Design and preparation of a crosslinkable,oil-resistant,and bio-based elastomer from fumarate

Poly(diethyl fumarate-co-methoxyethyl acrylate-co-vinyl chloroacetate)(PDEFMV),a novel bio-based elastomer with a saturated structure,was synthesized via redox emulsion polymerization.The glass-transition temperatures of PDEFMV,adjusted through the variation of the diethyl fumarate-to-methoxyethyl acrylate feeding ratio,ranged from-36.1 to-14.8 ℃.The number-average molecular weights of PDEFMV ranged from 384,000 to 46,000 g/mol.In designing the molecular structure,vinyl chloroacetate was used to provide active sites for subsequent vulcanization and crosslinking.The active chlorine groups within the PDEFMV chain reacted with the crosslinking agent trithiocyanuric acid under high temperature and pressure to form a nonsulfur crosslinked three-dimensional network structure.To achieve the desired properties,carbon black(CB,N330) was incorporated to reinforce PDEFMV,leading to the formation of PDEFMV/CB composites.A comprehensive study was conducted on the high-temperature oil resistance of PDEFMV/CB composites.Following immersion in IRM903 oil at temperatures of 150 and 200 ℃ for 72 h,the mass and volume changes in PDEFMV/CB were lower than those observed in commercially available acrylate rubber(AR)/CB,indicating that PDEFMV exhibited superior oil resistance.Furthermore,the aging characteristics and mechanisms of oil resistance in the PDEFMV/CB and AR/CB composites were investigated at different temperatures(150,200,and 250 ℃).The results provide insights into the operational temperature ranges suitable for PDEFMV/CB and offer valuable guidance for potential industrial applications.

Current trends in bio-based elastomer materials

Elastomers play an irreplaceable role in our society due to their unique properties.Natural rubber is directly obtained from plants and is widely used in tires,shoes,etc.Recently,modified natural rubbers are proposed to expand the application of natural rubber.However,these natural rubbers have a limited variety of molecular structures and may not be able to meet ever-demanding applications.Traditional synthetic elastomers have a variety of molecular structures and their properties are used in various fields,but mainly originate from fossil resources.This review deals with bio-based elastomers,and more specifically natural rubber and bio-based synthetic elastomers.Based on reprocessability,bio-based elastomers can also be divided into bio-based chemically cross-linked ones and thermoplastic ones.Compared to traditional fossil-based elastomers,bio-based ones may alleviate environmental pollution and promote the sustainable development of the elastomer industry.

Synthesis and evaluation of bio-based elastomer based on diethyl itaconate for oil-resistance applications

Bio-based elastomer poly(diethyl itaconate-co-isoprene)(PDEII) was designed and synthesized by redox-initiated emulsion polymerization from diethyl itaconate and isoprene with mass ratio of 20:80, 40:60, 60:40 and 80:20. The number-average molecular weights of PDEII exceeded 140000 with relatively high yields. The physical properties of PDEII, such as glass transition temperatures and thermostability, were comparable with conventional synthetic elastomers and can be readily tuned by varying the ratio of diethyl itaconate to isoprene. The interaction between silica and PDEII macromolecules was effectively enhanced with the increase of diethyl itaconate content by endowing high polarity. The oil-resistance relevant properties of silica/PDEII80(80% diethyl itaconate, 20% isoprene) such as retention of tensile strength, retention of elongation at break and change in volume even surpass those of silica/NBR 240 S after soaked in ASTM 3# oil at different temperatures.

A sustainable process to 100%bio-based nylons integrated chemical and biological conversion of lignocellulose

Considerable progress has been made in recent years to the development of sustainable polymers from bio-based feedstocks.In this study,100%bio-based nylons were prepared via an integrated chemical and biological process from lignocellulose.These novel nylons were obtained by the melt polymerization of 3-propyladipic acid derived from lignin and 1,5-pentenediamine/1,4-butanediamine derived from carbohydrate sugar.Central to the concept is a three-step noble metal free catalytic chemical funnelling sequence(Raney Ni mediated reductive catalytic fractionation-reductive funnelling-oxidative funnelling),which allowed for obtaining a single component 3-propyladipic acid from lignin with high efficiency.The structural and thermodynamic properties of the obtained nylons have been systematically investigated,and thus obtained transparent bio-based nylons exhibited higher Mw(>32,000)and excellent thermal stability(Td5%>265℃).Considering their moderate Tg and good melt strength,these transparent bio-based nylons could serve as promising functional additives or temperature-responsive materials.

Test for the deep:magnetic loading characterization of elastomers under extreme hydrostatic pressures

Soft robot incarnates its unique advantages in deep-sea exploration,but grapples with high hydrostatic pressure’s unpredictable impact on its mechanical performances.In our previous work,a self-powered soft robot showed excellent work performance in the Mariana Trench at a depth of 11000 m,yet experienced notable degradation in deforming capability.Here,we propose a magnetic loading method for characterizing elastomer’s mechanical properties under extremely high hydrostatic pressure of up to 120 MPa.This method facilitates remote loading and enables in-situ observation,so that the dimensions and deformation at high hydrostatic pressure are obtained and used for calculations.The results reveal that the Young’s modulus of Polydimethylsiloxane(PDMS)monotonously increases with pressure.It is found that the relative increase in Young’s modulus is determined by its initial value,which is 8% for an initial Young’s modulus of 2200 kPa and 38% for 660 kPa.The relation between initial Young’s modulus and relevant increase can be fitted by an exponential function.The bulk modulus of PDMS is about 1.4 GPa at 20℃ and is barely affected by hydrostatic pressure.The method can quantify alterations in the mechanical properties of elastomers induced by hydrostatic pressure,and provide guidance for the design of soft robots which serve in extreme pressure environment.

Bio-based rejuvenators in asphalt pavements:A comprehensive review and analytical study

The pressing demand for sustainable advancements in road infrastructure has catalyzed extensive research into environmentally conscious alternatives for the maintenance and restoration of asphalt concrete pavements.This paper offers a comprehensive review and analysis of bio-based rejuvenators as a promising avenue for enhancing the longevity and sustainability of asphalt.Through a multifaceted exploration,it delves into various aspects of this innovative approach.Providing a thorough overview of bio-based rejuvenators,the study highlights their renewable and environmentally friendly characteristics.It conducts an in-depth examination of a wide spectrum of bio-derived materials,including vegetable oils,waste-derived bio-products,and biopolymers,through a comprehensive survey.The paper evaluates how bio-based rejuvenators enhance aged asphalt binders and mixes,effectively mitigating the adverse impacts of aging.Furthermore,it investigates how these rejuvenators address environmental concerns by identifying compatibility issues,assessing long-term performance,and evaluating economic feasibility.Finally,the paper outlines potential advancements and research pathways aimed at optimizing the utilization of bio-based rejuvenators in asphalt concrete,thereby contributing to the sustainable evolution of road infrastructure.

Aqueous-phase reforming of hydroxyacetone solution to bio-based H_(2)over supported Pt catalysts

Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.

Interfacial friction effects on sealing performances of elastomer packer

Elastomer sealing performance is of critical importance for downhole tools application including the use of fracturing(Frac)plugs during multi-stage hydraulic fracking.In practice sealing performances of such plugs are normally evaluated through pressure tests,and in numerical simulation studies,maximum contact stress,average contact stress and contact length data are used to determine sealing quality between a packer and casing.In previous studies,the impact of friction forces on sealing performance is often overlooked.This work aims to fill this knowledge gap in determining the influence of friction forces on elastomer packer sealing performances.We first determined the most appropriate constitutive hyperelastic model for the elastomers used in frac plug.Then we compared analytical calculation results with Finite Element Analysis simulation using a simplified tubular geometry and showed the significant influences on interfacial friction on elastomer packer stress distribution,deformation,and contact stress after setting.With the demonstration of validity of FEA method,we conducted systematic numerical simulation studies to show how the interfacial friction coefficients can affect the maximum contact stress,average contact stress,contact stress distribution,and maximum mises stress for an actual packer used in plug products.In addition,we also demonstrated how the groove in a packer can affect packer deformation and evolvement during setting with the consideration of interfacial stress.This study underscores the critical role that friction forces play in Frac plug performance and provides a new dimension for optimizing packer design by controlling interfacial interactions at the packer contact surfaces.

Bioremediation Potential of the Macroalga Ulva lactuca (Chlorophyta) for Ammonium Removal in Elastomer Industry Wastewater

During the production of nitrile rubber, significant amounts of nitrogen in the form of ammonium are generated in the wastewater. The discharge of this high-nitrogen wastewater can lead to serious environmental issues, including eutrophication, disruption of aquatic ecosystems, and groundwater contamination. To mitigate these impacts, this research explored the bioremediation capabilities of the macroalgae Ulva lactuca (Chlorophyta) for removing nitrogen from nitrile rubber production wastewater. The study employed single-phase and Michaelis-Menten decay models based on ammonium consumption, using various dilutions of wastewater to identify the optimal concentration for treatment. The physiological state of the macroalgae was monitored by measuring the photosynthetic capacity and specific growth rate during the experiments. In the presence of U. lactuca, ammonium concentrations decreased in all treatment groups, confirming that the ammonium kinetics conformed to both applied models. Our results show that U. lactuca effectively reduces ammonium concentrations, with an approximate removal rate of 0.020 µM·g−1·min−1 across different wastewater concentrations (70%, 80%, 90%, and 100%). Notably, the treatments with 70%, 80%, and 90% wastewater strength achieved about 67% reduction in ammonium, demonstrating the alga’s capacity to treat high-nitrogen wastewater. The photosynthetic performance of U. lactuca initially declined in control conditions but stabilized across all treatments, highlighting its adaptability. The kinetic analysis using the Michaelis-Menten model indicated a Vmax of 1342 μM·g−1·DMh−1, suggesting a robust capacity for ammonium uptake when fully saturated. Our study underscores the potential of Ulva lactuca as a cost-effective and efficient agent for wastewater bioremediation, particularly in settings with high nitrogen loads.

Stability analysis of a liquid crystal elastomer self-oscillator under a linear temperature field

Self-oscillating systems abound in the natural world and offer substantial potential for applications in controllers,micro-motors,medical equipments,and so on.Currently,numerical methods have been widely utilized for obtaining the characteristics of self-oscillation including amplitude and frequency.However,numerical methods are burdened by intricate computations and limited precision,hindering comprehensive investigations into self-oscillating systems.In this paper,the stability of a liquid crystal elastomer fiber self-oscillating system under a linear temperature field is studied,and analytical solutions for the amplitude and frequency are determined.Initially,we establish the governing equations of self-oscillation,elucidate two motion regimes,and reveal the underlying mechanism.Subsequently,we conduct a stability analysis and employ a multi-scale method to obtain the analytical solutions for the amplitude and frequency.The results show agreement between the multi-scale and numerical methods.This research contributes to the examination of diverse self-oscillating systems and advances the theoretical analysis of self-oscillating systems rooted in active materials.

Investigation on Magnetorheological Effect of Novel Self-healing Magnetorheological Elastomers

Magnetorheological elastomers(MREs)hold significant promise in various fields such as automotive engineering,and civil engineering,where they serve as intelligent materials.Depending on the application of an external magnetic field,these materials exhibit varying magnetorheological and viscoelastic properties,including shear stress,yield stress,dynamic moduli,and damping.In this work,a new type of MRE,termed self-healing MREs(SH-MREs),has been developed by adding a novel self-healing agent into existing MREs.The dynamic modulus and loss factor of SH-MREs with different compositions have been characterized under various conditions of frequency,temperature,and strain.The results show that as the strain value increases,the loss factor also increases.Moreover,the loss factor initially increases and then decreases with increasing magnetic field strength.Although higher concentrations of ferromagnetic particles increase the loss factor,they enhance the operational range due to their better responsiveness to magnetic fields.SH-MREs demonstrate improved damping capabilities,attributed to the formation of coordination bonds between ferromagnetic particles and the self-healing agent.The stable structure increases the viscosity of MREs.The results of the regression model suggest a direct proportionality between sensitivity to the magnetic field and the ferromagnetic particle concentration.

In silico optimization of actuation performance in dielectric elastomercomposites via integrated finite element modeling and deep learning

Dielectric elastomers(DEs)require balanced electric actuation performance and mechanical integrity under applied voltages.Incorporating high dielectric particles as fillers provides extensive design space to optimize concentration,morphology,and distribution for improved actuation performance and material modulus.This study presents an integrated framework combining finite element modeling(FEM)and deep learning to optimize the microstructure of DE composites.FEM first calculates actuation performance and the effective modulus across varied filler combinations,with these data used to train a convolutional neural network(CNN).Integrating the CNN into a multi-objective genetic algorithm generates designs with enhanced actuation performance and material modulus compared to the conventional optimization approach based on FEM approach within the same time.This framework harnesses artificial intelligence to navigate vast design possibilities,enabling optimized microstructures for high-performance DE composites.

Preparation and Properties of Spray Polyurea Elastomer for Aquaculture Foam Floating Balls

[Objectives] This study was conducted to develop a polyurea elastomer which can be sprayed on the surface of expanded polystyrene (EPS) floating balls, so as to improve the surface strength and service life of the floating balls. [Methods] The effects of the types and amounts of isocyanate, chain extenders and polyether polyols on the gelation rate, adhesion and wear resistance of polyurea elastomer were investigated, and it was finally determined the preparation process of polyurea elastomer using liquid isophorone diisocyanate (IPDI) and amino-terminated polyether (D2000) as the main raw materials, dimethylthiotoluene diamine (E300) as the chain extender and silica as the wear resistance modifier through two-step solution polymerization of prepolymerization and chain extension. [Results] The physical properties and chemical resistance tests of spray polyurea elastomer showed that it had good physical properties and acid and alkali resistance, and could meet the requirements of spraying and protection of EPS floating ball surface in marine environment. [Conclusions] Polyurea elastomer coating can improve the aging resistance, wear resistance and acid and alkali resistance of EPS floating balls, and prevent them from being fragile and floating randomly to form marine floating garbage which results in "white pollution".

Elastic Bio-based Polyurethane Nanofibrous Membrane with Robust Waterproof and Breathable Properties

Elastic bio-based waterproof and breathable membranes(EBWBMs) allow the passage of water vapor effectively and resist the penetration of liquid water,making it ideal for use under extreme conditions.In this study,we used a facile strategy to design the bio-based polyurethane(PU) nanofibrous membranes with the nanoscale porous structure to provide the membranes with high waterproof and breathable performances.The optimization of nanofibrous membrane formation was accomplished by controlling the relative ambient humidity to modulate the cooperating effects of charge dissipation and non-solvent-induced phase separation.The obtained EBWBMs showed multiple functional properties,with a hydrostatic pressure of 86.41 kPa and a water vapor transmission(WVT) rate of 10.1 kg·m^(-2)·d^(-1).After 1 000 cycles of stretching at 40% strain,the EBWBMs retained over 59% of the original maximum stress and exhibited an ideal elasticity recovery ratio of 85%.Besides,even after 80% deformation,the EBWBMs still maintained a hydrostatic pressure of 30.65 kPa and a WVT rate of 13.6 kg·m^(-2)·d^(-1),suggesting that bio-based PU nanofibrous membranes could be used for protection under extreme conditions.

Fully Bio-Based Composites of Poly(Lactic Acid)Reinforced with Cellulose-Graft-Poly-(ε-Caprolactone)Copolymers

Due to the increasing demand for modified polylactide(PLA)meeting“double green”criteria,the research on sustainable plasticizers for PLA has attracted broad attentions.This study reported an open-ring polymerization method to fabricate cellulose(MCC)-g-PCL(poly(ε-caprolactone))copolymers with a fully sustainable and biodegradable component.MCC-g-PCL copolymers were synthesized,characterized,and used as green plasticizers for the PLA toughening.The results indicated that the MCC-g-PCL derivatives play an important role in the compatibility,crystallization,and toughening of the PLA/MCC-g-PCL composites.The mechanical properties of the fully bio-based PLA/MCC-g-PCL composites were optimized by adding 15 wt%MCC-g-PCL,that is,the elongation at break was 22.6%(~376%higher than that of neat PLA),the tensile strength was 47.3 MPa(comparable to that of neat PLA),and the impact strength was 26 J/m(~130%higher than that of neat PLA).DSC results indicated that MCC-g-PCL reduced the Tg of the PLA blend.When the addition amount was 15 wt%,the Tg of the blend was 58.4°C.Compared with MCC,MCC-g-PCL polyester plasticizer has better thermal stability,T5%(°C)can still be maintained above 300°C.The rheological results showed that MCC-g-PCL acted as a plasticizer,the introduction of PCL flexible chain increased the mobility of PLA molecular chain,and decreased the complex viscosity,storage modulus and loss modulus of PLA blends.The MCC-g-PCL derivatives,as a new green plastic additive,have shown an interesting prospect to prepare fully bio-based composites.

Eco-friendly physical blowing agent mass loss of bio-based polyurethane rigid foam materials

Through systematical experiment design, the physical blowing agent(PBA) mass loss of bio-based polyurethane rigid foam(PURF)in the foaming process was measured and calculated in this study, and different eco-friendly PBA mass losses were measured quantitatively for the first time. The core of the proposed method is to add water to replace the difference, and this method has a high fault tolerance rate for different foaming forms of foams. The method was proved to be stable and reliable through the standard deviations σ1and σ2for R1(ratio of the PBA mass loss to the material total mass except the PBA) and R2(ratio of the PBA mass loss to the PBA mass in the material total mass) in parallel experiments. It can be used to measure and calculate the actual PBA mass loss in the foaming process of both bio-based and petroleumbased PURF. The results show that the PBA mass loss in PURF with different PBA systems is controlled by its initial mass content of PBA in PU materials ω. The main way for PBA to dissipate into the air is evaporation/escape along the upper surface of foam. This study further reveals the mechanism of PBA mass loss: the evaporation/escape of PBA along the upper surface of foam is a typical diffusion behavior. Its spread power comes from the difference between the chemical potential of PBA in the interface layer and that in the outside air. For a certain PURF system, R1has approximately linear relationship with the initial mass content of PBA in PU materials ω, which can be expressed by the functional relationship R1= kω, where k is a variable related to PBA’s own attributes.

Frequency domain analysis of pre-stressed elastomeric vibration isolators

Two types of elastomeric vibration isolators used for equipment vibration isolation in aerospace vehicles are considered for the present study. These isolators are constructed using elastomers mounted in steel encasings. These isolators are initially deformed statically and dynamic loads are applied on the deformed configuration. To capture the static deformation, equivalent static load corresponding to its load rating and specified displacements are created. Static deformation is computed using Finite Element methods with four node axi-symmetric element which include the geometric non-linear effect for steel and with standard Yeoh hyper-elastic material model for elastomers(Muhammed and Zu, 2012) [1]. Yeoh material constants are derived from uni-axial tension test data of the elastomer specimen. These isolators are subjected to harmonic and random excitations in the pre-deformed state. For numerical analysis, elastomeric constants at dynamic conditions are obtained as complex function of frequency using Dynamic Mechanical Analyzer(DMA) for a range of frequencies. The standard material model of Yeoh is modified incorporating frequency dependant material characteristics and damping in the range of frequencies of interest. A multiplicative non-separable variables law is derived for Yeoh material model to include the effect of static pre-stress, based on the methodology given in literature(Nashif et al.,1985;Beda et al., 2014) [2,3]. The modifications of Yeoh model suitable for frequency domain analysis is the novelty in the present study. In the analysis, while dynamic loads are applied, the configuration is updated considering initial static loading. The frequency response of the isolators is computed using material properties evaluated at progressive dynamic strains until a match in natural frequency is observed. Appropriate damping corrections are then incorporated to match the test observed transmissibility. Then updated material properties are used to compute the random response which showed good agreement with results of experiments, validating the approach taken for the development of this model.

CO_(2)-Responsive Smart Foams Stabilized by an Extremely Rigid Bio-Based Surfactant

Environment friendly and intelligent surfactants have attracted great attention in recent years.A bio-based CO_(2)responsive surfactant rosin acid dimaleimide choline(R-BMI-C)with an extremely rigid skeleton was prepared using rosin and choline as raw materials by Diels-Alder addition reaction and acid-base neutralization reactions.Its structure was confirmed by IR and^(1)H NMR spectra.The foams’properties of R-BMI-C could be adjusted by bubbling CO_(2)/N_(2)to change the structure of the surfactant.At pH 10.4,R-BMI-C forms an unstable foam with a half-life of 1.5 h.When the pH was reduced to 7.4 by bubbling CO_(2),R-BMI-C forms an extremely stable foam with a half-life of 336 h.The surfactant R-BMI-C changed from bola type to conventional type when bubbling CO_(2).And the internal aggregation structure of R-BMI-C aqueous solution changed from spherical micelles to laminar micelles according to the cryogenic-transmission electron microscope.We know that the lamellar structure tends to adsorb at the air/water interface or is trapped in the foam film,which slows down the foam coarsening and agglomeration process,resulting in a significant increase in foam stability.R-BMI-C could be used in oil extraction,fire-fighting and chemical decontamination due to its excellent foaming,stabilization and defoaming properties.

Piezoresistive behavior of elastomer composites with segregated network of carbon nanostructures and alumina

Electrically conductive elastomer composites(CECs)with segregated networks of conductive nanofillers show high potential in stretchable strain sensors due to balanced mechanical and electrical properties,yet the sensitivity at low strain is generally insufficient for practical application.Herein,we report an easy and effective way to improve the resistive response to low strain for CECs with segregated network structure via adding stiff alumina into carbon nanostructures(CNS).The CEC containing 0.7 wt%CNS and 5 wt%Al_(2)O_(3) almost sustains the same elasticity(elongation at break of~900%)and conductivity(0.8 S/m)as the control,while the piezoresistive sensitivity is significantly improved.Thermoplastic polyurethane(TPU)composites with a segregated network of hybrid nanofillers(CNS and Al_(2)O_(3))show much higher strain sensitivity(Gauge factor,GF-566)at low strain(45%strain)due to a local stress concentration effect,this sensitivity is superior to that of TPU/CNS composites(GF-11).Such a local stress concentration effect depends on alumina content and its distribution at the TPU particle interface.In addition,CECs with hybrid fillers show better reproducibility in cyclic piezoresistive behavior testing than the control.This work offers an easy method for fabricating CECs with a segregated filler network offering stretchable strain sensors with a high strain sensitivity.

Synthesis,Characterization and Water Absorption Analysis of Highly Hygroscopic Bio-based Co-polyamides 56/66

This study aims to develop highly hygroscopic bio-based co-polyamides(CPs)by melt co-polycondensation of polyamide(PA)56 salt and PA66 salt with varying molar fractions.The functional groups and the chemical structure of the prepared samples were determined by Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(^(1)H-NMR)spectroscopy.The relative viscosity was determined with an Ubbelohde viscometer.The melting behavior and the thermal stability of CPs were investigated by differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA).Furthermore,the water absorption behavior of CP hot-pressed film was studied.The results reveal that the melting point,the crystallization temperature and the crystallinity of CPs firstly decrease and then increase with the molar fraction of PA66 in CPs.The copolymerization of PA56 with PA66 leads to an obvious increase in water absorption.The CPs with PA66 molar fraction of 50%possess a high saturated water absorption rate of 17.6%,compared to 11.6%for pure PA56 and 7.8%for pure PA66.