Optical and thermal spectroscopic studies of luminescent dye doped poly(methyl methacrylate) as solar concentrator

A luminescent solar concentrator was prepared that was based on a bulk sheet of poly(methyl methacrylate) doped with different luminescent dyes (K1, K27, and Lpero) during the polymerization process. Photo‐ and thermal‐stability studies revealed that the Lpero dye system is the most stable one. The electronic transition mechanism for the concentrator systems was obtained by the darktrap and phototrap spectroscopy technique. The results were correlated with the outdoor test measurements over 1 year. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3316–3323, 1999     

Optical waveguiding in doped poly(methyl methacrylate)

Poly(methyl methacrylate) doped with the photoinitiators benzil and benzildimethylketal is dissolved in the monomer MMA. From the solutions, planar waveguides and optically-recorded strip waveguides are fabricated on quartz substrates. Mode spectra and total losses are investigated and indicate a minimum loss value of about 0.015 dB mm^?1 for photoinitiator concentrations of about 10%. The results also point to a considerable influence of surface irregularities.     

Fluorescence from fluorescent dye based polyurethane ionomer(III)

A series of reactive fluorescent dyes were successfully synthesized and their structure was proven by IR spectra, NMR spectra, elemental analysis, and mass spectra. The fluorescence performance 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione and 2‐benzyl‐6‐hydroxy‐benzo[de]isoquinoline‐1,3‐dione appears at around 276 and 437.4 nm, respectively, and their quantum yields are 0.662 and 0.562, respectively. It is important to indicate that the fluorescence performance is better for 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione than for as a result of more electron donating groups linked to the 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione molecule. These fluorescent dyes further react with toluene diisocyanate and other additives to form fluorescent dye based polyurethane (PU) ionomer molecules, and their structures are demonstracted by IR spectra. In aqueous solution, the fluorescence performance appears to be better for 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione based PU ionomer than for 6‐amino‐2‐phenyl‐ethyl‐benzo[de]isoquinoline‐1,3‐dione based PU ionomer. For the fluorescent dye based PU ionomer molecule system, the number‐average particle sizes of the fluorescent dye based PU ionomer molecules in water increase with increasing concentration of the fluorescent dye, as a result of the increased free volume of the ionomer molecule. This may be the result of increased intermolecular interactions between ionomer– molecules themselves. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 455–465, 2005     

Electrical conduction and dielectric properties of poly(methyl methacrylate)/perylene solar concentrators

Poly(methyl methacrylate) doped with fluorescent perylene dye was prepared by both radical polymerization of methyl methacrylate and solvent casting from polymer solutions. The samples were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, electrical conductivity, and dielectric properties. Both conductivity and dielectric properties were measured in the temperature range 303–433 K and the frequency range 10³ to 5 × 10⁶ Hz. The results show that the direct‐current electrical conductivity increased by increasing dye content in solvent‐cast samples, whereas it decreased radically polymerized samples. The results of alternating‐current conductivity suggest electron hopping between filled and empty localized states. The study of dielectric properties showed two relaxation peaks corresponding to the dipole segmental and dipole group losses. Explanations based on the polymer free volume and acid–base interactions were proposed to examine the influence of the sample preparation and perylene dye concentration on the glass‐transition temperature and dielectric relaxation of the samples. The obtained results recommend the thermal and molecular stability of luminescent solar concentrator (LSC) matrices prepared by radical polymerization over those prepared by solvent casting. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 793–805, 2003     

Optical percolation and oxygen diffusion in poly(divinylbenzene) doped poly(methyl methacrylate) latex flms

A simple fluorescence technique is proposed for the measurement of the diffusion coefficient of oxygen into poly(methyl methacrylate) (PMMA) latex‐poly(divinylbenzene) (PDVB) composite films. Percolation model was used by using photon transmission (PT) technique to interpret the distribution of PDVB particles in PMMA lattice. Optical results were interpreted according to site percolation theory. The optical percolation threshold value and critical exponent were calculated as, R_c = 0.03 and, β = 0.34, respectively. PT measurements were performed for eight different PDVB content (0, 1.5, 3, 5, 10, 20, 40, and 60) wt%. Pyrene (P) functionalized PDVB cross‐linked spherical microspheres with diameters of 2.5 μm were synthesized by using precipitation polymerization technique followed by click coupling reaction. The diameter of the PMMA particles prepared by emulsion polymerization was in the range of 0.5–0.7 μm. PMMA/PDVB composite films were then prepared by physically blending of PMMA latex with PDVB microspheres at various compositions. The steady‐state fluorescence method was used to monitor oxygen diffusion into these (0, 5, 10, 20, and 40 wt%) latex films. Diffusion coefficients, D, of oxygen were determined by the fluorescence quenching method by assuming Fickian transport and were found to be increased from 1.8 × 10⁻¹¹ to 36.6 × 10⁻¹¹ cm² s⁻¹ with increasing PDVB content. This increase in D values was explained with formation of microvoids in the film by using PT technique. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Preparation and fluorescence of Nd3+ doped poly(methyl methacrylate) fibre

Neodymium octanoate (NdOA) was synthesized from neodymium oxides and dissolved into poly(methyl methacrylate) (PMMA) forming a solid solution of Nd³⁺ doped PMMA (Nd-PMMA). Investigation of the absorption spectrum of Nd-PMMA showed that it was similar to that of Nd³⁺ doped silica glasses, but with about 5 nm of blue shift. The glass transition temperature (T_gs) of all the Nd-PMMA samples were about 10°C higher than that of pure PMMA for Nd³⁺ concentrations of 60–700ppm. The Nd-PMMA was used to draw a fibre. The emission output of the fibre at 585 nm was observed under a green source pumping at 532 nm by optimization of the Nd³⁺ concentration and the length of the fibre. Under 1 W pumping radiation, 60 μW output was obtained for the fibre with Nd³⁺ concentration of 70 ppm and length of 15 cm.     

Spectroscopic study on poly(methyl methacrylate) doped with metal dithizonates

The IR and UV spectra of poly(methyl methacrylate) (PMMA) doped with metal dithizonate were investigated. Films of the doped samples were heated in air at various temperatures from 25 to 140°C for 2 h. Other films were also exposed to UV irradiation. The doped samples were treated with iodine. The experimental results provided strong evidence that certain weak reaction occurs between the dopants and the polymer, and the rate of reaction depends on the concentration of the dopant and the nature of the metal ions. It was found that heat treatment of the doped films induces considerable changes in the intensities of their IR bands. The magnitude of these changes depends also on the concentration and the nature of the metal ion. Moreover, the results proved that exposure of the doped films to UV irradiation has no effect on their absorption spectra. Furthermore, the treatment of the doped samples with iodine causes considerable changes in their UV absorption spectra.     

Synthesis and characterization of novel multifunctional poly(methyl methacrylate)s as potential fluorescent labels for electron‐beam lithography

A series of novel fluorophore‐rich polymers has been synthesized with the aim of developing radiation‐sensitive materials as electron‐beam resists. The polymers were characterized using FTIR and NMR spectroscopy, and gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis measurements. These polymers showed strong absorbance in the region of 330–380 nm, and can be patterned by an electron‐beam in their pure form or mixed with other components. All polymers also generated intense emission in the range 510–565 nm when irradiated by a laser source operating at a wavelength of 488 nm. The sensitivity of the polymeric fluorescence label as an electron‐beam resist was also discussed. Moreover, through immobilization of the fluorophores onto a polymer backbone, we managed to avoid the crystallization of fluorophores inside the polymer film. Copyright © 2005 Society of Chemical Industry     

Synthesis of fluorescent poly(methyl methacrylate) via AGET ATRP

Polymerization of methyl methacrylate (MMA) was successfully carried out via activator generated by electron transfer for atom transfer radical polymerization technique with naphthalene-1,5-diyl-bis (2-bromo-2-methylpropanoate) as an initiator, CuCl₂/bpy complex as a catalyst and tin(II) 2-ethylhexanoate (Sn(EH)₂) as a reducing agent in anisole. The polymerization showed typical features of “living”/controlled radical polymerization such as a linear increase of the molecular weights of the polymers with monomer conversion and relatively narrow polydispersities throughout the polymerization process. The resultant fluorescent poly(methyl methacrylate) was characterized by nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, ultraviolet absorption spectrophotometry and fluorescence spectrophotometry.     

Molecular weight variations in perylene‐doped poly(methyl methacrylate) for luminescent solar concentrators

Integrating highly efficient luminescent dyes into poly(methyl methacrylate) matrices with well‐defined parameters, such as degree of polymerization and dispersity, is a key step in the development of emerging technologies such as fiber‐based solar collectors, sensors, contactless coupling devices and integrated light sources. In this work, four perylene‐based fluorescent dyes, perylene from Sigma‐Aldrich, Lumogen F Yellow 083 from BASF, Perylene Orange from TCI and Lumogen F Red 300 from BASF, were polymerized in bulk with methyl methacrylate. The molecular weight distribution was controlled by the ratio between the chain transfer agent and initiator and was measured by size exclusion chromatography. A dopant‐dependent increase in the degree of polymerization, in which the dye causes a drop in the concentration of active growing polymer chains, was observed. Spectroscopic online monitoring of the process in transmission mode confirmed this observation and indicated the formation of stable perylene radicals during the polymerization. Comparative experiments with fluorescent (metal) organic dyes did not show a similar effect. Fitting models for the dye‐dependent molecular weights for Lumogen Yellow and Lumogen Red are proposed. © 2018 Society of Chemical Industry     

Optical and physical properties of zirconium dioxide reinforced poly(methyl methacrylate) nanocomposite films

The objective of this study was to investigate the fundamental aspects of acrylic resin and zirconia nanoparticle interaction to analyze the optical properties and subsequent changes in refractive index with incremental loading of nanoparticles. Poly(methyl methacrylate) (PMMA) reinforced with zirconia nanoparticles were prepared by dip coating, spin coating and solvent casting techniques. An overall understanding of the polymer nanocomposite film has been achieved using the spectroscopic and morphological studies. The vital aspect of this whole study is to derive a simple yet an efficient nanocomposite film capable of imparting extraordinary optical properties. Within the limitations of this research a very crucial property of the material has been revealed. The RI as well as the optical transparency of the nanocomposite film has been steadily maintained with a significant increase of RI by the magnitude of 0.06 and ~100% light transmittance on incorporation of pure zirconia nanoparticles into PMMA matrix has been achieved. The best technique found was spin coating as it could yield thin films and better transparency and higher refractive index.     

Synthesis of donor-acceptor poly(perylene diimide-altoligothiophene) copolymers as n-type materials for polymeric solar cells

Donor-acceptor alternated copolymers based on perylene diimide units linked in bay positions with oligothiophene units were prepared and used as acceptor material in polymeric solar cells. The copolymers have exhibited ambipolar electrochemical properties, high electronic affinities and wide electronic absorption in the visible spectrum. The spectroscopical characterization of the copolymer blends with poly-3-hexylthiophene showed evidences indicative of a charge transfer from the perylene-based copolymers to the polythiophene. All-polymeric solar cells were prepared with the blends and the photovoltaic characterization of these devices showed conversion efficiencies of 0.8% and 0.4%. The results demonstrate the potentialities of perylene-based copolymers as processable photoactive acceptor in organic solar cells.     

Atomic force microscopy studies of poly(methyl methacrylate) doped with photoinitiator

Atomic force microscopy has been applied for measuring the nanomechanical characteristics of poly(methyl methacrylate) thin films containing 5% photoinitiator (Irgacure 651). The nanohardness, Young's modulus, and adhesion to AFM tip have been evaluated for the unexposed samples and after UV‐irradiation. Additionally, FTIR spectroscopy and differential scanning calorimetry (DSC) have been applied to explain the observed changes in nanomechanical properties. It was found that the exposure to ultraviolet changed the nanomechanical properties of polymer because of photo‐oxidative degradation and relaxation processes. These studies lead to the conclusion that the applied photoinitiator has no noticeable effect on nanohardness and Young modulus during PMMA irradiation, but efficiently participates in polymer photo‐oxidation increasing the surface hydrophilicity and adhesion to Si₃N₄. Moreover, the initiator hampers the relaxation of PMMA macromolecules, what was proved by DSC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Photoinitiated synthesis of poly(poly(ethylene glycol) methacrylate-co-diethyl amino ethyl methacrylate) superabsorbent hydrogels for dye adsorption

Random copolymers of poly(ethylene glycol) methacrylate (PEGM), and diethyl amino ethyl methacrylate (DEAEM) were synthesized at low, and high conversions by photoinitiation. Crosslinked poly(PEGM-co-DEAEM) samples were obtained, and characterized by FTIR, SEM, DSC, TGA, and elemental analyses. Swelling behavior of the copolymers revealed that the copolymers acted as superabsorbent hydrogels. The monomer reactivity ratios were calculated using Fineman Ross, Extended Kelen Tüdøs , and Mayo Lewis methods that gave r₁(PEGM) = 0.90, r₂(DEAEM) = 0.14 at low conversions. At high conversions r₁ and r₂ values were calculated as 1.01 and 0.40, respectively. Adsorption isotherms of methyl orange (MO) onto hydrogels were studied using Langmuir, Freundlich, and Temkin models. The experimental data fitted well with the Langmuir equation. The maximum adsorption capacity for MO was 212.7 mg g⁻¹ at pH = 3. The adsorption data gave best fit with the pseudo-second order kinetic model. Thermodynamic evaluation showed spontaneous nature for MO adsorption onto poly(PEGM-co-DEAEM) hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47707.     

Photoinduced reversible refractive index changes in doped poly(methyl methacrylate) lightguides

Planar polymer lightguides of poly(methyl methacrylate)(PMMA) doped with the azo dye, N,N-dihexyl-4-amino-4′-nitro-azobenzene (DHANA) were fabricated on a suitable glass substrate or on one surface of a regular prism. The absorption of this azo dye is strong in the green spectral region. With the red light of a HeNe laser (633 nm) these polymer films may be used as lightguides. However, in this spectral region, the guided light influences the waveguiding properties of the polymer film, making this combination a possible candidate for an all optical device material. The observed refractive index changes are intensity dependent and the response time is of the order of 100ms.     

The transport of methyl methacrylate monomer in poly(methyl methacrylate)

The absorption kinetics and equlibria of methyl methacrylate monomer into poly(methyl methacrylate) were studied over a range of penetrant activities. The interval sorption kinetics at elevated activities were determined, compared, and contrasted with the integral sorption experiments in previously unpenetrated film samples. The sorption kinetics in previously unpenetrated films were predominantly case II or relaxation controlled at high activities. A Fickian contribution to the overall kinetics was apparent at lower activities. In contrast, interval sorption, at elevated activities in previously equilibrated and plasticized samples, followed Fickian kinetics rather closely, whereas resorption, over an activity range which involved a traversal of the effective T_g, was characterized by more complicated kinetics involving a super case II mechanism at long times. These composite results reinforce the notion that the kinetics describing penetration of a single penetrant into a single polymer are extremely sensitive to the boundary condition imposed upon the polymeric sorbent.     

Drying of grape pomace with a double pass solar collector

This study aims to analyze the performance of a novel design of the double pass solar air collector (DPSAC)-assisted drying system and investigate the drying kinetics of grape pomace which is an agricultural by-product. The samples were dried to a moisture content of 0.01?g water/g dry matter between 100 and 250?min depending on the weather conditions. The average thermal efficiencies of DPSAC were calculated as 79.77, 79.85, and 69.46%. Average values of the coefficient of performance of DPSAC were determined as 5.32, 5.13, and 4.32. The highest specific moisture extraction rate value was achieved as 617.18?g water/kWh. Whereas the mass transfer coefficient (h_m) values ranged from 9.15E?11 to 1.04E?7?m/s, the effective moisture diffusivity (D_e) values were obtained between 3.04E?13 and 1.02E?10?m²/s. The qualitative analysis showed that the drying using DPSAC may be an alternative for drying applications in terms of short drying time and energy usage. Nevertheless, these results clearly suggest a complex and effective interplay between thermal performance and drying kinetics.     

Optical and mechanical properties of optically transparent poly(methyl methacrylate) composites

Highly transparent poly(methyl methacrylate) (PMMA) composites have been made by carefully matching the refractive index of the glass fiber reinforcement with the PMMA matrix. Composites containing 10.4 vol% glass fibers and 0.68 mm in thickness had an overall optical transmission of 92%. The transparency of the composites is temperature dependent because of the different temperature coefficients of refractive index for the glass fiber and PMMA. The tensile strength of the composites at room temperature was twice that of pure PMMA and decreased with increasing temperature, as predicted by the rule of mixtures.     

Thermo-oxidative stability of poly(methyl methacrylate)/poly(methyl methacrylate)-grafted SiO2 nanocomposites

Thermo-oxidative stability of PMMA-grafted SiO₂ and PMMA/PMMA-grafted SiO₂ nanocomposites was investigated by conventional non-isothermal gravimetric technique. It was interesting to find that PMMA-grafted SiO₂ nanoparticles exhibited higher thermo-oxidative stability than that of PMMA. The apparent activation energy of PMMA-grafted SiO₂ nanoparticles increased with the grafting ratio of PMMA from SiO₂, which was estimated by Kissinger method. This indicates that the strong interactions existing between the grafted chains are responsible for the enhanced thermo-oxidative stability of PMMA-grafted SiO₂ nanoparticles. However, the grafting ratio of PMMA from SiO₂ in nanoparticles has only limited effect on the thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites due to a much lower content of grafted PMMA in the nanoparticles relative to PMMA. The increased thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites is possibly resulted from the increased SiO₂ content in the nanocomposites, in which the grafting ratio of PMMA in PMMA-grafted SiO₂ nanoparticles is kept almost as a constant. The glass transition temperature (T _g) of PMMA/PMMA-grafted SiO₂ nanocomposites is about 25 °C and is higher than that of PMMA. The grafting ratio of PMMA from SiO₂ in the nanoparticles has no qualitative effects on the T _g of the nanocomposites.