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.     

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.     

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。     

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.     

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.     

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.     

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.     

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.     

Preparation of low density TiO2/poly (methyl methacrylate) composite particles by emulsifier-free emulsion polymerization

Based on the 3-(trimethoxysilyl) propylmethacrylate (MPS) modified TiO₂ particles, the TiO₂/poly (methyl methacrylate) (PMMA) composite particles have been prepared successfully via emulsifier-free emulsion polymerization in water. A facile floating-sinking method is proposed to roughly evaluate the composite particles’ density. Chemical component of obtained composite particles was identified by Fourier transform infrared spectra (FTIR). The morphology and grain size of the composite particles were investigated by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Thermal analysis of the composite particles was measured by differential thermal analysis-thermo gravimetric analysis (DTA-TGA). The zeta potential and electrophoretic mobility of composite particles with suitable density in water was measured by dynamic light scattering (DLS).     

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.     

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.     

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.     

SERS studies of DNA nucleobases using new silver poly(methyl methacrylate) nanocomposites as analytical platforms

The implementation of polymer‐based composites provides a plausible alternative to develop efficient, handy and scalable substrates for surface‐enhanced Raman spectroscopy (SERS) aiming the widespread use of this technique for chemical analysis and molecular sensing. In this research, new poly(methylmethacrylate) based nanocomposites for SERS were prepared by in situ miniemulsion polymerization in the presence of organically capped metal silver nanoparticles. The ensuing composites have been investigated as analytical platforms for SERS detection of DNA constituents for variable analytical conditions. Finally, we show that in special cases, selective detection of DNA bases by SERS can be possible by varying the pH of the solution under analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.     

Electrical conductivity behaviour of pure and polyblends samples of polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA)

Electrical conductivity of pure PVC, PMMA and their polyblends samples has been studied in detail as a function of polarizing fields at constant temperatures. Different plots were drawn to investigate the nature of mechanism responsible for conduction. The nature of all the thermograms is nonlinear but similar for all temperatures. The plots have two slopes, i.e., ohmic conduction with slope of curve ≈1 at lower voltage region and a non-ohmic conduction with slope ≈1.9 at higher voltage region are observed. The increase in the conductivity and decrease in the activation energy, suggest that plasticization effect is taking place between the polymers when they are blended. Fowler–Nordheim plots are not consistent and showing negative and positive slopes simultaneously for lower as well as higher values of applied voltage. Theoretical and experimental values of β_SR and β_PF were calculated and the β_exp of pure and polyblend samples is in agreement with theoretically β_PF. The β_exp value lies close to β_PF, this shows that Poole–Frenkel mechanism is also effective. The calculated metal electrode potential barrier at a constant voltage suggests that the dominant charge carrier mechanism is Schottky–Richardson type. Hence in the present case both SR and PF mechanisms are seem to be operative.     

Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions

Films of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend were derived from a special procedure of casting semi-dilute solutions. Hydrophilic character and crystallization of PVDF were optimized by variation of PMMA concentration in PVDF/PMMA blends. It was found that a PVDF/PMMA blend containing 70 wt% PMMA has a good performance for the potential application of hydrophilic membranes via thermally induced phase separation. The films presented β crystalline phase regardless of PMMA content existed in the blends. Thermal analysis of the blends showed a promotion of crystallization of PVDF with small addition of PMMA which induced larger lamellar thickness of PVDF, leading to the largest spherulitic crystal of PVDF (10 wt% PMMA) is about 8 μm. SEM micrographs illustrated no phase separation occurred in blends, due to the high compatibility between PVDF and PMMA.     

Origin of broad visible luminescence in poly[methyl(phenyl)silylene] thin films

The luminescence spectrum of poly[methyl(phenyl)silylene] (PMPSi) thin films shows a strong narrow peak at 353 nm, which is of excitonic nature (related to (σ^*-σ) transitions), and a broad emission peak with the maximum located at around 470 nm, which is related to polymer branching, charge-transfer transitions, and defect states (backbone scission). The exciton photoluminescence band strongly decreases when photodegradation of the main Si chain occurs. At the same time, new traps for holes 0.45 eV deep are formed. Their formation causes the shift of the blue visible photoluminescence observed for virgin PMPSi film into the light-green region. This effect, which is associated with the interaction of intramolecular charge-transfer excitons with trapped holes, is reversible—the reverse shift from the light-green back to blue region follows the thermal trap annealing. The decay of isothermal recombination luminescence can be described by a power function I_ITRL∼At^−m. The non-monotonic temperature dependence of the exponent m is explained by peculiarities of energetic relaxations of photogenerated charge carriers and their subsequent recombination in a disordered medium.     

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.      

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.