Converting renewable cellulose into glucose via cellulase catalysis for further production of biofuel has been recognized as one of the most promising ways for solving energy crisis. However, the hydrolysis performance of immobilized cellulase was not satisfactory for practical application due to the reduced catalytic efficiency and lack of β-glucosidase (BG) component in cellulase. Here, a facile method was developed to sequentially co-immobilize BG and cellulase by polymeric microparticles with hierarchical structure. In this strategy, BG was firstly entrapped into the cross-linked poly(ethylene glycol) (PEG) microparticles via inverse emulsion polymerization initiated by isopropyl thioxanthone (ITX) under the irradiation of visible light, leaving the formed ITX semi-pinacol (ITXSP) dormant groups on surface of BG-loaded microparticles, which could be further activated by visible light irradiation and initiated a graft polymerization to introduce poly(acrylic acid) (PAA) brush on the PEG core. After that, cellulase was covalently bonded on the PAA chains via carbodiimide reaction. The synergic effect of BG and cellulase was verified in the dual enzyme immobilization system, which led to a better stability at a wide range of temperature and pH than free enzymes. The dual enzymes system exhibited excellent reusability, which could retain 75% and 57% of the initial activity after 10 cycles of hydrolysis of carboxyl methyl cellulose and 5 cycles of hydrolysis of filter paper, respectively, indicative of the potential in biofuel areas in a cost-effective manner.

Polymer microspheres with uniform size, composition, and surface property have gained extensive researches in past decades. Conventional bottom-up approaches are using monomers or oligomers to build up desired polymer microspheres. However, directly shaping high-molecular-weight polymers into well-ordered polymer microspheres remains a great challenge. Herein, we reported a facile and efficient top-down approach to fabricate microspheres with high-molecular-weight polymer microfibers. By harnessing interfacial engineering-control during the polymer microspheres formation, uniformly sized microspheres could be produced with widely ranged diameters (from 10 μm to the capillary length of each polymer melt). The size limitation of this approach could be further extended by a controllable Plateau-Rayleigh instability phenomenon. Principally, the top-down approach allows fabrication of microspheres by various polymer melts with surface energy higher than 25 mN/m. Our work paves a way for green, cost-effective, and customizable production of a variety of functional polymer microspheres without any chemical reaction assistant.

It remains a significant challenge to fabricate self-healing aerogels with excellent flame retardancy. Herein, we develop a class of biomass aerogels by electrostatically assembling chitosan (CS), phytic acid (PA), and itaconic acid (IA). The electrostatic interaction between CS and IA is weak and dynamic, so freeze-drying the solution of CS and IA enables the formation of continuous aerogel skeleton with self-healing ability and re-programmability; in comparison, the electrostatic interaction between CS and PA is strong and less dynamic, and thus mixing PA with CS in aqueous solution leads to fine precipitates of high flame retardancy due to the synergistic phosphorus-nitrogen effect. Integrating the continuous skeleton and the fine precipitates results in self-healing aerogles with UL-4 V-0 rating of flame retardancy aerogels and auto-extinguishable feature. Interestingly, the aerogels after burning in flame for 30 s form a skin-core structure, and the carbonized skin protects the integrity of the aerogels and the self-healing ability of the internal parts. Therefore, this work provides a facile strategy to develop multi-functional aerogels which hold great promise for advanced applications.

Neodymium complexes containing N-heterocyclic carbene (NHC) ligands, NdCl₃[1,3-R₂(NCH=)₂C:]·THF_x (Nd1: R = 2,6-ⁱPr₂C₆H₃, x = 0; Nd2: R = 2,6-Et₂C₆H₃, x = 1; Nd3: R = 2,4,6-Me₃C₆H₂, x = 1) were synthesized and employed as precatalysts for the coordination polymerization of conjugated dienes (butadiene and isoprene). In combination with triisobutylaluminium (TIBA), Nd1 promoted butadiene polymerization to produce extremely high cis-1,4 (up to 99.0%) polybutadienes with high molecular weight (M_w = 250−780 kg·mol⁻¹). The Nd1/TIBA catalytic system also exhibited both high catalytic activity and cis-1,4 selectivity (up to 97.8%) for isoprene polymerization. The catalytic activity, molecular weight and molecular weight distribution of resulting polydienes were directly influenced by Al/Nd molar ratio, aging method, and polymerization temperature. Very interestingly, the high cis-1,4 selectivity of the catalyst towards butadiene and isoprene kept almost unchanged under different reaction conditions. The cis-1,4 polyisoprenes with high molecular weight (M_w = 210−530 kg·mol⁻¹) and narrow molecular weight distribution (M_w/M_n = 1.9−2.7) as well as high cis-1,4 selectivity (~97%) could be synthesized by using the aged Nd1/TIBA catalytic system in the presence of isoprene (100 equivalent to Nd) at low Al/Nd molar ratios of 6−10. Polyisoprenes with low molecular weights (M_w = 12−76 kg·mol⁻¹) and narrow molecular weight distributions (M_w/M_n = 1.7−2.6) were obtained by using Nd2 and Nd3 as precatalysts, indicating that the molecular weight of resulting polyisoprenes can be adjusted by changing the substitutes of ligand in Nd complex.

In lithium-ion batteries (LIBs), separators play a vital role in lithium-ion (Li⁺) transport, and thus affect rate performance, battery life, and safety. Here, a new kind of multifunctional copolymer poly(acrylonitrile-co-lithium acrylate-co-butyl acrylate) (PAAB-Li) is synthesized through soap-free emulsion polymerization, and is used to form homogeneous-covered separator based on PP matrix by a simple dip-annealing process. Compared to the bare PP separator, the modified separators with PAAB-Li enable higher ionic conductivity, higher lithium ion transference number (increased from 0.360 to 0.525), and lower interface impedance (reduced from 155 Ω to 34 Ω). It has been indicated that PAAB-Li functional layer significantly promotes the fast transport of Li⁺ and improves the compatibility of the separator/electrolyte-electrode interface. The LiCoO₂/graphite cells with the PAAB-Li-assisted separator demonstrate excellent cycle stability and rate performance. In addition, the Li symmetric cells with the modified separator stably cycle over 800 h, indicating the functional layer effectively suppresses the lithium dendrite growth. This facile strategy can be easily applied to LIBs requiring high safety and even be scalable to Li metal batteries. Moreover, the possible mechanism of the PAAB-Li functional layer promoting fast and uniform Li⁺ transport is discussed in this paper.

The crystalline and amorphous regions were alternately arranged in the hard elastic polypropylene (PP) films with row-nucleated lamellae. In this work, their structure evolution during stretching and recovery at room temperature was followed and the elastic recovery mechanism was discussed by twice cyclic tensile experiment. During the first stretching to 100%, the lamellae crystals are parallel separated and the intercrystallite crazing is formed at the first yield point. Many nano-cavities within the intercrystallite crazing appear when the strain reaches 20%. The strain-hardening process accompanies with the lamellae long period increasing and the intercrystallite crazing enlargement. After the secondary yield point, the lamellae cluster is further separated and more nano-cavities appear. The first and second recovery processes are complete overlap. During recovery, firstly, the energy elasticity provided by nano-cavities surface tension drives the shrinkage of material, and then the entropy elasticity related to amorphous chain relaxation plays a leading role when the strain is smaller than the secondary yield point. The elastic recovery process of hard elastic material is the co-contribution of energy elasticity and entropy elasticity. This work gives a clearer recognition about the source of hard elastic property and the role of amorphous region in material’s deformation.

High transparency and toughness are prerequisites for sustainable polymers if they are to find wide application as alternatives to petroleum-based polymers. However, the utility of sustainable polymers such as commercially available polylactide (PLA) is limited by their inherent brittleness and high cost. Unfortunately, toughening PLA-based materials via cost-effective blending strategies without sacrificing transparency remains a challenge. Herein, we report a novel strategy involving active refractive index matching for creation of highly transparent and tough PLA blends. Specifically, we engineered the refractive index of a promising renewable poly(epichlorohydrin-co-ethylene oxide) elastomer by introducing polar ionic moieties via a simple chemical method, and we blended the resulting ionomers with PLA. The best blend showed an impact strength of > 80 kJ/m², an elongation at break of 400%, and high transparency (90%). These characteristics are of great importance for potential applications such as packaging. Our strategy offers a versatile new way to prepare high-performance sustainable polymer materials with excellent transparency.

A convenient tape-casting method was applied to prepare high performance aromatic polyamide (PA) films based on Technora^®. During the polycondensation, CaO was introduced to improve the solubility of the PA resin, and the generated halides were totally removed from the film via a simple water bath, without leaving any defects in PA films. The factors of processing temperature and immersion time had been systematically investigated, and the experimental results demonstrated that both of them had impressive impacts on aggregation state and comprehensive properties of the PA film. It was suggested that immersion in water for more than 1 min and baking below 300 °C for 10 min were the optimal conditions for the thermal, tensile, tear, and optical properties to be in the best equilibrium. The resultant PA films integrated outstanding film-forming ability and excellent general performance, especially the tensile property and tear resistance.

The mechanism of nucleating agents (NAs) accelerating the crystallization of semi-crystalline polymers has received continuous attention due to the extreme importance in academic research and industry application. In this work, the nucleation effect and probable mechanism of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) on promoting the crystallization of syndiotactic polypropylene (sPP) was systematically investigated. Our results showed that DMDBS could significantly accelerate the crystallization process and did not change the crystalline form of sPP. The in situ infrared spectra recorded in the crystallization process showed that in pristine sPP the tttt conformers decreased and the ttgg conformers increased subsequently. In sPP/DMDBS system, DMDBS could promote the increase of ttgg conformers rather than the decrease of tttt conformers. The further analysis by 2D-IR spectra revealed that ttgg conformers increased prior to the decrease of tttt conformers in the sPP/DMDBS system comparing with pristine sPP. Considering that ttgg conformers were basic elements of helical conformation of Form I crystal for sPP, we proposed a probable nucleation mechanism of DMDBS for sPP:DMDBS could stabilize the ttgg conformers which induced these ttgg conformers to pre-orientate and aggregate into helical conformation sequences as initial nuclei quickly and early to promote the sPP crystallization. Our work provides some new insights into the nucleation mechanism of NAs for sPP.

Poly(L-lactic acid) (PLLA) has drawn much attention due to its excellent medical and pharmaceutical applications for decades. As a semi-crystalline polymer, morphology and crystal structure of PLLA greatly determine its properties. Here, we demonstrate, for PLLA films, a non-conventional texture featuring two types of spherulites emerging in pairs to form a distinct nested structure where a small spherulite (~10 μm) is embedded in a large one (100 μm to 300 μm). In addition to the size, the molecular weight and polymorph are different in the large and small spherulites. Crystallographic α-form and relatively low molecular weight are identified in the large spherulites, while meta-stable α′-form and relatively high molecular weight in the small ones. These differences suggest that the polydisperse PLLA polymers fractionate during film formation and the high-molecular-weight fraction crystallizes into the small spherulites with meta-stable structure because of its complicated polymer entanglement and high viscosity. In contrast, the rest of polymers crystallize into the large spherulites with the thermodynamically stable polymorph. Furthermore, this texture exhibits accelerated PLLA degradation initiated from the small spherulites, which is distinct from the typical PLLA spherulites. Insights provided by this work may lead to new texture-properties relationship associated with polydispersity of molecular weight.

Transparency is often an important property in the practical applications of temperature-responsive shape-memory gels. We investigated the mechanism of significant transparency improvement upon a change in two copolymer gels with their molar ratios between stearyl acrylate and N,N-dimethylacrylamide from 1:1 to 0.75:1. By means of Flash DSC measurement, we made the thermal analysis characterization of crystallization and glass transition in two copolymer gels and compared the results to the parallel experiments of corresponding homopolymers. The results showed that the slightly lower content of stearyl acrylate sequences suppresses crystallization in their side chains due to the chemical confinement of comonomers on copolymer crystallization; meanwhile it shifts up the glass transition temperature of the backbone N,N-dimethylacrylamide sequences. Eventually on cooling, crystallization gives its priority position to glass transition in copolymer gels, resulting in a higher transparency of the gel without losing the shape-memory performance. To confirm the chemical confinement, we further compared the isothermal crystallization kinetics of stearyl acrylate side chains in the copolymer gel to that of their homopolymer. Our observations facilitate the rational design of the temperature-responsive shape-memory gels for the transparency property.

The composition and structure of polymer largely determine the properties of its final products. As a novel polymer material, the composition, structure, and properties of the isotactic polypropylene/polybutene-1 in-reactor alloy (iPP/iPB alloy) synthesized by sequential two-stage polymerization with Ziegler-Natta catalyst were correlated for the first time in this work. The iPP/iPB alloy was fractionated by temperature rising elution fractionation (TREF) in a broad temperature ranged from –30 °C to 140 °C, and the chain microstructures and sequence distributions of isolated fractions were analyzed by DSC, GPC, ¹³C-NMR, and FTIR. The iPP/iPB alloy was composed of five components, namely high isotactic PB (iPB, 85.8 wt%), medium isotactic PB (mPB, 5.1 wt%), poly((butene-1)-block-propylene) copolymers (PB-b-PP, 4.1 wt%) which contained PB and PP blocks with different lengths according to the isolation temperature, isotactic PP (iPP, 2.7 wt%), and atactic PB (aPB, 2.3 wt%). Compared to other commercial pipe materials, the iPP/iPB alloy presented outstanding thermal creep resistance and gas permeability resistance, high strength and low deformation at high temperature, and appropriate flexural strength. The roles of PP and PB-b-PP components in the alloy were interpreted. This work is expected to elucidate the potential application of iPP/iPB alloy as pipe materials and provide solutions for the design and synthesis of high performance pipe materials.

Oriented “shish-kebab” structures could be obtained by shearing to enhance the mechanical properties of polymer samples markedly. However, the effect of shear mode on mechanical properties is still uncertain. The study of stepped hoop shear field on the isotactic polypropylene (iPP) pipe was developed through applying a self-designed rotational shear system (RSS). The effect of stepped shear field on the microstructure and comprehensive properties of iPP pipe was investigated by the comparison with continuous shear. It could be found that the loosely-assembled shish-kebabs with the larger size were formed in the continuous shear pipes, but the smaller and tightly-stacked ones existed in the pipes with stepped shear. Surprisingly, due to differential morphologies under different shear modes, better comprehensive mechanical properties were obtained in the pipes with stepped shear.

The study of the critical behavior is important for classifying different configuration states. Recently, machine learning is capable of discriminating polymer states in the presence of human supervision. Here, we introduce an unsupervised approach based on the self-organizing map (SOM) and the autoencoder network to locate critical phase transitions from raw configuration without the necessity for manual feature engineering. High-dimensional configuration data can be encoded to low-dimensional codes by employing neural network of multilayer restrictive Boltzmann machines and the intermediate code can also be reconstructed to high-dimensional input vector. And then the codes are used to cluster different configuration states for polymers adsorbed on the homogeneous and the stripe-patterned surface by the SOM network and K-Means method. This work presents an unusual tool to identify polymer configuration.

A mesoscopic simulation is applied to investigate the effects of hydrodynamic interactions and axial chains on the dynamics of threaded rings. The hydrodynamic interactions significantly speed up the diffusion and relaxation of both free and threaded rings. The decoupled diffusion and relaxation dynamics indicate the broken of the Einstein-Stokes relationship. The diffusion of a ring threaded on a flexible chain exhibits a synergism effect compared to that on an axial rod, which originates from the self-diffusion of the ring and the reptation-like motion of the axial chain. Meanwhile, hydrodynamic interactions significantly improve the synergism effect, leading to an enhanced sliding motion of the threaded ring. The faster sliding of threaded rings suggests that the entropic barrier is negligible, which agrees well with the basic assumption of barrier-less confining tube at equilibrium in tube theory. Our results provide a new perspective on analysis of the effects of topology constraints on polymer dynamics.

Stretched polyethylene (PE) fibers are found to have super high thermal conductivity, while the bulk of polyethylene is usually thermal insulating even for those with high crystalline degree. A molecular dynamic simulation is deliberately carried out to examine the relationship between chain configuration and thermal conductivity of polyethylene. In this simulation study, independent and interacting PE chains being stretched are compared with the aim to find out the effect of stretching on thermal conductivity of PE. Various crystallization conditions for PE bulk are considered. It is found that heat transports predominately along the covalent chain rather than across chains in PE crystals. Our simulation study helps to understand experimental findings on thermal conductivity of PE at different states. We also predict that amorphous PE may be super thermally conductive if chains are strictly stretched along heat flux.

Controlling the formation of the conductive network in the polymer nanocomposites (PNCs) is very meaningful to enhance their electrical property. In this work, we investigated the effect of grafted nanoparticles (NPs) on the conductive probability of PNCs in the quiescent state as well as under the shear field via a coarse-grained molecular dynamics simulation. It is found that the smallest percolation threshold is realized at the moderate grafting density, the moderate length of grafted chains or the moderate interaction between grafted chains and free chains. Corresponding to it, the dispersion state of NPs varies from the contact aggregation to the uniform dispersion. By analyzing the connection mode among NPs, the probability of NPs which connect three other ones reaches the maximum value at their moderate dispersion state which is responsible for the optimal conductive probability. In addition, the main cluster size is characterized to better understand the conductive network which is consistent with the percolation threshold. It is interesting to find that the percolation threshold is smaller under the shear field than under the quiescent state. The shear field induces more NPs which connect three other ones. This benefits the formation of the new conductive network. Meanwhile, the anisotropy of the conductive probability is reduced with increasing the grafting density. In summary, this work provides a clear picture on how the conductive network of grafted NPs evolves under the shear field.