Acrylate-based Polymer Research Articles

Rhodamine-B absorption and fluorescence enhancement in the near field of gold nanoparticles in an acrylate-based polymer matrix

We describe the preparation of polymer microstructures doped with Rhodamine B organic dye and study the effect of a pinned gold-nanoparticle plasmon resonance on the optical properties of this dye in an acrylate-based polymer matrix. We find that the optical absorption and fluorescence intensity of Rhodamine B in the polymer matrix are enhanced under plasmon resonance.

Enhancement of the absorption and fluorescence of rhodamine B in the near field of gold nanoparticles in an acrylate-based polymer matrix

Enhancement of the absorption and fluorescence of rhodamine B in the near field of gold nanoparticles in an acrylate-based polymer matrix

Stretchable and patchable composite electrode with trimethylolpropane formal acrylate-based polymer

With the huge variety of wearable/stretchable electronic devices that require materials with different properties depending on the applications, securing the large reserves of stretchable material systems is crucial. In this study, trimethylolpropane formal acrylate (TFA)-based polymer films are explored to develop stretchable composite electrodes. The TFA resin containing 1-hydroxycyclohexyl phenyl ketone as a photoinitiator is UV curable and shows a high optical transmittance of ∼93.0 ± 0.3% and a low haze of ∼0.29 ± 0.03%. The TFA films can withstand a tensile strain up to 100% and show excellent mechanical reliability during 30 cycles of tensile tests. Furthermore, the elastomeric TFA films are attachable to polymer or glass substrates, and during multiple adhesion tests, show a lower degradation of the adhesion properties than that showed by typical adhesive materials such as scotch tapes. The electrodes fabricated by embedding Ag nanowires in the surface of the TFA films (TFA/Ag nanowire electrodes) function as stretchable/patchable conductors under severe mechanical deformation such as stretching and crumpling. Furthermore, a patchable/stretchable supercapacitor comprising the TFA/Ag nanowire electrodes as a current collector is demonstrated that shows a reliable electrochemical performance under bending, stretching, and twisting conditions.

The Effect of Localized Plasmons in Silver and Gold Thin Films on the Optical Properties of Organic Dyes in an Acrylate Polymer Matrix

We present the results of our investigation into the effect of localized surface plasmon resonances of gold and silver nanoparticles on the emissivity of two organic dyes—2-(4-(dimethylamino)styryl)-1-methylpyridinium and rhodamine B—in acrylate-based polymer matrices formed on the surface of island metal films by the UV lithography method. We show that the presence of plasmon resonances significantly enhances both the optical absorption and the fluorescence intensity of these organic dyes in polymer matrices.

Characterization of a new polymer optical fiber with enhanced sensing capabilities using a Bragg grating.

We present results for the mechanical characterization of a bisphenol-A acrylate-based polymer optical fiber (POF) manufactured using a novel light polymerization spinning (LPS) process. The particular manufacturing process allows the development of POFs having unique mechanical characteristics, which result from an exceptionally low Young's modulus. The lower Young's modulus enables optical sensors for measuring stress or pressure with improved sensitivity and potentially a higher tunable mechanical range than conventional POFs. Moreover, properties such as the storage modulus variations with respect to the temperature and humidity were studied. Fiber Bragg gratings (FBGs), were inscribed in the POF using the plane-by-plane femtosecond laser, direct-write method for selective FBG mode excitation, and were characterized for changes to temperature, pressure, and relative humidity. The response of FBGs in this LPS-POF for all the three aforementioned measurands was several times higher than that measured for conventional POFs.

Linear shear and nonlinear extensional rheology of unentangled supramolecular side-chain polymers

Supramolecular polymers are important within a wide range of applications including printing, adhesives, coatings, cosmetics, surgery, and nano-fabrication. The possibility to tune polymer properties through the control of supramolecular associations makes these materials both versatile and powerful. Here, we present a systematic investigation of the linear shear rheology for a series of unentangled ethylhexyl acrylate-based polymers for which the concentration of randomly distributed supramolecular side groups is systematically varied. We perform a detailed investigation of the applicability of time temperature superposition (TTS) for our polymers; small amplitude oscillatory shear rheology is combined with stress relaxation experiments to identify the dynamic range over which TTS is a reasonable approximation. Moreover, we find that the “sticky-Rouse” model normally used to interpret the rheological response of supramolecular polymers fits our experimental data well in the terminal regime, but is less successful in the rubbery plateau regime. We propose some modifications to the “sticky-Rouse” model, which includes more realistic assumptions with regard to (i) the random placement of the stickers along the backbone, (ii) the contributions from dangling chain ends, and (iii) the chain motion upon dissociation of a sticker and reassociation with a new co-ordination which involves a finite sized “hop” of the chain. Our model provides an improved description of the plateau region. Finally, we measure the extensional rheological response of one of our supramolecular polymers. For the probed extensional flow rates, which are small compared to the characteristic rates of sticker dynamics, we expect a Rouse-type description to work well. We test this by modeling the observed strain hardening using the upper convected Maxwell model and demonstrate that this simple model can describe the data well, confirming the prediction and supporting our determination of sticker dynamics based on linear shear rheology.

The effects of huntite–hydromagnesite inclusion in acrylate-based polymer paste coating process on some textile functional performance properties of cotton fabric

In this study, cotton fiber fabrics were coated with polyacrylate-based polymer paste containing huntite–hydromagnesite by knife over roll process. The flame retardancy properties of the cotton fabrics were tested according to vertical flame test, limit oxygen index (LOI) test, smoldering cigarette and match flame tests. Thermal behavior of cotton fabrics was investigated by DTA–TG analysis. The antibacterial activities of coated cotton fabrics were qualitatively determined according to AATCC Method 147. Mechanical properties of cotton fabrics were evaluated with the help of tear strength, abrasion strength, thickness and stiffness measurements. Air permeability, UV protection and color properties were also investigated. Free formaldehyde content of the coatings on cotton fabrics were determined according to Japanese Law 112. The microstructural properties of cotton fabrics were characterized using SEM and FTIR (ATR) analysis. Furthermore, the mineral content and mean particle size value of huntite–hydromagnesite were also determined with X-ray fluorescence spectrometer and particle size analyzer. The flame retardancy and antibacterial properties of the cotton fabrics were improved after coating with acrylate-based polymer paste containing huntite–hydromagnesite. Mechanical properties such as tear strength of the cotton fabric decreased after coating process however huntite–hydromagnesite addition into coating paste did not lead to further increase on the tear strength loss of cotton fabric. Despite this, the resultant maximum abrasion cycles significantly increased following coating process application. Furthermore, colorimetric properties such as whiteness and lightness of cotton fabric did not significantly change after applied coating processes. SEM and FTIR analyses confirmed the constancy of microstructure of cotton fibers after coating process.

Smart Polymers in Micro and Nano Sensory Devices

The present review presents the most recent developments concerning the application of sensory polymers in the detection and quantification of different target species. We will firstly describe the main polymers that are being employed as sensory polymers, including, for example, conducting or acrylate-based polymers. In the second part of the review, we will briefly describe the different mechanisms of detection and the target species, such as metal cations and anions, explosives, and biological and biomedical substances. To conclude, we will describe the advancements in recent years concerning the fabrication of micro and nano sensory devices based on smart polymers, with a bibliographic revision of the research work published between 2005 and today, with special emphasis on research work presented since 2010. A final section exposing the perspectives and challenges of this interesting research line will end the present review article.

Synthesis and Characterization of Butyl Acrylate-based Graft Polymers with Thermo-responsive Branching Sites via the Diels-Alder Reaction of Furan/Maleimide

Thermo-responsive butyl acrylate/furfuryl methacrylate copolymer-based (PBF backbone) graft (co)polymers with dynamic covalent linkages between their backbones and side chains via the Diels-Alder reaction of furan/maleimide were synthesized. Atom transfer radical polymerization (ATRP) was used to synthesize graft copolymers with thermo-responsive transformation from graft copolymers to linear polymers with bimodal or wide MWD. The NMR measurements indicated that the Diels-Alder reaction and retro-Diels-Alder reaction occurred, depending on the change of the temperature, meaning that the side chains could be cleaved and reformed according to the variation of the temperature. GPC measurements demonstrated that the molecular weights of the polymers were thermoresponsive. Furthermore, three graft copolymers with various branching chains (PBF-g-PBA, PBF-g-P(BMA-co-MA) and PBF-g-PBMA) were compared to study the influence of compatibility between the backbone and the branching chain on the efficiency of Diels-Alder reaction after the cleavage of the DA linkage. The results showed that the ability of the side chains to come back to the main chain was strongly affected by the compatibility between the backbone and the side chains and the flexibility of the polymer chains.

Tuning the Morphology of an Acrylate-Based Metallo-Supramolecular Network: From Vesicles to Cylinders

This work investigated the morphological behavior of an acrylate-based metallo-supramolecular polymer system. RAFT (reversible addition–fragmentation chain transfer) polymerization techniques were used to synthesize low molar mass, linear prepolymers of n-butyl acrylate and a 2,6-bis(1′-methylbenzimidazolyl)pyridine–acrylate monomer (MeBIP–Ac) of varying concentration (2–10%). This synthesis incorporated a systematic increase of cross-link points (MeBIP ligands) pendent to the polymer backbone. A zinc(II) salt (Zn(ClO4)2) complexed with the pendent MeBIP ligands in a 1:2 ratio to form cross-linked polymers as free-standing films. The morphology of the neat films as well as those with added unbound MeBIP–zinc–MeBIP metal–ligand (ML) complex were characterized using transmission electron microscopy (TEM), HAADF-STEM (high angle annular dark field scanning transmission electron microscopy), energy dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), energy-filtered TEM (EFTEM), and ...

Acrylate-based coatings to protect lead substrates

This study investigates the surface protection treatment of hydrophobic acrylate-based polymers with built-in carboxylic acid groups produced using a controlled Reversible Addition Fragmentation chain Transfer (RAFT) polymerization. The synthesized polymers are dissolved in a water-organic solvent mixture and afterwards deposited on lead substrates by immersing them in the solution. The coatings produce a hydrophobic film, which slows down the lead corrosion processes. The protective properties of the coatings are analyzed using non-destructive odd random phase multisine electrochemical impedance spectroscopy (ORP-EIS) in an acetic acid corrosive solution containing tertbutylammonium bromide (TBAB) supporting electrolyte. The impedance data and electron images of the coatings demonstrate that the coating thickness, pore formation, diffusion and electrolyte uptake profile depend on the polymer’s acrylic acid content and the molecular weight. All these parameters have a clear impact on the inhibition of the corrosion process.

A Lithium/Polysulfide Battery with Dual-Working Mode Enabled by Liquid Fuel and Acrylate-Based Gel Polymer Electrolyte

The low density associated with low sulfur areal loading in the solid-state sulfur cathode of current Li-S batteries is an issue hindering the development of this type of battery. Polysulfide catholyte as a recyclable liquid fuel was proven to enhance both the energy density and power density of the battery. However, a critical barrier with this lithium (Li)/polysulfide battery is that the shuttle effect, which is the crossover of polysulfides and side deposition on the Li anode, becomes much more severe than that in conventional Li-S batteries with a solid-state sulfur cathode. In this work, we successfully applied an acrylate-based gel polymer electrolyte (GPE) to the Li/polysulfide system. The GPE layer can effectively block the detrimental diffusion of polysulfides and protect the Li metal from the side passivation reaction. Cathode-static batteries utilizing 2 M catholyte (areal sulfur loading of 6.4 mg cm-2) present superior cycling stability (727.4 mAh g-1 after 500 cycles at 0.2 C) and high rate capability (814 mAh g-1 at 2 C) and power density (∼10 mW cm-2), which also possess replaceable and encapsulated merits for mobile devices. In the cathode-flow mode, the Li/polysulfide system with catholyte supplied from an external tank demonstrates further improved power density (∼69 mW cm-2) and stable cycling performance. This novel and simple Li/polysulfide system represents a significant advancement of high energy density sulfur-based batteries for future power sources.

Controlled Release of Antimicrobial ClO2 Gas from a Two-Layer Polymeric Film System.

We report a two-component label system comprising a chlorite-containing polymer film and an acid-containing polymer film that can release antimicrobial ClO2 gas upon adhering the two films together to enable a reaction of the chlorite and acid under moisture exposure. The chlorite-containing film comprises a commercial acrylate-based pressure-sensitive adhesive polymer impregnated with sodium chlorite. The acid-containing film comprises a commercial poly(vinyl alcohol) polymer loaded with tartaric acid. Both of the films were prepared on low ClO2-absorbing substrate films from stable aqueous systems of the polymers with high reagent loading. Rapid and sustained releases of significant amounts of ClO2 gas from the label system were observed in an in situ quantification system using UV-vis spectroscopy. It was found that the ClO2 release is slower at a lower temperature and can be accelerated by moisture in the atmosphere and the films. Controlled release of ClO2 gas from the label system was demonstrated by tailoring film composition and thickness. A model was developed to extract release kinetics and revealed good conversions of the label system. This two-component system can potentially be applied as a two-part label without premature release for applications in food packaging.

Core/Shell Systems for Delayed Delivery of Concentrated Mineral Acid

Summary Acid stimulation, for both oil and gas wells, greatly supports the industry as a versatile means of enhancing production. Although acids enhance carbonate reservoir permeability to hydrocarbons, the reaction rates of the acid [e.g., hydrochloric acid (HCl)] with the rock often are too rapid at high temperatures, leading to a reduction in acid penetration. Several methods exist to improve the effectiveness of acidizing in high-temperature reservoirs (e.g., greater than 120°C), including the use of conventional emulsified-acid systems, mixtures of HCl and organic acids, and gelled acids. Many of the aforementioned techniques are effective forms of treatment; however, they hold significant limitations such as reduction in acid efficiency, poor control over penetration depth, and the requirement of corrosion inhibitors. Accordingly, encapsulated HCl holds potential as an attractive alternative to address these shortcomings because its prolonged release profile would permit transport of acid deep within the reservoir. In addition, when successfully encapsulated, this technology could eliminate, or at the very least minimize, the use of corrosion inhibitors. Herein, we demonstrate the design and preparation of highly modular core/shell particles comprising concentrated HCl encapsulated within an acrylate-based thermoset polymer shell. We show that the shell-generation mechanism (i.e., photopolymerization of acrylate monomers) is compatible with concentrated HCl and further detail the encapsulation process. Our results demonstrate that the acid-release profiles are dictated by the properties of the shell material, enabling a prolonged delivery of HCl in laboratory studies. This is a first step toward the design of particle-shell systems that can tolerate harsh reservoir conditions, including high temperatures, pressures, and salinity of mixing water. A tunable core/shell delivery system that encompasses a sufficient amount of strong mineral acid is well-poised to address the unmet need of deeper penetration of HCl into the reservoir, enabling greater stimulation efficiency.

A highly-safe lithium-ion sulfur polymer battery with SnO2 anode and acrylate-based gel polymer electrolyte

Safety is a prime concern associated with the use of metallic lithium in high-capacity Li–S batteries. Recent studies have shown that replacing lithium metal with other high performance anodes and assembling as lithium-ion sulfur battery (LISB) are effective methods to enhance the safety coefficient of the battery. However, the volume expansion of anodic active materials and gradual thickening of solid electrolyte interface (SEI) on the anode, as well as the ever-existing detrimental shuttle effect of sulfur cathode still limit the performance of LISBs. In this work, we propose and prepare a lithium-ion sulfur polymer battery (LISPB) that employs a stable SnO2 anode and a bi-functional gel polymer electrolyte (GPE). We demonstrate that graphene and carboxymethyl cellulose (CMC) are able to form a robust anode structure and simultaneously maintain a stable SEI in ether-based electrolyte, while the acrylate-based GPE immobilizes the polysulfides and protects the anodic SEI from side deposition reactions. The LISPB renders a superior high rate capability (608.2mAhg−1 at 5C), while maintaining excellent retention at both high and low current densities (83.3% after 300 cycles at 0.3C and 82.1% after 500 cycles at 1C). This novel and simple LISPB system represents a significant advancement of high-safety sulfur-based batteries.

Chip-based electrochromatography coupled to ESI-MS detection.

In this study, we present the coupling of chip-based electrochromatography to MS using a glass chip with a monolithically integrated nanoelectrospray emitter. As separation column, an acrylate-based porous polymer monolith is implemented into the glass chip by photopolymerization. For the establishment and development of this method, we used a test mixture detectable with both fluorescence and ESI-MS. After successful evaluation of the approach with the test solutes, it was applied exemplarily for drug analysis such as high-speed separations of benzodiazepines in pharmaceuticals.

Hydrophilic Organic Electrodes on Flexible Hydrogels.

Prompted by the rapidly developing field of wearable electronics, research into biocompatible substrates and coatings is intensifying. Acrylate-based hydrogel polymers have gained widespread use as biocompatible articles in applications such as contact and intraocular lenses. Surface treatments and/or coatings present one strategy to further enhance the performance of these hydrogels or even realize novel functionality. In this study, the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is deposited from the vapor phase onto hydrated hydrogel substrates and blended with biocompatibilizing coconstituents incorporating polyethylene glycol (PEG) and polydimethyl siloxane (PDMS) moieties. Plasma pretreatment of the dehydrated hydrogel substrate modifies its surface topography and chemical composition to facilitate the attachment of conductive PEDOT-based surface layers. Manipulating the vapor phase polymerization process and constituent composition, the PEDOT-based coating is engineered to be both hydrophilic (i.e. to promote biocompatibility) and highly conductive. The fabrication of this conductively coated hydrogel has implications for the future of wearable electronic devices.

Controlled Deposition of Polymer Coatings on Cylindrical Photonic Devices

We present a simple system for coating cylindrical devices for photonic related applications based on a wire coating method. Characterization of the system was done using two different polymeric materials, silicon-based PDMS and an acrylate-based polymer, obtaining different coating thicknesses upon varying the parameters of the process. Layers with controlled thickness ranging from hundreds of nanometers to 1 mm can be readily applied over devices with different diameters. We demonstrate the system capabilities for coating tapered optical fibers and glass capillaries. The fabrication of a tunable fused fiber coupler with a photoresponsive polymer layer is also demonstrated.

Synthesis and characterization of novel ABA-type azobenzene-containing tri-block copolymers from telechelic polystyrene

The telechelic polystyrene (tPS) was used as a macro-reversible addition fragmentation chain transfer (RAFT) agent to prepare the ABA-type tri-block copolymers (TBCs), poly{4-[4-(11-acryloyloxyundecyloxy)phenylazo]benzonitrile}-b-polystyrene-b-poly{4-[4-(11-acryloyloxyundecyloxy)phenylazo]benzonitrile} [poly(AUPAB)-b-PS-b-poly(AUPAB)] with 4-[4-(11-acryloyloxyundecyloxy)phenylazo]benzonitrile (AUPAB) as a monomer by the RAFT polymerization process. The poly(AUPAB) was used as a reference to probe the role of polystyrene block in poly(AUPAB)-b-PS-b-poly(AUPAB) macromolecular chain. The TBCs were characterized by spectral techniques, thermal analysis, and polarizing optical microscopic studies and compared the results with individual blocks, poly(AUPAB), and tPS. The TBCs exhibited higher thermal stability and liquid crystal–isotropic phase transition peak temperature (TLC-I), and glass transition temperature (Tg) values compared to the poly(AUPAB). TBC TLC-I value was dependent on the AUPAB wt% in macromolecular chain. Furthermore, the acquired results by optical microscopy suggest that after incorporation of the polystyrene block in acrylate-based pendant azobenzene polymer chain resulted in lower domain size of focal conic texture, which is characteristic of smectic-A liquid crystalline phase compared to the homopolymer. The photophysical properties of the TBCs were similar to those of the poly(AUPAB). Microphase-separated nano-segregation was observed in annealed thin films of TBCs.

Preparation and thermal reliabilities of microencapsulated phase change materials with binary cores and acrylate-based polymer shells

Abstract Using suspension-like polymerization method, a series of microencapsulated phase change materials (micro-PCMs) with acrylate-based polymer shells and binary core materials were prepared. The phase change properties of the binary mixtures composed of paraffin and butyl stearate were investigated. SEM photographs showed that these micro-PCMs have relatively spherical profiles and compact surfaces with diameter ranging from 10 to 80 μm. DSC results indicated that the microencapsulation ratio of these micro-PCMs ranging from 46 wt% to 68 wt%. Moreover, after being subjected to thermal-cycling test for 500 times, these micro-PCMs kept good thermal reliabilities that the microencapsulation ratio decreased by less than 4 wt%. TGA analysis demonstrated that these micro-PCMs can ensure their thermal stability below 210 °C.