Application of sample-sample two-dimensional correlation spectroscopy to determine the glass transition temperature of poly(ethylene terephthalate) thin films

The glass transition temperatures (Tg) of poly(ethylene terephthalate) (PET) thin films with different thicknesses are determined by analyzing their in situ reflection-absorption infrared (RAIR) spectra measured over a temperature range of 28 to 84 degrees C. The criterion of standard deviation of the covariance matrices is used as a graphical indicator for the determination of the Tg present in the sample-sample two-dimensional (2D) correlation spectra calculated from the temperature-dependent RAIR spectra. After two data pretreatments of the first derivative of the spectral absorbance versus temperature and the mean normalization over the wavenumbers are sequentially carried out on the RAIR spectra, an abrupt change of the first-derivative correlation spectra with respect to temperature is quickly obtained. It reflects the temperature at which the apparent intensity changes in pertinent absorption bands of PET thin films take place due to the dramatic segmental motion of PET chain conformation. The Tg of the thin PET films is accordingly determined. The results reveal that it decreases with a great dependence on the film thickness and that sample-sample 2D correlation spectroscopy enables one to determine the transition temperature of polymer thin films in an easy and valid way.     

保鲜膜包装对西兰花采后花蕾黄化的影响

目的 研究聚乙烯(polyethylene,PE)、聚乳酸(polylactic acid,PLA)和聚偏二氯乙烯(polyvinylidene chloride,PVDC)等3种保鲜膜包装对西兰花花蕾黄化的影响,以探索西兰花采后常温货架期间适宜的包装方式.方法 以西兰花为实验材料,采用3种保鲜膜分别对西兰花进行包装,以无膜包装作为对照,研究不同处理对西兰花采后常温货架期间花蕾黄化及品质的影响.结果 常温货架期间,4组西兰花花蕾均逐渐由绿变黄,但对照组西兰花的黄化速度最快,PVDC处理组的西兰花黄化速度次之.常温货架前期(0～2 d),对照组与PVDC处理组的西兰花较其他2组的西兰花提前出现呼吸强度峰值.对照组西兰花质量损失最为严重,PLA处理组次之.对照组西兰花的叶绿素a、叶绿素b和总叶绿素含量均显著低于3种保鲜膜处理组的西兰花,进一步研究结果表明,这可能与叶绿素降解途径关键酶叶绿素酶(chlorophyllase,Chlase)、脱镁螯合酶(Mg-dechelatase,MDCase)、脱镁叶绿素酶(pheophytinase,PPH)的高活性有关.3种保鲜膜包装并没有持续保证西兰花中维生素C含量处于显著高水平.结论 采后常温货架期间,PE保鲜膜包装对西兰花花蕾的护绿效果较好,PLA保鲜膜次之,但PLA处理组的西兰花质量损失率较大.     

红外光谱法快速鉴别PE和PVC保鲜膜

利用傅立叶变换红外光谱仪直接采集PE和PVC食品保鲜膜的红外投射光谱,比较了两种食品保鲜膜的红外光谱特征,明确了各自主要特征峰的归属.通过检索标准谱库与标准谱图进行对照,对两种保鲜膜进行了定性鉴定.该方法不需要任何样品前处理过程,具有快速、方便、准确的优点,是对市场上两种食品保鲜膜进行快速定性鉴别的理想方法之一.     

Hydrodynamic surface fluctuations of polymer films by coherent X-ray scattering

We have applied X-ray photon correlation spectroscopy (XPCS) to measure the surface dynamics of polymer films of thicknesses down to a few times of the polymer radius of gyration. XPCS is currently the only technique to measure selectively dynamics of surface and/or interfacial fluctuations of the films thanks to high brilliance and coherence of the third generation synchrotron source. The results show the behavior of the capillary waves expected in viscous liquid when the film thickness is thicker than four times of the radius of gyration. However, thinner films show a deviation indicating the need to account for viscoelasticity. We present also the theory for surface dynamics of the thermally excited fluctuations on homogenous single-layer film with arbitrary depth is generalized to describe surface and interfacial dynamics of polymeric liquid bilayer films in terms of susceptibilities, power spectra and characteristic relaxation time constants. The effects on surface dynamics originating from viscosity inhomogeneities close to surface region are investigated by the bilayer theory and compared with the surface dynamics from homogeneous single-layer films under non-slip and slip boundary conditions.     

Improvement of the interferometric method for measuring electro-optic coefficients of poled polymer thin films

The interferometric method for measuring the linear electro-optic coefficients of polymer films has been improved. This improved method is based on using the antipiezoelectric effect of a quartz crystal to compensate for the change in the optical path length that is due to the electro-optic effect of a polymer film. The electro-optic coefficients of six kinds of new poled polymer film have been determined at a wavelength of 633 nm by this new method. This technique offers a simple, rapid, and highly sensitive method for measuring the electro-optic coefficients of polymer films.     

Annealing characteristics of Si doped amorphous silica films by rf sputtering

Si doped amorphous silica films were prepared by rf magnetron sputtering technique. As-deposited films which had relatively low Si dopant were annealed in inert atmosphere, and spectroscopic analyses were performed for as-deposited and all the annealed samples by infrared (IR) absorption, X-ray fluorescence analysis, X-ray photoelectron spectroscopy (XPS) and 29Si magic angle sample spinning nuclear magnetic resonance spectroscopy (29Si MAS-NMR). When the sample was annealed at 800°C, the IR absorption peak located at 1080 cm–1 shifted to slightly higher wave number. On the other hand, the decrease of Si clusters or Si–Si bonds in as-deposited film was deduced from X-ray fluorescence and XPS spectra for the sample annealed at 800°C. These annealing characteristics of the films prepared in this study were discussed based on the random bonding model of SiOx film, and the spectral variations with thermal annealing were interpreted by the rearrangement of Si and O atoms in as-deposited films, rather than the simple clustering of excess Si atoms.     

Mass transfer from and through packaging materials

The use of polymer films for food packaging requires a knowledge of their transport properties under varying conditions. The permeability to gases and water vapour of the packaging films at the specific conditions of use, i.e. temperature, relative humidity and pressure gradient, are needed for selecting the optimum packaging system to ensure the required shelf-life of the packed product. Migration from, and absorption by, plastic films also play an important role in their selection. The 0₂ and CO₂ permeabilities of three plastic films at four different temperatures were evaluated and shown to follow the Arrhenius relationship in the range tested. The effects of four thicknesses of one film on its permeability are also reported. Three methods to evaluate migration from polymeric films were compared using different weight/volume ratios. The extraction method recommended by the FDA, using n-hexane in a stirred flask, was found to be best. The shelf-life of Matzoth (Jewish Passover bread) packed in polyethylene (stored at 25°C) was found to be longer than the shelf-life of those packed in the higher barrier PVDC/PE. This was apparently due to the absorption of undesirable oxidation compounds, given off from the Matzoth by the PE, which were not absorbed at detectable levels by the PVDC/PE.     

Behavior and products of mechano-chemical dechlorination of polyvinyl chloride and poly (vinylidene chloride)

The mechano-chemical (MC) dechlorination of polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC) was performed by mechanical milling PVC/PVDC powder with zinc powder in a planetary ball mill, and the products of dechlorination were characterized by Infrared spectra (IR), X-ray diffraction (XRD), Raman spectroscopy, gas chromatography-mass spectrometry (GC-MS), and 13C solid-state nuclear magnetic resonance (NMR). The experimental results show that PVC/PVDC can be easily dechlorinated by milling with zinc powder, and formed various kinds of inorganic and organic products. Inorganic compounds included Zn2OCl(2).2H2O, Zn5(OH)8Cl2.H2O etc., and organic products involved diamond-like carbon, carbyne fragment, polyacetylene etc. Organic products formed following the paths of dechlorination, dehydrochlorination, crosslink, and oxidation. The mechano-chemical dechlorination process of PVC/PVDC may be an effective approach for carbyne synthesizing in the appropriate condition.     

Vibrational circular dichroism of matrix-assisted amino acid films in the mid-infrared region

Vibrational circular dichroism (VCD) spectra in the mid-infrared region of amino acid films are reported here for the first time. Amino acid films are formed from aqueous solutions with alpha-cyclodextrin (CD) serving as the matrix to facilitate the film formation. This film method eliminates the strong interfering water absorption seen in the solution study and makes it easier to measure the VCD in the 1800-1200 cm-1 region. VCD spectra for films of six amino acids, L-alanine, L-proline, L-methionine, Lhistidine, L-phenylalanine, and L-tryptophan, are obtained. For amino acids with low solubility (L-phenylalanine and L-tryptophan), VCD could not be measured in solution, so the film method is the only means of obtaining the VCD spectra for such amino acids. For amino acids with moderate solubility (L-alanine, L-proline, L-methionine, and L-histidine), VCD spectra are also obtained in the solution state and compared with their corresponding spectra in the film state. A good correlation is found between the film and solution spectra for both absorption and VCD. The VCD spectra of L-methionine, L-histidine, L-phenylalanine, and Ltryptophan are reported here in the mid-infrared region for the first time. The present study broadens the application range of the VCD technique and enhances its role in the detection and analysis of biologically important compounds.     

Optical switch from silver nanocomposite thin films

Silver nanoparticles capped with sodium alginate were assembled into thin films by using the layer-by-layer dipping technique. Composite films were built by sequential dipping of a glass slide in either anionic alginate capped nanoparticles or cationic Poly(diallyldimethylammonium chloride) (PDADMAC). The growth of the film was characterized using UV-Vis spectroscopy by monitoring the increase in absorbance at 420 nm which correspond to the silver nanoparticles plasmon band. The final films formed onto glass slides displayed and interesting color shift upon exposure to water or to a less polar solvent such as ethanol. In this research, changes in spectral absorbance of the nanoparticles film were monitored as a function of ethanol content (0, 20, 40, 60, 80 and 100%) in water. The color shift from yellow to red color was explained by the changes in the dielectric constant of the silver nanoparticles surrounding medium which induce a shift in their plasmon band absorbance. These composite thin films displayed fast color change and could therefore be used in sensing application as well as for optical switches.     

液体农药软包装的研究现状及展望

液体农药因含有毒性较大且腐蚀性较强的甲苯、二甲苯等有机溶剂,其软包装材料应具备较强的耐腐蚀性能和阻隔性能。目前国内市场上液体农药软包装常用的材料主要有PET/Al/CPP(或PE)复合膜、PET/VMPET/CPP(或PE)复合膜、含PA或EVOH的PP,PE多层共挤膜、PET/PVDC(或EVOH)/CPP(或PE)透明复合膜等,常用的胶黏剂为聚氨酯胶黏剂。液体农药包装废弃物的处理一般采取随意丢弃和集中填埋焚烧2种方式,均对环境及人类健康危害较大,必须采取相应的措施以降低其危害。液体农药软包装必须朝绿色环保方向发展,研发并推广可降解材料与水溶性膜。     

Development of attenuated total reflection based compression modulation step-scan Fourier transform infrared spectroscopy and its applications to rheo-spectral characterizations of polymer films

Dynamic compression modulation attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopic methods have been developed in this paper for characterizing polymer films. To obtain dynamic compression polarized ATR spectra, internal reflection element (IRE) secure assemblies made of tungsten carbide with very high hardness (Knoop hardness of > 1000 kgf/mm(2)) have been designed. These assemblies are mounted on the Harrick Seagull ATR attachment and measured by step-scan FT-IR spectroscopy. The effect of static compression, air gaps, and refractive index changes were examined. Experimental and simulated results showed that the effect of air gaps between the sample and IRE and refractive index changes of the sample and IRE are negligible at values larger than a static torque of 40 cN m and good signal-to-noise ratios (SNR) and reproducible data can be obtained. Uniaxially and biaxially drawn poly(ethylene terephthalate) films were measured by the presented method. Both bipolar and unipolar bands were observed in the dynamic in-phase ATR spectra, which can be associated with their micro-structural environmental changes. This technique shows promise in evaluating various polymer film materials, including biaxially oriented films, multilayer coated film surfaces, and molecular interactions between polymer-polymer and polymer-additives at the film surface.     

Undoped and indium-doped CdS films prepared by chemical vapour deposition

Undoped and In-doped films of CdS were deposited at different temperatures by the chemical vapour deposition technique on glass and In-coated (30 nm) glass, respectively. Both kinds of film present a columnar microstructure, low porosity and good adherence to the substrate. The doped films have higher electron mobility values compared with the undoped ones. Shifts in the transmission spectra (Moss-Burstein effect) were observed with increased doping. Small crystals grew over the doped films during the deposition stage, mainly at the higher substrate temperatures.     

Broadband coherent anti-Stokes Raman spectroscopy characterization of polymer thin films

Broadband coherent anti-Stokes Raman spectroscopy (CARS) is demonstrated as an effective probe of polymer thin film materials. A simple modification to a 1 kHz broad bandwidth sum frequency generation (SFG) spectrometer permits acquisition of CARS spectra for polymer thin films less than 100 nm thick, a dimension relevant to organic electronic device applications. CARS spectra are compared to the conventional Raman spectra of polystyrene and the resonance-enhanced Raman spectra of poly(3-hexylthiophene). The CARS spectra obtained under these conditions consistently demonstrate enhanced signal-to-noise ratio compared to the spontaneous Raman scattering. The sensitivity of the CARS measurement is limited by the damage threshold of the samples. The dielectic properties of the substrate have a dramatic effect on the detected signal intensity. For ultrathin films, the strongest signals are obtained from fused silica surfaces. Similar to surface-enhanced Raman scattering (SERS), Au also gives a large signal, but contrary to SERS, no surface roughening is necessary.     

Effect of high‐pressure processing on the permeance of selected high‐barrier laminated films

This study investigated the effects of high pressure processing (HPP) on the barrier properties of eight multilayer films. Pouches made from these films were filled with distilled water, sealed and then pressure processed at 600 and 800 MPa for 5, 10 and 20 min at 45°C. Controls were similarly prepared but exposed to atmospheric pressure. After processing, all pouches were dried and their oxygen, carbon dioxide and water vapour permeance determined. Films used in this study were PET/SiO_x /LDPE, PET/Al₂O₃/LDPE, PET/PVDC/nylon/HDPE/PE, PE/nylon/EVOH/PE, PE/nylon/PE, metallized‐PET/EVA/LLDPE, PP/nylon/PP and PET/PVDC/EVA. Results showed that metallized PET was most severely affected by HPP, as its permeance values for oxygen, carbon dioxide and water increased as much as 150%. Copyright © 2000 John Wiley & Sons, Ltd.     

Applications of moving window two-dimensional correlation spectroscopy to analysis of phase transitions and spectra classification

Our recently proposed idea of moving window two-dimensional (2D) correlation spectroscopy, which partitions a data set into series of relatively small submatrices (windows) and calculates their covariance maps in succession, is tested for three convoluted data set. Phase-transition temperatures of oleic acid and poly-(N-isopropylacrylamide) in an aqueous solution are sought by analyzing covariances of their temperature-dependent near-infrared and infrared spectra, respectively, while Raman spectra of three kinds of polyethylene (PE) pellets are investigated to find the spectral differences among them and to classify randomly ordered spectra by a sample-sample (SS) covariance map. The criterion of mean of standard deviation of covariance matrices is used as an indicator of the crucial information present in these matrices so that only a few of them are discussed in details. The results are obtained quickly after very simple calculations and are studied at length. The baseline variation is not removed prior to the calculations but is found to be of use for the determination of the phase-transition temperatures. Randomly ordered Raman spectra of the PE pellets are classified by innovatively used and interpreted SS slice spectra, with the relation to principal component analysis discussed.     

Cartesian-structure analysis in cast films by advanced infrared multiple-angle incidence resolution spectroscopy

Multiple-angle incidence resolution spectroscopy (MAIRS) has been improved to be an advanced algorithm so that the Cartesian structure in organic thin films can be analyzed. The infrared MAIRS technique was originally proposed as a totally new spectroscopic technique to reveal structural anisotropy in thin films on an infrared-transparent substrate, which yields both in-plane- (IP; X and Y) and out-of-plane (OP; Z)-mode spectra from an identical sample. Since this technique employs an analytical concept based on a signal decomposition of light intensity (not absorbance spectra), the algorithm intrinsically has high potential for further development. In the present study, the theoretically deduced matrix that correlates the light intensity to the angle of incidence has been modified to further decompose the IP-mode spectrum into X and Y components. As a result, anisotropic measurements of infrared spectra of thin film have become possible for the X, Y, and Z directions (Cartesian coordinate) simultaneously. With this advanced algorithm, the Cartesian structural changes in a cast film prepared on a germanium substrate have readily been analyzed, and a change from the biaxial to the uniaxial film structure with aging has spectroscopically been revealed.     

Enhanced bioactivity of polyvinylidene chloride films using argon ion bombardment for guided bone regeneration

Polyvinylidene chloride (PVDC) is a long chain carbon synthetic polymer. The objective of this study was to improve the bioactivity of PVDC films through surface modification using argon (Ar) ion bombardment to create Ar-modified PVDC films (Ar-PVDC) to address the clinical problems of guided bone regeneration (GBR), which is technique-sensitive, and low bone regenerative ability. First, the effects of Ar ion bombardment, a low temperature plasma etching technique widely used in industry, on PVDC film wettability, surface chemistry, and morphology were confirmed. Next, fibroblast-like and osteoblast-like cell attachment and proliferation on Ar-PVDC were assessed. As a preclinical in vivo study, Ar-PVDC was used to cover a critical-sized bone defect on rat calvaria and osteoconductivity was evaluated by micro-computed tomography analysis and histological examinations. We found that the contact angle of PVDC film decreased by 50° because of the production of –OH groups on the PVDC film surface, though surface morphological was unchanged at 30 min after Ar ion bombardment. We demonstrated that cell attachment increased by about 40 % and proliferation by more than 140 % because of increased wettability, and 2.4 times greater bone regeneration was observed at week 3 with Ar-PVDC compared with untreated PVDC films. These results suggest that Ar ion bombardment modification of PVDC surfaces improves osteoconductivity, indicating its potential to increase bone deposition during GBR.     

Evaluation of SOCl2 doping effect on electrical conductivity of thin films of SWNTs and SWNT/PEDOT-PSS composites

Transparent conductive thin films of single-walled carbon nanotubes (SWNTs) and their nanocomposites with an organic conductive polymer, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) with different CNT loadings ranging from 20 to 90 wt% were prepared and doped by exposing them to thionyl chloride (SOCl2) vapors. After exposure to SOCl2 vapor for 1 h, the SWNT film showed about 15-18% increase of electrical conductivity, while on the other hand pristine polymer film showed a decrease of electrical conductivity. The SWNT-polymer composite films showed a drastic increase in conductivity by doping with SOCl2 vapor, most interestingly, the doping effect was much higher for composite films with less CNT weight fraction and it was linearly decreased with increasing CNT loading. For instance, composite film with 10% and 90% CNT loading demonstrated about 65% and 10% increase of electrical conductivity, respectively. The interaction of SOCl2 vapors on SWNTs and composite films is investigated by UV-visible absorption and Raman spectroscopy.     

Study of crystallization of LiNbO3 films from metal alkoxides

The crystallization process of epitaxial LiNbO₃ films on sapphire (0 0 0 1) substrates was investigated by Raman microprobe spectroscopy. LiNbO₃ gel films were prepared by the sol-gel method using metal alkoxide precursors on sapphire (0 0 0 1) substrates and heat treated at various temperatures below 500 °C to produce epitaxial LiNbO₃ films. Analyses by electron spectroscopy for chemical analysis and SEM revealed LiNbO₃ films were stoichiometric and homogeneous. Raman spectra of the film prepared at 250 °C indicated that the NbO₆ octahedral coordination structure in LiNbO₃ began to form as the initial state of crystallization. As the heat-treatment temperature was raised, the Raman bands became sharper and increased in spectral intensity and were seen to be the characteristic Raman bands of crystalline LiNbO₃. Refractive indices of the obtained films indicated appropriate values. As a method to crystallize the more highly preferred orientation to (0 0 6) LiNbO₃ film at relatively low temperature, the formation of an underlayer film from diluted solution prior to multiple dip-coating, was found to be very promising.