Plasma Treatment of Polymers

Abstract

Plasma treatment of polymers encompasses a variety of plasma technologies and polymeric materials for a wide range of applications and dates back to at least the 1960s. In this article we provide a brief review of the United States patent literature on plasma surface modification technologies and a brief review of the scientific literature on investigations of the effects of plasma treatment, the nature of the plasma environment, and the mechanisms that drive the plasma–surface interaction. We then discuss low‐radio‐frequency capacitively coupled nitrogen plasmas and their characteristics, suggesting that they provide significant plasma densities and populations of reactive species for effective plasma treatments on a variety of materials, particularly when placing the sample surface in the cathode sheath region. We further discuss surface chemical characterization of treated polymers, including some results on polyesters treated in capacitively coupled nitrogen plasmas driven at 40 kHz. Finally, we connect plasma characterization with surface chemical analysis by applying a surface sites model to nitrogen uptake of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) treated in a 40 kHz nitrogen plasma. This example serves to suggest an interesting practical approach to comparisons of plasma treatments. In addition, it suggests an approach to defining the investigations required to conclusively identify the underlying treatment mechanisms.     

Ein Vergleich zwischen radioaktiver Markierung und Indikator-Aktivierungsanalyse bei der Messung von Verweilzeitspektren

An VK-Z-Rohren zur Herstellung von Polyamid wurden Verweilzeitspektren mit der Methode der radioaktiven Markierung und der Methode der Indikatoraktivierungsanalyse gemessen. Die nach den beiden Methoden ermittelten Verweilzeitspektren werden miteinander verglichen. Die Übereinstimmung der Verweilzeitspektren wird durch Gegenüberstellung der statistischen Momente und durch einen Test nach Kolmogoroff-Smirnov geprüft. Es wird der experimentelle Aufwand beider Verfahren diskutiert und eine Fehlerabschätzung durchgeführt.     

旋转滑动弧氩等离子体裂解甲烷制氢

采用切向气流和磁场协同驱动的旋转滑动弧氩等离子体,先通过光谱分析法计算了其电子温度和电子密度,了解其物理特性,将其应用于甲烷裂解制氢,研究了进气流量和CH_4/Ar比对反应效果的影响。结果表明,该滑动弧系统电子温度为1.0-2.0 e V,电子密度高达1015cm~(-3),是介于热与低温等离子体之间的一种等离子体形式,具有独特的物理特性,可以在达到较高反应效率的同时,保持较大的处理量;在CH_4裂解制氢实验中,CH_4转化率可达22.1%-70.2%,并随进气流量和CH_4/Ar比的增大均逐渐降低;H_2选择性为21.2%-61.2%,并随进气流量的增大先基本不变后有所增大,随CH_4/Ar比的增大逐渐降低;与应用于甲烷裂解的不同形式的低温等离子体对比(如微波、射频、介质阻挡放电等)可以发现,旋转滑动弧在获得较高甲烷转化率、较高H_2选择性和较低制氢能耗的同时,还可以保持较大的处理量,即进气流量可达6-20 L/min。     

Well‐controlled ATRP of 2‐(2‐(2‐azidoethyoxy)ethoxy)ethyl methacrylate for high‐density click functionalization of polymers and metallic substrates

The combination of atom transfer radical polymerization (ATRP) and click chemistry has created unprecedented opportunities for controlled syntheses of functional polymers. ATRP of azido‐bearing methacrylate monomers (e.g., 2‐(2‐(2‐azidoethyoxy)ethoxy)ethyl methacrylate, AzTEGMA), however, proceeded with poor control at commonly adopted temperature of 50 °C, resulting in significant side reactions. By lowering reaction temperature and monomer concentrations, well‐defined pAzTEGMA with significantly reduced polydispersity were prepared within a reasonable timeframe. Upon subsequent functionalization of the side chains of pAzTEGMA via Cu(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) click chemistry, functional polymers with number‐average molecular weights (M_n) up to 22 kDa with narrow polydispersity (PDI < 1.30) were obtained. Applying the optimized polymerization condition, we also grafted pAzTEGMA brushes from Ti6Al4 substrates by surface‐initiated ATRP (SI‐ATRP), and effectively functionalized the azide‐terminated side chains with hydrophobic and hydrophilic alkynes by CuAAC. The well‐controlled ATRP of azido‐bearing methacrylates and subsequent facile high‐density functionalization of the side chains of the polymethacrylates via CuAAC offers a useful tool for engineering functional polymers or surfaces for diverse applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1268–1277     

Quantification of Noncovalent Interactions in Azide–Pnictogen, –Chalcogen,and –Halogen Contacts

The noncovalent interactions between azides and oxygen-containing moieties are investigated through a computational study based on experimental findings. The targeted synthesis of organic compounds with close intramolecular azide–oxygen contacts yielded six new representatives, for which X-ray structures were determined. Two of those compounds were investigated with respect to their potential conformations in the gas phase and a possible significantly shorter azide–oxygen contact. Furthermore, a set of 44 high-quality, gas-phase computational model systems with intermolecular azide–pnictogen (N, P, As, Sb), –chalcogen (O, S, Se, Te), and –halogen (F, Cl, Br, I) contacts are compiled and investigated through semiempirical quantum mechanical methods, density functional approximations, and wave function theory. A local energy decomposition (LED) analysis is applied to study the nature of the noncovalent interaction. The special role of electrostatic and London dispersion interactions is discussed in detail. London dispersion is identified as a dominant factor of the azide–donor interaction with mean London dispersion energy-interaction energy ratios of 1.3. Electrostatic contributions enhance the azide–donor coordination motif. The association energies range from −1.00 to −5.5 kcal mol⁻¹.     

Lewis Acids as Activators in CBS‐Catalysed Diels–Alder Reactions: Distortion Induced Lewis Acidity Enhancement of SnCl4

The effect of several Lewis acids on the CBS catalyst (named after Corey, Bakshi and Shibata) was investigated in this study. While ²H NMR spectroscopic measurements served as gauge for the activation capability of the Lewis acids, in situ FT‐IR spectroscopy was employed to assess the catalytic activity of the Lewis acid oxazaborolidine complexes. A correlation was found between the Δδ(²H) values and rate constants k_DA, which indicates a direct translation of Lewis acidity into reactivity of the Lewis acid–CBS complexes. Unexpectedly, a significant deviation was found for SnCl₄ as Lewis acid. The SnCl₄–CBS adduct was much more reactive than the Δδ(²H) values predicted and gave similar reaction rates to those observed for the prominent AlBr₃–CBS adduct. To rationalize these results, quantum mechanical calculations were performed. The frontier molecular orbital approach was applied and a good correlation between the LUMO energies of the Lewis acid–CBS–naphthoquinone adducts and k_DA could be found. For the SnCl₄–CBS–naphthoquinone adduct an unusual distortion was observed leading to an enhanced Lewis acidity. Energy decomposition analysis with natural orbitals for chemical valence (EDA‐NOCV) calculations revealed the relevant interactions and activation mode of SnCl₄ as Lewis acid in Diels–Alder reactions.     

Spin State Tunes Oxygen Atom Transfer towards FeIVO Formation in FeII Complexes

Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [Fe^II(CH₃CN)₂L](SbF₆)₂ ( [1](SbF₆)₂ and [2](SbF₆)₂ ) and [Fe^II(CF₃SO₃)₂L] ( [1](OTf)₂ and [2](OTf)₂ ( 1 , L=^Me,HPytacn; 2 , L=^nP,HPytacn; ^R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu₄NIO₄ to form the corresponding [Fe^IV(O)(CH₃CN)L]²⁺ ( 3 , L=^Me,HPytacn; 4 , L=^nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl⁻ as entering ligand, which indicates that formation of [Fe^IV(O)(CH₃CN)L]²⁺ is kinetically controlled by substitution in the starting complex to form [Fe^II(IO₄)(CH₃CN)L]⁺ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species.     

A non-conforming monolithic finite element method for problems of coupled mechanics

In this study, a Lagrange multiplier technique is developed to solve problems of coupled mechanics and is applied to the case of a Newtonian fluid coupled to a quasi-static hyperelastic solid. Based on theoretical developments in [57], an additional Lagrange multiplier is used to weakly impose displacement/velocity continuity as well as equal, but opposite, force. Through this approach, both mesh conformity and kinematic variable interpolation may be selected independently within each mechanical body, allowing for the selection of grid size and interpolation most appropriate for the underlying physics. In addition, the transfer of mechanical energy in the coupled system is proven to be conserved. The fidelity of the technique for coupled fluid–solid mechanics is demonstrated through a series of numerical experiments which examine the construction of the Lagrange multiplier space, stability of the scheme, and show optimal convergence rates. The benefits of non-conformity in multi-physics problems is also highlighted. Finally, the method is applied to a simplified elliptical model of the cardiac left ventricle.     

A model for the stabilization of atomic hydrogen centers in borate glasses

A previously proposed model describing the trapping site of the interstitial atomic hydrogen in borate glasses is analyzed. In this model the atomic hydrogen is stabilized at the centers of oxygen polygons belonging to B–O ring structures in the glass network by van der Waals forces. The previously reported atomic hydrogen isothermal decay experimental data are discussed in the light of this microscopic model. A coupled differential equation system of the observed decay kinetics was solved numerically using the Runge Kutta method. The experimental untrapping activation energy of 0.7×10⁻¹⁹ J is in good agreement with the calculated results of dispersion interaction between the stabilized atomic hydrogen and the neighboring oxygen atoms at the vertices of hexagonal ring structures.     

Straightforward preparation of polymers based on oligodimethylsiloxane and alkylamine

Novel oligodimethylsiloxane‐based polymers with alkyl side chain were synthesized in bulk by step‐growth polymerization between α,ω‐glycidyl ether oligodimethylsiloxanes and a monoalkylamine in the absence of catalyst and at temperatures ranging between 80 and 180 °C. Matrix assisted laser desorption ionization time of flight results attested for the high reactivity of the amine functions with the glycidyl groups and revealed that the main polymer structure was (A₂B₂)_n type with alkyl moieties as dangling chains. No etherification was observed during the reaction even at high temperatures and the nature of the end groups strongly depended on the molar ratio between glycidyl and amine functions. Polymerization reactions were followed by ¹H NMR and the kinetics of the glycidyl‐amine reaction pointed out the dependence of temperature, molar ratio, and the molar mass of the oligodimethylsiloxane. High conversion rates were obtained, especially with the lowest molecular weight oligodimethylsiloxane. An optimized kinetic model derived from the Horie's model was discussed and permitted to correctly fit the experimental data. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012