradiated surface. For the PTFE film irradiated with 150 keV protons, the spectral absorbance ΔA_λ in the wavelengths longer than 300 nm increase unmonotonously with proton fluence, and an abnormally recovery decrease of the ΔA_λ with the increase of fluence in the range of 5×10¹³ cm^?2 to 10¹⁵ cm^?2 is observed. The change of the ΔA_λ could be related to the competition of the carbonification and the substituting effect. The carbonification increases the ΔA_λ, while the substituting increases the amorphousness amount, leading to an increase in the transparency of the film. In addition, the creation of radicals can also contribute to the increase in absorbance. Copyright © 2003 John Wiley & Sons, Ltd.     

Characterization of thermo-oxidative stability of polymer optical fibers using chemiluminescence technique

The thermo-oxidative stability of commercially available polymer optical fibers (POFs) and their components (cores and claddings) was investigated. All the bare POFs (core and cladding only) studied here were based on poly(methyl methacrylate) (PMMA) core. The fibers were exposed to 100 °C/low humidity for about 4200 h. Chemiluminescence (CL) technique was applied to investigate the thermo-oxidative stability and for measuring the transmission loss during exposure a prototype device called multiplexer was used. POFs exhibited variation in thermo-oxidative stability although they possessed identical core material PMMA. This was due to difference in the chemical compositions of claddings. Claddings were more susceptible to the thermo-oxidative degradation compared to cores. The thermo-oxidative degradation of both the cladding and the core was found in POFs as a result of climatic exposure. POFs showed an early drop-off followed by a slow decline of transmission. The early drop-off of transmission was attributed to physical changes like thermal expansion and the slow decline of transmission to chemical changes like oxidative degradation of POFs. A good linear relationship between optical transmission stability and thermo-oxidative stability of POFs was established from these studies.     

不对称-NO等取代2,4-二苯基方酸的非线性光学性质的FF/AM1研究

对-NH2,-NO和NO2取代的2,4-二苯基方酸采用量子化学半经验AM1方法进行优化,在优化稳定构型的基础上计算了各体系的电子光谱,并通过FF/AM1方法计算了各体系的一阶分子超极化率(β ijk)和二阶分子超极化率(γ ijkl).计算结果表明,各体系均有非常大的βijk和γijkl,其最大值分别可达-2.406×10-26 C*m和1.845×10-24 C*m.     

Development of an optical fibre reflectance sensor for p-aminophenol detection based on immobilised bis-8-hydroxyquinoline

2,2′-(1,4-Phenylenedivinylene)bis-8-hydroxyquinoline (PBHQ), a highly sensitive reagent used for the colorimetric determination of p-aminophenol (PAP), was successfully immobilised on XAD-7 and coupled with optical fibres to investigate a sensor-based approach for determining p-aminophenol. The solid-state sensor is based on the reaction of PAP with PBHQ in presence of an oxidant to produce an indophenol dye. The reflectance measurements were carried out at a wavelength of 647 nm since it yielded the largest divergence different in reflectance spectra before and after reaction with the analyte. The linear dynamic range of PAP was found within the concentration range of 0.1-2.18 mg l⁻¹ with its LOD of 0.02 mg l⁻¹. The sensor response from different probes (n = 7) gave a R.S.D. of 4.4% at 1.09 mg l⁻¹ PAP concentration. The response time of the optical one-shot sensor was 5 min for a stable solution. As this PAP sensor is irreversible, a fresh sensor has to be used for each measurement. All the experimental parameters were optimized for the determination of PAP. Using the optical sensing probe, PAP in pharmaceutical wastewater and paracetamol was determined. The effect of potential interferences such as inorganic and organic compounds was also evaluated. Potential on-site determination of PAP with such sensors can indirectly aid detection of organo-phosphorus nerve agents and pesticides in the field by inhibition of acetylcholine esterase-catalyzed hydrolysis of p-aminophenyl acetate to p-aminophenol.     

Effect of the preparation conditions on the formation of asymmetric poly(vinylidene fluoride) hollow fibre membranes with a dense skin

Integrally skinned asymmetric poly(vinylidene fluoride) hollow fibre membranes were prepared and characterized. The effects of phase inversion methods (dry-wet or wet) and spinning conditions, such as the type of solvent (NMP, DMAc), the concentration of polymer in dope solution, temperature of the external coagulation bath and the composition of the inner coagulant on the morphology and on the formation of a dense skin layer were investigated. The structure of the membranes was analyzed by scanning electron microscopy and the gas permeation properties with six different gases (He, H₂, N₂, O₂, CH₄ and CO₂) were measured at 25 °C to confirm the integrity of the selective skin layer. Under the proper conditions highly selective and permeable PVDF hollow fibre membranes were thus obtained by dry-wet spinning of a 30 wt.% PVDF solution in DMAc, using hot water (50 °C) as the external coagulant and a bore fluid of pure water as the internal coagulant. The best membrane had a selective outer skin with an effective thickness of approximately 0.2 μm. The ideal selectivity of the hollow fibres approached or even exceeded the intrinsic ideal selectivity of a dense PVDF film, for instance the selectivity for He over N₂ was 86.2 for the hollow fibre, whereas it was 83.5 for a dense PVDF reference film. DSC and FT-IR/ATR analysis indicated a higher fraction of the β-crystal phase in the selective skin and a high overall crystallinity than in the melt-processed film. The latter explains the relatively high selectivity and low permeability of the membranes. Intrinsic polymer properties make the membranes also suitable for vapour transport than for gas separation.     

Optical fibre reflectance sensor for the determination and speciation analysis of iron in fresh and seawater samples coupled to a multisyringe flow injection system

A novel optical fibre reflectance sensor coupled to a multisyringe flow injection system (MSFIA) for the determination and speciation analysis of iron at trace level using chelating disks (iminodiacetic groups) is proposed. Once iron(III) has been retained onto a chelating disk, an ammonium thiocyanate stream is injected in order to form the iron(III)-thiocyanate complex which is spectrophotometrically detected at 480 nm. Iron(III) is eluted with 2 M hydrochloric acid so that the chelating disk is regenerated for subsequent experiments. The determination of total iron is achieved by the on-line oxidation of iron(II) to iron(III) with a suitable hydrogen peroxide stream.A mass calibration was feasible in the range from 0.001 to 0.25 μg. The detection limit (3s_b/S) was 0.001 μg. The repeatability (RSD), calculated from nine replicates using 1 ml injections of a 0.1 mg/l concentration, was 2.2%. The repeatability between five chelating disks was 3.6%. The applicability of the proposed methodology in fresh and seawater samples has been proved.The proposed technique has been validated by replicate analysis (n = 4) of certified reference materials of water with satisfactory results.     

Synthesis and characterization of interpenetrating polymer networks with nonlinear optical properties

We report the synthesis and characterization of interpenetrating polymer networks (IPNs) exhibiting nonlinear optical (NLO) properties. The network consists of aliphatic polycarbonate urethane (PCU) and poly(methyl methacrylate-co-N,N-disubstituted urea), with a nonlinear optical (NLO) chromophore incorporated into N,N-disubstituted urea. The full IPNs have only one T_g, as determined by differential scanning calorimetry (DSC), together with scanning electron microscopy (SEM) observations, suggest a single phase morphology. The thin films of IPNs are transparent and the unpoled samples produced second harmonic generation (SHG) signals at room temperature. This result indicates that the NLO chromophore is oriented noncentrosymmetrically during the IPN formation process and is tightly held between the permanent entanglements of the two component networks of the IPN. © 1996 John Wiley & Sons, Inc.     

Molecular structure and nonlinear optical properties of a tetrasilver(I) phosphonitocavitand

A tetrasilver(I) phosphonitocavitand was synthesized and structurally characterized. The compound crystallizes in the monoclinic space group P2₁/n with a=15.0151(13), b=39.832(4), c=15.2479(14) Å, β=95.1000(2)°, V=9083.3(14) Å³ and Z=4. The structure contains four coplanar silver atoms bridged by four μ-Cl and one central trapped μ₄-Cl atoms in the inside of the closing bowl-shaped cavitand. Nonlinear optical properties of this metal-cavitand were investigated. Optical limiting effect with threshold of 0.6 J cm⁻² was observed with the laser pulses of 7 ns at 532 nm.