Electron impact,electron capture negative ionization and positive chemical ionization mass spectra of organophosphorus flame retardants and plasticizers

Phosphate esters are important commercial products that have been used both as flame retardants and as plasticizers. To analyze these compounds by gas chromatographic mass spectrometry, it is important to understand the mass spectra of these compounds using various ionization modes. This paper is a systematic overview of the electron impact (EI), electron capture negative ionization (ECNI) and positive chemical ionization (PCI) mass spectra of 13 organophosphate esters. These data are useful for developing and optimizing analytical measurements. The EI spectra of these 13 compounds are dominated by ions such as H₄PO₄⁺, (M ? Cl)⁺, (M ? CH₂Cl)⁺ or (M)⁺ depending on specific chemical structures. The ECNI spectra are generally dominated by (M ? R)^?. The PCI spectra are mainly dominated by the protonated molecular ion (M + H)⁺. The branching of the alkyl substituents, the halogenation of the substituents and, for aromatic phosphate esters, ortho alkylation of the ring are all significant factors controlling the details of the fragmentation processes. EI provides the best sensitivity for the quantitative measurement of these compounds, but PCI and ECNI both have considerable qualitative selectivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Investigation on the Stability of the Dispersion System of Cross-Linked Polyacrylamide Microspheres

The salt resistance, temperature resistance, and shear stability of a cross-linked polyacrylamide microsphere system are studied by microfiltration, light diffraction analysis, and optical microscopy. The results show that other conditions being equal, the particle diameter of cross-linked polyacrylamide microspheres decreases with increased NaCl concentration. When NaCl concentration is lower than 10,000 mg/L, its effect on the plugging performance of a cross-linked polyacrylamide microsphere system in regard to the nuclear pore membrane is weak in comparison with a linked polymer solution, but the former system has better salt tolerance. Particle diameter decreases with increased swelling temperature. When the swelling temperature is below 90°C, its effect on the plugging performance of the cross-linked polyacrylamide microsphere system in regard to nuclear pore membrane is weak in comparison with the linked polymer solution, but has better temperature tolerance. Particle size shows little change, with shearing rate being increased, while the shape remains about the same and the effect of shearing on the plugging performance of the cross-linked polyacrylamide microsphere dispersion system in regard to the nuclear pore membrane is weak in comparison with the linked polymer solution, but has better shear stability. The salt tolerance, temperature tolerance, and shear stability of microspheres are associated with a particular cross-linked structure.     

宽离子能量检测范围垂直引入反射式飞行时间质谱仪的研制

本实验室研制了国内首台宽离子能量检测范围飞行时间质谱仪。仪器采用紧凑式电子轰击源设计,配合离子透镜系统有效的调制离子流,飞行时间质量分析器采用了离子垂直引入式,双场加速和双场反射以及大尺寸MCP检测装置设计。仪器单离子信号半峰宽约2 ns,仪器分辨率优于1600FWHM,检测实际样品质量范围为1~127 amu(仪器理论质量检测上限优于800 amu),可检测离子能量范围优于2个数量级(3~140 eV)。若该TOF质量分析器与短瞬高压脉冲放电离子源耦合联用,可广泛应用于高能离子束的快速检测,如真空阴极放电对制备薄膜、离子注入材料的表征,导电材料的离子电荷态分布以及离子扩散速度的测定等。     

Shear‐induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N‐alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X‐ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50°C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at “Plateau borders” with three or more sides. Where walls meet three at a time, they do so at approximately 120° angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self‐organised monodomains, as observed in these systems, is expected to play an important role in potential applications.     

Concerted effect of boron and porosity on shear thickening behavior of hybrid mesoporous silica dispersions

In the present work, the influence of porosity and boron on shear thickening behavior of hybrid mesoporous silica has been studied. Three different levels of boron modification were performed by varying the molar composition of boric acid viz., 1.5 mmol, 2.5 mmol, and 3.5 mmol in a co-condensation approach. The incorporation of boron in mesoporous silica network was confirmed by various techniques such as Fourier transform infra-red (FTIR), and ¹¹B solid- state nuclear magnetic resonance (NMR) spectroscopy. The morphology and particle size were confirmed by using scanning and transmission electron microscopy. To evaluate the effect of boron and porosity on the shear thickening behavior, dispersions were prepared from mesoporous boron- modified silica (MSiB), control mesoporous silica (MSi), non-porous boron-modified silica (SiB), and control non-porous silica (Si) in polyethylene glycol. The shear thickening behavior was studied using steady shear rheology. The dispersion prepared from different loadings of synthesized MSiB containing 1.5 mmol boron showed more than 16 times increase in viscosity (657.7 Pa.s) compared to that of MSi (39.2 Pa.s) at a fairly low volume fraction (φ = 0.15) of silica. It is expected that the highly ordered mesoporous architecture of hybrid silica has improved the interaction between the particle and the dispersing medium through hydrogen bonding. The porous morphology of the hybrid mesoporous silica as well as the incorporation of boron in the silica network favors the formation of a frictional contact network, and a transition from continuous shear thickening (CST) to discontinuous shear thickening (DST) behavior was observed. Therefore, silica prepared via incorporation of boron as well as porosity can be material of interest in variety of applications, for example, soft body armors, sporting goods, and shear thickening electrolytes for high impact resistant batteries.     

Surface modification of PBO fibers with 2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane in supercritical carbon dioxide for enhancing interfacial strength

PBO fiber is one of the most promising reinforcements in resin matrix composite because of its excellent mechanical properties. However, the inert and smooth surfaces make it the poor interface adhesion with resin matrix, which seriously limits the application in composites. In this article, we report a method to modify the surface of PBO fibers with 2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane（BisAPAF）in supercritical CO₂ to enhance interfacial properties. Chemical structures, surface elemental composition and functional groups, and surface morphology were characterized by FT-IR spectrometer, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM), respectively. The mechanical properties of the samples were tested by a tensile tester. Static contact angle and microdebonding tests were used to characterize the wetting ability and interfacial shear strength (IFSS) of the fiber and epoxy resin. The results showed that the BisAPAF could be solved in scCO₂ and introduced more groups, –NH₂, –OH, and –CF₃ on the fiber surface, resulting in the mechanical properties and the wettability of PBO fiber slightly improved. Moreover, the fiber surface roughness was also increased obviously. The IFSS between the modified PBO fiber and epoxy resin increased from 8.18 MPa to 31.4 MPa when the treating pressure was 14 MPa. In general, the method to modify PBO fibers surface using BisAPAF in scCO₂ can effectively improve their interfacial properties.     

Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.     

Synthesis of linseed oil based biodegradable homo and copolymers: role as multifunctional greener additives in lube oil

Abstract

Homopolymer of linseed oil and its four copolymers with styrene, 1-decene, isodecyl acrylate and octyl acrylate, respectively, have been synthesized in this present context. The prepared polymers are characterized by NMR and FTIR spectroscopy. The molecular weights have been measured by gel permeation chromatography. Their effectiveness as pour point depressant (PPD), viscosity index improver (VII) and their shear stability in terms of permanent shear stability index have been evaluated in lube oil. The copolymers acted as better PPDs than the homopolymer whereas the homopolymer of linseed oil excelled as VII. Further it was observed that all the prepared polymers were stable enough under severe mechanical shear.     

长链支化聚丙烯的非线性流变行为

通过大幅振荡剪切试验方法, 研究了长链支化聚丙烯的非线性流变学行为, 揭示了长链支化结构与非线性黏弹响应的关系. 利用傅里叶变换流变学方法得到试样的三次倍频相对振幅I_3/1与应变的标度关系, 用于界定线性聚丙烯和长链支化聚丙烯非线性流变行为的差异, 并定义了非线性系数来量度长链支化程度. 在高应变下, I_3/1与应变的变化关系可以进一步描述长链支化在非线性流场下的特性, 并得到了长链支化程度与其非线性响应之间的变化关系. 通过应力波的Lissajous曲线分解, 发现了环内和环间黏弹性的差异, 长链支化结构在大应变流场下的非线性黏弹性响应弱于线性结构, 支化程度越高非线性响应越弱.