Chain Entanglement Research Articles

Improving Miscibility of Polymer Donor and Polymer Acceptor by Reducing Chain Entanglement for Realizing 18.64 % Efficiency All Polymer Solar Cells.

All-polymer solar cells have experienced rapid development in recent years by the emergence of polymerized small molecular acceptors (PSMAs). However, the strong chain entanglements of polymer donors (PDs) and polymer acceptors (PAs) decrease the miscibility of the resulting polymer mixtures, making it challenging to optimize the blend morphology. Herein, we designed three PAs, namely PBTPICm-BDD, PBTPICγ-BDD and PBTPICF-BDD, by smartly using a BDD unit as the polymerized unit to copolymerize with different Y-typed non-fullerene small molecular acceptors (NF-SMAs), thus achieving a certain degree of distortion and giving the polymer system enough internal space to reduce the entanglements of the polymer chains. Such effects increase the chances of the PD being interspersed into the acceptor material, which improve the solubility between the PD and PA. The PBTPICγ-BDD and PBTPICF-BDD displayed better miscibility with PBQx-TCl, leading to a well optimized morphology. As a result, high power conversion efficiencies (PCEs) of 17.50 % and 17.17 % were achieved for PBQx-TCl : PBTPICγ-BDD and PBQx-TCl : PBTPICF-BDD devices, respectively. With the addition of PYFT-o as the third component into PBQx-TCl : PBTPICγ-BDD blend to further extend the absorption spectral coverage and finely tune microstructures of the blend morphology, a remarkable PCE of 18.64 % was realized finally.

Improving Miscibility of Polymer Donor and Polymer Acceptor by Reducing Chain Entanglement for Realizing 18.64 % Efficiency All Polymer Solar Cells

AbstractAll‐polymer solar cells have experienced rapid development in recent years by the emergence of polymerized small molecular acceptors (PSMAs). However, the strong chain entanglements of polymer donors (PDs) and polymer acceptors (PAs) decrease the miscibility of the resulting polymer mixtures, making it challenging to optimize the blend morphology. Herein, we designed three PAs, namely PBTPICm‐BDD, PBTPICγ‐BDD and PBTPICF‐BDD, by smartly using a BDD unit as the polymerized unit to copolymerize with different Y‐typed non‐fullerene small molecular acceptors (NF‐SMAs), thus achieving a certain degree of distortion and giving the polymer system enough internal space to reduce the entanglements of the polymer chains. Such effects increase the chances of the PD being interspersed into the acceptor material, which improve the solubility between the PD and PA. The PBTPICγ‐BDD and PBTPICF‐BDD displayed better miscibility with PBQx‐TCl, leading to a well optimized morphology. As a result, high power conversion efficiencies (PCEs) of 17.50 % and 17.17 % were achieved for PBQx‐TCl : PBTPICγ‐BDD and PBQx‐TCl : PBTPICF‐BDD devices, respectively. With the addition of PYFT‐o as the third component into PBQx‐TCl : PBTPICγ‐BDD blend to further extend the absorption spectral coverage and finely tune microstructures of the blend morphology, a remarkable PCE of 18.64 % was realized finally.

Effect of curdlan on the gel properties and interactions of whey protein isolate gels

This study investigated the influence of curdlan on the gel properties of whey protein isolate (WPI). Results demonstrated that curdlan significantly improved the water-holding capacity, gel strength and rheological properties of the WPI gels. Moreover, it promoted the unfolding of the molecular structures of WPI, which was manifested by the transition from α-helix to β-sheet, an increase in free sulfhydryl content and a decrease in surface hydrophobicity. Furthermore, 4 % curdlan promoted the formation of WPI with uniform and compact elastic gel network structures, primarily attributed to disulphide bonds, hydrogen bonds and hydrophobic interactions. However, when the addition of curdlan exceeds 4 %, excessive entanglement of curdlan chains and steric hindrance effects hinder the unfolding and folding of protein structures, weaken their interaction, result in a loose network structure and affect the gel properties. In conclusion, this study demonstrates that curdlan can effectively improve the gelling properties of WPI, suggesting its potential application in low-calorie gel-based dairy products.

A super-stretchable and anti-fatigue silicone gel by regulating chain entanglement and cross-link density

Applications of silicone gel in flexible devices and soft machines require it to maintain excellent stretchability and antifatigue. However, the reported fatigue threshold of traditional silicone gels is in the range of 1–100 J m−2 and the stretchability below 2000 %. Herein, we report a simple strategy for constructing soft polydimethylsiloxane gels, which possesses high stretchability up to 8300 %, and high fatigue resistance (321 J m−2). This is achieved by controlling the ratio of chemical crosslinking and physical entanglement in the polydimethylsiloxane gels. The symbiotic relationship of this combination includes: extending the polymer chains helps them unfold to increase softness and intrinsic toughness; controlling the physical entanglement and chemical cross-linking helps to further increase the tensile rate and fatigue threshold, and adding small-molecule dimethyl PDMS as a solvent further increases fatigue resistance and tensile properties. This work provides a facile approach for developing super-stretchable and anti-fatigue silicone gel, which promises wide range of applicant in flexible devices and soft machines.

Tailoring molecular structure and electromechanical properties of polydimethylsiloxane elastomer for enhanced energy conversion efficiency

AbstractThe molecular structure of dielectric elastomers dictates their mechanical, electrical, and properties to react under external stimuli, influencing their suitability for applications such as actuators, sensors, and energy harvesting devices. The molecular structure of polymers can be tailored by incorporating plasticizers and particulate fillers to achieve multifunctional properties. However, achieving a balance between flexibility and maintaining mechanical strength due to incorporation of fillers induced phase separation and compromised intermolecular interactions remains challenging. In the present work, polydimethylsiloxane (PDMS) composites are synthesized using plasticizer and particulate fillers, polyethylene glycol (H‐(OCH2CH2)nOH) and titanium diboride (TiB2) respectively in various concentrations using shear mixing and doctor blade casting technique. Molecular structure of synthesized PDMS composite is confirmed by observing peaks of Raman spectra sift, which exhibits robust CO bonds dominating for both fillers. Chain entanglement due to filler incorporation significantly affects the crosslink density of PDMS composite, it increases with the concentration of plasticizer and possesses inverse relation for particulate. Furthermore, interdependence of the filler types and concentration are found on the mechanical as well as electrical properties. The specific deformation energy exhibits a significant increase of 118.9% when comparing particulate to the plasticizer at concentration of 8 wt.%. Although plasticizer increases the actuation strain and energy conversion efficiency but decreases the electrical breakdown voltage in comparison to particulate. By systematically varying fillers concentration, subtle changes in multifunctional properties are achieved. Overall, this investigation provides a framework for tailoring dielectric elastomer composites with desired electromechanical characteristics through the amalgamation of filler types and crosslinking densities, all intricately tied to the molecular architecture for electromechanical sensors.Highlights Filler incorporation changes DE molecular structure and materials properties. Formation of additional bonds and micro‐capacitors in DE enhances capacitance. Actuation strain in DE depends on filler type and concentration. Energy conversion efficiency varies with the concentration of filler.

Solvent Engineering of Thermo-Responsive Hydrogels Facilitates Strong and Large Contractile Actuations.

Thermo-responsive hydrogels can generate the actuation force through volumetric transitions in response to temperature changes. However, their weak mechanical properties and fragile actuation performance limit robust applications. Existing approaches to enhance these properties have typically depended on additional components, leading to an unavoidable interference to the actuation performance. In this work, robust thermo-responsive hydrogels are fabricated through solvent engineering. A particular solvent, N-methylformamide, interacts affinitively with the carbonyl group of N-isopropylacrylamide monomer, solubilizes the monomer with extremely high concentration, stabilizes chain propagation during polymerization, and greatly increases chain lengths and entanglements of the resulting polymer. The synthesized hydrogels are highly elastic, strong, and tough, displaying remarkable thermo-responsive contractile actuation. The simple synthetic process can broaden its applicability in designing robust functional hydrogel applications.

Entanglements of Macromolecules and Their Influence on Rheological and Mechanical Properties of Polymers.

Flexible macromolecules easily become entangled with neighboring macromolecules. The resulting network determines many polymer properties, including rheological and mechanical properties. Therefore, a number of experimental and modeling studies were performed to describe the relationship between the degree of entanglement of macromolecules and polymer properties. The introduction presents general information about the entanglements of macromolecule chains, collected on the basis of studies of equilibrium entangled polymers. It is also shown how the density of entanglements can be reduced. The second chapter presents experiments and models leading to the description of the movement of a single macromolecule. The next part of the text discusses how the rheological properties change after partial disentangling of the polymer. The results on the influence of the degree of chain entanglement on mechanical properties are presented.

Universal hydrogel adhesives with robust chain entanglement for bridging soft electronic materials

Ensuring stable integration of diverse soft electronic components for reliable operation under dynamic conditions is crucial. However, integrating soft electronics, comprising various materials like polymers, metals, and hydrogels, poses challenges due to their different mechanical and chemical properties. This study introduces a dried-hydrogel adhesive made of poly(vinyl alcohol) and tannic acid multilayers (d-HAPT), which integrates soft electronic materials through moisture-derived chain entanglement. d-HAPT is a thin (~1 µm) and highly transparent (over 85% transmittance in the visible light region) adhesive, showing robust bonding (up to 3.6 MPa) within a short time (<1 min). d-HAPT demonstrates practical application in wearable devices, including a hydrogel touch panel and strain sensors. Additionally, the potential of d-HAPT for use in implantable electronics is demonstrated through in vivo neuromodulation and electrocardiographic recording experiments while confirming its biocompatibility both in vitro and in vivo. It is expected that d-HAPT will provide a reliable platform for integrating soft electronic applications.

Potassium Phthalimide Doped with Delta‐Site Structures to Construct Ultra‐Long Cycle Life Aqueous Zn‐Polymer Batteries

AbstractAqueous Zn‐polymer batteries hold great promise for environmentally friendly energy storage systems. However, the poor cycling performance caused by irreversible structural deformation and polymer chain entanglement during the embedding and de‐embedding processes of Zn2+ and H+ ions is one of the key challenges facing their development. Here a new polyaniline cathode doped is developed with potassium phthalimide using a secondary doping approach. This polymeric electrode integrates the conjugated backbone for charge transport with an anionic phthalimide dopant for constructing a triangular‐site structure, as illustrated by the density functional theory calculations. This unique molecular structure is favorable for improving conductivity and structural stability by effectively modulating the localized electron cloud density. The Zn‐polymer battery holds an outstanding capacity retention of 76.1% after 25,000 cycles at a current density of 1 A g−1 with the coulombic efficiency maintained above 99.4%. This secondary doped polymer strategy offers a new host alternative for the ultra‐long cycle life of Zn‐polymer batteries. The molecular design strategy and the insight into the relationship between the structure and performance may provide some guidelines for developing polymer cathodes with high stability.

Unlocking the potential of supramolecular polymers with bimodal molecular weights for instant and strong underwater adhesion

Developing adhesives suitable for underwater environments remains a formidable challenge due to the barrier presented by water, hindering contact between the adhesive and adherend. In this work, supramolecular adhesives prepared by mixing low and high molecular weight poly(butyl acrylate)-based copolymers are manifested to function effectively for underwater adhesion regardless of substrates’ affinity to water. Optimization of adhesion performance is achieved by manipulating the copolymer composition, resulting in the remarkable adhesion strengths of 1290 N m-1 and 1047 N m-1 to hydrophobic PET and hydrophilic glass substrates, respectively. The observed high underwater adhesion is attributed to a synergistic effect: instant and efficient removal of the hydration layer facilitated by the low molecular weight polymer strands, and mechanical resilience conferred by the high molecular weight strands featured by chain entanglements. Adequate interfacial interactions are attained by the supramolecular interactions including cation-π and π-π bonding. Notably, owing to its inherent hydrophobicity, the adhesive can be stored underwater for over a week and still displays 842 N m-1 peel strength to glass substrate. This work unlocks the potential of supramolecular adhesives with bimodal molecular weight distribution for instant and strong underwater adhesion, providing a straightforward yet scalable strategy to produce high-performance underwater adhesives.

Prediction of Ultrasonic Welding Parameters for Polymer Joining

Welding of polymers is a useful assembly process that eliminates the need for adhesives or mechanical fasteners, saving consumable costs. One of the most common polymer welding processes is ultrasonic welding. Effective welding requires that the molten polymer chains at the joint surface diffuse across the joint and become entangled with polymer chains in the parts to be welded. This intermolecular diffusion and chain entanglement are the fundamental characteristics of welding. Using fundamental theories of heat generation and melt flow, optimal weld parameters can be calculated to ensure that diffusion across the weld joint occurs during ultrasonic welding.

Controlled dissolution of physically cross-linked locust bean gum – κ-carrageenan hydrogels

Most hydrogels swell but do not dissolve in water since their chains are tied to each other. Nevertheless, some hydrogels disintegrate under physiological conditions, a property that could be beneficial in emerging applications, including sacrificial materials, 3D bioprinting, and wound dressings. This paper proposes a novel approach to control the dissolution rate of hydrogels based on the integration of kappa carrageenan nanoparticles (KCAR-NPs) into kappa carrageenan (KCAR) and locust bean gum (LBG) hydrogels to obtain a three-component hybrid system. KCAR and LBG are known to have synergistic interactions, where physical interactions and chain entanglements lead to their gelation. We hypothesized that integrating the bulky nanoparticles would disturb the three-dimensional network formed by the polysaccharide chains and enable manipulating the dissolution rate. Compression, water absorption, rheology, and cryo-scanning electron microscopy measurements were performed to characterize the physical properties and structure of the hydrogels. The hybrid hydrogels displayed much faster dissolution rates than a control system without nanoparticles, which did not completely dissolve within 50 days and offered a cutting-edge means to finely adjust hydrogel dissolution through modulation of KCAR and KCAR-NPs concentrations. The new hydrogels also exhibited shear-thinning and self-healing properties resulting from the weak and reversible nature of the physical bonds.

Superabsorbent ZnO/rubber-based hydrogel composite for removal and photocatalytic degradation of methylene blue

A superabsorbent hydrogel was prepared by the free-radical copolymerization of natural rubber (NR) latex with poly(acrylic acid) (PAA) at NR loadings up to 50 wt%. An NR/PAA hydrogel containing 40 wt% of NR (NR-40) had a water absorption capacity of 214 g/g (21,400 %) of its dry weight. The compressive modulus increased 512 % and sample integrity was improved due to the physical entanglement of NR chains. NR-40 hydrogel removed 97 % of methylene blue (MB) from the aqueous solution in 1 h (at initial concentrations of 10–1000 mg/L) and produced a maximum removal of 1191 mg MB/g of hydrogel at an initial MB concentration of 4500 mg/L. The adsorption of MB was an endothermic process. Fourier transform infrared spectroscopy indicated that hydrogen bonding and electrostatic interaction drove the process. After the in-situ incorporation of ZnO into NR-40, absorbed energy from sunlight generated active species that could photocatalytically degrade adsorbed MB in the hydrogel matrix. The scavenger tests indicated that superoxide radical anions and hydroxyl radicals were the main species for this process. The hydrogel composite material showed good stability and could be regenerated and reused over 10 cycles, degrading >80 % of the adsorbed dye. This novel natural-based hydrogel provides double functions of adsorption and photodegradation of toxic dyes without the requirement of chemicals and a separation process.

The influence of low-temperature shear on crystallization of shish-kebab of unimodal/ bimodal C4 short-chain branching polyethylene

The shish crystal, a crucial structure in the formation of shish-kebab crystals, has drawn widespread attention due to its highly oriented chain arrangement, significantly enhancing the mechanical properties of products. This study utilizes polyethylene samples with longer C4 short branches, employing in-situ synchrotron SAXS/WAXD to investigate the influence of short branch length and content on the formation of shish-kebab crystals in unimodal and bimodal polyethylene under low-temperature shear conditions (with supercooling degrees of 13.5 °C and 10.5 °C). The results reveal that the presence of C4 short-chain branching affects system crystallization, but low-temperature shear induces stronger mechanical action on the melt, resulting in better-oriented lamellar crystals compared to high-temperature shear (superheat degrees of 22.5 °C and 19.5 °C), achieving higher orientation. This achieves the control of shish-kebab crystal generation through the stretched network mechanism. Both types of samples with different C4 short-chain branching contents generate shish-kebab crystals during the shear stage, with relatively higher short-chain branching content inducing more shish crystal formation but with less regular structure. The bimodal polyethylene exhibit higher proportions and absolute amounts of final shish crystals compared to the unimodal polyethylene, indicating that high molecular weight portions are conducive to shish crystal generation under shear. The result demonstrates the feasibility of generating shish-kebab crystals during the low-temperature shear process of PE in the presence of C4 branches using the stretched network mechanism under shear flow conditions. Moreover, controlling the degree of entanglement of molecular chains by adjusting shear temperature, branch content, and branch length can modulate two formation mechanisms of shish crystals—coil-stretch transition mechanism at high temperature and stretched network mechanism at low-temperature.

Extreme condition-tolerant stretchable flexible supercapacitor and triboelectric nanogenerator based on carrageenan-enhanced gel for energy storage, energy collection and self-powered sensing

As flexible electronics devices for energy storage, mechanical energy collection and self-powered sensing, stretchable flexible supercapacitor and triboelectric nanogenerator (TENG) have attracted extensive attention. However, it is difficult to satisfy the requirements of high safety and resistance to extreme conditions. Dual roles of mechanical and electrical enhancement of inorganic salt are put forward, and a carrageenan (CG) enhanced poly (N-hydroxyethyl acrylamide)/CG/lithium chloride/glycerol (PCLG) conductive gel is prepared by designing hydrogen bonding self-crosslinking and chain entanglement. A high concentration and rapid deposition strategy is proposed to prepare a PCLG gel-based stretchable flexible all-in-one supercapacitor for energy storage, and a single electrode PCLG gel-based TENG is designed for mechanical energy collection, self-powered strain and tactile sensing. The supercapacitor has high capacitance, excellent cycling stability. The TENG possesses efficient energy harvesting with high and stable output voltage and power density, and sensitive and stable self-powered strain and tactile sensing without external power supply. Even under extreme conditions such as low temperatures, self-healing after damage, prolonged placement, deformation, post-deformation, multiple continuous work, pinprick and burning, the supercapacitor and TENG still have excellent properties. Therefore, we provide novel ideas to design flexible supercapacitor and TENG used under extreme conditions for future wearable electronics.

Percolating coordinated ion transport cells in polymer electrolytes to realize room-temperature solid-state lithium metal batteries

Polymer electrolytes, notable for their good mechanical properties, superior processability, and high electrochemical stability, are promising for high-energy-density lithium metal batteries. However, the ionic conduction of polymer electrolytes is seriously constrained by either the entanglement of polymer chains or binding of anions, particularly at ambient temperatures, making their practical application impossible. Herein, we employ a high-salt-concentration strategy with poly(vinylene carbonate) to construct a percolating network by linking coordinated ion transport cells. The cells, consisting of lithium-ion at the core surrounded by coordinated poly(vinylene carbonate), N,N-dimethylformamide, or incompletely bonded bis(trifluoromethanesulfonyl)imide, ensure an efficient coordination and de-coordination process for ion transport. Thus, a high rate of Li+ transport is realized, achieving an ionic conductivity of 0.82 mS cm−1 at 30 °C. Consequently, the formulated solid-state lithium metal batteries with the poly(vinylene carbonate) electrolyte enable superior stability in cycling under a wide temperature range (0–60 °C), high working voltage (4.5 V), and high mass load (>10 mg cm−2). This simple strategy for creating an ion-percolating network by linking coordinated ion transport cells not only offers new insights into understanding the mechanism for ion transport in polymer electrolytes but also paves the way for the application of solid-state lithium metal batteries.

Polysaccharide Hydro-Gel from Arid Plant Seed

There is a limited information on the structure and gelation process in mucilagepolysaccharides because of the complex conformation and non-homogeneity of the constituent polysaccharides that typically show large molecular weights in excess of 1 MDa. Only a few works have been done in this area of characterizing mucilage structure and rheological behaviour for different gel solutions. Exploring this area would surely open the new horizons for drug delivery, soil conditioning and pharmaceutical industry. In this study, we aimed to extract polysaccharides found in P.ovata Seed (Isabgol) via mucilage extraction controlling molecular weight of polymers in hot water extraction stage and tried to formulate gel formation dissolving different conc. of extracted freeze-dried material along with the characterization of gel network through Rheological studies and Dynamic Light Scattering (DLS) studies in different solvents. The study confirmed the relationship between molecular associations, chain relaxation time and entanglement behaviour of P. ovata hot water extracted (HW) solutions using polydispersity index and shear rheology. Moreover, two power law regions obtained for different concentration solution are of great importance because of their wide applications in the industrial prospective.

Stereocomplex crystallization of equimolar Poly(L-lactic acid)/Poly(D-lactic acid) blends from melt with lowered chain entanglements

Understanding polymer crystallization at the molecular level is one of the key open questions of polymer physics. Here, high molecular weight equimolar poly(L-lactic acid)/poly(D-lactic acid) (PLLA/PDLA) blends with lowered chain entanglements are prepared by the freeze-drying method. The role of chain entanglements in stereocomplex (SC) crystallization is explored. A significant increase in the crystallization kinetics of SC is observed with decreasing the entanglement density, and thus highly crystallized SC is obtained in the PLLA/PDLA blends by a process of non-isothermal crystallization. With reducing the chain entanglements of PLLA/PDLA blends, an intriguing phenomenon that SC crystallization stops at a high temperature around 200 °C and starts again at ∼160 °C on continuous cooling is observed, verifying the new concept of “poisoning by purity”. Further studies reveal that the PLLA/PDLA blends with lowered chain entanglements are more likely to form regularly folded SC lamellae, which nucleate and grow at higher temperatures. Meanwhile, the reduced chain entanglements also reduce the activation energy for chain diffusion. These two effects may be the main reason for the significantly accelerated crystallization kinetics of SC. This study provides a new idea for producing highly crystallized SC in PLLA products to improve their thermal resistance and other properties.

Mechanical reinforcement by bridging chains in polymer nanocomposites

The adsorption-induced bridging of polymer chains between adjacent nanoparticles was studied in poly(vinyl acetate)/silica nanocomposites with different polymer molecular weights, interaction strengths, nanoparticle sizes, and silica loading fractions. The polymer bridging contribution is successfully decoupled from the apparent rubbery plateau modulus by subtracting the hydrodynamic and trapped chain entanglement contributions. The bridging modulus depends on the nearest interparticle surface distance through a power-law relation with a universal exponent −3. Polymer molecular weight can enhance the bridging modulus only when nanoparticles have a high density of adsorption sites due to the emergence of direct bridging of multiple particles by one chain in addition to the regular bridging through self-similar carpets. Our results illustrate that bridging chains can dominate modulus enhancement at nanoparticle's loading at about 10 vol% in polymer nanocomposites with long polymer chains and high surface silanol density.

Extraction of Dual‐Switch Fluorescent Nanosheets from Asphaltenes under Ambient Conditions

AbstractAsphaltene, often regarded as an undesirable by‐product of petroleum processing, possesses abundant reserves but limited market value. In this study, a simple and environmentally friendly solvent extraction method is conducted under ambient conditions to convert low‐value asphaltene into high‐value asphaltene‐based fluorescent carbon nanosheets (a‐FCS). This approach yields dual‐switch a‐FCS capable of emitting orange‐red fluorescence in solid‐state or water environment and exhibiting blue‐to‐yellow fluorescence in organic solvents. Moreover, the redshift observed in the fluorescence emission wavelength in the solvent is attributed to its intrinsic self‐assembly behavior, which becomes more pronounced with increasing concentration. Upon introduction to water, hydrophobic interactions induce the aggregation of a‐FCS. This aggregation triggers the orange‐red fluorescence by restricting intramolecular rotation on the surface, a phenomenon facilitated by the entanglement of aliphatic chains from asphaltene molecules. This unique property makes them applicable in anti‐counterfeiting and determination of ethanol content in aqueous solution.