Spectroscopic analysis and in situ monitoring of impregnation and extraction of polymer films and powders using supercritical fluids

A range of vibrational spectroscopic techniques are used to monitor supercritical fluid extraction and impregnation of polymers. Impregnation processes of this type show potential as alternative apporaches to the synthesis of polymer based catalysts and new materials. Methods have been devised using conventional Fourier transform infrared spectroscopy for real time monitoring of the extraction and impregnation of polyethylene films using an organometallic complex, CpMn(CO)₃ (Cp = η⁵ ? C₅ H₅) as a spectroscopic probe. Both low and high density powdered polyethylene may be impregnated using supercritical carbon dioxide. The resulting materials are analysed using FTIR photoacoustic spectroscopy, diffuse reflectance infrared spectroscopy and FT Raman spectroscopy to probe both the impregnated bulk of the polymer and surface-coated material. © 1994 John Wiley & Sons, Inc.     

Quinone‐Rich Poly(dopamine) Magnetic Nanoparticles for Biosensor Applications

Novel core‐shell quinone‐rich poly(dopamine)–magnetic nanoparticles (MNPs) were prepared by using an in situ polymerization method. Catechol groups were oxidized to quinone by using a thermal treatment. MNPs were characterized by using X‐ray diffraction, X‐ray photoelectron spectroscopy, atomic force microscopy, magnetic force microscopy, UV/Vis, Fourier‐transform infrared spectroscopy, and electrochemical techniques. The hybrid nanomaterial showed an average core diameter of 17 nm and a polymer‐film thickness of 2 nm. The core‐shell nanoparticles showed high reactivity and were used as solid supports for the covalent immobilization of glucose oxidase (Gox) through Schiff base formation and Michael addition. The amount of Gox immobilized onto the nanoparticle surface was almost twice that of the nonoxidized film. The resulting biofunctionalized MNPs were used to construct an amperometric biosensor for glucose. The enzyme biosensor has a sensitivity of 8.7 mA M ^?1 cm^?2, a low limit of detection (0.02 mM ), and high stability for 45 days. Finally, the biosensor was used to determine glucose in blood samples and was checked against a commercial glucometer.     

Characterization of interfacial phenomena occurring during exposure of a thin copper film to an aqueous suspension of an acidic polysaccharide

A Fourier transform infrared spectrometer equipped with a cylindrical internal reflection element was used to sample the solid—liquid interface of a metallic copper film submerged in an aqueous acidic polysaccharide solution. The presence of a polysaccharide absorption band at 1050 cm⁻¹ in a water-subtracted spectrum supported previous spectroscopic data indicating polymer accumulation at the surface of the film. Firm binding of the polysaccharide to the surface after a 17-day exposure period was demonstrated by the retention of the 1050-cm⁻¹ absorption band in spectra obtained after gentle rinsing of the film surface with polymer-free water. The sampling technique also provided evidence which suggests that acidic polysaccharides, including the firmly bound exopolymers produced by adherent cells of a freshwater sediment bacterium, promoted deterioration of the copper film. Internal reflection Fourier transform infrared spectroscopy appeared to be a useful, nondestructive method to study the sorption of biomolecules to a solid metal surface submerged in an aqueous medium.     

High density cationic polymer brushes from combined “click chemistry” and RAFT‐mediated polymerization

A simple method for preparing cationic poly[(ar‐vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes was used by combined technology of “click chemistry” and reversible addition‐fragmentation chain transfer (RAFT) polymerization. Initially, silicon surfaces were modified with RAFT chain transfer agent by using a click reaction involving an azide‐modified silicon wafer and alkyne‐terminated 4‐cyanopentanoic acid dithiobenzoate (CPAD). A series of poly(VBTAC) brushes on silicon surface with different molecular weights, thicknesses, and grafting densities were then synthesized by RAFT‐mediated polymerization from the surface immobilized CPAD. The immobilization of CPAD on the silicon wafer and the subsequent polymer formation were characterized by X‐ray photoelectron spectroscopy, water contact angle measurements, grazing angle‐Fourier transform infrared spectroscopy, atomic force microscopy, and ellipsometry analysis. The addition of free CPAD was required for the formation of well‐defined polymer brushes, which subsequently resulted in the presence of free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface. In addition, by varying the polymerization time, we were able to obtain poly(VBTAC) brushes with grafting density up to 0.78 chains/nm² with homogeneous distributions of apparent needle‐like structures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Hierarchical fractal‐structured allophanate‐derived network formation in bulk polyurethane synthesis

Polyurethanes are among the most applied and researched polymers worldwide. Nevertheless, polyurethane synthesis is accompanied by a side‐reaction occurring between isocyanate groups and the secondary nitrogen of already formed urethane groups, leading to the formation of crosslinking allophanates. This inevitably requires the development of highly diagnostic direct analytical methods that can be performed in the solid state of the polymer. The present research focused on the direct investigation and diagnostic determination of the chemical structure formation in bulk polyurethane synthesis, using a combination of Fourier transform infrared and solid‐state ¹³C nuclear magnetic resonance analysis. Polyurethane syntheses were performed in bulk and designed as to obtain significantly strong diagnostic analytical measurements signals for the accurate identification of each of the investigated chemical structures. The present research results led to the conclusive analytical identification of allophanate formation during polyurethane synthesis. In addition, the occurrence of a new reaction mechanism was discovered in the present research. It was demonstrated in the present research that this newly described reaction occurs via the further reaction of the allophanate secondary nitrogen with an isocyanate group, the reaction creating a tertiary nitrogen and an additional reactive secondary nitrogen, and so on, in a consecutive step progression, leading to the formation of a 3‐dimensional hierarchical fractal‐like crosslinked polymeric structure. Solid‐state ¹³C nuclear magnetic resonance analysis results were highly consistent with the Fourier transform infrared results. The discovery of this newly described reaction can facilitate the optimization of industrial processes and potentially opens a new door to the development of a vast variety of biomedical and nanotechnology applications.     

Characterization of nano FeIII-tannic acid modified polyacrylate in controlled-release coated urea by Fourier transform infrared photoacoustic spectroscopy and laser-induced breakdown spectroscopy

Polyacrylate polymer (PA) has been widely applied in coating products for decades. Recently, it has been used in controlled-release fertilizers. Nano Fe^III-tannic acid modified PA (PA-Fe) provides a better nutrient controlled release performance than conventional PA. In this work, a preliminary database of molecular and elemental information about the polymer was obtained using FTIR-PAS (Fourier transform infrared photoacoustic spectroscopy) and LIBS (laser-induced breakdown spectroscopy), respectively. The PA-Fe polymer contained more hydrophobic groups (–CH₃) and fewer hydrophilic groups (–COOR, –COOH) than PA. More elements were detected for PA-Fe than PA. LIBS was useful to identify and classify PA and PA-Fe samples using principal component analysis. The combination of spectroscopic results and a film formation process model explained the lower nutrient release rate of PA-Fe. These results showed the strong analytical capabilities of FTIR-PAS combined with LIBS for identifying and characterizing modified PA.     

Synthesis of a novel methacrylic monomer iniferter and its application in surface photografting on crosslinked polymer substrates

(Methacryloyl ethylenedioxycarbonyl) benzyl N,N‐diethyldithiocarbamate (HEMA‐E‐In) was synthesized and used as a monomer iniferter to develop a novel, photopatternable grafting technology. This molecule functions as both a methacrylic monomer and a photoiniferter (photoinitiator–transfer agent–terminator). The structure of HEMA‐E‐In was characterized by ¹H NMR, Fourier transform infrared, and ultraviolet–visible spectroscopies. In the presence of the monomer iniferter, methyl methacrylate was polymerized by exposure to 365‐nm ultraviolet radiation, confirming the initiation capability of HEMA‐E‐In. After the copolymerization of HEMA‐E‐In into a methacrylate‐based polymer, attenuated total reflectance Fourier transform infrared spectra revealed that the photoiniferter functionality was present at the surface of this polymeric substrate. Photografting of poly(ethylene glycol) monomethacrylate monomer from the surface caused a significant change in the hydrophobicity of the surface as demonstrated by contact angle measurements. The novel monomer photoiniferter HEMA‐E‐In initiates the polymerization of bulk monomer and provides a reactive functionality that facilitates further initiation and polymer modification by the polymerization of different monomers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1885–1891, 2002     

Comprehensive studies on polymer electrolyte and dye-sensitized solar cell developed using castor oil-based polyurethane

Comprehensive characterization of new polymer electrolyte system prepared using polyurethane derived from castor oil polyol was undertaken. The castor oil polyol was synthesized via transesterification and reacted with 4,4′-diphenylmethane diisocyanate to form polyurethane. Polyurethane electrolyte films were prepared by addition of sodium iodide in different weight percentage with respect to the weight of the polymer. The electrolyte films were analyzed using Fourier transform infrared spectroscopy, dynamic mechanical analysis, electrochemical impedance spectroscopy, transference number measurement, and linear sweep voltammetry. Fourier transform infrared spectroscopy results confirmed the complexation between polymer and salt. Tan delta peak observed in the tan δ–temperature curve plotted using data obtained from dynamic mechanical analysis indicated that the glass transition temperature of polyurethane decreased with the addition of sodium iodide. The highest conductivity of 4.28 × 10^?7 S cm^?1 was achieved for the film with 30 wt% of sodium iodide. The performances of dye-sensitized solar cell using the electrolyte systems were analyzed in terms of short-circuit current density, open-circuit voltage, fill factor, and energy conversion efficiency. The polymer electrolyte with 30 wt% sodium iodide showed the best performance with energy conversion efficiency of 0.80%.     

Highly transparent nancomposite films based on polybutylmethacrylate and functionalized cellulose nanocrystals

Efficient surface functionalization of cellulose nanocrystals (CNC) with hydroxyl butyl acrylate monomer (HBA) was carried on under mild condition using N,N′-carbonyldiimidazole as an activator. The grafting of the acrylic monomer was shown to bring about the high yield grafting of polymer chains on the functionalized CNC during in situ polymerization process. Surface functionalization of CNC with HBA and the polymer grafting on the modified CNC were confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Nanocomposite film prepared from in situ polybutylmethacrylate polymerization process using HBA functionalized nanocrystals exhibited high transparency degree here assigned to improved dispersion. DMA analysis proved that the best mechanical/rheological performance is obtained for HBA–CNC contents of 4 %.     

Preparation and artificial ageing tests in stone conservation of fluorosilicone vinyl acetate/acrylic/epoxy polymers

In this work, a series of fluorosilicone vinyl acetate/acrylic/epoxy (FVAE) polymers for protection of stone relics were prepared with different content of hexafluorobutyl methacrylate (HFBMA) by the seed emulsion polymerization process. Properties and structure of FVAE materials were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), and transmission electron microscopy (TEM). Viscosity, particle size, surface tension, gel content, adhesion and surface hardness of polymer materials were also determined. Surface morphology of the stone sample was observed by scanning electron microscopy (SEM). Compared with a commercial copolymer, ethyl methacrylate/methyl acrylate (EM/MA, Paraloid B72), protection ability of the prepared FVAE polymer was investigated using artificial ageing tests such as the freeze-thaw aging test, acid aging test and the soluble salts aging test. It was found that the FVAE polymers prepared can effectively prevent corrosion caused by H⁺, formation of an interface crack and further weathering, which indicates their possible application in stone protection.     

Dendronized Cellulose Nanocrystals as Templates for Preparation of ZnS and CdS Quantum Dots

Cellulose nanocrystals (CNC) isolated from bleached bagasse pulp were modified with a second-generation isocyanate dendron (G2-dendron) to prepare dendronized cellulose nanocrystals (DCN). Transmission electron microscopy (TEM), elemental analysis for nitrogen, Fourier transform infrared (FTIR) and ¹³C magic angle spinning nuclear magnetic resonance (¹³C MAS NMR) proved occurrence of the modification of cellulose nanocrystals surfaces. The dendronized cellulose nanocrystals were used as templates for formation of ZnS and CdS quantum dots with uniform diameter at low temperature in water. The prepared DCN/QDs were highly soluble in water. TEM images showed that the size of the prepared quantum dots was about 5 nm in diameter. UV-Visible and fluorescence spectroscopy showed absorption and emission at wavelength values lower than that reported for bulk ZnS and CdS.     

Structural,thermal, vibrational,and electrochemical behavior of lithium ion conducting solid polymer electrolyte based on poly(vinyl alcohol)/poly(vinylidene fluoride) blend

The present study focuses on the preparation and characterization of poly(vinyl alcohol)/poly(vinylidene fluoride) blend polymer electrolyte doped with lithium triflate (LiCF₃SO₃). Interaction of lithium triflate with the host polymer in the solid polymer electrolyte was studied using X-ray diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry analysis. It was found that 15% salt doped polymer electrolyte possesses the highest ionic conductivity (2.7 × 10^–3 S/cm) at 303 K, the higher thermal stability at 175°C. Linear sweep voltammetry results revealed that the film is electrochemically stable up to 3.4 V.     

具有低表面自由能有机介电薄膜的制备及表征

通过自主开发的有机镀膜技术在Mg-Mn-Ce镁合金表面制备了具有低表面自由能和较高介电常数的有机纳米薄膜. 利用X射线光电子能谱(XPS)分析了表面有机镀膜过程的反应机理, 借助傅里叶变换红外(FT-IR)光谱进一步确认表面有机膜层的存在, 采用接触角测量仪测定了有机薄膜的蒸馏水接触角和表面自由能变化, 使用椭圆偏振光谱仪研究了薄膜的厚度, 并借助精密阻抗分析仪评价了薄膜的介电性能. 有机镀膜后镁合金表面形成了一层纳米级厚度的有机薄膜, 接触角从基体的70.8°上升至150.5°, 表面自由能从基体的37.96 mJ·m^-2降低到1.57 mJ·m^-2, 镁合金表面从亲水性转变为疏水性; 薄膜的厚度和质量随有机镀膜时间延长先增加后有所减小, 在镀膜20 min时薄膜性能最佳, 此时膜重达到23.5 μg·cm^-2, 膜厚最大为147.48 nm, 其相对介电常数也达到最大, 在1 kHz下可达24.922.     

In Situ ATR-FTIR and UV-Visible Spectroscopy Study of Photocatalytic Oxidation of Ethanol over TiO2 Nanotubes

The photocatalytic oxidation of ethanol over TiO₂ nanotubes (NTs) was investigated by in situ attenuated total reflection using Fourier transform infrared spectroscopy (ATR-FTIR) and ultraviolet (UV)-visible spectroscopy. In the ATR-FTIR study, the TiO₂ NTs were spread in a ZnSe crystal trough that was used as the reactor. The evolution of the reaction under UV irradiation was investigated by in situ monitoring of changes in the species at the surface of the TiO₂ NTs. Ethanol adsorbed on the TiO₂ NTs surface, forming alkoxide and hydroxide groups, which were then attacked by ^?OH, with the formation of a vinyl alcohol intermediate that was finally transformed to acetic acid. In addition, the species changes in the reaction solution were also investigated by in situ UV-visible spectroscopy using a small volume flow-through cell. The UV-visible data further confirmed the oxidation mechanism of ethanol on TiO₂ NTs elucidated by ATR-FTIR data.     

Inhibitive properties of a phosphonate-based formulation for corrosion control of carbon steel

The aim of the present work was to study the corrosion inhibition of carbon steel using a ternary formulation. This new ternary inhibitor formulation, viz., 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), with zinc ions and silicate ions was used to protect carbon steel from corrosion in a low-chloride environment. The gravimetric studies showed that 96 % inhibition efficiency was achieved with the ternary system consisting of 50 ppm PBTC, 50 ppm Zn²⁺ ions, and 10 ppm silicate ions. Out of 0.310 mmol of Zn²⁺ ions, 0.218 mmol was diffused from the bulk of the solution to the metal surface, as revealed from the studies of the solutions by atomic absorption spectroscopy (AAS). Electrochemical methods (potentiostatic polarization and electrochemical impedance spectroscopy) and surface characterization techniques [Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), and atomic force microscopy (AFM)] were used to ascertain the nature of the protective film and for explaining the mechanistic aspects of corrosion inhibition.     

Properties of poly(dimethylsiloxane)/hydrogel multicomponent systems

The properties of surface‐ and bulk‐modified poly(dimethylsiloxane) (PDMS) were examined. Laser‐induced surface grafting of poly(2‐hydroxyethyl methacrylate) (PHEMA) on PDMS and a sequential method for preparation of interpenetrating polymer networks of PDMS/PHEMA were, respectively, used for surface and bulk modifications. The hydrogel content and water‐uptake capability of the modified samples were also investigated. The modified PDMS samples were examined by performing attenuated total reflection/Fourier transform infrared spectroscopy, dynamic mechanical thermal analysis, scanning electron microscopy, and water contact‐angle measurements. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2145–2156, 2003     

双亲性光敏感遥爪聚合物C-PNIPAAm的合成与性能

以7-羟基-4-甲基香豆素为原料,依次与环氧氯丙烷、二硫化钠反应得一含香豆素基元的二硫化物(C-S-S-C),并以其与三丁基膦复合体系为链转移剂,偶氮二异丁腈(AIBN)为引发剂,N-异丙基丙烯酰胺(NIPAAm)为单体制备了末端为香豆素光响应基元的双亲性遥爪聚合物(C-PNIPAAm).用傅里叶变换红外(FT-IR)光谱、凝胶渗透色谱(GPC)、氢核磁共振(1H-NMR)等对该聚合物进行了结构表征.研究显示该双亲性遥爪聚合物可在水中直接形成胶束,并以荧光素为疏水性客体考察了聚合物胶束的光控释放行为.在波长大于310 nm的紫外光照射下,聚合物链末端的香豆素单元可进行光二聚,胶束结构随之改变,因而所负载的荧光素可得到逐步有效释放.动态激光光散射(DLS)检测显示,光二聚反应使聚合物胶束平均粒径从56.6 nm增大至101.0 nm.     

Solid polymer electrolyte based on tragacanth gum-ammonium thiocyanate

Research towards solid polymer electrolytes based on biopolymers has grown extensively over the past years due to its abundance in nature, non-toxicity, low cost, and biodegradability. When compared to standard biopolymers, electrochemical study on natural gums is very limited. Therefore, in the present work, polymer electrolytes based on gum tragacanth have been prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), electrochemical impedance spectroscopy (EIS), thermogravimetry, and transference number studies. The polymer-salt complex formation is confirmed using FTIR studies while XRD spectra reveal the amorphous nature of the polymer membranes. The highest conductivity of 9.161?×?10^?3 S/cm was obtained for the film with 1 g of gum tragacanth and 0.5 g of ammonium thiocyanate. The Thermogravimetry study showed that the electrolyte is thermally stable. The transference number study confirmed that the main charge carriers are ions. The primary battery has been constructed using the prepared electrolyte, and the OCV was found to be 1.31 V.

     

Morphological change of crystalline polymer films by annealing: substrate‐ and heating/cooling‐rate‐dependent surface roughness

We study the morphological change of crystalline polymer films by annealing using atomic force microscope, X‐ray diffraction, and Fourier transform infrared spectroscopy techniques. As typical samples, we employ high‐density and low‐density polyethylene films prepared by the cast method. After annealing at 135 °C for 4 h, the surface roughness of polyethylene films by the atomic force microscope significantly increases, and the crystallite size by the X‐ray diffraction also shows some increase, while the Fourier transform infrared spectroscopy spectrum hardly exhibits any change. This can be well explained as a result of the growth of crystal structure by recrystallization during annealing. More interestingly, we find that the choice of the substrate and also the heating/cooling rates for annealing significantly influences the surface roughness of the films. Copyright © 2017 John Wiley & Sons, Ltd.     

All solid polymer electrolytes based on polar side group rotation for rechargeable lithium batteries

A novel polymer matrix with a polar carbonyl group was designed and used to prepare an all‐solid polymer electrolyte in lithium rechargeable batteries. The ionic conductivity of this type of polymer electrolyte was examined. The relationship between the lithium salt concentration and ionic conductivity was investigated by Fourier transform infrared (FTIR) spectroscopy. The carbonyl groups in the polymer matrix effectively interacted with the lithium salt, which improved the ionic conductivity at a large range of temperatures. The ionic conductivity of this type of polymer electrolyte was approximately 10^?4 S cm^?1 at room temperature. The stability of the interface between electrode and electrolyte was evaluated by measuring the alternating current (AC) impedance. Copyright © 2009 John Wiley & Sons, Ltd.