Generation of excess charge carriers in molecularly doped polymers by electron-beam irradiation

The processes of generation and transport of excess charge carriers in molecularly doped polycarbonate and polystyrene were experimentally studied at room temperature. The polymers were ionized by 7-and 50-keV electrons. The radiation-chemical yield of free ions was determined by means of the universal method based on the combination of the time-of-flight technique in two carrier generation modes (surface and bulk generation) with the measurement of nonsteady-state conductivity. It was shown that the radiation-chemical yield of free ions under irradiation by 7-keV electrons is almost the same as that in the case of 50-keV electrons, despite the substantially different values of the linear energy transfer for these electrons.     

Theoretical description of electron transport in homo-and molecularly doped polymers

The general aspects of electron transport in disordered organic media (polymers, organic glasses, molecularly doped polymers) are considered. A critical analysis of experimental results and their interpretation in terms of basic theoretical models and experimental methods used in research in this area is presented. Particular attention is given to the comparative analysis of the data obtained by the time-of-flight technique and in studying the radiation conductivity of polymers, in particular, to the possibility of describing the conductivity data in terms of the Gaussian disorder model.     

Positive and negative ion desorption from PVC as studied by electron stimulated desorption

With the aim of performing time-of-flight studies of electron stimulated ion desorption (ESID) from polymers bombarded with a variable energy electron beam source, an experimental set-up including a homemade time-of-flight mass spectrometer has been developed for positive and negative ion analysis. This system uses as a trigger for the experiments either the pulsed electron beam or the pulsed (positive/negative) extraction high voltage applied to the sample. Results for both positive and negative ion desorption from poly(vinyl chloride) (PVC) obtained in ESID measurements with these two different modes of operation will be presented and discussed.     

Automated multiple-layer spotting for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of synthetic polymers utilizing ink-jet printing technology

Recently, a new multiple-layer matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample spotting technique for poly(ethylene glycol), offering improved analysis possibilities, was described. In this contribution the application of ink-jet printing to automated, multiple-layer MALDI-TOFMS sample preparation of synthetic polymers is presented, allowing accurate deposition of matrix, additive and analyte solutions. The new sample preparation technique was evaluated for poly(ethylene glycol) as well as poly(methyl methacrylate) standards, and optimized settings for both synthetic polymers have been obtained.     

Generation and transport of charge carriers in polyvinylcarbazole

The processes of generation and transport of excess charge carriers in polyvinylcarbazole at room temperature and at 353 K were experimentally studied. The polymer was charged with pulses of electrons at energies of 7 and 50 keV, which differed in both linear energy transfer and track structure. A universal method of investigation based on the combination of the time-of-flight technique in the both (surface and bulk) modes with the measurement of radiation-induced conductivity was used. The radiation-chemical yield of free charges was measured using two independent procedures. It was shown that the radiation chemical yield of free charges at 293 K was somewhat smaller for 7-keV than for 50-keV electrons; in the latter case, G = 1.1 in an electric field of 2 × 10⁷ V/m. The parameters of the generalized physical model were determined for polyvinylcarbazole.     

Direct chemical analysis of uv laser ablation products of organic polymers by using selective ion monitoring mode in gas chromatography/mass spectrometry

Trace quantities of laser ablated organic polymers were analyzed by using commercial capillary column gas chromatography/mass spectrometry; the instrument was modified so that the iaser ablation products could be introduced into the capillary column directly and the constituents of each peak in the chromatogram were identified by using a mass spectrometer. The present study takes advantage of the selective ion monitoring mode for significantly improving the sensitivity of the mass spectrometer as a detector, which is critical in anatyzing the trace quantities and confirming the presence or absence of the species of interest in laser ablated polymers. The initial composition of the laser ablated polymers was obtained by using an electron impact reflectron time-of-flight mass spectrometer and the possible structure of the fragments observed in the spectra was proposed based on the structure of the polymers.     

Evaluation of a new multiple-layer spotting technique for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of synthetic polymers

A new multiple-layer matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample-spotting technique is described. This fast and easy technique was evaluated with poly(ethylene glycol) (PEG) standards and optimized conditions for these synthetic polymers were obtained. PEGs up to 35 kDa were detectable with this approach and single monomer resolution was observed up to 20 kDa. The spotting was performed using a multiple-layer approach, which offers the capability of complex sample preparation without the requirement of premixing the different matrix, analyte and doping salt solutions. The technique reduces the time required for sample preparation and offers high flexibility with respect to sample composition and solvents utilized for the crystallization of the compounds. The technique is thus perfectly suited for applications in combinatorial material research.     

The universal nature of dispersive transport in molecularly doped polymers

The time-of-flight technique is used to measure hole mobility in molecularly doped polycarbonate and polystyrene that contain both polar and weakly polar additives. The two versions of the technique with the bulk and surface generation of charge carriers under small-signal conditions are employed. Numerical calculations show that the time dependence of the transient-current curves obtained with the first version of the technique is in agreement with the theory of multiple trapping for an exponential energy distribution of traps. In the case of time-of-flight curves with surface generation, the run of the post-transit branch is likewise consistent with the theory, whereas this consistency is often violated for the pretransit branch of the curves. This result is due to the effect of the defective surface layer of a polymer, which is not taken into account in numerical calculations. The results show that the hole transport in the studied molecularly doped polymers is dispersive. An increase in the polarity of the polymer matrix and the dopant drastically decreases the hole mobility and, at the same time, increases its field and temperature dependence.     

基质辅助光解吸电离飞行时间质谱测定双二氮杂萘酮苯醚芳香聚合物

基质辅助光解吸电离飞行时间质谱测定双二氮杂萘酮苯醚芳香聚合物;MALDI-TOF MS     

基质辅助激光解吸与离子化时间飞行质谱在高分子研究中的应用

对基质辅助激光解吸与离子化时间飞行质谱的发展历程和基本原理作了简要介绍,对这一分析技术在高分子研究中的应用进行了全面的综述和展望。本文表明,ＭＡＬＤＩ－ＴＯＦ－ＭＳ能快速准确地测定窄分布高分子的分子量,可测分子是一达１５０００００,所得平均分子量值及分子量分布指数与ＧＰＣ等常规方法相符;能用于高分子末端基的检测,从而推断聚合反应机理;也能用于共聚反应与共聚物结构的分析;另外,还能从分子量分布理到自     

Laser desorption/ionization on the layer of graphene nanoparticles coupled with mass spectrometry for characterization of polymers

A novel method for the characterization of polymers by laser desorption/ionization on the layer of graphene nanoparticles coupled with time-of-flight mass spectrometry was demonstrated. Various polymers including polypropylene glycol, polystyrene and polymethyl methacrylate with average molecular weights from 425 to 3500 Da were analyzed.     

Hyperbranched Polyborosiloxanes: Non-traditional Luminescent Polymers with Red Delayed Fluorescence

Non-traditional fluorescent polymers have attracted significant attention for their excellent biocompatibility and diverse applications. However, designing and preparing non-traditional fluorescent polymers that simultaneously possess long emission wavelengths and long fluorescence lifetime remains challenging. In this study, a series of novel hyperbranched polyborosiloxanes (P1–P4) were synthesized. As the electron density increases on the monomer diol, the optimal emission wavelengths of the P1–P4 polymers gradually red-shift to 510, 570, 575, and 640 nm, respectively. In particular, P4 not only exhibits red emission but also demonstrates delayed fluorescence with a lifetime of 9.73 μs and the lowest critical cluster concentration (1.76 mg/mL). The experimental results and theoretical calculations revealed that the synergistic effect of dual heteroatom-induced electron delocalization and through-space O⋅⋅⋅O and O⋅⋅⋅N interaction was the key factor contributing to the red-light emission with delayed fluorescence. Additionally, these polymers showed excellent potential in dual-information encryption. This study provides a universal design strategy for the development of unconventional fluorescent polymers with both delayed fluorescence and long-wavelength emission.     

基质辅助激光解析电离飞行时间质谱分析合成聚合物样品制备的研究进展

基质辅助激光解析电离飞行时间质谱（MALDI-TOF-MS）在合成聚合物的表征手段中具有不可替代的优点,可以提供聚合物的质量分布、嵌段长度、端基等信息.但由于合成聚合物的离子化效率通常不佳,因此样品制备是分析成功的关键.从基质、基质添加剂以及混样方式3个方面综述了MALDI-TOF质谱分析合成聚合物样品制备的研究进展.     

Naphthalene-Diimide-Based Ionenes as Universal Interlayers for Efficient Organic Solar Cells

Self-doping ionene polymers were efficiently synthesized by reacting functional naphthalene diimide (NDI) with 1,3-dibromopropane ( NDI-NI ) or trans-1,4-dibromo-2-butene ( NDI-CI ) via quaternization polymerization. These NDI-based ionene polymers are universal interlayers with random molecular orientation, boosting the efficiencies of fullerene-based, non-fullerene-based, and ternary organic solar cells (OSCs) over a wide range of interlayer thicknesses, with a maximum efficiency of 16.9 %. NDI-NI showed a higher interfacial dipole (Δ), conductivity, and electron mobility than NDI-CI , affording solar cells with higher efficiencies. These polymers proved to efficiently lower the work function (WF) of air-stable metals and optimize the contact between metal electrode and organic semiconductor, highlighting their power to overcome energy barriers of electron injection and extraction processes for efficient organic electronics.     

Electron transport of holes in molecularly doped polycarbonate and its radiation-induced conductivity

The salient features of charge transport in a typical molecularly doped polymer (polycarbonate + 30 wt % DEH hydrazone) were studied by time-of-flight and nonsteady-state radiation-induced conductivity measurements. It was shows that the mobility of holes (major carriers) is due to dispersive transport in the temperature range 296–353 K covering the glass transition temperature at an observation time of up to a few seconds. The appearance of a plateau on the current transient, presumably manifesting the establishing of quasiequilibrium (Gaussian) transport, is the artifact of the time-of-flight technique when the charge carrier generation takes place at the sample surface. All of the obtained results can be satisfactorily rationalized in terms of the Rose-Fowler-Weisberg model with a uniform set of parameters of the model. Such an approach is compatible with the basic concepts of the radiation chemistry of condensed phase (the Onsager theory and the Langevin recombination mechanism), structural features of a disordered medium (transport zone, structural traps), and rotational diffusion of small molecules or their molecular groups in vitrified polymers.     

Size Exclusion Chromatography of Poly(vinylpyrrolidone)

Abstract

Poly(vinylpyrrolidone) and poly(ethylene oxide) separate by hydrodynamic volume on Toyo Soda TSK-PW columns in a mixed solvent mobile phase of 50:50 (v/v) MeOH/H₂O containing 0.1M LiNO₃. From this separation a single universal calibration curve based on hydrodynamic volume [η]M can be obtained. Accurate weight average molecular weights of PVP were obtained by both SEC/LALLS and universal calibration showing good agreement between the two methods. SEC/LALLS overestimates the number average molecular weight for broad distribution polymers due largely to the lack of sensitivity of the LALLS detector to the low molecular weight portion of the polymers, while the universal calibration method slightly underestimates the number average molecular weight as compared to osmometric values.     

Laser mass spectrometry: an overview of techniques,instruments and applications

Lasers have been used to produce intact molecular ions and structurally informative fragment ions of otherwise intractable biomolecules for examination by mass spectrometry. While laser microprobes have been used for this purpose, this paper focusses on other instrumental configurations, which require less focussed laser beams and which record ions that are produced by mechanisms which can be described thermodynamically. The time-of-flight and Fourier-transform ion-cyclotron resonance mass spectrometers emerge as the most suitable for use with pulsed laser desorption. Classes of compounds which are amenable to the technique include industrial polymers and carbohydrates.     

Radiation-induced conductivity in polymers during long-term irradiation

Radiation-induced conductivity (RIC) in polystyrene, poly(ethylene terephthalate), polyvinylcarbazole, and low-density polyethylene during long-term (to 3.6 × 10³ s) irradiation with 50-keV electrons (dose rate of 6–830 Gy/s) was experimentally and theoretically studied. It was shown that the nonmonotonic RIC kinetics in the polymers is a direct consequence of the generation and the subsequent transport of charge carriers in them in the presence of traps distributed over a broad energy range almost according to the exponential law. This phenomenon has no relation to degradation and crosslinking processes that occur in irradiated polymers. The nonmonotonic RIC kinetics in polymers is a universal phenomenon, and it is described satisfactorily in terms of the Rose-Fowler-Vaisberg model.     

The evolution of viscoelasticity near the gel point of end-linking poly(dimethylsiloxane)s

The linear viscoelasticity of polymers near the gel point can be described by two scaling laws. The material at the gel point has a power-law linear viscoelastic relaxation modulus, and the relaxation exponent has been found to vary with the composition of the precursor materials, i.e., it is not universal for gelation. A second scaling law describes the evolution of the linear viscoelastic properties through the gel point. The rate of change of the dynamic mechanical modulus/viscosity is observed to scale as a power-law function of frequency. This power-law function defines a dynamic critical exponent, and this has been found to be independent of precursor composition for end-linking poly(dimethylsiloxane) polymers and equal to κ = 0.21 ± 0.02. This exponent may be a universal measure of gelation. The technique of Time Resolved Mechanical Spectroscopy is used to observe the evolution of linear viscoelastic properties of crosslinking polymers in situ in the rheometer. A stretched exponential relaxation modulus describes the evolution of mechanical properties in the vicinity of the gel point very well. The exponents which characterize the divergence of the zero-shear viscosity and the equilibrium modulus are not universal, since they are related to the relaxation exponent and the dynamic critical exponent.     

Measurements of total cross sections for electron scattering from helium and argon

A time-of-flight (TOF) electron spectrometer has been used to measure absolute total cross sections (TCS) scattered from helium and argon over the energy range from 1 to 50 eV. The TOF spectrometer and experimental procedure are described briefly, and experimental results are presented together with associated errors. The results are found to be in good agreement with other experimental and theoretical data.