Preparation and luminescence of SrAl2O4: Eu2+,Dy3+ phosphors coated with maleic anhydride

In this paper, maleic anhydride is directly coated on the surface of SrAl₂O₄: Eu²⁺, Dy³⁺ (SAO‐ED) phosphors by an interfacial coordination chemistry method. Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectra (XPS), X‐ray diffraction (XRD), and scanning electron microscopy (SEM) methods are used to characterize the coating. The experimental result shows that a dense coating layer is consisting of maleic anhydride coordination with metal ions on the surface of the phosphors and the coating process does not destroy the crystal structure of the phosphors. It is also found that the introduction of maleic anhydride does not change the excitation and emission spectra of SAO‐ED phosphors, but decreases the luminous intensity, which is verified by the photoluminescence (PL) measurement. Afterglow delay curves show that the initial brightness of coated SAO‐ED phosphors decreases, but the afterglow decay rate of coated phosphors is slower than that of uncoated phosphors after they both are immersed into water for one month. This indicates that the coating layer protects the phosphors and the crystal structure of coated phosphors in water was not destroyed.     

Atomic layer deposition (ALD) of nanoscale coatings on SrAl2O4-based phosphor powders to prevent aqueous degradation

The aqueous degradation of Eu²⁺-activated and Dy³⁺-codoped strontium aluminate (SrAl₂O₄:Eu²⁺, Dy³⁺, SA2-Green) long afterglow phosphors synthesized from solid-state reaction and coated with nanoscale metal oxide protective layers (≤12 nm) via atomic layer deposition (ALD) is investigated. Uncoated phosphor powders degrade rapidly upon water immersion and lose their green phosphorescence within 48 hours of water exposure. Postmortem investigations reveal hydration and decomposition of the SrAl₂O₄ phase. ALD of ~10 nm Al₂O₃ or ~12 nm TiO₂ is found to significantly improve the powder's resistance to aqueous degradation. All ALD-coated powders show minimal structural and chemical degradation and retain phosphoresence after 48 hours of water immersion. This enhanced durability offers a new pathway for applying long afterglow phosphors to outdoor applications like roadway markings or safety signage and for their incorporation into more eco-friendly waterborne coatings.     

Transparent poly(methyl methacrylate‐co‐butyl acrylate) nanofibers

Nanofibers of n‐Butyl Acrylate/Methyl Methacrylate copolymer [P(BA‐co‐MMA)] were produced by electrospinning in this study. P(BA‐co‐MMA) was synthesized by emulsion polymerization. The structural and thermal properties of copolymers and electrospun P(BA‐co‐MMA) nanofibers were analyzed using Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR–ATR), Nuclear magnetic spectroscopy (NMR), and Differential scanning calorimetry (DSC). FTIR–ATR spectra and NMR spectrum revealed that BA and MMA had effectively participated in polymerization. The morphology of the resulting nanofibers was investigated by scanning electron microscopy, indicating that the diameters of P(BA‐co‐MMA) nanofibers were strongly dependent on the polymer solution dielectric constant, and concentration of solution and flow rate. Homogeneous electrospun P(BA‐co‐MMA) fibers as small as 390 ± 30 nm were successfully produced. The dielectric properties of polymer solution strongly affected the diameter and morphology of electrospun polymer fibers. The bending instability of the electrospinning jet increased with higher dielectric constant. The charges inside the polymer jet tended to repel each other so as to stretch and reduce the diameter of the polymer fibers by the presence of high dielectric environment of the solvent. The extent to which the choice of solvent affects the nanofiber characteristics were well illustrated in the electrospinning of [P(BA‐co‐MMA)] from solvents and mixed solvents. Nanofiber mats showed relatively high hydrophobicity with intrinsic water contact angle up to 120°. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4264–4272, 2013     

Thermoluminescence and Temperature‐Dependent Afterglow Properties in BaSi2O2N2:Eu2+

BaSi₂O₂N₂:Eu²⁺ phosphor was successfully synthesized by using a simple solid‐state reaction method. Its properties were systematically investigated utilizing XRD, photoluminescence, excited state decay curve, afterglow emission spectra, and thermoluminescence (TL) glow curve. With increasing temperature, its emission intensity decreases with the broadening full widths at half maximum. Particularly, its temperature‐dependent afterglow emission spectra were investigated for the first time. Based on the information from TL glow curve, temperature‐dependent afterglow decay curves, and afterglow emission spectra, a model was constructed to explain the mechanism of afterglow. This study provides a new perspective to use the temperature‐dependent luminescence properties for studying the afterglow processes of long‐lasting phosphorescence phosphors.     

Synthesis of an acrylate elastomer with UV stabilization and its application in polyoxymethylene

In this study, an acrylate elastomer with light‐stable functional groups was synthesized by methyl methacrylate (MMA), butyl acrylate (BA), and a polymerizable UV stabilizer 2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone (BPMA) via emulsion polymerization, and the product was poly[methyl methacrylate‐co‐butyl acrylate‐co‐2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone] [poly(MMA‐co‐BA‐co‐BPMA)]. The composition and characteristics of poly (MMA‐co‐BA‐co‐BPMA) were determined by using Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H‐NMR), and ultraviolet–visible absorption spectroscopy (UV–vis). Further, the obtained poly(MMA‐co‐BA‐co‐BPMA) was blended with polyoxymethylene (POM) to modify its photostabilization, as well as the mechanical properties of POM composite were tested before and after UV irradiation. The result showed that poly(MMA‐co‐BA‐co‐BPMA) can be dispersed well in the POM matrix, which could play a role of improving compatibility with and toughening for POM, and its light‐stable functional groups could increase the UV resistance of POM composite. Mechanical properties of modified POM were kept well with higher impact strength and elongation at break than pure POM after UV irradiation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Luminescent properties of long‐lasting BaAlxOy:Eu2+,Dy3+ nanocomposites

BaAl_xO_y:Eu²⁺,Dy³⁺ blue‐green phosphor samples were synthesized by a combustion method at the low temperature of 500°C. Phosphor nanocrystallites with high brightness were obtained without significantly changing the crystalline structure of the host. The crystallite sizes determined from the Scherrer equation ranged between 34 and 41 nm. Different volume fractions of the BaAl_xO_y:Eu²⁺,Dy³⁺ powder were then introduced in LDPE polymer. The resulting composites were similarly analyzed and also thermally characterized by means of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). PL results indicate that the LDPE‐phosphor interface, which is considered to have an influence on the composite behavior, did not significantly change the spectral positions of the phosphor materials, whose major emission peaks occurred at about 505 nm. The improved afterglow results for the composites may have been caused by morphological changes due to increased surface area and defects. Thermal results indicate that the BaAl_xO_y:Eu²⁺,Dy³⁺ particles acted as nucleating centers and enhanced the overall crystallinity in the LDPE nanocomposite while preventing lamellar growth, hence reducing the crystallite sizes in LDPE. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Temperature‐Dependent Emission Spectra of Ca2Si5N8:Eu2+, Tm3+ Phosphor and its Afterglow Properties

The nitrides Ca₂Si₅N₈:0.5%Eu²⁺, x%Tm³⁺(x = 0, 0.5, 1, 2, 4) (CSN:0.5E, xT) phosphors were prepared via the high temperature solid‐sintering method using CaH₂ as calcium source. These phosphors exhibited strong orange long‐lasting phosphorescence (LLP) after turning off the activating light. Besides, the CSN:0.5E, 1T phosphor with an afterglow time of more than 200 min (0.32 mcd/m²). Furthermore, the temperature‐dependent emission spectra of CSN:0.5E, 1T were investigated from temperature 80–500 K and an anti‐quenching phenomenon that the emission intensities increased then decreased under excitation at increased temperature was found. Ultimate, the proposed mechanism on temperature dependence of luminescence was analyzed. This study provides a new perspective for the impact of temperature‐dependent problem as a consequence of heating processes in luminescent materials.     

Synthesis and characterization of poly(HEMA‐co‐MMA)‐g‐POSS nanocomposites by combination of reversible addition fragmentation chain transfer polymerization and click chemistry

New hybrid poly(hydroxyethyl methacrylate‐co‐methyl methacrylate)‐g‐polyhedral oligosilsesquioxane [poly(HEMA‐co‐MMA)‐g‐POSS] nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and click chemistry using a grafting to protocol. Initially, the random copolymer poly(HEMA‐co‐MMA) was prepared by RAFT polymerization of HEMA and MMA. Alkynyl side groups were introduced onto the polymeric backbones by esterification reaction between 4‐pentynoic acid and the hydroxyl groups on poly(HEMA‐co‐MMA). Azide‐substituted POSS (POSS? N₃) was prepared by the reaction of chloropropyl‐heptaisobutyl‐substituted POSS with NaN₃. The click reaction of poly(HEMA‐co‐MMA)‐alkyne and POSS? N₃ using CuBr/PMDEATA as a catalyst afforded poly(HEMA‐co‐MMA)‐g‐POSS. The structure of the organic/inorganic hybrid material was investigated by Fourier transformed infrared, ¹H‐NMR, and ²⁹Si‐NMR. The elemental mapping analysis of the hybrid using X‐ray photoelectron spectroscopy and EDX also suggest the formation of poly(HEMA‐co‐MMA)‐anchored POSS nanocomposites. The XRD spectrum of the nanocomposites gives evidence that the incorporation of POSS moiety leads to a hybrid physical structure. The morphological feature of the hybrid nanocomposites as captured by field emission scanning electron microscopy and transmission electron microscopic analyses indicate that a thick layer of polymer brushes was immobilized on the POSS cubic nanostructures. The gel permeation chromatography analysis of poly(HEMA‐co‐MMA) and poly(HEMA‐co‐MMA)‐g‐POSS further suggests the preparation of nanocomposites by the combination of RAFT and click chemistry. The thermogravimetric analysis revealed that the thermal property of the poly(HEMA‐co‐MMA) copolymer was significantly improved by the inclusion of POSS in the copolymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of the MMA content on the emulsion polymerization process and adhesive properties of poly(BA‐co‐MMA‐co‐AA) latexes

In the past work, the shear resistance of pure poly(n‐butyl acrylate) was low, even incorporation of inorganic filler, silica in the composition. It is well‐known that the copolymerization of n‐butyl acrylate (BA) with methyl methacrylate (MMA) will increase the glass transition temperature, and enhance the shear resistance of acrylic polymers. In the current work, the preparation of a series of acrylic water‐borne pressure‐sensitive adhesives (PSAs) with the controlled composition and structure for the copolymerization of BA and acrylic acid (AA) with different MMA contents, poly(BA‐co‐MMA‐co‐AA) was reported and its effects on adhesive properties of the latices were investigated. The latices of poly(BA‐co‐MMA‐co‐AA) were prepared at a solid content of 50% by two‐stage sequential emulsion polymerization, and this process consisted of a batch seed stage giving a particle diameter of 111 nm, which was then grown by the semicontinuous addition of monomers to final diameter of 303 nm. Dynamic light scattering (DLS) was used to monitor the particle diameters and proved that no new nucleation occurred during the growth stage. Copolymerization of BA with MMA raised the glass transition temperature (T_g) of the soft acrylic polymers, and had the effect of improving shear resistance, while the loop tack and peel adhesion kept relatively high. The relationship between pressure‐sensitive properties and molecular parameters, such as gel content and molecular weight, was evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Achieving thermally stable and anti-hydrolytic Sr2Si5N8:Eu2+ phosphor via a nanoscale carbon deposition strategy

Chemical stability of phosphors is critical to the efficiency and lifetime of the white light-emitting diodes. Therefore, many strategies have been adopted to improve the stability of phosphors. However, it is still lack of report on the improvement of thermal stability and hydrolysis resistance of phosphors by a single layer coating. Due to the high transmittance and high chemical inertness of graphene, it was coated on the surface of Sr₂Si₅N₈:Eu²⁺ phosphor by chemical vapor deposition, aiming to improve its thermal stability and hydrolysis resistance. The chemical composition and microstructure of the coating were characterized and analyzed. A nanoscale carbon layer was attached on the surface of Sr₂Si₅N₈:Eu²⁺ phosphor particles in an amorphous state. In coated Sr₂Si₅N₈:Eu²⁺ phosphor, the oxidation degree of Eu²⁺ to Eu³⁺ was significantly suppressed. At the same time, the surface of Sr₂Si₅N₈:Eu²⁺ particle turned from hydrophilic to hydrophobic after carbon coating, and consequently the hydrolysis resistance of Sr₂Si₅N₈:Eu²⁺ phosphor was greatly improved. After tests at 85 °C and 85% humidity for 200 h, the carbon coated Sr₂Si₅N₈:Eu²⁺ phosphor still maintained about 95% of its initial luminous intensity as compared with 35% of the uncoated. By observing the in-situ microstructure evolution of coated phosphor in air-water vapor environment, remained presence of the carbon layer even at 500 °C explained the excellent chemical stability of carbon coated Sr₂Si₅N₈:Eu²⁺ phosphor in complex environment. These results indicate that a nanoscale carbon layer can be used to provide superior thermal stability and hydrolysis resistance of (oxy) nitrides phosphors.     

Preparation and characterization of titanium dioxide core/polymer shell hybrid composite particles prepared by emulsion polymerization

Titanium dioxide inorganic core and polymer shell composite poly(methyl methacrylate‐co‐butylacrylate‐co‐methacrylic acid) [P(MMA‐co‐BA)‐MAA] particles were prepared by emulsion copolymerization. Fourier transform IR (FTIR) spectroscopy was used to measure the content of MAA composite particles. Dynamic light scattering (DLS) characterized the composite particle size and size distribution. The field emission SEM (FE‐SEM) results of the composite particles showed regular spherical shape and no bare TiO₂ was detected on the whole surface of the samples. The composite particles were produced, showing good spectral reflectance compared with bare TiO₂. TGA results indicated the encapsulation efficiency and estimated density of composite particles. Encapsulation efficiency was up to 78.9% and the density ranged from 1.76 to 1.94 g/cm³. Estimated density of the composite particles is suitable to 1.73 g/cm³, due to density matching with suspending media. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2970–2975, 2004     

Preparation of SrSi2O2N2:Eu2+ Phosphor by SrSi Alloy Precursor and Its Long‐lasting Phosphorescence Properties

Oxynitride long‐lasting phosphorescence (LLP) phosphor SrSi₂O₂N₂:Eu²⁺ was prepared by a new method using SrSi alloy as a precursor. Its properties were systematically investigated utilizing XRD, photoluminescence, excited‐state decay curve, long‐lasting phosphorescence, and thermoluminescence spectrum. This phosphor was found to be well‐crystallized by calcinations of the Sr_1?xEu_xSi alloy and the SiO₂ mixture at 1400°C for 3 h. After irradiation under the 280 nm UV light, the afterglow emission of Eu²⁺ (4f⁶5d¹ → 4f⁷) was obviously observed for at least 2 h in the limit of light perception of dark‐adapted human eyes (0.32 mcd/m²). Furthermore, the possible mechanism for the LLP of SrSi₂O₂N₂:Eu²⁺ phosphor is also discussed in this article.     

Luminescence Properties of Dual‐Emission (UV/Visible) Long Afterglow Phosphor SrZrO3: Pr3+

A dual‐emission (UV/Visible) phosphor SrZrO₃: Pr³⁺ was prepared by a high‐temperature solid‐state reaction method. The afterglow including ultraviolet (UV) and visible region which originated from self‐trapped excitons and f–f transitions in Pr³⁺ was first observed after the short UV‐irradiation. All as‐prepared phosphors were studied systematically by X‐ray diffraction, photoluminescence (PL) spectra, decay curves, long afterglow spectra (LAG), and thermoluminescence (TL) glow curves. The PL intensity and the performance of afterglow are dependent on the concentration of Pr³⁺ ions. The optimal concentration of Pr³⁺ ions for the brightest PL emission and the best afterglow characteristic were experimentally to be 0.5% and 0.4%, respectively. The different mechanisms for concentration quenching in both cases were discussed. A model was proposed on the basis of experimental results to discuss the mechanism of LAG in SrZrO₃: Pr³⁺ in detail.     

Polypropylene separator coated with a thin layer of poly(lithium acrylate‐co‐butyl acrylate) for high‐performance lithium‐ion batteries

In this paper, poly(lithium acrylate‐co‐butyl acrylate) [P(AALi‐co‐BA)] was synthesized, and a P(AALi‐co‐BA)‐coated polypropylene (PP) separator was prepared by a simple dip‐coating process. In contrast to the conventional thick, dense gel polymer coating layer, a thin P(AALi‐co‐BA) layer was formed on the PP separator, which had less influence on the pore structure of the original PP separator and was beneficial for the migration of lithium ions through the separator. Furthermore, the AALi units in the copolymer could improve the wettability of the separator, while the BA units provided the separator with strong adhesion to the electrodes. As expected, the modified separators showed good wettability, high ionic conductivity, and excellent interface stability. In addition, the cycle stability and rate performance were also improved significantly. This facile, affordable, and effective method has great application potential for the modification of polyolefin‐based separators. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46423.     

Aqueous polyacrylate/poly(silicone‐co‐acrylate) emulsion coated fertilizers for slow nutrient‐release application

Waterborne polyacrylate/poly(silicone‐co‐acrylate) emulsions were synthesized to develop coated fertilizers. The effects of the n‐butyl acrylate (BA)/methyl methacrylate (MMA) ratio, vinyltriethoxysilane, and synthesis method on the water resistance, glass‐transition temperature, mechanical properties, and nutrient‐release profiles were investigated. The results show that miniemulsion polymerization with a BA/MMA ratio of 55:45 was the most suitable for slow nutrient‐release applications. Under these conditions, the preliminary solubility rate of the nutrient was about 3%, and the 30‐day cumulative nutrient release was 15% at 25°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40369.     

Highly Stable Red‐Emitting Sr2Si5N8:Eu2+ Phosphor with a Hydrophobic Surface

One of the biggest problems in white light‐emitting diodes (WLEDs) is the moisture‐induced degradation of phosphors. This paper proposes a simple and feasible surface modification method to solve it, whereby a hydrophobic surface layer is developed on the surface of the phosphors. The particular case of orange‐red‐emitting Sr₂Si₅N₈:Eu²⁺ (SSN) phosphor was investigated. The mechanism to develop the hydrophobic layer involves hydrolysis and polymerization of tetraethylorthosilicate (TEOS) and polydimethylsiloxane (PDMS). The experimental results showed that the surface layer of SSN phosphor was successfully modified to a hydrophobic nanolayer (8 nm) of amorphous silicon dioxide that contains CH₃ groups in the surface. This hydrophobic surface layer gives the modified phosphor superior stability in high‐pressure water steam conditions at 150°C.     

Alumina encapsulated SrAl2O4:Eu, Dy phosphors

Alumina encapsulation on SrAl₂O₄: Eu²⁺, Dy³⁺ phosphors by a new type of chemical precipitation process was reported for the first time to the best of our knowledge. X-ray fluorescent measurements revealed that using glycol instead of the distilled water as the disperse medium is helpful to alumina encapsulation. Scanning electron micrographs and BET measurements showed that a dense and homogeneous off-white alumina layer was formed on the phosphor surface after encapsulation. Water resistance and heat resistance measurements showed that when the encapsulation amount reached to 5 wt.% (fed value), the encapsulated phosphors began to show good water resistance and heat resistance with little loss of persistent phosphorescence.     

Mechanical properties and surface morphology of photodegraded polyoxymethylene modified by a core–shell acrylate elastomer with UV stabilization

In order to improve the photostability of polyoxymethylene (POM), a core‐shell acrylate elastomer with UV stabilization, i.e. poly[(methyl methacrylate)‐(butyl acrylate)‐2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxypropoxy)benzophenone] (core‐shell poly(MMA‐BA‐BPMA)), was added into the POM matrix using a melt‐mixing method. The effect of the modification with core‐shell poly(MMA‐BA‐BPMA) on POM was compared with that of poly(MMA‐ co ‐BA‐ co ‐BPMA) copolymer. Scanning electron microscopy, metallographic microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, X‐ray diffraction and X‐ray photoelectron spectroscopy were employed to characterize POM blends before and after UV irradiation, and the mechanical properties of the POM blends were investigated. The results showed that core‐shell poly(MMA‐BA‐BPMA) improved well the compatibility with and toughness of the POM matrix, and its light‐stable functional groups could increase the UV resistance of POM blends. During UV aging, the impact strength and elongation at break of POM/core‐shell poly(MMA‐BA‐BPMA) blends were retained, the growth rate of surface cracks of POM was inhibited effectively by core‐shell poly(MMA‐BA‐BPMA) and the degree of photo‐oxidation of POM blend surfaces was improved to a certain extent. Compared with poly(MMA‐ co ‐BA‐ co ‐BPMA), core‐shell poly(MMA‐BA‐BPMA) had a better UV stabilization effect on the POM matrix. Our results indicate that the core‐shell acrylate elastomer with toughening and UV stabilization functions can significantly improve the long‐term UV stability of POM. Copyright © 2012 Society of Chemical Industry     

Mechanical recycling of nanocellulose containing multilayer packaging films

The aim of this study was to demonstrate mechanical recycling of low density polyethylene (LDPE) films coated with a thin layer of cellulose nanofibrils (CNFs). CNF acts as an effective barrier against oxygen and mineral oil residues. Two different CNF grades were tested, and both were applied onto plasma activated LDPE film using a pilot coating line. The coated films were shredded with the help of liquid nitrogen, compacted and compounded with virgin LDPE and compatibilizer, and processed into cast films and injection molded test specimens. The CNF coatings were completely blent as microscale agglomerates in the LDPE matrix. The effect of these agglomerates on the barrier and heat sealing properties was statistically insignificant compared to recycled uncoated LDPE. The mechanical properties were only moderately changed. CNF‐coated LDPE films can therefore be recycled back into films without sacrificing the characteristic properties of the base polymer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46237.     

Synthesis and characterization of paraffin/TiO2‐P(MMA‐co‐BA) phase change material microcapsules for thermal energy storage

Microcapsules based on a phase changing paraffin core and modified titanium dioxide–poly(methyl methacrylate‐co‐butyl acrylate) [P(MMA‐co‐BA)] hybrid shell were prepared via a Pickering emulsion method in this study. The microcapsules exhibit an irregularly spherical morphology with the size range of 3–24 µm. The addition of BA can enhance the toughness of the brittle polymer poly(methyl methacrylate) and improve the thermal reliability of the phase change microcapsules. The ratio of BA/MMA is in the range of 0.09–0.14, and the ratio of the monomer/paraffin is varied from 0.45 to 0.60. These microcapsules exhibit a well‐defined morphology and good thermal stability. The actual core content of the microcapsules reaches 36.09%, with an encapsulation efficiency of 73.07%. Furthermore, the prepared microcapsules present the high thermal reliability for latent‐heat storage and release after 2000 thermal cycles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46447.