Trade-offs between ion-conducting and mechanical properties: The case of polyacrylate electrolytes

Polymer electrolytes(PEs)have been long recognized as the key materials to enable energy-dense batteries and render flexible energy devices practically viable,owing to their chemical and mechanical reliability.However,much of their promise is yet to be realized.The roomtemperature ion conductivity of existing PEs still falls short of the implementation criterion of 10^(-4) S cm^(-1) on the promise of acceptable mechanical properties,thereby precluding their practical application.The twin but inversely related duties of polymers,that is,functioning as both an ion-conducting medium and a structural backbone,underlie this issue but are less elucidated systematically.The polyacrylate(PA)family is among promising polymer matrices on account of ester polarity,electrode compatibility,chemical tunability,and mechanical durability.The extensive applicability of PA in plasticized gels,dry solids,and emerging composites makes PA-based PEs representative to illustrate the trade-off between ion conduction and mechanical strength.We herein seek to outline the stated long-standing conflict exemplified by PA-based PEs,focusing on crucial strategies toward balancing and reconciling the two mutually exclusive properties,with the intention of offering designing guidelines for next-generation PEs.

Quantitative lithium substitution of carboxyl hydrogens in polyacrylic acid binder enables robust SiO electrodes with durable lithium storage stability

The design of advanced binders plays a critical role in stabilizing the cycling performance of large-volume-effect silicon monoxide(SiO)anodes.For the classic polyacrylic acid(PAA)binder,the self-association of-COOH groups in PAA leads to the formation of intramolecular and intermolecular hydrogen bonds,greatly weakening the bonding force of the binder to SiO surface.However,strengthening the binder-material interaction from the perspective of binder molecular regulation poses a significant challenge.Herein,a modified PAA-Li_(x)(0.25≤x≤1)binder with prominent mechanical properties and adhesion strength is specifically synthesized for SiO anodes by quantitatively substituting the carboxylic hydrogen with lithium.The appropriate lithium substitution(x=0.25)not only effectively increases the number of hydrogen bonds between the PAA binder and SiO surface owing to charge repulsion effect between ions,but also guarantees moderate entanglement between PAA-Li_x molecular chains through the ion-dipole interaction.As such,the PAA-Li_(0.25)/SiO electrode exhibits exceptional mechanical properties and the lowest volume change,as well as the optimum cycling(1237.3 mA h g^(-1)after 100cycles at 0.1 C)and rate performance(1000.6 mA h g^(-1)at 1 C),significantly outperforming the electrode using pristine PAA binder.This work paves the way for quantitative regulation of binders at the molecular level.

Adsorption of sodium polyacrylate at interface of dicalcium silicate-sodium aluminate solution

The adsorption isotherm of sodium polyacrylate on dicalcium silicate（2CaO-SiO2） in sodium aluminate solution at 80 ℃ was studied.The type of surface adsorption of sodium polyacrylate is saturated adsorption,and the adsorption behavior belongs to L-type,according with the monolayer adsorption model of Langmuir equation.The surface coverage of sodium polyacrylate is 1.06 mol/μm2.The relation curve between the surface pressure and the molecular area of adsorption film was obtained by Gibbs formula.The variation of interfacial energy caused by adsorption as well as the relationship between the relation curve and the type of adsorption was discussed.

SYNTHESIS AND APPLICATION OF NEW DETERGENT BUILDER POLYACRYLATE SODIUM

The low molecular weight polyacrylate sodium (PAA Na) detergent builder was synthesized with K 2S 2O 8 as initiator in a neutral aqueous medium. The influences of reaction conditions on the viscosity average molecular weight were studied. The critical value of synthetic PAA Na inhibiting the precipitation of CaCO 3 was determined and compared with that of other common builders. It is confirmed from SEM graphs that PAA Na can make CaCO 3 crystal defective. Washing tests show synthetic PAA Na can partially replace sodium tripolyphosphate (STPP) and is a potential polymeric detergent builder in low phosphate powder detergents.

QSPR Study on the Glass Transition Temperature of Polyacrylates

Structural parameters of 22 polyacrylic compounds were computed at two levels using Hartree-Fock and DFT methods. Based on the experimental data of glass transition temperature （Tg）, four-parameter （energy of the lowest unoccupied molecular orbital （ELoMO）, the highest positive charge （Qmax^＋）, dipole moments（μ） and the next highest occupied molecular orbital （ENLOMO）） dependent equations were developed using structural parameters as theoretical descriptors. Especially, Tg dependent equation calculated at the HF/6-31G（d） level is more advantageous than others in view of their correlation and predictive abilities. This dependent equation was validated by variance inflation factors （VIF） and t-test methods.

Influence of Carboxyl Groups on the Particle Size and Rheological Properties of Polyacrylate Latices

The PAL was synthesized with BA,MMA and some monomers containing carboxyl groups（for example,acrylic acid（AA） and methacrylic acid（MAA）） as co-monomers by semi-continuous seeded emulsion polymerization technique.The influences of alkalinization temperature,the feeding manner of AA or MAA on the particles size,rheological properties and carboxyl distribution of the latex were discussed,and the rheological mechanism was analyzed.The experimental results show that the PAL system has preferable viscosity and particle size when the alkalinization temperature is 50 ℃.Different distribution of carboxyl group in the particles and different resultant rheological properties are obtained by different feeding manner of AA or MAA into the system.The TEM images show that the particle is a smooth globe with carboxyl group concentrating on the surface and stabilized with electric double layer and nonionic adsorbed layer.The concentration of carboxyl functional group on the surface of particles can be achieved by the specific polymerization technique.The rheologyical properties are determined by accretion of particle volume and variation of the two phase volume ratio resulted from the carboxyl group spreading layer.

Synthesis and Characterization of Fluorine-containing Polyacrylate Emulsion with Core-Shell Structure

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorobutyl methacrylate （HFMA） as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum （FT-IR）, transmission electron microscopy （TEM）, particle size analysis, X-ray photoelectron spectroscopy （XPS）, contact angle （CA）, differential scanning calorimetry （DSC） and thermogravimetry （TG） analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.

GELCASTING OF NANO-SIZE Y-TZP

The green specimens of nano-size Y-TZP are formed by gelcasting method. Using polymer electrolytes NaPAA and NH_4PAA, we have studied the rheological properties of slurry.The optimum pH range is between 8 to 10. The proper amount of dispersant changes with the solid content.The rheological measurements of suspension containing NH_4PAA show lower viscosity.The theoretical green density has been calculated.

SYNTHESIS, CROSSLINKING MECHANISM AND PROPERTIES OF A POLYACRYLATE/POLYURETHANE COMPOSITE COATING

A polyacrylate/polyurethane (P(A)/P(U)) composite coating has been prepared by crosslinking an acetoacetylated polyacrylate with a vinylic group terminated polyurethane at room temperature. A model Michael reaction between ethyl acetoacetate (EAA) and methyl acrylate (MA) was designed to study the crosslinking mechanism. It was found that the two active hydrogen atoms in acetoacetyl group can both add to vinylic groups and the yield of mono-and bis-adducts are much affected by the molar ratio of acetoacetyl to vinylic groups. Higher crosslinking degree and better properties could be obtained with decreasing the molar ratio of the two active groups from 1/1 to 0.6/1 in the composite coatings.

Properties of Polyacrylate Latex Prepared Under Different Emulsified Systems

The polyacrylate latexes were synthesized via pre-emulsified and semi-continuous seeded emulsion polymerization technology when conventional surfactant or polymerizable surfactant was used as emulsifiers. The resultant latexes and their films were characterized with the contact angle determinator and rheometer. Effect of the polymerizable surfactant on water resistance, stability and rheology of the latex was studied. Results show that the water resistance of film is increased first then decreased with the increase of the amount of the polymerizable surfactant. There exists the optimum value of the amount of the polymerizable surfactant for the water resistance of the film. In comparison with the latex prepared with the conventional surfactant, both the mechanical stability and the freezing-thaw stability of the latex are improved when the polymerizable surfactant is used during the course of the emulsion polymerization. The resultant latex has rheological properties of pseudo-plastic fluid and belongs to non-Newtonian fluid.

Investigation on the Use of the Weakly Basic Polyacrylate Anion-Exchanger Amberlite IRA-68 for Sorption and Separation of Iminodiacetate Complexes of Rare Earth Elements

Based on the determined affinity series of rare earth element complexes with IMDA for the anion-exchangers, purification of macroquantities of Nd 3+ from Y 3+, Sm 3+ from Ho 3+, La 3+ from Nd 3+ and La 3+ from Pr 3+ on the weakly basic gel anion-exchanger Amberlite IRA-68 was studied. Using the presented method on 1 L of Amberlite IRA-68 in the acetate form, it is possible to obtain about 240 g Nd 2O 3 purified from Y 2O 3. Great difference in affinity of La 3+ and Nd 3+ as well as Pr 3+ complexes for this anion-exchanger in the acetate form indicates the possibility of applying this process for purification of lanthanum on the increased scale. On 1 L of Amberilte IRA-68 in the acetate form it is possible to obtain about 1125 g La 2O 3 purified from Nd 2O 3. On the basis of these results it can be assumed that unique properties of polyacrylate anion-exchangers enable their application for separation of rare earth elements.

Synthesis of Nano-sized Yttria via a Sol-Gel Process Based on Hydrated Yttrium Nitrate and Ethylene Glycol and Its Catalytic Performance for Thermal Decomposition of NH_4ClO_4

Nano-sized yttria particles were synthesized via a non-aqueous sol-gel process based on hydrated yttrium nitrate and ethylene glycol. The effects of the molar ratio of ethylene glycol to yttrium ion and calcination temperature on crystallite size of the products were studied. The catalytic performance of the as-prepared yttria for the ammonium perchlorate （AP） decomposition was investigated by differential scanning calorimetry （DSC）. The results indicate that the nano-sized cubic yttria particles with less than 20 nm in average crystallite size can be obtained after 2 h reflux at 70℃, dried at 90 ℃, forming xerogel, and followed by annealing of xerogel for 2 h, and that the addition of the nano-sized yttria to AP incorporates two small exothermic peaks of AP in the temperature ranges of 310 - 350 ℃ and 400 - 470 ℃ into a strong exothermic peak of AP and increases the apparent decomposition heat from 515 to over 1110 J·g^- 1. It is also clear that the temperature of AP decomposition exothermic peak decreases and the apparent decomposition heat of AP increases with the increase of the amount of nano-sized yttria. The fact that the addition of the 5 % nano-sized yttria to AP decreases the temperature of AP exothermic peak to 337.7℃ by reduction of 114.6℃ and increases the apparent decomposition heat from 515 to 1240 J·g^-1, reveals that nano-sized yttria shows strong catalytic property for AP thermal decomposition.

Determination of Ni^(2+) in Waters with Sodium Polyacrylate as a Binding Phase in Diffusive Gradients in Thin-films

An aqueous solution containing sodium polyacrylate（PAAS） was used in diffusive gradient in thin-films technique（DGT） to measure DGT-labile Ni2＋ concentrations.The DGT devices（PAAS DGT） were validated in four types of solutions,including synthetic river water containing metal ions with complexing EDTA or that without complexing EDTA,natural river water（Ling River,Jinzhou,China） spiked with Ni2＋,and an industrial wastewater （Jinzhou,China）.Results show that only free metal ions were measured by PAAS DGT,recovery=97.36% in the solutions containing only free metal ions,recovery=49.62% in a solution with metal/EDTA molar ratio of 2：1 and recovery=0 in the solutions with metal/EDTA molar ratios of 1：1 and 1：2.These indicated that the complexes of Ni-EDTA were DGT-inert.The DGT performance in spiked river water（recovery=18.24%） and in industrial wastewater（recovery=12.25%） were investigated,which indicated that the measurement of metals by this DGT device did not include the humic substances complexed fractions of metals.The binding properties of PAAS DGT for Ni2＋ were investigated under different conditions of pH value and ionic strength.Conditional stability constants（lgK） of PAAS-Ni complexes were also evaluated.

NiMo/Al_2O_3 catalyst containing nano-sized zeolite Y for deep hydrodesulfurization and hydrodenitrogenation of diesel

Two mixed-matrix NiMo/Al2O3 catalysts containing nano-and micro-sized zeolite Y have been prepared to explore the size effect of zeolite Y particle on the hydrodesulfurization（HDS）and hydrodenitrogenation（HDN）activities of fluid catalytic cracking（FCC）diesel.They were characterized by SEM,BET,XRD,H2-TPR,NH3-TPD and HRTEM.The results show that the catalyst containing nano-sized zeolite Y possesses larger average pore diameter,higher pore volume,weaker and lesser acid sites,more easily reducible metal phases,shorter MoS2 slabs and more slab layers than the catalyst containing micro-sized zeolite Y.The catalysts were also evaluated with a high-pressure fixed-bed reactor using real FCC diesel as feed.The results display that the catalyst containing nano-sized zeolite Y bears higher HDS and HDN activities and exhibits higher relative rate constant for the removal of total sulfur or nitrogen than the one containing micro-sized zeolite.

Synthesis and Characterization of Nano-sized Boron Powder Prepared by Plasma Torch

Hydrogen thermal plasma jet was employed to prepare nano-sized boron powder with hydrogen reduction of BCI3. The maximum yield of nano-sized boron powders was about 50% with the operational conditions of H2/BCl3 of 4.5：1, total feed of 4.9 m3/h, and plasma power of 25 kW. The samples were analyzed by X-ray diffraction （XRD）, field emission scanning electron microscopy （FE-SEM）, and inductively coupled plasma - mass spectrometry （ICP-MS）, inductively coupled plasma - atomic emission spectrometry （ICP-AES）, inductive combustion infrared absorption （ICIA） and infrared thermal conductivity of oxygen and nitrogen analyzer （ITCA）. The results show that the boron powders have different crystal structures with higher dispersion and purity. The average diameter is about 50 nm, and the purity is 90.29% or so. This new technology can use simple process to produce high quality boron powders, and is feasible for industrial production.

Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.

Effect of nano-size nickel particles on wear resistance and high temperature oxidation resistance of ultrafine ceramic coating

In order to improve the wear resistance and high temperature oxidation resistance of titanium and titanium alloy, the high temperature ultra fine ceramic coating containing nano-size nickel particles was prepared by flow coat method on the surface of industrially pure titanium TB1-0. The effects of nano-size nickel particles on the wear resistance and high temperature oxidation resistance of coating substrate system were investigated through oxidation kinetics experiment and wear resistance test. The morphologies of the specimens were examined by means of optical microscopy, scanning electron microscopy and X-ray diffraction. The results show that the high temperature ultra fine ceramic coating has notable protection effect on industrially pure titanium TB1-0 from oxidation. The oxidation and wear resistance properties of the coating can be effectively improved by adding nano-size nickel particles. The oxidative mass gain of the specimen decreases from 11.33 mg·cm-2 to 5.25 mg·cm-2 and the friction coefficient decreases from 1.1 to 0.6 by adding nano-size nickel particles, and the coating containing 10% （mass fraction） nano-size nickel shows the optimum properties.

Studies on the Morphology of Natural Rubber/Polyacrylate Interpenetrating Polymer Networks

The interpenetrating polymer network(IPN) systems have attracted a lot of attention because of their unique two-phase structure and properties. There have been many publications concerning the IPNs in which poly (isoprene) (PIP) or polyacrylates (PAC) is formed as one of the networks.In the present study, Four serles of natural rubber(NR)/PAC IPNs were prepared and their morphologies were investigated with dynamic mechanics analysis(DMA) and transmission electron microscopy (TEM).

Corrosion resistance of waterborne epoxy coating pigmented by nano-sized aluminium powder on steel

A novel kind of waterborne epoxy coating pigmented by nano-sized aluminium powders on high strength steel was formulated. Several coatings with different pigment volume content (PVC) were prepared. The coating morphology was observed using scanning electron microscopy (SEM), and the electrochemical properties were investigated by electrochemical impedance spectroscopy (EIS). Immersion test and neutral salt spray test were also conducted to investigate the corrosion resistance of the coating. It is demonstrated that the critical pigment volume content (CPVC) value is between 30% and 40%. The coating with PVC of 30% exhibits good corrosion resistance in 3.5% (mass fraction) NaCl solution.

Effects of nano-sized aluminum on detonation characteristics and metal acceleration for RDX-based aluminized explosive

Nano-sized aluminum(Nano-Al)powders hold promise in enhancing the total energy of explosives and the metal acceleration ability at the same time.However,the near-detonation zone effects of reaction between Nano-Al with detonation products remain unclear.In this study,the overall reaction process of 170 nm Al with RDX explosive and its effect on detonation characteristics,detonation reaction zone,and the metal acceleration ability were comprehensively investigated through a variety of experiments such as the detonation velocity test,detonation pressure test,explosive/window interface velocity test and confined plate push test using high-resolution laser interferometry.Lithium fluoride(LiF),which has an inert behavior during the explosion,was used as a control to compare the contribution of the reaction of aluminum.A thermochemical approach that took into account the reactivity of aluminum and ensuing detonation products was adopted to calculate the additional energy release by afterburn.Combining the numerical simulations based on the calculated afterburn energy and experimental results,the parameters in the detonation equation of state describing the Nano-Al reaction characteristics were calibrated.This study found that when the 170 nm Al content is from 0%to 15%,every 5%increase of aluminum resulted in about a 1.3%decrease in detonation velocity.Manganin pressure gauge measurement showed no significant enhancement in detonation pressure.The detonation reaction time and reaction zone length of RDX/Al/wax/80/15/5 explosive is 64 ns and 0.47 mm,which is respectively 14%and 8%higher than that of RDX/wax/95/5 explosive(57 ns and 0.39 mm).Explosive/window interface velocity curves show that 170 nm Al mainly reacted with the RDX detonation products after the detonation front.For the recording time of about 10 ms throughout the plate push test duration,the maximum plate velocity and plate acceleration time accelerated by RDX/Al/wax/80/15/5 explosive is 12%and 2.9 ms higher than that of RDX/LiF/wax/80/15/5,respectively,indicating that the aluminum reaction energy significantly increased the metal acceleration time and ability of the explosive.Numerical simulations with JWLM explosive equation of state show that when the detonation products expanded to 2 times the initial volume,over 80%of the aluminum had reacted,implying very high reactivity.These results are significant in attaining a clear understanding of the reaction mechanism of Nano-Al in the development of aluminized explosives.