SERS study on surface chain geometry of atactic poly (methyl methacrylate) film and nanosphere

The surface chain geometry of atactic poly (methyl methacrylate) (a‐PMMA) film and nanosphere (NS) was revealed by surface‐enhanced Raman scattering (SERS) spectra. The Ag nanoparticles and nanoplates were prepared by electrochemical deposition and chemical synthesis for SERS substrates. The experimental results suggested that the molecular chain axis of a‐PMMA film adopted a trans‐conformation on bonding to Ag surface ascribed to the short‐range chemical (CHEM) effect according to the SERS selection rules. However, for the well‐coated monolayer of a‐PMMA NSs, the α‐CH₃ in polymer chains stood vertically to the Ag surface due to the giant local electromagnetic effect, then the chain conformation presented in the interface between a‐PMMA NSs and Ag metal was adopted the opposite orientation compared with a‐PMMA film. The Raman enhancement of the Ag nanoparticles was more prominent than that of the Ag nanoplates due to the free energies of face‐centered cubic crystal faces in nanoparticles, but the single crystals with (111) plane of Ag nanoplates could improve the stability of SERS signals when the annealed temperature was above T_g of a‐PMMA NSs. The present work can provide some useful information of surface chain geometry and conformation of NSs for designing various materials with well‐defined structure via a‐PMMA NSs template. Copyright © 2013 John Wiley & Sons, Ltd.     

Photochemical kinetics for holographic grating formation in phenanthrenequinone doped poly (methyl methacrylate) photopolymer

The photochemical kinetics of phenanthrenequinone (PQ) doped poly (methyl methacrylate) photopolymer in holographic recording was studied theoretically and experimentally. The diffusion of PQ molecules during holographic recording was negligible because of its small diffusion coefficient at room temperature. A photochemical reaction kinetics model of PQ/PMMA was established. The analytical expressions for the temporal variations of transmittance and diffraction efficiency were derived. By fitting the experimental curves, some parameters related with the polymer components were obtained by the proposed model, which can be used to analyze the photochemical process and will be helpful to the optimization of material preparation.     

Electrical characteristics of top contact pentacene organic thin film transistors with SiO<Subscript>2</Subscript> and poly(methyl methacrylate) as gate dielectrics

Organic thin film transistors (OTFTs) were fabricated using pentacene as the active layer with two different gate dielectrics, namely SiO₂ and poly(methyl methacrylate) (PMMA), in top contact geometry for comparative studies. OTFTs with SiO₂ as dielectric and gold deposited on the rough side of highly doped silicon (n⁺-Si) as gate electrode exhibited reasonable field effect mobilities. To deal with poor stability and large leakage currents between source/drain and gate electrodes in these devices, isolated OTFTs with reduced source/drain contact area were fabricated by selective deposition of pentacene on SiO₂/PMMA through shadow mask. This led to almost negligible leakage currents and no degradation in electrical performance even after 14 days of storage under ambient conditions. But, the field effect mobilities obtained were lower than 10⁻³ cm² V⁻¹ s⁻¹, whereas by using PMMA as gate dielectric with chromium deposited on the polished side of n⁺-Si as gate electrode, improved field effect mobilities (>0.02 cm² V⁻¹ s⁻¹) were obtained. PMMA-based OTFTs also exhibited lower leakage currents and reproducible output characteristics even after 30 days of storage under ambient conditions.      

Radiation effects on poly(methyl methacrylate) induced by pulsed laser irradiations

Poly(methyl methacrylate) (PMMA) was irradiated using a medical UV-ArF excimer laser operating at the fundamental wavelength of 193 nm. Characterized by a beam diameter of 1.8 mm and energy of 180 mJ with a Gaussian energy profile, it operates in a single mode or at 30 Hz repetition rate. Mechanical profilometry was carried out on ablation craters in order to study the rugosity and the ablation yield in the various operative conditions. Optical transmission and reflection measurements at six wavelengths were conducted in order to characterize the optical properties of the irradiated surfaces. Measured crater depths in PMMA were lower with respect to the forecasted ones in corneal tissue, while the lateral crater aperture was maintained. The rugosity produced at the crater bottom after irradiation was about 0.3 μm, and the ablation yield was about 10¹⁵ molecules/laser pulse, while etching depth and diameter show a roughly linear dependence on the number of laser shots. These experiments constitute a base for deeper clinical investigations.     

Surface modification of hydroxyapatite with poly(methyl methacrylate) via surface-initiated ATRP

This article describes the fabrication of hydroxyapatite (HAP) nanocomposites grafted with poly(methyl methacrylate) (PMMA). Surface-initiated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was carried out from hydroxyapatite particles derivatized with ATRP initiators. The structure and properties of the nanocomposites were investigated by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), differential scanning calorimeter (DSC) measurements, and contact angle analyses. TGA was used to estimate the grafting density of ATRP initiators (0.49 initiator/nm²) and the amount of grafted PMMA on the HAP surface. The contact angle analyses indicated that grafting PMMA onto the HAP surface dramatically increased the hydrophobicity of the surface. Moreover, the HAP nanocomposites showed excellent dispersibility in both aqueous solution and organic solvent.     

Preparation and characterization of poly(lactic acid)/poly(methyl methacrylate) blend tablets for application in quantitative analysis by micro Raman spectroscopy

Poly(lactic acid) (PLA) is a biodegradable polymer that has a variety of applications, one of which is as biomaterial in surgery or as functional layers on implants, due to its compatibility with living tissue. This paper reports the possibilities of quantification of poly(lactic acid) (PLA) in a polymer matrix such as poly(methyl methacrylate) (PMMA) by micro Raman spectroscopy (MRS). Blends of amorphous poly(DL‐lactic acid) with poly(methyl methacrylate) were prepared by the procedure of dissolution/precipitation. Thermal properties of the blends such as the glass transition temperature (Tg) were characterized by differential scanning calorimetry (DSC). The PLA/PMMA blends exhibited only a single glass transition region, indicating that this system is miscible. The PLA/PMMA system obeys the Gordon–Taylor equation (Tg versus PLA content). Various concentration ratios of PLA blends were prepared to use as a basis for quantitative analysis by MRS. Intensities of the characteristic bands at 813 cm⁻¹ (νCOC of PMMA) and 873 cm⁻¹ (νC―COO of PLA) were used for the calculation. The calibration graph showed a good linear correlation with an R² value of 0.9985. On the basis of the calibration curve obtained, the determined content of several PLA/PMMA blends was in good agreement when compared with nominal contents. The limit of detection (LOD) and quantification (LOQ) were calculated by the calibration data set as signal‐to‐noise method. The relative standard deviation of this method was lower than 10% and the accuracy better than 4%. This study demonstrated that Raman spectroscopy provides an alternative non destructive method for quantitative analysis of PLA in a PMMA matrix. Copyright © 2015 John Wiley & Sons, Ltd.     

Computational investigation into the mechanisms of UV ablation of poly(methyl methacrylate)

Molecular dynamics simulations with an embedded Monte Carlo based reaction scheme were used to study UV ablation of poly(methyl methacrylate) (PMMA) at 157 nm. We discuss the onset of ablation, the formation and distribution of products in the plume and stress relaxation of the polymer matrix. Laser induced heating and bond-breaks are considered as ablation pathways. We show here that depending on the nature of energy deposition the evolution of ablation plume and yield composition can be quite different. If all of photon energy is converted to heat it can set off ablation via mechanical failure of the material in the heated region. Alternatively, if the photon energy goes towards breaking bonds first, it initiates chemical reactions, polymer unzipping and formation of gaseous products inside the substrate. The ejection of these molecules has a hollowing out effect on the substrate which can lead to ejection of larger chunks. No excessive pressure buildup due to creation of gaseous molecules or entrainment of larger polymer chunks is observed in this case.     

Ionic conductivity studies of 49% poly(methyl methacrylate)-grafted natural rubber-based solid polymer electrolytes

The potential of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) as a solid polymer electrolyte film in rechargeable batteries system were explored. The flat, thin, and flexible films were prepared by solution casting technique. The ionic conductivity was investigated by alternating current impedance spectroscopy. The highest conductivity of 2.3 × 10⁻⁷ Scm⁻¹ was obtained at 20wt.% of LiBF₄ salts content, while 4.0 × 10⁻⁸ Scm⁻¹ was obtained at 15wt.% LiClO₄ salts loading. The observation on structure performed by X-ray diffraction shows the highest conductivity appears at amorphous phase.     

Generation of microcellular poly(methyl methacrylate) by compressed gases

Abstract

Generation of microcellular poly(methy1 methacrylate) (PMMA) was studied in CO₂ and N₂O at pressures from 2 to 15MPa at three temperatures, 293.2K, 308.2K, and 323.2 K. The average diameter d and average number density N of voids generated by a rapid expansion of compressed gases in PMMA were measured by use of an optical microscope. Effects of gases, temperature, and pressure on the d and N values were examined. Even at pressure below glass transition pressure of PMMA with both gases, voids of diameter being as small as those found at high pressure, 15MPa, were obtained at each temperature. However, the void density of PMMA at lower pressure by both gases was not so good as those obtained at high pressures.     

Femtosecond laser induced photoluminescence in poly(methyl methacrylate) and three-dimensional optical storage

We report on a femtosecond-laser induced photoluminescence (PL) in poly(methyl methacrylate) and its potential application to three-dimensional optical storage. Irradiation with a focused 800 nm, 1 kHz, 100 fs pulsed laser induced a strong PL change in UV-visible region. Absorption spectra and Fourier-transform infrared spectra before and after laser irradiation indicate the PL may result from the emissive oxidized products of photo-degradation reaction of PMMA. This makes it possible to read out the stored data by detecting the PL change. The pulse energy threshold of the light-induced PL change of PMMA is found to be at ∼2 μJ/pulse and the optimal recording energy is ∼3 μJ/pulse. A ten-layer pattern inside the bulk sample recorded by tightly focusing a pulsed laser beam was read out by a reflection-type fluorescent confocal microscope, which detected the emission in visible range as the signal. High-contract fluorescent images with a much higher signal-to-noise ratio were obtained without crosstalk in comparison with the ordinary reflection mode.     

Phase Ordering and Crystallization Kinetics in Ultrathin Poly(ethylene oxide)/Poly(methyl methacrylate) Blend Films

Crystallization in ultrathin Poly(Ethylene Oxide)/Poly(Methyl Methacrylate) (PEO/PMMA) blend films with thickness of ca. 10 nm was investigated by means of microscopic and in situ spectroscopic methods. It was revealed that the blend films undergo a phase ordering in a humid atmosphere before or during crystallization, with PEO de-mixing with PMMA and segregating to the free film interface on the PMMA layer. The de-mixed PEO chains crystallize into a fractal-like morphology by a diffusion-limited process, and the crystal growth is 1-dimensional with Avrami exponent n ≈ 1, resulting in flat-on crystal lamellae with the PEO chains oriented normal to the film plane.     

Effects of UV-irradiation on the thermo-mechanical properties of optical grade poly(methyl methacrylate)

We studied the evolution of the thermo-mechanical properties of poly(methyl methacrylate) (PMMA) materials exposed to ultra-violet (UV) light. To do so we measured important mechanical parameters including the fracture strength, the stress-strain relation, and Young's modulus as a function of the UV-irradiation dose. We concluded that the mechanical properties of PMMA are affected by UV light. The ductility disappears and the strength and strain at rupture strongly decrease (over 30%). The evolution of the Young's modulus is discussed as a function of the cross-linking degree of the materials. Moreover we observed the occurrence of surface damage, which in its turn enhances the degradation of these mechanical parameters.     

无规聚甲基丙烯酸甲酯立构复合的红外光谱研究

用红外光谱研究了无规聚甲基丙烯酸甲酯的丙酮、苯、氯仿溶液成膜样品的立构复合状况。结果表明无规聚甲基丙烯酸甲酯在丙酮和苯中确能形成立构复合结构,结构的形成主要是依靠分子链中间规和等规链段的相互作用。对丙酮样品的退火实验表明,在退火过程中能够发生间规链段的自聚集现象。     

Enrichment of poly(methyl methacrylate) and its graft copolymer of polybutadiene on the surface of polypropylene blends

Poly(methyl methacrylate) (PMMA) and its graft copolymer of polybutadiene were used as the macromolecular surface modifiers of polypropylene. The enrichment and diffusion of the modifiers onto the surface of polypropylene blends were investigated using FTIR-ATR, CDA and SEM. It has been found that the selective aggregation of the modifier component on the surface of polypropylene was mainly affected by the content, molecular weight and size of the segregated domains. Lower content and higher surface energy die were in favor of the enrichment of the additive. PMMA with higher molecular weight showed larger domain phase and lower diffusion velocity which resulted in less enrichment on the surface of PP blends.     

Increase of photoluminescence from fullerenes-doped poly (alkyl methacrylate) under laser irradiation

Increase of photoluminescence (PL) from fullerenes (C₆₀ and C₇₀)-doped poly(alkyl methacrylate), such as poly(ethyl methacrylate) (PEMA), poly(isopropyl methacrylate) (PiPMA) and poly(isobutyl methacrylate) (PiBMA), have been studied under laser irradiation with wavelength of in air. After laser irradiation, PL peaks of all fullerenes doped-polymers are broadened and blue-shifted. This PL increase depends on the fullerene concentrations. By comparing with fullerenes-doped PMMA, fullerenes-doped PEMA have the greatest PL increase among the four kinds of polymers, including PEMA, PiPMA, PiBMA and PMMA. PL intensity of C₇₀-doped polymers increases much more quickly than the corresponded C₆₀-doped polymers at the initial stage of laser irradiation. Great change on their UV-visible absorption spectra before and after laser irradiation indicate some great variation on chemical structure of fullerene molecules dispersed in polymer matrix under laser irradiation. This great PL increase may be attributed to formation of fullerene oxide-polymer and oxidized fullerene-polymer adducts due to laser-induced photochemical reactions among fullerene, oxygen and polymer.     

Fabrication and characterization of superparamagnetic and thermoresponsive hydrogels based on oleic-acid-coated Fe3O4 nanoparticles, hexa(ethylene glycol) methyl ether methacrylate and 2-(acetoacetoxy)ethyl methacrylate

Stimuli-responsive hydrogel nanocomposites comprised of swollen polymer networks, in which magnetic nanoparticles are embedded, are a relatively new class of “smart” soft materials presenting a significant impact on various technological and biomedical applications. A novel approach for the fabrication of hydrogel nanocomposites exhibiting temperature- and magneto-responsive behavior involves the random copolymerization of hexa(ethylene glycol) methyl ether methacrylate (HEGMA, hydrophilic, thermoresponsive) and 2-(acetoacetoxy)ethyl methacrylate (AEMA, hydrophobic, metal-chelating) in the presence of preformed oleic-acid-coated magnetite nanoparticles (OA·Fe₃O₄). In total, two series of hydrogel nanocomposites have been prepared in two different solvent systems: ethyl acetate (series A) and tetrahydrofuran (series B). The degrees of swelling (DSs) of all conetworks were determined in organic and in aqueous media. The nanocrystalline phase adopted by the embedded magnetic nanoparticles was investigated by X-ray diffraction (XRD) spectroscopy. The obtained diffraction patterns indicated the presence of magnetite (Fe₃O₄). Deswelling kinetic studies that were carried out at ∼60 °C in water demonstrated the thermoresponsive properties of the hydrogel nanocomposites, attributed to the presence of the hexaethylene glycol side chains within the conetworks. Moreover, thermal gravimetric analysis (TGA) measurements showed that these materials exhibited superior thermal stability compared to the pristine hydrogels. Further to the characterization of compositional and thermal properties, the assessment of magnetic characteristics by vibrational sample magnetometry (VSM) disclosed superparamagnetic behavior. The tunable superparamagnetic behavior exhibited by these materials depending on the amount of magnetic nanoparticles incorporated within the networks combined with their thermoresponsive properties may allow for their future exploitation in the biomedical field.     

二苯基乙二胺在银胶表面吸附的表面增强拉曼光谱研究

以银纳米粒子作为SERS活性基底,研究了二苯基乙二胺(DPEDA)在银表面的吸附行为,并研究了溶液的pH值和DPEDA的浓度对吸附构型的影响。对比DPEDA的Raman和SERS谱图,可以认为DPEDA是通过氮原子的孤对电子吸附在银胶表面。在酸性介质中DPEDA的氨基被质子化生成胺正离子,导致DPEDA不容易吸附到银胶表面,所以DPEDA的SERS信号强度随着溶液酸性的增加而减弱。DPEDA的浓度变化对其吸附构型中芳香环的取向影响不大,但是其C-N键与表面的角度会有一定的变化。从SERS光谱得到的信息可以加深我们对DPEDA修饰的金属催化剂的多相不对称催化机理的认识。     

小牛胸腺DNA分子Langmuir-Blodgett复合膜的表面增强拉曼光谱研究

本文利用Langmuir-Blodgett(LB)技术将小牛胸腺DNA分子沉积在银基底上,测试并讨论了它的π-A等温曲线,原子力图及表面增强拉曼光谱(SERS)。通过利用LB技术,获得了DNA分子的LB复合膜的高质量的SERS。在DNA分子LB膜的表面增强拉曼光谱中,DNA的核糖和碱基腺嘌呤是吸附活性部位,它们的振动光谱得到增强。DNA的其它碱基和磷酸基团的拉曼光谱强度也明显的得到增强。分析认为DNA分子增强的拉曼光谱主要是由于LB膜的有序结构的贡献,使得SERS效应得到进一步的增强。因此利用LB技术是得到DNA的高质量SERS很好的方法。     

甲基橙-银胶体系pH和氯离子效应的光谱研究

研究了甲基橙-银胶体系的光吸收和光致发光信号随pH值和加入氯离子的变化规律.实验发现随着pH值的增加, 分子的荧光发射峰与银胶的光吸收峰的重叠增大, 引起体系中能量转移效率的增加, 即428 nm分子荧光峰的淬灭和560 nm聚集体的特征光致发光峰增强现象的加剧.另外, 不同pH值下氯离子的加入都会使染料分子更加密集的吸附在胶体银颗粒表面, 形成分子吸附更加紧密的聚集体, 造成体系中受表面吸附分子影响的光致发光峰获得了极大的增强.同时, 因聚集体表面吸附层染料分子对入射光的大量吸收, 导致到达内核银表面的入射光强度减弱, 致使体系能量转移通道在一定程度上受阻, 表现为428 nm荧光峰的淬灭幅度减小.参照分子聚集体的形成理论, 接合体系光谱的变化, 从pH值的改变和Cl^-的加入对分子结构及加剧聚集体的形成等方面的影响来解释发光和光吸收的显著变化.     

IR laser ablation of doped poly(methyl methacrylate)

We investigate the TEA CO₂ laser ablation of films of poly(methyl methacrylate), PMMA, with average M_W 2.5, 120 and 996 kDa doped with photosensitive compounds iodo-naphthalene (NapI) and iodo-phenanthrene (PhenI) by examining the induced morphological and physicochemical modifications. The films casted on CaF₂ substrates were irradiated with a pulsed CO₂ laser (10P(20) line at 10.59 μm) in resonance with vibrational modes of PMMA and of the dopants at fluences up to 6 J/cm². Laser induced fluorescence probing of photoproducts in a pump and probe configuration is carried out at 266 nm. Formation of naphthalene (NapH) and phenanthrene (PhenH) is observed in NapI and PhenI doped PMMA, respectively, with relatively higher yields in high M_W polymer, in similarity with results obtained previously upon irradiation in the UV at 248 nm. Above threshold, formation of photoproducts is nearly complete after 200 ms. As established via optical microscopy, bubbles are formed in the irradiated areas with sizes that depend on polymer M_W and filaments are observed to be ejected out of the irradiated volume in the samples made with high M_W polymer. The implications of these results for the mechanisms of polymer IR laser ablation are discussed and compared with UV range studies.