Ethoxylated Trimethylolpropane Triacrylate Research Articles

Döner (Spin) Kaplama ile İki Boyutlu Polimerik Nanokompozitlerin Geniş Alanlı Üretimleri

The aim of this study is to obtain high crystal quality colloidal templates using spin-coating technique and to determine the production conditions of nanocomposites produced from these templates. For this purpose, the glass surfaces were coated by spin- coating technique on various surfaces using homogeneously dispersed silica colloids in the prepared acrylate monomer. With this coating technique based on centrifugal forces, and following polymerization step, high quality nanoarrays of colloidal crystals in two dimensions were successfully prepared. In ethanol, the dilute silica nanospheres were removed and then dissolved with ethoxylated trimethylolpropane triacrylate monomer having a viscosity of 60 cps to <20% volumetric fractions. This prepared colloidal suspension-monomer mixture was coated on glass surfaces in a very uniform manner. The thickness of the film can only be controlled by changing the rotation speed and time of spin coating. Selective removal of the polymer matrix and silica spheres was achieved by reactive ion abrasive and hydrofluoric acid treatments, yielding large area colloidal crystals and macroporous polymers, respectively. The normal transmission spectra in the visible and near infrared regions and the apparent peaks of Bragg diffraction from these two-dimensional nanostructures were determined by graphs. Based on optical disc-scale coating, this technique is compatible with standard semiconductor microfabrications and optical biosensor production. Crystallization application based on centrifugal force of spin coating process can be easily used in technological applications based on coating techniques.

Complex emulsions for shape control based on mass transfer and phase separation.

Complex emulsions are used to fabricate new morphologies of multiple Janus droplets, evolving from non-engulfing to complete engulfing core/shell configuration. The produced droplets contain an aqueous phase of dextran (DEX) solution and an oil phase, which is mixed with ethoxylated trimethylolpropane triacrylate (ETPTA) and poly(ethylene glycol) diacrylate (PEGDA). The PEGDA in the oil phase is transferred into the aqueous phase to form complex morphologies due to the phase separation of PEGDA and DEX. The effects are investigated including the ratio of oil to aqueous phase, the content of initial PEGDA, DEX and surfactants, and the type of surfactants. DEX/PEGDA-ETPTA core/shell-single phase Janus droplets are formed with an increasing engulfed oil droplet into the aqueous droplet while the ratio of oil to aqueous phase increases or the initial PEGDA content increases. The high DEX content leads to the DEX-PEGDA-ETPTA doublet Janus. The use of surfactants polyglycerol polyricinoleate (PGPR) and Span 80 results in the formation of DEX/PEGDA/ETPTA single core/double shell and DEX/PEGDA-ETPTA core/shell-single phase Janus droplets, respectively. These complex emulsions are utilized to fabricate solid particles of complex shapes. This method contributes to new material design underpinned by mass transfer and phase separation, which can be extended to other complex emulsion systems.

Preparation of encoded bar-like core-shell microparticles on a microfluidic chip

This work presented a microfluidic multi-phase droplet system for preparing encoded bar-like core-shell microparticles. The integration of T-junction and flow-focusing junction on one microfluidic chip was designed to form water-in-oil-in-water double emulsions. And the double emulsions were used as templates to fabricate the encoded bar-like core-shell particles on the chip. The encoded particles were of small and uniform size. The core droplets were filled with different quantum dots and dyes for providing encoding information, and the outer oil phase droplets of trimethylolpropane ethoxylate triacrylate were solidified into the shell of the encoded particles for confining the core droplets in them and supplying the surface for capturing targets. The sequence of the core droplets could be confined by the configuration of the micro-channels when the core droplets were encapsulated in the outer droplets. Thus a new multi-mode encoding method was defined by combining dual-optical encoding and graphical encoding. Different quantum dots provided the wavelength code and the intensity code, multiple dyes provided the color code, and the single order of core droplets in the shell offered the position code. Compared with the conventional encoding methods, this approach increases the encoding number by hundred times, and has great potential for high-throughput multiplexed analysis.

Confining Hyperbranched Star Poly(ethylene oxide)-Based Polymer into a 3D Interpenetrating Network for a High-Performance All-Solid-State Polymer Electrolyte.

The original poly(ethylene oxide)-based polymer electrolytes normally show low ionic conductivity and inferior mechanical property, which greatly restrict their practical application in all-solid-state lithium-ion batteries (LIBs). In this work, a hyperbranched star polymer with poly(ethylene glycol) methyl ether methacrylate flexible chain segments is embedded into a three-dimensional (3D) interpenetrating cross-linking network created by the rapid one-step UV-derived photopolymerization of the cross-linker (ethoxylated trimethylolpropane triacrylate) in the presence of lithium salt. The rigid 3D network framework provides the polymer electrolyte with not only enhanced mechanical behavior, including film-forming and dendrite-inhibiting capabilities, but also nanoconfinement effects, which can speed up polymer chain segmental dynamics and reduce the crystallinity of the polymer. Depending on this unique rigid-flexible coupling network, the prepared solid polymer electrolyte shows enhanced ionic conductivity (6.8 × 10-5 S cm-1 at 50 °C), widened electrochemical stability window (5.1 V vs Li/Li+), and enough mechanical stability to suppress the growth of uneven Li dendrite (the Li symmetrical cells can operate steadily at both current densities of 0.05 and 0.1 mA cm-2 for 1000 h). Moreover, the assembled LiFePO4//Li cell also exhibited good cycle performance at 50 °C, making the hyperbranched star polymer electrolyte with a nanoconfined cross-linking structure to have potential application in high-safety and high-performance LIBs.

Monolithic integration of flexible lithium-ion battery on a plastic substrate by printing methods

Energy storage devices with flexible form factor have become critical components of wearable electronic systems. Inspired by methods of monolithic integration in the microelectronics fabrication process, we propose a planar flexible full-solid-state lithium-ion battery (FSLB) architecture and a layer-by-layer stencil printing assembly method for fabricating batteries on polyethylene terephthalate (PET) substrate. FSLBs use quasi-solid electrolyte based on LiTFSI and ultraviolet (UV)-curable ethoxylated trimethylolpropane triacrylate (ETPTA) polymeric matrix in combination with Li4Ti5O12 (LTO)/LiFePO4 (LFP)-based electrodes. Excellent mechanical flexibility (< 10 mm bending radius) can be achieved. The electrochemical characteristics of electrolyte, including ion conductivity, physical stability during room-temperature and tender assembly processes, are promising. A complete thin film-shape FSLB demonstrated working operation both under planar and bending conditions. The unique architecture and assembly processes open new ways for planar flexible devices to be integrated with flexible energy devices.

Long cycling, thermal stable, dendrites free gel polymer electrolyte for flexible lithium metal batteries

Gel polymer electrolyte (GPE) is considered to be a promising electrolyte to realize flexible and safe lithium-based batteries. However, the potential is severely hindered by low ionic conductivity under room temperature, undesirable mechanical property and unstable thermal performance. Herein, these puzzling issues can be effectively settled by constructing a 3D cross-linked network GPE through in-situ polymerization methyl methacrylate (MMA) and ethoxylated trimethylolpropane triacrylate (ETPTA) monomers on electrospun polyacrylonitrile (PAN) nanofibers. The shape conformable GPE presents a high ionic conductivity (0.33 mS cm−1 at room temperature), extended cycling stability even at high temperature and excellent ability to restrain the growth of the lithium dendrite. Consequently, Li|GPE|LiFePO4 cell shows 134.8 mAh g−1 initial discharge capacity and maintains 78.6% capacity retention after 600 cycles at 2 C under room temperature. More significantly, 112.3 mAh g−1 discharge capacity is still achieved at 2 C and under 50 °C after 300 cycles, which is far more superior than liquid electrolyte with PAN substrate separator. Notably, pouch cells remain working under bending and cutting conditions showing excellent flexibility. The eminent performances provide a promising and alternative way in electrolyte fabrication for lithium-based batteries.

A self-standing, UV-cured semi-interpenetrating polymer network reinforced composite gel electrolytes for dendrite-suppressing lithium ion batteries

A self-standing, flexible and lithium dendrite growth-suppressing composite gel polymer electrolyte membrane was designed for the use of room-temperature lithium ion batteries. The multi-functional composite semi-interpenetrating polymer network (referred to as “Cs-IPN”) electrolyte membrane was fabricated by combining a UV-cured ethoxylated trimethylolpropane triacrylate (ETPTA) macromer with alumina nanoparticles in the presence of liquid electrolyte and thermoplastic linear poly(ethylene oxide) (PEO). The polymer electrolyte membrane exhibits a semi-interpenetrating polymer network structure and a higher room temperature ionic conductivity, which impart the electrolyte with a significant cycling (120 mAh g−1 after 200 cycles) and a remarkable rate (137 mAh g−1 at 0.1 °C, 130 mAh g−1 at 0.5 °C, 119 mAh g−1 at 1 °C and 100 mAh g−1 at 2 °C) performance in Li/LiFePO4 battery. More importantly, the polymer electrolyte possesses superior ability to inhibit the growth of lithium dendrites, which makes it promising for next generation lithium ion batteries.

Reconfigurable Anticounterfeiting Coatings Enabled by Macroporous Shape Memory Polymers

Here, we report a new type of reconfigurable anticounterfeiting coating enabled by integrating the scientific principles of photonic crystal and shape memory polymer (SMP). The autonomous infusion of uncured oligomers in a polydimethylsiloxane (PDMS) stamp into a templated macroporous SMP photonic crystal coating, which was confirmed by quantitative X-ray photoelectron spectroscopy analysis, can program an iridescent pattern on the transparent SMP membrane with deformed macropores. By manipulation of the unconventional all-room-temperature shape memory effects exhibited by the shape memory copolymer comprising polyethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, the iridescent pattern can be easily and instantaneously concealed and revealed by immersing in common household liquids (e.g., ethanol and water). Systematic experiments and theoretical simulations using scanning electron microscopy, atomic force microscopy, optical spectroscopy, scalar wave approximation modeling, and c...

UV-curable-based plastic crystal polymer electrolyte for high-performance all-solid-state Li-ion batteries

An all-solid-state polymer electrolyte has been prepared by polymerizing a monomer ethoxylated trimethylolpropane triacrylate (ETPTA) using ultraviolet irradiation (UV-curing) into crystal electrolyte (referred to as UV-PCCE) in this paper, which has the merit of outstanding interfacial compatibility with electrode materials. Otherwise, on account of the appearance of a unique plastic-crystalline phase, this polymer electrolyte presents a great electrochemical window (4.78 V vs Li/Li+) and a high ionic conductivity at ambient temperature. The cell of LiFePO4/UV-PCCE/Li displays a high initial discharge capacity of 147.1 mAh g−1 at 0.5 C and 118.0 mAh g−1 at a rate of 8.0 C at room temperature. At the same time, it may deliver a high initial discharge capacity of 150.0 mAh g−1 and the coulombic efficiency approximate 100% over 120 cycles at 2.0 C at 55 °C. Its superior performances demonstrate that the UV-PCCE-based electrolyte via an ultraviolet irradiation is applied to the actual, which can be used for high-performance lithium-ion batteries. This technology can also be compatible with existing lithium-ion battery equipment.

Fabrication and characterization of thiol-triacrylate polymer via Michael addition reaction for biomedical applications

Thiol-acrylate polymers have therapeutic potential as biocompatible scaffolds for bone tissue regeneration. Synthesis of a novel cyto-compatible and biodegradable polymer composed of trimethylolpropane ethoxylate triacrylate-trimethylolpropane tris (3-mercaptopropionate) (TMPeTA-TMPTMP) using a simple amine-catalyzed Michael addition reaction is reported in this study. This study explores the impact of molecular weight and crosslink density on the cyto-compatibility of human adipose derived mesenchymal stem cells. Eight groups were prepared with two different average molecular weights of trimethylolpropane ethoxylate triacrylate (TMPeTA 692 and 912) and four different concentrations of diethylamine (DEA) as catalyst. The materials were physically characterized by mechanical testing, wettability, mass loss, protein adsorption and surface topography. Cyto-compatibility of the polymeric substrates was evaluated by LIVE/DEAD staining® and DNA content assay of cultured human adipose derived stem cells (hASCs) on the samples over over days. Surface topography studies revealed that TMPeTA (692) samples have island pattern features whereas TMPeTA (912) polymers showed pitted surfaces. Water contact angle results showed a significant difference between TMPeTA (692) and TMPeTA (912) monomers with the same DEA concentration. Decreased protein adsorption was observed on TMPeTA (912) -16% DEA compared to other groups. Fluorescent microscopy also showed distinct hASCs attachment behavior between TMPeTA (692) and TMPeTA (912), which is due to their different surface topography, protein adsorption and wettability. Our finding suggested that this thiol-acrylate based polymer is a versatile, cyto-compatible material for tissue engineering applications with tunable cell attachment property based on surface characteristics.

High-Throughput Assessment and Modeling of a Polymer Library Regulating Human Dental Pulp-Derived Stem Cell Behavior.

The identification of biomaterials that modulate cell responses is a crucial task for tissue engineering and cell therapy. The identification of novel materials is complicated by the immense number of synthesizable polymers and the time required for testing each material experimentally. In the current study, polymeric biomaterial-cell interactions were assessed rapidly using a microarray format. The attachment, proliferation, and differentiation of human dental pulp stem cells (hDPSCs) were investigated on 141 homopolymers and 400 diverse copolymers. The copolymer of isooctyl acrylate and 2-(methacryloyloxy)ethyl acetoacetate achieved the highest attachment and proliferation of hDPSC, whereas high cell attachment and differentiation of hDPSC were observed on the copolymer of isooctyl acrylate and trimethylolpropane ethoxylate triacrylate. Computational models were generated, relating polymer properties to cellular responses. These models could accurately predict cell behavior for up to 95% of materials within a test set. The models identified several functional groups as being important for supporting specific cell responses. In particular, oxygen-containing chemical moieties, including fragments from the acrylate/acrylamide backbone of the polymers, promoted cell attachment. Small hydrocarbon fragments originating from polymer pendant groups promoted cell proliferation and differentiation. These computational models constitute a key tool to direct the discovery of novel materials within the enormous chemical space available to researchers.

One-pot synthesis of an emulsion-templated hydrogel-microsphere composite with tunable properties

The development of composite hydrogels is enjoying ever-increasing research interests and applications due to the high flexibility of these materials in composition and properties. This study develops an emulsion-templated hydrogel-microsphere composite with tunable properties using a one-pot synthetic approach. The composite consists of poly(trimethylolpropane ethoxylate triacrylate) microspheres crosslinked by a hydrogel, which is formed by a starch-based bifunctional emulsion stabilizer. Composites with a higher compositional ratio of the hydrogel have been found to have lower erosion susceptibility and swelling capacity. As an illustration of the unique practical potential of its amphiphilic character and tunable swelling properties, as well as its large surface area for adsorption, the composite has been loaded with model compounds with various degrees of hydrophilicity, and has been shown to be useful for applications such as drug loading and pollutant removal. The composite is a novel material displaying application potential that warrants further development.

(Invited) Photo-Polymerized Organic Host Network of Ionogels for Lithium Batteries: Effects of Mesh Size and of Ethylene Oxide Content

Solid ionogel electrolytes are rather competitive compared to liquid carbonates based electrolyte regarding ionic conductivity but they show much better safety. It is striking that the ionogels presented here are obtained within few minutes by UV curing which triggers the formation of the polymer host network confining N-methyl,N-propylpyrrolidinium bis-(trifluoromethyl)sulfonylimide with lithium bis-(trifluoromethyl)sulfonylimide salt at the concentration of 1M. This fast and easy process allows to obtained all-solid like micro-batteries. Herein the effect of mesh size and ethylene content of various host networks is deciphered. An optimum balance between mesh size, ethylene oxide and lithium content is identified. The ionogel formed from trimethylolpropane ethoxylate triacrylate and 1,6-hexanediol diacrylate confining 90 %wt of ionic liquid shows a mesh size close to 5 nm, with an enhanced fragility of the confined ionic liquid, as referred to that of the bulk one. Along with these last features, its ethylene oxide content allows a very good lithium ion diffusion. At room temperature and at C/5 cycling rate, prototype batteries LiFePO4 | ionogel | Li metal battery can restitute 70% of the initial capacity during up to 1200 cycles. Figure 1

Photo-Polymerized Organic Host Network of Ionogels for Lithium Batteries: Effects of Mesh Size and of Ethylene Oxide Content

Solid ionogel electrolytes are rather competitive compared to liquid carbonates based electrolyte regarding ionic conductivity but they show much better safety. It is striking that the ionogels presented here are obtained within few minutes by UV curing which triggers the formation of the polymer host network confining N-methyl,N-propylpyrrolidinium bis-(trifluoromethyl)sulfonylimide with lithium bis-(trifluoromethyl)sulfonylimide salt at the concentration of 1M. This fast and easy process allows to obtained all-solid like micro-batteries. Herein the effect of mesh size and ethylene oxide content of various host networks is deciphered. An optimum balance between mesh size, ethylene oxide and lithium content is identified. The ionogel formed from trimethylolpropane ethoxylate triacrylate and 1,6-hexanediol diacrylate confining 90 %wt of ionic liquid shows a mesh size close to 5 nm, with an enhanced fragility of the confined ionic liquid, as referred to that of the bulk one. Along with these last features, its ethylene oxide content allows a very good lithium ion diffusion. At room temperature and at C/5 cycling rate, prototype batteries LiFePO4 | ionogel | Li metal battery can restitute 70% of the initial capacity during up to 1200 cycles.

Electro-wetting lenticular lens with improved diopter for 2D and 3D conversion using lens-shaped ETPTA chamber.

In this paper, we introduce a method for improving the lens diopter of 2D/3D convertible devices using electro-wetting. For stable operation, an electro-wetting device requires high dioptric performance and this was achieved using bi-convex liquid-liquid-solid phases. 1-Chloronaphthalene with a refractive index of 1.633 was used as an oil phase to achieve high diopters. ETPTA (trimethylolpropane ethoxylate triacrylate), a UV-sensitive material with low chemical reactivity to the 1-Chloronaphthalene, was used as a chamber material. This resulted in a diopter of 3030D for high quality multi-view images without unstable oil movement or trembling. The ETPTA was molded on a 0.3mm thick glass substrate that was coated with UV adhesive (NOA 81). The maximum diopter capable of stable operation was 3425D. 2D and 3D conversion and parallax motion were demonstrated.

Fabrication of PAA-PETPTA Janus Microspheres with Respiratory Function for Controlled Release of Guests with Different Sizes.

Poly(acrylic acid)-poly(ethoxylated trimethylolpropane triacrylate) (PAA-PETPTA) Janus microspheres with "respiratory" function for controlled release were prepared by polymerization of acrylic acid-ethoxylated trimethylolpropane triacrylate (AA-ETPTA) Janus microdroplets in a continuous oil phase in a simple capillary-based microfluidic device with the assistance of UV radiation. The flow rate ratios of AA and ETPTA phases and surfactant content in the continuous oil phase have a significant effect on the structure of the Janus microspheres. PAA part in the Janus microspheres has respiratory function for loading and release due to the different stimuli responses to different pHs. The hollow structure of PETPTA part with different sizes of opening serves as the host materials for PAA and could control release rate further due to the different opening sizes. The obtained PAA-PETPTA Janus microspheres showed high rhodamine B (RhB) loading of 860 mg g-1 and different controlled-release behavior in water with different pHs. The release rate increases with the increase of pH and the contact area of PAA part with water. The maximum controlled-release time for RhB was about 3 h in water with pH of 5. In addition, the Janus microspheres also showed controlled-release behavior for larger size guests, e.g., 150 nm polystyrene beads, which indicated a wide range of application. The loading and release behaviors for guests, for instance, for RhB, have almost no change even after six times of reuse, which indicated a high stability.

Photo-Polymerized Organic Host Network of Ionogels for Lithium Batteries: Effects of Mesh Size and of Ethylene Oxide Content

Solid ionogel electrolytes are rather competitive compared to liquid carbonate based electrolyte regarding ionic conductivity but they show much better safety. It is striking that the ionogels presented here are obtained within few minutes by UV curing which triggers the formation of the polymer host network confining N-methyl,N-propylpyrrolidinium bis-(trifluoromethyl)sulfonylimide with lithium bis-(trifluoromethyl)sulfonylimide salt at the concentration of 1M. This fast and easy process allows for obtaining all-solid like micro-batteries. Herein the effect of mesh size and ethylene oxide content of various host networks is deciphered. An optimum balance between mesh size, ethylene oxide and lithium content is identified. The ionogel formed from trimethylolpropane ethoxylate triacrylate and 1,6-hexanediol diacrylate confining 90% wt of ionic liquid shows a mesh size close to 5 nm, with an enhanced fragility of the confined ionic liquid, as referred to that of the bulk one. Along with these last features, its ethylene oxide content allows a very good lithium ion diffusion. At room temperature and at C/5 cycling rate, prototype batteries LiFePO4 | ionogel | Li metal battery can restitute 70% of the initial capacity during up to 1200 cycles.

Quantum-dot-encapsulated core-shell barcode particles from droplet microfluidics.

The development of robust quantum dot (QD) barcode particles with specific compositions and simple identification is important to meet the demand for high-throughput assays. Here, we present a multiple-inner phase channel capillary microfluidic approach to generate novel QD-encapsulated core-shell barcode particles with distinctive features for multiplexing analysis. By using different QD dispersed polyethylene glycol diacrylate (PEGDA) solutions as the inner phases, the particles were endowed with hydrogel locked QD cores, which could maintain the dispersed status and provide distinctive identification for the particles. The shells of the barcode particles were silica nanoparticle-dispersed ethoxylated trimethylolpropane triacrylate (ETPTA) resin, which could not only improve the stability and biocompatibility of QDs, but also provide functional groups for immobilization of biomolecules due to the assembling of the silica nanoparticles on their surfaces. Due to the advanced emulsification capability of the capillary microfluidic device, double emulsion templates with multiple inner droplet phases and their resultant multicomponent QD-encapsulated core-shell barcode particles could be continually generated. These particles showed remarkable spectral coding capacity in practice, which make them ideal for biomedical applications.

Multidose Preservative Free Eyedrops by Selective Removal of Benzalkonium Chloride from Ocular Formulations.

About 70% of eye drops contain benzalkonium chloride (BAK) to maintain sterility. BAK is an effective preservative but it can cause irritation and toxicity. We propose to mitigate ocular toxicity without compromising sterility by incorporating a filter into an eye drop bottle to selectively remove BAK during the process of drop instillation. The filter is a packed bed of particles made from poly(2-hydroxyethyl methacrylate) (pHEMA), which is a common ophthalmic material. We showed that pHEMA particle prepared by using ethoxylated trimethylolpropane triacrylate as crosslinker can be incorporated into a modified eyedrop bottle tip to selectively remove the preservative as the formulation is squeezed out of the bottle. Hydraulic permeability of the plug is measured to determine the resistance to eye drop squeezing, and % removal of BAK and drugs are determined. The modified tip has a hydraulic permeability of about 2 Darcy, which allows eyedrops formulations to flow through without excessive resistance. The tip is designed such that the patients can create an eyedrop of solution of 1-10cP viscosity in 4s with a nominal pressure. During this short contact time, the packed particles removed nearly 100% of benzalkonium chloride (BAK) from a 15mL, 0.012% BAK solution but have only minimal impact on the concentration of contained active components. Our novel design can eliminate the preservative induced toxicity from eye drops thereby impacting hundreds of millions of patients with chronic ophthalmic diseases like glaucoma and dry eyes.

Multicolor Printing Using Electric‐Field‐Responsive and Photocurable Photonic Crystals

AbstractEfficient and large scale printing of photonic crystal patterns with multicolor, multigrayscale, and fine resolution is highly desired due to its application in smart prints, sensors, and photonic devices. Here, an electric‐field‐assisted multicolor printing is reported based on electrically responsive and photocurable colloidal photonic crystal, which is prepared by supersaturation‐induced self‐assembly of SiO2 particles in the mixture of propylene carbonate (PC) and trimethylolpropane ethoxylate triacrylate (ETPTA). This colloidal crystal suspension, named as E‐ink, has tunable structural color, controllable grayscale, and instantly fixable characteristics at the same time because the SiO2/ETPTA‐PC photonic crystal has metastable and reversible assembly as well as polymerizable features. Lithographical printing with photomask and maskless pixel printing techniques are developed respectively to efficiently prepare multicolor and high‐resolution photonic patterns using a single‐component E‐ink.