Reaction‐Induced Phase Separation in Polyoxyethylene/Polystyrene Blends. I. Ternary Phase Diagram

Abstract

Reaction‐induced, phase separation has been studied in polymer blends. A model crystalline‐amorphous system consisted of semicrystalline polyoxyethylene (POE) dissolved in the monomer styrene, which was used as a reactive solvent to ease processing. When the styrene was polymerized to polystyrene (PS) in the mold, phase separation and phase inversion are induced, and a polymer blend was formed. Polyoxyethylene was selected with a molar mass, M _n  = 8578 g mol^?1 and a polydispersity of 1.19, as determined by using gel permeation chromatography. The polymerization of styrene was initiated by using 1 wt% benzoin methyl ether and 0.2 wt% 2,2′‐azobisisobutyronitrile under ultraviolet light. The polymerization kinetics were determined by monitoring the reduction in the intensity of the C?C stretching vibration band at 1631 cm^?1 in the Raman spectrum of styrene. The onset times for the liquid–solid (L–S) phase separation and crystallization of POE from styrene/PS were observed by using simultaneous small‐angle x‐ray scattering (SAXS) and wide‐angle x‐ray scattering. Onset times for L–S phase separation determined from the SAXS data were combined with the styrene polymerization kinetics to plot the L–S phase separation data onto a ternary phase diagram for the reactive system POE/styrene/PS at 45°C and 50°C.     

Phase Behavior of Poly(Ethylene Oxide) Studied by Modulated‐Temperature DSC—Influence of the Molecular Weight

Abstract

Melting and crystallization behavior of poly(ethylene oxide) (PEO) with different molecular weight was investigated by modulated‐temperature differential scanning calorimetry (MT‐DSC)—step‐scan alternating DSC. It was found that by separating the reversing and nonreversing components of the (total) heat flow, PEO 10000, which exhibits the highest degree of crystallinity, shows the smallest nonreversing signal during crystallization. This effect can be attributed to the favorable structural features associated with spacial alignment. On the other hand, the crystallization process of PEO with molecular weight of 3400 is hindered by a relatively high content of end groups that may cause defects in the crystal lattice. For PEO 35000, low segmental mobility and chain entanglements lower the rate of crystallization. The area of the reversing component of PEO melting for different molecular weight fractions confirms that for PEO 10000, recrystallization is less intensive than for both the lower and higher molecular weight analogues.     

Investigation of the Melt‐Crystallization of Polypropylene by a Temperature Slope Method

Abstract

To investigate the in‐situ ordering process of isotactic polypropylene (iPP) from a melt state, a stationary growth front was prepared by the temperature slope crystallization (TSC) method. During the melt‐crystallization, iPP was crystallized into the α‐phase or β‐phase depending on the crystallizing conditions. The mechanism of the melt‐crystallization at the growth front was precisely observed by wide‐angle and small‐angle x‐ray scattering (WAXS and SAXS) using a strong synchrotron beam. In the TSC apparatus, the sample was crystallized in between a heater, controlled to 220°C, and a cooler, cooled by water to 25°C. We define the z‐axis parallel to the temperature gradient. A‐lamellae and B‐lamellae are also defined as those whose lamellar normal are perpendicular and parallel to the z‐axis, respectively. In a sample‐stop (SS) stage before the TSC, the original α‐phase lamellae became thicker, approaching to the melt‐solid boundary by annealing. The annealing process showed that the α‐phase B‐lamellae remained and the SAXS reflection was stronger on the meridian near the melt‐solid boundary in the SS stage. In the beginning of the TSC, the α‐phase B‐lamellae developed as a primary crystallization. During secondary crystallization under high supercooling, the SAXS cross pattern appeared showing that the α‐phase developed both A‐ and B‐lamellae. As the growth direction of A‐lamellae is parallel to the z‐axis, A‐lamellae grow faster than B‐lamellae. By the self‐epitaxial mechanism on the side surface of the A‐lamellae, the B‐lamellae grow on the base of the A‐lamellae. Following appearance of a spontaneous β‐nucleus, the β‐phase lamellae grew preferentially, excluding the α‐phase, and occupied the whole area of the sample. In this case also, A‐lamellae are advantageous to grow because of the growth direction parallel to the z‐axis. As a result, the SAXS β‐phase reflection appeared on the equator.     

Simultaneous spectral calibration of two phase plates

Based on a new model for the spectral calibration of phase plates in pairs, experimental results are presented for three mica plates between 430 and 684 nm. One of the plates is 36.4 μm thick and the remaining two are identical, each being 28.6 μm thick. In the studied spectral range, the retardances varied from 123.5° to 86.8° for the first plate and from 96.9° to 68° for each of the two other plates. Different procedures for performing the calibration of the plates and the special case of two identical plates are discussed.     

Influence of Cd addition on the phase transformations of β Cu–Al alloys

Cu–Al alloys in the hyper- and hypoeutectoid region with addition of Cd are studied. The phase transformation sequence during continuous heating and cooling has been followed by resistometry, calorimetry, and optical microscopy.     

Phase retrieval in two-wavelength DSSI using a combined filtering method

Phase retrieval in two-wavelength DSSI (digital speckle shearing interferometry) using a combined filtering method is proposed for small deformation derivative measurement. A simultaneous two-wavelength illumination and 3-CCD camera are employed in the experimental setup. The proposed method, which uses a two-wavelength technique does not require the conventional spatial phase unwrapping and has the advantage of good noise suppression for phase retrieval. Experimental results obtained show that using the proposed combined filtering method sensitivity similar to the single wavelength technique can be achieved.     

条纹图象的数字化自动分析处理技术之二:相位分析法

相位分析法是目前光学条纹图象数字化自动分析处理中的最重要方法之一。本文较全面地介绍了相位分析技术,并对相位分析的关键技术--相位的滤波和解包络方法做了重点说明。文中给出了相位解包络的实例并讨论了图象数字化自动分析处理技术的实际应用状况。     

Measurement of sub-surface delaminations in carbon fibre composites using high-speed phase-shifted speckle interferometry and temporal phase unwrapping

A high-speed phase-shifted speckle interferometer has been developed recently for studying dynamic events. Speckle interferograms are continuously recorded by a CCD camera operating at 1 kHz with temporal phase shifting carried out by a Pockels cell running at the same frequency. Temporal phase unwrapping through sequences of more than 1000 frames allows the determination of time-varying absolute displacement maps. This paper presents the application of this speckle interferometry system to the detection and measurement of sub-surface delamination defects in carbon fibre specimens. The influence of re-referencing the temporal phase unwrapping algorithm after different time intervals is analysed to reduce the random phase errors produced by speckle decorrelation and vibration. The performance of several phase-shifting algorithms to minimize the influence of the vibration noise caused by the vacuum pump used to load the specimen is also investigated.     

Phase structures and stability in barium titanate ferroelectric ultrathin films

Under taking into account both stress and surface effects, an extended Landau–Devonshire theory is developed to investigate the phase structures and ferroelectric stability in barium titanate ultrathin films. The phase diagrams of temperature-stress, film thickness-stress and polarization-film thickness are calculated. For the surface polarization smaller than the bulk, the paraelectric phase starts at temperature below the bulk Curie temperature under small stresses and the ferroelectric phases can be stabilized in the ultrathin films under large stresses. For the surface polarization larger than the bulk, the paraelectric phase appears at temperature above the bulk Curie temperature and the ferroelectricity can be sustained in the ultrathin films by the “superpolarized” surface layer.     

光折变相位型波带片

利用成象方法和光折变效应,在LiNbO₃:Fe晶体中成功地写入了光折变相位型波带片.其衍射效率可达到21%.该制作方法具有实时、简便等优点.在集成光学和光学信息处理中具有重要的应用前景.     

异核多脉冲实验的相位循环设计方法

本文介绍了异核多脉冲实验相位循环的设计方法.先分别设计两个不同核的相位循环编码行列,然后根据正交检测相位要求把两个列数相等的行列以并联方式结合起来,就可得异核多脉冲实验的相位循环.     

普通显微镜改装成相衬显微镜的一种新方法

本文提出了一种新的相衬显微镜的光路系统,这种系统非常适用于将普通显微镜改装成相衬显微镜。首先,叙述了相衬法的基本原理;接着提出了一种将相衬板置于物镜前方的相衬显微镜系统,并运用傅里叶光学证明了在非柯勒照明条件下在物镜前方确实存在物体的频谱面。这种相衬显微镜系统对于将普通显微镜改装成相衬显微镜来说,不仅简单实用,而且杂散光小,有利于提高灵敏度。     

In situ calibration of a Michelson type, speckle-shearing interferometer: Wobbling mirror effect

In situ calibration of piezoelectric transducers in a phase stepping, Michelson type, speckle-shearing interferometer can be affected by mirror wobbling introduced by the transducers. When this happens, a modulation of the curves employed for calibration can be readily detected in imaging systems with large apertures. A calibration method that takes into account the modulation of these curves is, therefore, essential to insure the required regularity of the phase steps. A computer model of speckle-shearing interferometry is used to deal with piezoelectric non-linearities and mirror wobbling in the interferometer, and to show how the calibration curves are affected when both phenomena are present. Computer simulated and experimental results validate the calibration technique advanced here.     

X射线相位成像的最佳衬度

根据Zernike相衬观察法的基本思想和Fresnel–Kirchhoff衍射理论,采用傅里叶变换和卷积处理,考虑到临床实际,利用振幅近似和相位缓变条件,将X射线经过生物组织产生的相位改变转换成强度分布.在所导出的理论公式的基础上,作出相位衬度和吸收衬度与物平面到像平面距离的关系曲线.分析得到X射线相位衬度成像的最佳物像距离,并通过微聚焦X射线成像装置对蟑螂成像的实验加以验证,其结果表明理论所预言的成像最佳位置符合度较高.     

Conversion from phase map to coordinate: Comparison among spatial carrier, Fourier transform, and phase shifting methods

For full-field phase measurement methods, many algorithms have been developed to extract a phase map from fringe image(s). Both phase wrapping and unwrapping algorithms have been extensively investigated by many researchers, but few papers can be found on how to calculate the coordinates of surface points from a phase map. This paper focuses on algorithms that show how a phase map can be used to calculate coordinates. Details are given for single image methods such as Fourier transform, spatial carrier methods, and multiple image methods like traditional phase-shifting methods. Algorithms that can be used to convert a phase map to coordinates and some issues related to these conversion algorithms are discussed. An artifact is measured using these phase measurement methods. The results show that using the correct algorithm to convert a phase map to coordinates is a key to obtaining accurate measurement results.     

Anisotropy of two-photon absorption in gallium selenide at 1064 nm

The Bridgman method is used to grow single crystals of ε-GaSe. The two-photon absorption (TPA) coefficient β was measured for especially un-doped crystals at room temperature for the ordinary o-ray (β_⊥) and extraordinary e-ray (β_∥) using single-wavelength excitation by a Nd:YVO₄ laser at 1.064 μm with a pulse duration of 10 ps and a repetition rate of 81 MHz. No large anisotropy was observed for the TPA coefficients between the two geometries. The TPA coefficients were found to be β_⊥ = 1.07 × 10⁻⁹ cm/W and β_∥ = 1.88 × 10⁻⁹ cm/W. It was found that doping slightly increases the TPA coefficient. The value of the TPA for crystals doped with 0.5 at.% of Tl is β_⊥ = 7.56 × 10⁻⁹ cm/W.     

Self-marking phase-stepping electronic speckle pattern interferometry (ESPI) for determining a phase map with least residues

Different from most of the electronic speckle pattern interferometry (ESPI) approaches, which involve the correlation fringe formulation followed by speckle noise elimination (or filtering), to develop a wrapped phase map, this study adopts the approach proposed by Creath in 1985 instead. However, Creath's approach is so critical of its applying interferograms, the influence of which is dependent on the robustness of the applied phase-shifting algorithm and the accuracy of the phase shifter. The self-marking technique proposed by Huang and Chou in 2000 is adopted herein to help overcome any unfavorable conditioning, including hysteresis, nonlinearity or plane tilting, of the pieozo-electrical transducer (PZT), to enable the successful implementation of the Creath's method. With its help, the whole phase stepping history of a practical work (i.e., an ESPI experiment for the present study) can be fully recorded and monitored. Thus, the required phase stepping frames can be accordingly decided and their further calculation will yield a phase map with least number of residues.     

二维电子光谱仪器研制与指标分析

介绍了一种利用光栅分光,光子回波矩阵构型的二维光谱实验装置．利用快速,高灵敏度的EMCCD对信号进行外差单脉冲测量．并对仪器的指标进行了检测,30 min内12路相干光的相位抖动均方差达到λ/200,19 min内染料IR140溶液外差回波信号的稳定性达到λ/90,通过移动平移台测量了仪器的光谱准确性,相移偏差均方差为λ/90,对平移台移动不均匀导致的光谱失真进行了数值模拟．另外在位相调整时为解决样品泵浦探测信号有干涉的问题,提出了相位移动的方法．将散射信号扣除,大大提高了位相调整的准确性．对染料IR144溶液,光合蛋白色素复合体B820的测量与文献一致．     

Phase-difference amplification using a Sagnac interferometer

In this paper, we describe a new method for achieving phase-difference amplification, which is quick and convenient, operates in real time, and requires no photographic steps. Magnification factors of 2, 4 or 6 are achieved easily in one step. Because the system operates in real time, phase stepping may be applied to extract the amplified phase distributions. Our method is a variation on longitudinally reversed shearing interferometry, using first- or higher-order diffraction from a grating (hologram) which is in fact the interferogram of the wavefront under test. The grating is derived from a standard two-beam interferometer which is phase-stepped, and displayed in real time on a spatial light modulator in the phase-difference amplification setup. It is illuminated by the two output beams from a Sagnac interferometer, similar to the set up used by (Barnes et al. Barnes TH, Eiju T, Matsuda K. Appl Opt 1986; 25:1864). for spectral resolution enhancement, and a phase-amplified fringe pattern is obtained by spatial filtering using a Fourier transform lens. We demonstrate operation of the phase amplifier and show amplified phase maps retrieved by phase-stepping. We believe this is the first time that real-time phase amplification without photographic steps and with phase stepping has been demonstrated.