最新刊期
卷 ， 期 7 ， 2016
- 摘要：Polyanline-grafted hollow mesoporous silica nanoparticles (HMSs-PANI) were successfully prepared by in situ chemical oxidative polymerization.The functionalized processes of nanoparticles were characterized by transmission electron microscopy (TEM),Fourier transform (FTIR),ultraviolet-visible spectroscopy (UV-Vis),thermogravimetric analyses (TGA) and zeta potentials test.The changes of the mesoporous properties of nanoparticles during the processes of modification were tested by N2 adsorption-desorption isotherms and small-angle powder X-ray diffraction (XRD).Then,cyclic voltammetry (CV) experiments of dispersed systems were carried out to study the electroactive properties of HMSs-PANI under different pH and showed good electroactive properties at acidic solution (pH=4) because of the effective acid doping.While at neutral solution,it lost electroactive properties.Moreover,HMSs-PANI as nanocontainers was used to load anti-cancer drug doxorubicin hydrochloride (DOX).Anticipative controlled release behavior of HMSs-PANI was observed by different pH stimulation in vitro.The release profiles of DOX from nanocontainers in pH=7.4 solutions were only 15% at 22 h.When the pH value is decreased to 5,the DOX molecules rapid released and the percentage of release reached 44% at 22 h.When the pH value further decreased to 4,the faster rate was observed and the percentage of release reached 60% at the same time.In short,the pH-responsiveness of HMSs-PANI may have practical applications in the field of drug delivery system.关键词：Hollow mesoporous silica spheres;Polyaniline;Electroactive;Controlled release
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发布时间：2021-03-19
Rapid Communications
- 摘要：For all polymer-based materials,polymer processing is required to fabricate them into useful articles with definite sizes,shapes and forms.This paper summarizes the progress in polymer processing and concludes that the emergence of numerous polymer processing technologies has benefited from nature and other material industries,such as solution spinning from spider silk,blow molding from glass blowing,and calendaring as well as solid-phase drawing forming from metal forging.Moreover,to deal with the big challenge of creating high-performance stereocomplexed polylactide (SC-PLA) products from melt-processed poly(L-lactide)/poly(D-lactide) (PLLA/PDLA) blends because of the poor melt stability of stereocomplex (SC) crystallites after complete melting as well as the serious degradation of PLA chains at elevated melt-processing temperatures,we report a new strategy to prepare highly transparent SC-PLA products with excellent heat resistance,mechanical strength,and hydrolytic stability by means of a low-temperature (i.e.,below the melting temperature of the SC crystallites) powder sintering technology inspired by the concept of powder metallurgy.关键词：Polymer processing;Processing technology;Powder metallurgy;Polylactide;Stereocomplex
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发布时间：2021-03-19 - 摘要：Clotting and thrombosis remain one of the most serious problems in the development of blood contacting devices.Strategies for developing antithrombotic surfaces are generally based on the idea of preventing clot formation.However,they have so far met with only limited success since coagulation appears to be inevitable when a foreign surface is in contact with blood.Alternatively,by designing the surface effectively to mimic the fibrinolytic system in the vasculature,it may be possible for clots to be lysed as they form.Over the past two decades,work on the fibrinolytic surface concept has established its validity.In this review we elaborate this concept and discuss ways in which such a surface could be realized.Developments in this area to the present time are reviewed,and some perspectives for future research are presented.We hope that this review may serve to stimulate additional research on this neglected but promising and potentially important approach to blood compatibility.关键词：Antithrombosis;Fibrinolysis;Surface modification;Blood compatible material
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发布时间：2021-03-19
Feature Articles
- 摘要：Four kinds of prepared plant-based porous carbon materials, including sugarcane bagasse carbon (SBC),bamboo leaf carbon (BLC),rice husk carbon (RHC),bamboo stalk carbon (BSC), as well as purchased carbon materials including,coconut shell charcoal (CSC),nut shell carbon (NSC),carbon nanotubes (CNTs),expansible graphite (EG),were respectively used in flame retardant epoxy resin (EP) with ammonium polyphosphate (APP).The influences of specific surface area,surface activity and morphology of carbon materials on combustion performances and thermal decomposition of flame retardant EP were investigated.The studies by physical adsorption (BET method),X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy indicated that all the carbon materials were micron-size dispersed in EP,and BSC had higher specific surface area (2063 m2/g) and larger contents of surface active groups such as C-C,C-O-,C O and COO- than others carbon materials.Meanwhile,the respective addition of BSC (0.8 wt%) and CNTs (0.8 wt%) in EP/APP (3.1 wt%) increased the LOI from 24.6% to 27.3% and 27.6%,resulted in V-1 rate in UL 94 test,and decreased the peak heat release rate by 27% and 28% from the cone calorimeter test (Cone),compared to EP/APP.The results show that the synergic effects mainly depend on the morphology; particle shaped carbon materials with the larger specific surface area,O/C ratio and higher active group contents have excellent flame retardancy.Moreover,thermo-gravimetric analysis (TGA),confocal Raman spectroscopy (CRS) and XPS study confirmed that carbon materials can improve the initial pyrolysis temperature and increase the residual char value of EP/APP.The large specific surface area and high surface activity as well as tubulose morphology not only increased the residual char value,promoted the formation of graphite-like char but also improved the pyro-oxidation of char.关键词：Carbon materials;Ammonium polyphosphate;Epoxy resin;Combustion performance;Thermal decomposition
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发布时间：2021-03-19 - 摘要：Thermosensitive copolymers with lower critical solution temperature (LCST) were prepared by copolymerization of N,N-dimethylacrylamide and diacetone acrylamide through conventional free radical polymerization in water using K2S2O8-Na2SO3 redox system as an initiator.The thermal responsiveness as well as temperature dependent structure of the copolymer solution was systematically examined through ultraviolet-visible spectroscopy(UV-Vis),dynamic light scattering (DLS),fluorescence spectrophotometer and 1H-NMR.All these results demonstrate that P(DMA-co-DAAM)s exhibit a significant thermal-induced association behavior.At lower temperatures P(DMA-co-DAAM) was disolved in the form of unimers while these unimers would transform to micellar aggregates due to the association of hydrophobic segments along the chains at higher temperatures.Such phenomenon was ascribed to the changes in hydrophilic-hydrophobic balance of DAAM pendant groups with increasing in temperature.Further research also implies that the association transition temperature of the copolymer solutions could be effectively regulated by changing the composition and concentration of the copolymers.Lower association transition temperatures could be obtained at higher contents of DAAM,which held a well linear relationship in our experiments.It demonstrates that the inter-chain heterogeneity and polydispersity originating from common radical polymerization exhibit little influence on the thermal sensitive behaviors of P(DMA-co-DAAM).关键词：Diacetone acrylamide;N,N-dimethylacrylamide;Hydrophilic/hydrophobic balance;Thermoassociating;Lower critical solution temperature
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发布时间：2021-03-19 - 摘要：A series of cation exchange membranes (CEMs) with different ion exchange capacitiy (IEC) values based on side-chain type partially fluorinated sulfonated poly(aryl ether)s (sSPFAEs) are prepared through aromatic nucleophilic substitution and solution casting,and subsequently used as the separator in microbial fuel cell (MFC).Their power production performances in double chamber MFCs are investigated and compared with commercial CEM.The obtained sSPFAE membranes have IEC of 0.97~1.56 mmol/g with thickness around 80 m,show water uptakes of about 20.9%~41.7%,and proton conductivities of 27.3~60.5 mS/cm,which are higher than those for commercial CEM with thickness of 420 m (22 mS/cm).For the MFCs with sSPFAE membranes,the intermal resistances are in the range of 29~64 according to the peak power density and the slope method from the polarization curves,and increase with the IEC; their columbic efficiencies are about 47.7%~55%.The membrane of sSPFAE-1.56 exhibits the maximum power output of 657.3 mW/cm2 and all the sSPFAE membranes outperform commercial CEM.According to the EIS analysis results for the whole MFC system by equivalent circuit simulation,the anodic diffusion resistances hold 87%~90% of the total resistances.Combining the CV analysis and EIS analysis with the electrode potential test results,the separating membranes have considerable influence upon the mass tranfer across the chambers as well as the anodic diffusion resistance.关键词：Microbial fuel cell;Separator;Side-chain sulfonation;Sulfonated poly(aryl ether);Diffusion resistance
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发布时间：2021-03-19 - 摘要：In order to analyze the dynamic mechanical properties and hysteresis loss of the tread rubber quantitatively,a viscoelastic constitutive equation based on generalized Maxwell model was developed,the model parameters of storage modulus and loss modulus for each temperature were determined according to the frequency sweeping experimental data under dynamic compression conditions,and an algorithm of non-linear regression was proposed and numerically implemented to get the minimum of error function.The finite element code ABAQUS/standard was used to simulate the process of tread rubber dynamic compression,which reflected the change of loss tangent at the different vibration frequencies,and then the simulated results were compared with the experimental data.It was proved that the viscoelastic constitutive model and the parameters identification method could be used to analyze the tread rubbers dynamic mechanical properties accurately.On this basis,the quantitative prediction of the tread rubber stress-strain hysteresis loop and the energy dissipation in a full deformation cycle under different temperatures and frequencies was carried out,the results showed that the energy dissipation of the unit volume increased gradually with the increase of frequency,and the increasing magnitude of the energy dissipation was scale-up with the decrease of temperature.关键词：Tread rubber;Generalized Maxwell model;Dynamic modulus;Parameter identification;Energy loss
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发布时间：2021-03-19 - 摘要：Tear strength is a very important mechanical property of polymer films and is associated with very fast deformation.In the present work,compressed and cast LLDPE films,made of resins with the same density,similar molecular weight but different comonomers (1-butene versus 1-octene),were studied with Elmendorf tear (very high deformation rate) and right angle tear (low deformation rate) methods,as well as small angle X-ray scattering (SAXS).Our study shows that the Elmendorf tear strength for the LLDPE with octene is much larger than that for the LLDPE with butene comonomer.However,no much difference in tear strength was observed for the two films with right angle testing method.The result indicates that the right angle method under low deformation rate,widely used in China for evaluation of tear strength for polymer films,may not reflect the true tear strength in actual applications.In order to have a better understanding of the fundamental differences for these two tear testing methods,structural studies were carried out for deformed films at low and very high strain rate (0.08 min-1 versus 500 min-1).Our SAXS study shows that for a given deformation,such as for a strain of 0.5,much more structural damages were observed under fast deformation rate than that under low deformation rate,such as,leading to significantly smaller long period in the former case.That is,the structure response of polymer films to low and very fast deformation can be very different,and this could explain why a big difference is observed for tear testing with right angle and Elmendrof methods.Discussion were also made in the present paper on tear strength versus structures for LLDPE films made with different comonomers.Films can have very similar aggregated structure at different size levels,but with very different tear strength due to different tie change concentrations,which reflects the different crystal connectivity in the films and plays an important role on tear property.关键词：Linear low density polyethylene;Cast film;Tear property;Orientation;Structure
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发布时间：2021-03-19 - 摘要：A rapid thermal cycling molding technology with electric heating and water cooling was developed to improve surface quality of microcellular polyoxymethylene (POM) cover plates injection molded using supercritical nitrogen as physical foaming agent.The temperature distribution uniformity on the whole mold cavity surface was obviously improved via optimization design.The effect of mold cavity surface temperature (TM) on the cellular structure and surface quality of the microcellular POM cover plates was quantitatively investigated and relevant mechanisms were analyzed.The results demonstrated that raising TM resulted in thinner unfoamed skin layer but somewhat larger and unevenly distributed cells in the microcellular POM cover plates.Raising TM from 40℃ to 150℃ greatly improved the surface quality of the cover plates and effectively reduced their surface roughness by about 85% without a significant increase in cycle time.The surface defects that usually occur in conventional microcellular injection molding were eliminated at a TM of 150℃.The TM should be appropriately high (about 130℃) to improve surface quality of the microcellular POM cover plates and keep good cellular structure simultaneously.关键词：Microcellular injection molding;Supercritical fluid foaming;Mold cavity temperature;Polyoxymethylene;Cellular structure;Surface quality
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发布时间：2021-03-19 - 摘要：A novel hybrid material synthesized by grafting fluorinated block polymer chains to silica nanoparticles via surface-initiated activators generated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP) was proposed.The components of the block copolymer 2-[[2-(perfluorohexyl)]-sulfonyl]methyl]-amino]ethyl-acrylate (C6SA) and methyl methacrylate were well designed,and verified by gel permeation chromatography measurements.Monodispersed silica nanoparticles prepared by Stber method and grafted by the fluorinated block copolymer could disperse well in the organic solvent.The form of fluorinated block copolymer grafted silica nanoparticles was confirmed by TEM.The composition and chemical structure were studied by FTIR and 1H-NMR.The presence of hierarchical multi-scale surface roughness in the samples was observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM).Furthermore,this inorganic/organic hybrid material,SiO2-P(MMA-b-C6SA),showed excellent thermal stability,tested by TGA measurements.Water and n-hexadecane contact angles on the hybrid surface were both larger than that of the pure fluorinated polymer P(MMA-b-C6SA) surface,which can impart the surface with olephobiity and water-repellence properties. More importantly,this inorganic/organic hybrid surface showed excellent self-cleaning properties,dust can be easily washed away by water or swept away by wind.According to the present study,it is reasonable to predict that the organic-inorganic hybrid coating will be a prospective anti-icing and self-cleaning candidate.关键词：ARGET ATRP;Inorganic/organic hybrid materials;Fluorinated block copolymer;Surface-initiate;Self-cleaning
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发布时间：2021-03-19 - 摘要：The fluorinated block polymer containing epoxy groups poly(2,2,3,4,4,4-hexafluorobutyl methacrylate)-b-poly(glycidyl methacrylate),PHFMA-b-PGMA,was prepared via AGET ATRP and used to modify bisphenol A type epoxy resins E51.The contact angle measurements indicated that the surface hydrophobicity and lipophobicity of the thermosets modified by PHFMA-b-PGMA were all better than those of pure epoxy,and it was also found that the thermosets modified by PHFMA-b-PGMA still had excellent surface stability after immersing in water or butanone for 80 h,or heated at 120℃ for 24 h.The results of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the thermosets modified by PHFMA-b-PGMA had better thermal stability than pure epoxy resins.The mechanical properties were investigated by tensile testing and impact testing,and the results showed that the toughness of thermosets modified by PHFMA-b-PGMA could be improved,and the mechanical tests of the thermosets modified by PHFMA-b-PGMA were all corresponding to the results of their fracture surface SEM tests.关键词：Epoxy-terminated fluorinated block polymer;ATRP;Epoxy resin;Modification
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发布时间：2021-03-19 - 摘要：The underlying mechanism regarding the driving force of thermo-sensitive behavior for poly(N-methacryloyl-L--isopropylasparagine),shorted as PA48,was investigated by the combination of UV-Vis turbid experiments,dynamic light scattering (DLS),circular dichroism (CD),temperature-dependant 1H-NMR analyses and solvent isotopic effect.Turbid experiments showed that the PA48 polymer at acidic solution exhibited a reversible LCST-type thermo-sensitivity.For example,at pH 1 it had a cloud point (CP) of 39.9℃ with a hysteresis of 0.9 K in the cooling circle.CD spectra revealed that the absorption wavelength did not change with temperature variation.Meanwhile,the PA48 polymer showed a dramatic solvent isotopic effect,e.g.,the CP of PA48 was 6 K lower in D2O than in H2O.DLS demonstrated that the PA48 was mono-molecular soluble in water under CP while formed aggregates near the CP,and further heating led to the dehydration and phase separation.Temperature-dependent 1H-NMR spectra indicated the dehydration process occured subsequently from hydrophobic backbones to hydrophilic aspartic acid side-chains.Based on these data,the thermo-sensitivity of PA 48 was concluded to be driven by hydrophobic association and followed with dehydration and phase separation from water.关键词：Thermo-sensitive;Aspartic acid;Dehydration;Phase separation;Driving force
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发布时间：2021-03-19 - 摘要：A series of polyoxymethylene (POM)/poly(butylene succinate-co-butylene adipate) (PBSA) alloys were prepared by melt blending method.Intermolecular interactions,miscibility and crystallization behavior of POM/PBSA blends were studied using FTIR,dynamic mechanical analysis (DMA),differential scanning calorimetry (DSC),polarized light microscopy (PLM) and WAXD.The results show that intermolecular hydrogen bonding forms between carbonyl groups of PBSA and hydroxyl groups of POM,which increases the miscibility between PBSA and POM.Meanwhile,melting and crystallization temperatures of POM decrease with addition of PBSA.However,it is worth noting that lower content of POM in alloys has great influence on PBSA crystallization.Incorporation of 15 wt% of POM shows significant nucleating effect for PBSA and promotes its crystallization,resulting in reduced lattice spacing.In addition,the miscibility between POM and PBSA is dependent on the PBSA content.Miscibility of POM/PBSA alloys improves with increasing PBSA content.But the addition of PBSA does not modify the crystal structure of POM.关键词：Polyoxymethylene;Poly(butylene succinate-co-butylene adipate);Melt blending;Intermolecular interaction;Crystallization;Miscibility
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发布时间：2021-03-19 - 摘要：A novel diamine monomer containing tert-butyl,ether linkages and bisphenol A unit,2,2-bis(3'-(tert-butyl)-4'-aniline-bisphenyl-4-ehter)propane (4),was designed and synthesized from 2-tert-butylaniline and bisphenol A.Then it was polymerized with several commercial aromatic dianhydrides,including OPDA,PMDA,6FDA and BPDA,via one-pot method to afford a series of aromatic polyimides.Their chemical structures are confirmed by NMR,FTIR and EA measurements.The number-averaged molecular weights of the resulting PIs are in the range from 1.9104 to 3.9104 with PDI from 2.63 to 4.63 by GPC measurements.They exhibit excellent solubility in many organic solvents,such as NMP,DMF,m-cresol,DMAc,THF and CHCl3 etc,which can be attributed to the incorporation of tert-butyl groups and bisphenol A units into their rigid backbones.They can form transparent films by solution casting and the light transparency was equal to or higher than 90% in the visible light range from 400 to 760 nm.The XRD results demonstrate that they are amorphous glassy polymers.Furthermore,their inherent outstanding performance is still retained,including the high 5% weight loss temperature in nitrogen and Tg,good mechanical properties and low water absorption rates.关键词：tert-Butyl;Bisphenol A unit;Solubility;Polyimide;Transparency
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发布时间：2021-03-19 - 摘要：Furan epoxy resin (FER) was firstly used to improve the compatibility between PLA and starch by reactive extrusion.The SEM results indicated that the compatibility between PLA and starch was significantly improved by the reactive compatibilization of FER.According to the static contact angle test,the surface chemical property of starch changed from hydrophilic to hydrophobic during the melting extrusion.The 1H-NMR,FTIR and XPS results demonstrated that the FER reacted with starch and PLA simultaneously during the melt blending,resulting in a better compatibility of PLA/starch composites.The DSC analysis indicated that the crystallinity of PLA matrix in PLA/FER/starch composites was increased from 4% to 29%.It was resulted from that FER could improve the interface property between PLA matrix and starch,then starch showed a better nucleation effect on PLA matrix.Moreover,the mechanical properties of PLA composites including flexible strength,flexible modulus and impact strength are all significantly improved,while maintaining the high strength and modulus of PLA,which was because of the rigid ring of FER.关键词：Furan epoxy resin;PLA/starch composites;Compatibility;Mechanical properties
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发布时间：2021-03-19 - 摘要：The real space self-consistent field theory was applied to investigate microstructures and transformation of linear triblock copolymer films induced by surface field.We choose symmetric composition of copolymers fA: fB:fC=0.2:0.6:0.2 and the incompatibility degrees of copolymers are set as AB=AC=BC=30.The thickness of films is set to be 4.5Rg or 9Rg in our simulation.In order to obtain a series of novel microstructures under the above two different thicknesses of films,we study two kinds of thin films with non-modified stripes and modified stripes.And in the process of simulation,we can adjust the surface field strength of the thin films regularly.The strongest surface field strength is set equal to the interaction between copolymers (iWN=30,iA,B,C).The surface interaction is increased from the weakest surface interaction (iWN=5) in turn to the strongest surface field strength,and the gap of adjacent two kinds surface field strength is set as iWN=5.Depending on changing these parameters of simulation,we have obtained a wealth of microstructures.The microstructures show that the copolymers tend to form a regular and ordered lamellar or perforated layer confined thin films with non-modified stripes,while in the case of films with modified stripes,the copolymers tends to self assemble into horizontal structures in their respective modified stripe areas.关键词：Self-consistent field theory;Linear triblock copolymer;Surface field;Modified stripes
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发布时间：2021-03-19 - 摘要：Novel bio-based composite nanoparticles (Papain/HA-Phe) were prepared through the electrostatic interaction,hydrogen bonding and hydrophobic interaction between papain and amphiphilic L-phenylalanine ethyl ester-modified hyaluronic acid (HA-Phe).The sizes and morphologies of the composite nanoparticles were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM).The results showed that the composite nanoparticles had uniformly spherical structure with a size of 308 nm.The composite nanoparticles were used as particulate emulsifiers to stabilize white oil,forming oil-in-water Pickering emulsions.Scanning electron microscopy (SEM) characterization of emulsions demonstrated that the composite nanoparticles were adsorbed at the oil-water interface and formed the adsorption layer of composite nanoparticles to stabilize emulsions.The influences of pH values and salt on the properties of composite nanoparticles and emulsifying performances were carefully investigated.The results showed that the adsorption number of composite nanoparticles at surface of oil drops decreased and emulsifying performances of composite nanoparticles decreased with increasing pH value; the deformation degree of composite nanoparticles gradually increased and emulsifying performances increased with increasing salt concentrations.The bioactivity and inhibitory activity against tyrosinase of papain in emulsions were further investigated.The studies showed that the emulsions retained the majority of bioactivity and some inhibitory activity against tyrosinase.关键词：Self-assembly;Composite nanoparticles;Hyaluronic acid;Papain
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发布时间：2021-03-19 - 摘要：Hybrid vesicles were prepared through surface-functionalization of hyperbranched polymer vesicles with noble metal nanoparticles.The vesicles were self-assembled from an amphiphilic hyperbranched polyether modified with dopamine groups at the terminal (HSP-DA).The dopamine groups can self-polymerize in alkaline aqueous solution,leading to the crosslinking of HSP-DA vesicles.Due to the strong adhesion characteristics of polydopamine,the Au nanoparticles (AuNPs) or Ag nanoparticles (AgNPs) hybrid vesicles can be obtained through mixing the so-formed HSP-PDA crosslinked vesicles and AuNPs or AgNPs together.The formation of AuNPs hybrid vesicles and AgNPs hybrid vesicles was confirmed through transmission electron microscope (TEM) and ultraviolet-visible (UV-Vis) spectroscopy measurements.The Raman spectra of hybrid vesicles showed a significant enhancement of the Raman signals of the ether bond (1280 cm-1,1140 cm-1) and aromatic rings (1590 cm-1) that was attributed to the components of HSP-PDA vesicles compared to the barely visible Raman signals from HSP-PDA vesicles.In other words,it could be used to in situ detect the vesicle components by using surface-enhanced Raman scattering (SERS) of the AuNPs or AgNPs hybrid vesicles.In addition,AgNPs hybrid vesicles were further used as SERS probes to detect Rhodamine 6G molecules with a concentration of 10-7 mol/L in the aqueous solution.In the Raman spectrum,the Raman signals of C-C stretching vibration (1311,1361,1508,1572 and 1648 cm-1),the C-H stretching vibration (772,921 and 1126 cm-1),and C-H in-plane bending vibration (1183 cm-1) from Rhodamine 6G can be recognized clearly,indicating the potentials of the as-prepared hybrid vesicles in trace detection.关键词：Au nanoparticles;Ag nanoparticles;Vesicles;Dopamine;Surface-enhanced Raman scattering
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发布时间：2021-03-19
Research Article
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