Copolymer Shell Research Articles

Polymerizable fatty acid surfactant: Encapsulation of organic pigments for excellent colloidal stability in aqueous solution and water-repellent property

Organic pigments are indispensable in various applications due to their vibrant colors and durability, yet their low polarity often hinders their dispersion in an aqueous solution, leading to large aggregation and sedimentation. To address these limitations, dispersants and encapsulation techniques have been explored. In this study, nanoscale encapsulated pigments were synthesized using a novel polymerizable surfactant, sodium 11-methacrylamidoundecanoic acid (NaMAAUA), along with hydrophobic monomer of styrene or butyl methacrylate. NaMAAUA contains a pendant group of amphiphilic fatty acid, and acts as a dispersant and emulsifier, forming a copolymer shell around the pigments. The apolar tail in NaMAAUA provides hydrophobic interaction with pigments, and the polar carboxyl headgroup exposes in the water phase and enables the formation of strong hydrogen bonds with cellulose. Therefore, the resulting encapsulated pigment exhibits excellent dispersion stability, water-repellent property, washing fastness and UV resistance when applied to paper and cotton fabric, expanding the practical utility of organic pigments in an environmentally conscious manner. Characterization via various analytical techniques validates the efficacy of this approach, paving the way for enhanced pigment applications.

Temperature-sensitive fragrance-releasing polymeric microcapsules

This research aimed to control release of fragrance using thermally-actuated microcapsules so that the release rate shows a considerable change at a certain temperature. Accordingly, four different polymers, namely, two grades of poly(methyl methacrylate) having different molecular weight as well as two poly[(methyl methacrylate)–co-(2-ethylhexyl acrylate)] copolymers, which were synthesized in this work, were designated as capsules’ shell. Number-average molecular weight of the copolymers and one of the two used PMMA grades was in the range of 47 to 56 kDa while that of the other PMMA grade was 344 kDa. Furthermore, Tg of the lower molecular weight grade PMMA and the two copolymers was determined as 119.3, 72.2 and 66.3 °C, respectively, using DSC experiments. Subsequently, R-Limonene as a model fragrance, was encapsulated by either of the polymers using solvent evaporation method. Effect of various parameters, including molecular weight and Tg of the shell polymer and concentration of emulsifier, on morphological characteristics of the microcapsules were investigated. Using two microscopic techniques, it was observed that increment of molecular weight of shell polymer enhances microcapsules’ size, shell thickness and porosity. Moreover, elevation of emulsifier concentration to a certain value of 1.5 wt% was shown to lessen size and porosity of microcapsules. The fragrance release profiles were determined and fitted to several mathematical models, proving that at least one more mechanism, in addition to diffusion, is involved in the release, which was attributed to capillary effects in the shell pores. Moreover, a pronounced increase in release rate upon elevation of temperature from 5 to 15 °C was observed for either of the copolymer shells. The effect was ascribed to remarkable strengthening of segmental mobility of the copolymers due to elevation of temperature and can be regarded as a promising way for the fabrication of smart microcapsules capable of thermal controlling fragrance release.

Robust and Durable Photonic Crystal with Liquid-Repellent Property for Self-Cleaning Coatings and Structural Colored Textiles.

Photonic crystal coatings with unique structural colors and self-cleaning properties have been providing an efficient way for substrate coloration. However, the enhancement of the robustness and durability of structural colored coatings to meet the requirements in diverse environments remains a challenging task. Here, to realize the application of photonic crystal films under various kinds of conditions, we present a poly(fluoroalkyl acrylate)-based colloidal photonic crystal (fCPC) coating. Fluorinated core-interlayer-shell (FCIS) colloidal particles of polystyrene (PS) core, poly(methyl methacrylate) (PMMA) interlayer, and poly(fluoroalkyl acrylate-ethyl acrylate-butyl acrylate) (P(FA-EA-BA)) shell copolymers have been first prepared by a stepwise emulsion polymerization. fCPCs with self-supporting property, reprocessing ability, friction resistance, as well as excellent wettability and liquid-repellent properties are successfully obtained via the bending-induced ordering technique (BIOT). When applied in antifouling applications, the fCPC film exhibits resistance against various oil and inorganic liquids. Furthermore, the fCPC coatings demonstrate their durability under outdoor conditions by maintaining stable color appearances during rainy and sunny conditions. Additionally, an electronic product adhered with the fCPC coatings is presented, which exhibits a surface that remains clean even after prolonged usage in comparison to the conventional CPC coating. Structural colored textiles with enhanced stability and functionalized liquid-repellent properties are achieved through a one-step process using FCIS particles. Therefore, the developed self-cleaning and comprehensive fCPC coatings capable of withstanding diverse conditions may open up new avenues for the advancement of structural coloration in decoration, vehicle, textile, and building.

Shell with Striped, Helical, and Bipolar Lamellae Structures from Soft Confinement-Induced Self-Assembly of AB Diblock Copolymers on a Nanocylinder.

The soft confinement-induced self-assembly of AB diblock copolymers on a nanocylinder is studied via a simulated annealing method. The formation of multiple copolymer shells was predicted by varying the interfacial interaction, the size of confinement, and the height and diameter of the nanocylinder. The competition between solvent repulsion and nanocylinder attraction determined the degree of encapsulation of the copolymer shell. The formation of a helical copolymer shell was induced by the maximization of conformational entropy. The preferential distribution position of copolymers on anisotropic nanocylinder surfaces was induced by interfacial energy minimization. Our study contributes to the understanding of the formation mechanism of the helical structure in block copolymer aggregates and the fabrication of copolymer shells with predesigned morphologies.

Residue-free and nondestructive separation of transparent adhesive thin films using the interfacial coating of thermo-responsive nanocapsules

The effective separation of flexible optoelectronic panels bonded with transparent adhesive films is an innovative technology that enables the reuse of expensive devices, reducing manufacturing costs in multilayered flexible displays. Herein, we present an effective, facile strategy for heat-triggered detachment of adhesive thin films with high optical transparency by interfacial coating with thermo-responsive nanocapsules. These temperature-sensitive nanocapsules, comprising reactive benzenesulfonyl hydrazide cores and polyacrylonitrile-poly(methyl methacrylate) copolymer shells, were simply prepared through a one-pot synthesis using surfactant-free emulsion polymerization. The synthesized nanocapsules were mixed with UV-curable resins and applied as a thin interfacial layer on the substrate through blade coating and UV curing, producing a transparent, uniform nanocapsule layer of 10 μm with extensive coverage. A transparent double-layered adhesive film was achieved by stacking optically clear adhesive film on the interfacial nanocapsule layer. Compared with pure transparent adhesive film, this double-layered adhesive film containing interfacial nanocapsule layer yields a remarkable optical transparency of 99.1 % and high initial adhesion strength of 98.2 %. Furthermore, a short-time heat treatment at 100 °C produces numerous gas microbubbles in the interfacial region between the substrate and optical thin film, facilitating their clean and spontaneous detachment with an outstanding desorption efficiency of 78.7 %. Our separation approach will be helpful for providing a promising way to dismantle polymer thin films without surface damage in wide industries from semiconductor packaging to flexible devices.

Enhancing solar photothermal conversion and energy storage with titanium carbide (Ti3C2) MXene nanosheets in phase-change microcapsules

We propose to enhance photothermal conversion via doping titanium carbide (Ti3C2) MXene nanosheets on the surfaces of phase-change microcapsules consisted of the n-Octadecane core and styrene divinylbenzene copolymer shell. Detected by scanning electron microscopy, the microcapsules showed a usually circular form with an appropriate dispersion. The thermal properties of the microcapsules were characterized using the differential scanning calorimetry and thermal conductivity instruments, realizing an excellent phase-change enthalpy of around 140 J/g, high encapsulation ratio of over 64 %, good heat transfer of 0.294 ± 0.003 W/(m·K), and great thermal reliability. More importantly, the microcapsules doped with Ti3C2 MXene nanosheets reach a solar-to-heat conversion efficiency of 85 ± 7 %, a substantial enhancement by 240 % in comparison with non-doping sample. The Ti3C2 MXene-doped microcapsules with excellent heat storage and solar-to-heat conversion capabilities offer great potential for high-efficiency solar energy utilization and can be applied to thermal energy storage systems and direct absorption solar collectors.

Dual stimuli-responsive mesoporous silica nanoparticles for efficient loading and smart delivery of doxorubicin to cancer with RGD-integrin targeting

The recent progress in nanoparticle applications, such as tumor-targeting, has enabled specific delivery of chemotherapeutics to malignant tissues with enhanced local efficacy while limiting side effects. However, existing delivery systems leave much room for improvement in terms of achieving enhanced colloidal stability in fluid medium, efficient targeting of intended sites, and effective release of therapeutic drugs into diseased cells. Here, an efficient stimuli-responsive nanocarrier for mammalian cells, termed RGD-NAMs, was developed, which enabled temperature- and pH-sensitive release of drug loads. The RGD-NAMs comprise two parts: a stimuli-responsive copolymer shell (NIBIm-AA-RGD) and drug-container core (MSNs). The RGD-NAMs have a stable drug-loading capacity with a marked difference in the release rate depending on the temperature and pH conditions. The RGD-NAMs also exhibit high colloidal stability in SBF (Stimulated body fluid) solutions and minimal toxicity in skeletal myoblasts (C2C12) and bovine arterial endothelial cells (BAEC). The doxorubicin-loaded RGD-NAMs induced a cytotoxic effect in a dose-dependent manner, which was furthered by an increase in temperature from 37 to 40 °C. Moreover, significant control of the release rate and the amount were achieved through pH change. This novel, smart drug-delivery system with high responsiveness to temperature and pH changes has wide application prospects in biomedical fields, including the theragnosis of tumors and vascular diseases.

Structure-Property Relationships of CO2 Absorbing Core-Shell Microparticles with Encapsulated Ionic Liquid.

The demand for new ionic liquid (IL)-based systems to selectively sequester carbon dioxide from gas mixtures has prompted the development of individual components involving the tailored design of IL themselves or solid-supported materials that provide excellent gas permeability of the overall material as well as the ability to incorporate large amounts of ionic liquid. In this work, novel IL-encapsulated microparticles comprising a cross-linked copolymer shell of β-myrcene and styrene and a hydrophilic core of the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide ([EMIM][DCA]) are proposed as viable materials for CO2 capture. Water-in-oil (w/o) emulsion polymerization of different mass ratios of β-myrcene to styrene (i.e. 100/0, 70/30, 50/50, 0/100) yielded IL-encapsulated microparticles, where the encapsulation efficiency of [EMIM][DCA] was dependent on the copolymer shell composition. Thermal analysis using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) revealed that both thermal stability and glass transition temperatures depend on the mass ratio of β-myrcene to styrene. Images from scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to observe the microparticle shell morphology as well as measure the particle size perimeter. Particle sizes were found to be between 5 and 44 μm. CO2 sorption experiments were conducted gravimetrically using TGA instrumentation. Interestingly, a trade-off between CO2 absorption capacity and ionic liquid encapsulation was observed. While increasing the β-myrcene content within the microparticle shell increases the amount of encapsulated [EMIM][DCA], the observed CO2 absorption capacity did not increase as expected due to reduced porosity compared to microparticles with higher styrene content in the microparticle shell. [EMIM][DCA] microcapsules with a 50/50 weight ratio of β-myrcene/styrene showed the best synergistic effect between spherical particle diameter (32.2 μm), pore size (0.75 μm), and high CO2 sorption capacity of ∼0.5 mmol CO2/g sample within a short absorption period of 20 min. Therefore, core-shell microcapsules composed of β-myrcene and styrene are envisioned as a promising material for CO2 sequestration applications.

Preparation and performance research of functional geopolymer filled with microencapsulated phase change materials enhanced by modified graphite

Energy consumption and carbon emission of building account for a large proportion of the world's total. Consequently, choosing environmentally friendly geopolymer and endowing it with thermal storage-release function as the building material applied in energy-efficient buildings can reduce energy consumption and carbon emission in the production of building materials and operation of buildings. In this study, a series of Microencapsulated Phase Change Materials (MPCM) enhanced by modified microcrystalline graphite were synthesized successfully, which have favorable thermal storage-release performance. And the structural characteristics and performances were studied. Among them, MPCM with better performance and low cost was filled into alkali-activated metakaolin-based geopolymer to functionalize it. In the meantime, thermal conductivity, thermal storage performance and compressive strength of the functional geopolymer were characterized. According to the results, the functional geopolymer has a maximum heat preservation effect of 3.5 °C compared to the blank geopolymer without significantly decrease in the thermal conductivity. This study conducts copolymerization method to prepare hydrophilic shell MPCM, which contraposes the mechanical property limitation of the functional geopolymer. And the mechanical property of geopolymer functionalized by copolymer shell MPCM meets the requirements of EN 998–2:2016 class M20.

PH-sensitive packaging of cationic particles by an anionic block copolymer shell

Cationic non-viral vectors show great potential to introduce genetic material into cells, due to their ability to transport large amounts of genetic material and their high synthetic versatility. However, designing materials that are effective without showing toxic effects or undergoing non-specific interactions when applied systemically remains a challenge. The introduction of shielding polymers such as polyethylene glycol (PEG) can enhance biocompatibility and circulation time, however, often impairs transfection efficiency. Herein, a multicomponent polymer system is introduced, based on cationic and hydrophobic particles (P(nBMA46-co-MMA47-co-DMAEMA90), (PBMD)) with high delivery performance and a pH-responsive block copolymer (poly((N-acryloylmorpholine)-b-(2-(carboxy)ethyl acrylamide)) (P(NAM72-b-CEAm74), PNC)) as shielding system, with PNAM as alternative to PEG. The pH-sensitive polymer design promotes biocompatibility and excellent stability at extracellular conditions (pH 7.4) and also allows endosomal escape and thus high transfection efficiency under acidic conditions. PNC shielded particles are below 200 nm in diameter and showed stable pDNA complexation. Further, interaction with human erythrocytes at extracellular conditions (pH 7.4) was prevented, while acidic conditions (pH 6) enabled membrane leakage. The particles demonstrate transfection in adherent (HEK293T) as well as difficult-to-transfect suspension cells (K-562), with comparable or superior efficiency compared to commercial linear poly(ethylenimine) (LPEI). Besides, the toxicity of PNC-shielded particles was significantly minimized, in particular in K-562 cells and erythrocytes. In addition, a pilot in vivo experiment on bone marrow blood cells of mice that were injected with PNC-shielded particles, revealed slightly enhanced cell transfection in comparison to naked pDNA. This study demonstrates the applicability of cationic hydrophobic polymers for transfection of adherent and suspension cells in culture as well as in vivo by co-formulation with pH-responsive shielding polymers, without substantially compromising transfection performance.Graphical

Enhanced microwave absorption performance of BiFeO3 nanopowders coated with Polyindole-PANI co-polymer in ku band frequency

It's still a significant difficulty to find microwave absorbers that have outstanding microwave dissipation performance in hostile environments. Herein, the core–shell structure of polyindole-PANI co-polymer@BiFeO3 nanocomposite is successfully prepared via in-situ polymerization method. The introduction of a co-polymer shell on the surface of magnetic BiFeO3 nanoparticles considerably tuned the attenuation constant and impedance matching characteristics. The electromagnetic characteristics and microwave absorption feature of the polyindole-PANI co-polymer@BiFeO3 nanocomposites may be found to be influenced by filler loading content regulation. The sample containing 40 wt% of polyindole-PANI co-polymer@BiFeO3 nanocomposite with a thickness of 1.5 mm had a minimum reflection loss of −17.8 dB and a 3.5 GHz effective absorption bandwidth at 13.6 GHz frequency. Polyindole-PANI co-polymer@BiFeO3 nanocomposite with outstanding microwave dissipation capabilities might be useful in a wide range of high-frequency wave applications.

Automatic Detoxification Medicine Delivery by Thermo-Sensitive Poly(ethylene glycol)-Based Nanogels.

During the medication-assisted treatment of drug abuse, side effects and addiction liabilities are commonly observed. Thus, control of the medication dose is very important. According to body temperature abnormalities in drug abusers, a thermo-sensitive nanogel was synthesized as a drug carrier to automatically deliver detoxification medicines. This nanogel was prepared through the synthesis of polystyrene (PS) core microspheres, followed by coverage with a nonlinear poly(ethylene glycol)-based copolymer shell. The PS core microspheres were found to be an ideal hydrophobic core for loading the detoxification medicines effectively. The nonlinear poly(ethylene glycol)-based copolymer shell layer consisted of 2-(2-methoxyethoxy)ethyl methacrylate (MEO2MA) and oligo(ethylene glycol) methyl ether methacrylates (Mn = 300 g mol−1, MEO5MA). The monomer feeding molar ratio n(MEO2MA)/n(MEO5MA) of 1:3 enabled PS@P(MEO2MA-co-MEO5MA) nanogels to exhibit a distinguished colloidal stability and an adjustable volume phase transition temperature which is within the drug addicts’ abnormally fluctuating temperature range. Importantly, it was found that the obtained PS@P(MEO2MA-co-MEO5MA) nanogels displayed good biocompatibility with rat aortic endothelial cells in the given concentration range. The nanogels also exhibited a satisfactory loading efficiency and thermo-sensitive/sustained release characteristics for three detoxification medicines: sinomenine, diltiazem and chlorpromazine.

Hafnium Oxide-Based Nanoplatform for Combined Chemoradiotherapy.

Recently, the combined therapy has become one of the main approaches in cancer treatment. Combining different approaches may provide a significant outcome by triggering several death mechanisms or causing increased damage of tumor cells without hurting healthy ones. The supramolecular nanoplatform based on a high-Z metal reported here is a suitable system for the targeted delivery of chemotherapeutic compounds, imaging, and an enhanced radiotherapy outcome. HfO2 nanoparticles coated with oleic acid and a monomethoxypoly(ethylene glycol)-poly(ε-caprolactone) copolymer shell (nanoplatform) are able to accumulate inside cancer cells and release doxorubicin (DOX) under specific conditions. Neither uncoated nor coated nanoparticles show any cytotoxicity in vitro. DOX loaded onto a nanoplatform demonstrates a lower IC50 value than pure DOX. X-ray irradiation of cancer cells loaded with a nanoplatform shows a higher death rate than that for cells without nanoparticles. These results provide an important foundation for the development of complex nanoscale systems for combined cancer treatment.

Core–Shell Copolymers with Brush-on-Hyperbranched Arm Architecture: Synthesis, Dual Thermoresponsive Behaviors, and Nanocarriers

Core–Shell Copolymers with Brush-on-Hyperbranched Arm Architecture: Synthesis, Dual Thermoresponsive Behaviors, and Nanocarriers

Effect of shell phase composition on the dielectric property and energy density of core‐shell structured BaTiO3 particles modified poly(vinylidene fluoride) nanocomposites

AbstractDielectric nanocomposites have attracted much attention due to their wide applications in electronics and electrical industry. Recently, incorporating core‐shell nanoparticles into polymer matrix to improve the dielectric properties of nanocomposites has been widely reported. Tailoring the interfacial region between the polymer and the nanoparticles plays a crucial role in achieving the desired dielectric and energy storage properties of nanocomposites. However, the effect of shell structure in the interface region on the dielectric and energy storage properties is rarely studied. Based on this, core‐shell BaTiO3 nanoparticles with two different shell polymers, a “hard‐soft” copolymer of methyl methacrylate and butyl acrylate (P[MMA‐BA]) and a “hard” homopolymer of methyl methacrylate (PMMA), were prepared in this paper. The effect of core‐shell BaTiO3 nanoparticles with different shell structures on the dielectric and energy storage properties of poly(vinylidene fluoride) (PVDF) was investigated in depth. Due to the formation of a tight interfacial region between P(MMA‐BA)@BT and PVDF matrix, P(MMA‐BA)@BT/PVDF nanocomposites not only have low dielectric loss but also higher energy efficiency than PMMA@BT/PVDF nanocomposites. This study suggests a potential strategy that fabricating a “hard‐soft” copolymer shell on BaTiO3 surface can obtain desirable energy storage efficiency than the single “hard” shell structure in dielectric nanocomposites.

Fabrication and characterization of hexadecyl acrylate cross-linked phase change microspheres

Abstract Microspheres with phase change properties were fabricated by polymerization of hexadecyl acrylate (HA) and different cross-linking agents. The samples were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA). The results show that, the samples that added cross-linking agents have a smooth surface and the latent heat of them is different. The experiments show that all of the cross-linked copolymer shells can be made into temperature controlled release microspheres. These materials can be potentially applied in the field of thermal energy storage. β-tricalcium phosphate was encapsulated in microspheres to obtain one with a fast release effect. It will effectively promote bone conduction when these microspheres were implanted into a bone defect. This microsphere can be used for orthopedic implant or coating of instrument in the future.

Core\u2013shell polymeric nanoparticles co-loaded with photosensitizer and organic dye for photodynamic therapy guided by fluorescence imaging in near and short-wave infrared spectral regions

BackgroundBiodistribution of photosensitizer (PS) in photodynamic therapy (PDT) can be assessed by fluorescence imaging that visualizes the accumulation of PS in malignant tissue prior to PDT. At the same time, excitation of the PS during an assessment of its biodistribution results in premature photobleaching and can cause toxicity to healthy tissues. Combination of PS with a separate fluorescent moiety, which can be excited apart from PS activation, provides a possibility for fluorescence imaging (FI) guided delivery of PS to cancer site, followed by PDT.ResultsIn this work, we report nanoformulations (NFs) of core–shell polymeric nanoparticles (NPs) co-loaded with PS [2-(1-hexyloxyethyl)-2-devinyl pyropheophorbide-a, HPPH] and near infrared fluorescent organic dyes (NIRFDs) that can be excited in the first or second near-infrared windows of tissue optical transparency (NIR-I, ~ 700–950 nm and NIR-II, ~ 1000–1350 nm), where HPPH does not absorb and emit. After addition to nanoparticle suspensions, PS and NIRFDs are entrapped by the nanoparticle shell of co-polymer of N-isopropylacrylamide and acrylamide [poly(NIPAM-co-AA)], while do not bind with the polystyrene (polySt) core alone. Loading of the NIRFD and PS to the NPs shell precludes aggregation of these hydrophobic molecules in water, preventing fluorescence quenching and reduction of singlet oxygen generation. Moreover, shift of the absorption of NIRFD to longer wavelengths was found to strongly reduce an efficiency of the electronic excitation energy transfer between PS and NIRFD, increasing the efficacy of PDT with PS-NIRFD combination. As a result, use of the NFs of PS and NIR-II NIRFD enables fluorescence imaging guided PDT, as it was shown by confocal microscopy and PDT of the cancer cells in vitro. In vivo studies with subcutaneously tumored mice demonstrated a possibility to image biodistribution of tumor targeted NFs both using HPPH fluorescence with conventional imaging camera sensitive in visible and NIR-I ranges (~ 400–750 nm) and imaging camera for short-wave infrared (SWIR) region (~ 1000–1700 nm), which was recently shown to be beneficial for in vivo optical imaging.ConclusionsA combination of PS with fluorescence in visible and NIR-I spectral ranges and, NIR-II fluorescent dye allowed us to obtain PS nanoformulation promising for see-and-treat PDT guided with visible-NIR-SWIR fluorescence imaging.

Recyclable low-temperature phase change microcapsules for cold storage

Recyclable low-temperature phase change microcapsules (LTPCMs) have the potential applications in the short-distance cold chain transportation due to their reliable reusability in cold storage. Herein, LTPCMs are synthesized via in-situ suspension copolymerization of styrene and methyl methacrylate in absence of harm substances, providing the non-crosslinking copolymer shells. n-Dodecane, n-tridecane and n-tetradecane, inducing the microphase separation of non-crosslinking copolymers, are successfully encapsulated to achieve n-do-LTPCMs, n-tri-LTPCMs and n-tetra-LTPCMs, which respectively bear the high phase change enthalpy of 110.53 J·g−1 at −8.69 °C, 38.33 J·g−1/93.71 J·g−1 at −17.61 °C/−4.96 °C and 166.79 J·g−1 at 8.59 °C and subsequently show the cold-discharging periods of 30 min, 40 min and 120 min. The multiple circulation of cold-discharging process indicates the excellent recyclability for cold storage owing to their unchanged cold-discharging period. Especially, n-tetra-LTPCM-65 bears the best comprehensive cold-storing performance in all the previously reported LTPCMs, such as narrow cold-discharging temperature range of 3–4 °C, long cold-discharging period of 69–120 min and low cold-discharging capacity of 33.4 J·g−1·K−1. This work successfully provided the recyclable LTPCMs for cold storage in the short-distance cold chain transportation.

Formation of Copolymer-Ag Nanoparticles Composite Micelles in Three-dimensional Co-flow Focusing Microfluidic Device

A novel method was presented to create composite micelles of amphiphilic copolymers and Ag nanoparticles (NPs) in a three-dimensional co-flow focusing microfluidic device (3D CFMD). Self-assembly of the copolymers was initiated by the fast mixing of water and a blend dispersion of hydrophobic Ag NPs and amphiphilic copolymers. At the same time, the hydrophobic Ag NPs enter the core of copolymer micelles, based on the hydrophobic interaction. The copolymer-Ag NPs composite micelles have a core-shell structure with copolymer shell and Ag NPs core. COMSOL Multiphysics is used to simulate the concentration distribution of copolymers and Ag NPs under different flow rates. Co-assembly microfluidic conditions are determined based on simulation results. Under suitable microfluidic conditions, both block copolymers and gradient copolymers can co-assemble with hydrophobic Ag NPs to form composite micelles, respectively. This microfluidic coassembly method will have a good prospect in the preparation of composite micelles of amphiphilic copolymers and metal nanoparticles.

Positive‐Temperature‐Coefficient Graphite Anode as a Thermal Runaway Firewall to Improve the Safety of LiCoO2/Graphite Batteries under Abusive Conditions

A positive‐temperature‐coefficient graphite anode as a thermal runaway firewall of LiCoO2/graphite lithium‐ion batteries (LIBs) is prepared by introducing thermally sensitive polymer microspheres (TSPMs) into the anode to improve battery safety under abusive conditions. The TSPMs are composed of an acrylonitrile and acrylate copolymer shell and a cyclopentane hydrocarbon core. Due to the thermally sensitive properties of TSPMs, the graphite anode swells under abusive conditions, and the electric connection of active materials and current collector can be cut off. Thus, the resistance of LIBs is increased to solve the thermal runaway and safety problems before the temperature of LIBs approaches explosion limit. The TSPMs with a size distribution of 4–20 μm and an initial foaming temperature of 95–110 °C exhibit excellent stability and foaming properties. Compared with the batteries without TSPMs, under abusive conditions including overcharge at 1 C/10 V, thermal shock from 20 to 130 °C, and external short circuit with a resistance of ≈80 mΩ, the batteries with TSPMs effectively mitigate thermal runaway. In addition, TSPMs do not show obvious influences on the conventional performances of LIBs, indicating that adding TSPMs into graphite anodes is a promising method to improve the safety of LIBs under abusive conditions.