聚合物热电复合材料的研究进展

本文综述了碳纳米材料/聚合物、半导体合金/聚合物、金属纳米粒子/聚合物以及聚合物/聚合物等热电复合材料的研究进展。简要分析了热电复合材料的性能提升机理及现有材料尚存在的问题,并指出了聚合物热电复合材料今后的发展方向。

MTA、iRoot BP Plus在难治性前牙根尖周病患者根管治疗中的应用比较

目的对比无机三氧化物聚合物(MTA)、iRoot BP Plus在难治性前牙根尖周病患者根管治疗中的应用效果。方法选取2016年3月—2018年3月承德医学院附属医院口腔科收治的246例难治性前牙根尖周病患者,均为单颗患病且实施根管倒充填治疗。其中82例患者采用MTA治疗(MTA组),84例患者采用iRoot BP Plus治疗(iRoot BP Plus组),80例患者接受氢氧化钙糊剂治疗(对照组)。对比根充质量、治疗前和治疗1周后局部红肿、疼痛评分,不同时刻旧根尖指数(O-PAI)变化及临床疗效。结果iRoot BP Plus组适充率较MTA组和对照组高(P<0.05)。MTA组治疗前和治疗1周后局部红肿、疼痛评分的差值较对照组高(P<0.05),iRoot BP Plus组最高(P<0.05)。iRoot BP Plus组O-PAI评级较MTA组、对照组低(P<0.05),相对效果较好;MTA组治疗后较对照组低(P<0.05),相对效果较好。iRoot BP Plus组临床总有效率最高(P<0.05)。结论在难治性前牙根尖周病患者根管治疗中MTA、iRoot BP Plus均优于氢氧化钙糊剂,且应用iRoot BP Plus可保证适充率,并有效减轻局部红肿、疼痛,改善O-PAI,疗效理想,有望替代MTA推广应用。

PREPARATION AND PROPERTIES OF GEL POLYMER ELECTROLYTE BASED ON PVDF/ACRYLATE INTERPENETRATING POLYMER NETWORK FOR DYE-SENSITIZED SOLAR CELL

The gel polymer electrolytes（GPEs）based on poly（vinylidence fluoride）（PVDF）/acrylate interpenetrating polymer network（IPN）are prepared.The micro-phase separation type GPEs are characterized by Fourier transform infrared（FTIR）spectroscopy,scanning electron microscope（SEM）,respectively.Moreover,the conductivity and the voltage-current curves of the electrolytes are measured by electrochemical workstation.The higher porosity and electrolyte uptake are observed in the membranes prepared at lower crosslinker concentration.The suitable cross-linking acrylate monomer improves the porosity and the electrochemical behavior of GPE.A dye-sensitized solar cell（DSSC）employing PGE based on PVDF/poly（ethylene glycol dimethacrylate）（PEGDMA）IPN yields an open-circuit voltage of 0.674 V,short-circuit current of 8.476 mA·cm-2and the conversion efficiency of 2.710% under 100 mW·cm-2illumination.

Characteristics of resistivity log response of oil layers under polymer flooding

Resistivity log responses are different when the oil layers is filled by a polymer solution or water and it seriously affects the log interpretation of the water flooded layer. In this paper, we first analyze the electrical properties of the polymer solution. Then, according to the different processes for polymer flooding the reservoir, we perform rock resistivity experiments and analyze the rock resistivity variations in different displacement phases. We also compare the resistivity log responses of oil layers filled with the polymer solution to those filled with water. The results show that when displacing the oil-bearing core by different polymers, the resistivity changes monotonously decrease and show either ＂W＂ type or ＂S＂ type. The resistivity log responses are weak when displacing water and there is no flooded show if the oil layer is injected by a fresh water polymer solution. If the oil layer is injected by a sewage polymer solution, the resistivity log response has similar characteristic as a polluted water flooded layer.

Preparation and Characterization of Non-porous Superparamagnetic Microspheres with Epoxy Groups by Dispersion Polymerization

Non-porous superparamagnetic polymer microspheres with epoxy groups were prepared by dispersion polymerization of glycidyl methacrylate (GMA) in the presence of magnetic iron oxide (Fe3O4) nanoparticles coated with oleic acid. The polymerization was carried out in the ethanol/water medium using polyvinylpyrrolidone (PVP) and 2,2’-azobisisobutyronitrile (AIBN) as stabilizer and initiator, respectively. The magnetic microspheres obtained were characterized with scanning electron microscopy (SEM), vibrating sample magnetometry (VSM) and Fourier transform infrared spectroscopy (FTIR). The results showed that the magnetic microspheres had an average size of-1μm with superparamagnetic characteristics. The saturation magnetization was found to be 4.5emu.g-1. There was abundance of epoxy groups with density of 0.028 mmol·g^-1 in microspheres. The magnetic PGMA microspheres have extensive potential uses in magnetic bioseparation and biotechnology.

Interpenetrating polymers supported on microporous polypropylene membranes for the transport of chromium ions

Modifying polypropylene membranes with interpenetrating polymer networks(IPNs) through the incorporation of poly(glycidyl methacrylate-N-methyl-D-glucamine)(P(GMA-NMG)) was performed by in situ synthesis via radical polymerization. The surface of the polypropylene membrane was activated by hydrophilic grafted polyelectrolyte, and then, pressure injection was used for the impregnation of the reactive solution in the membrane.Two types of pore-filled membranes were synthesized, chelating interpenetrating homopolymer networks of P(GMA-NMG), and chelating-ion exchange interpenetrating polymer networks(e.g., P(GMA-NMG)/P(AA),P(GMA-NMG)/P(AMPSA), and P(GMA-NMG)/P(Cl VBTA)). After their synthesis, the modified polypropylene membranes were characterized using techniques such as the electrokinetic potential, SEM, FT-IR, and Donnan dialysis to corroborate the chromium ion transport. The P(GMA-NMG) and complex network membranes exhibited a hydrophilic character with a water-uptake capacity between 20% and 35% and a percentage of modification between 4.0% and 7.0% in comparison with the behavior of the unmodified polypropylene membrane.Hexavalent chromium ions were efficiently transported from the food chamber at p H 9.0 when the 65.2%MTA1 P(Cl VBTA) homopolymer IPN membrane and 48.5% MTAG P(GMA-NMG)/P(Cl VBTA) IPN membrane were used. Similarly, hexavalent chromium ions were removed from the food chamber at pH 3.0 when MTAG(63.30%) and MTA1(35.68%) were used in 1 mol·L^(-1)Na Cl solution as the extraction reagent.

Synthesis of an Amphiphilic Dendrimer-Like Block Copolymer and Its Application on Drug Delivery

Dendrimer-like amphiphilic copolymer is a kind of three-dimensional spherical structure polymer. An amphiphilic dendrimer-like diblock copolymer, PEEGE-G2-b-PEO（OH）12, constituted of a hydrophobic poly（ethoxyethyl glycidol ether） inner core and a hydrophilic poly（ethylene oxide） outer layer, has been successfully synthesized by the living anionic ring-opening polymerization method. The intermediates and targeted products were charac-terized with 1H NMR spectroscopy and gel permeation chromatography. The application on drug delivery of dendrimer-like diblock copolymer PEEGE-G2-b-PEO（OH）12 using DOX as a model drug was also studied. The drug loading content and encapsulation e ciency were found at 13.07% and 45.75%, respectively. In vitro release experiment results indicated that the drug-loaded micelles exhibited a sustained release behavior under acidic media.

A new low-bandgap polymer acceptor based on benzotriazole for efficient all-polymer solar cells

The rational design of polymer acceptors with strong and broad absorption is critical to improve photovoltaic performance.In this work,a new polymer acceptor PY9-T based on heptacyclic benzotriazole(Y9-C16)as a building block and thiophene unit as the linking unit was synthesized,which exhibited a low bandgap(1.37 eV)and a high extinction coefficient of the neat film(1.44×10^(5) cm^(−1)).When PY9-T was blended with the wide bandgap polymer donor PBDB-T,the all-polymer solar cells(APSCs)showed a high power conversion efficiency(PCE)of 10.45%with both high open circuit voltage of 0.881 V and short-circuit current density of 19.82 mA/cm^(2).In addition,APSCs based on PY9-T show good thermal stability,as evidenced by slight changes morphologies when annealed at 100℃.These results suggest that Y9-C16 provides a new building block to develop efficient and stable polymer acceptors.

Utilization of Concrete Waste Aggregates Using Geopolymer Cement

Reuse of concrete waste, especially in large quantity, can save not only material but also cost for its disposal. This paper presents experiment results on the use of fine and coarse aggregates from concrete waste in geopolymer mortars and concretes. Geopolymeric cement is an inorganic compounds of aluminosilicates synthesized from precursors with high content of silica and alumina activated by alkali silicate solutions. Geopolymer in this experiment was synthesized from fly ash as the precursor and sodium silicate solution as the activator. Hardening of geopolymers was performed by heating the casted paste in an oven at -60~Cfor 3 to 36 hours. Compressive strength of geopolymer pastes and mortars using either fresh or waste fine aggregates were in the range of 19-26 MPa. Hardening time of 3 hours at 60~C followed by leaving the test pieces at room temperature for 7 day before testing results in similar strength to that of mortars cured for 36 hours at 60~C followed by leaving the samples at room temperature for 3 days. It suggests that optimum strength can be achieved by combination of heating time and rest period before testing, i.e the specimens age. Applying mix design with a target strength of 40 MPa, conventional Portland cement concretes using fresh aggregates reached 70% of its target strength at day-7. Compressive strength of geopolymer concretes with waste aggregates was -25 MPa at day-3 while geopolymer concretes with fresh aggregates achieved -39 MPa at day-3. It can be concluded that geopolymer concretes can achieve the target strength in only 3 days. However, the expected reinforcing effect of coarse aggregates in concrete was ineffective if waste coarse aggregates were used as the strength of the concretes did not increase significantly from that of the mortars. On the other hand, waste fine aggregates can be reused for making geopolymer mortars having the same strength as the geopolymer mortars using fresh aggregates.

Preparation and properties of geopolymer-lightweight aggregate refractory concrete

Geopolymer-lightweight aggregate refractory concrete (GLARC) was prepared with geopolymer and lightweight aggregate. The mechanical property and heat-resistance (950 ℃) of GLARC were investigated. The effects of size of aggregate and mass ratio of geopolymer to aggregate on mechanical and thermal properties were also studied. The results show that the highest compressive strength of the heated refractory concrete is 43.3 MPa,and the strength loss is only 42%. The mechanical property and heat-resistance are influenced by the thickness of geopolymer covered with aggregate,which can be expressed as the quantity of geopolymer on per surface area of aggregate. In order to show the relationship between the thickness of geopolymer covered with aggregate and the thermal property of concrete,equal thickness model is presented,which provides a reference for the mix design of GLARC. For the haydite sand with size of 1.18-4.75 mm,the best amount of geopolymer per surface area of aggregate should be in the range of 0.300-0.500 mg/mm2.

Time-dependent Diffusion Coefficient and Conventional Diffusion Constant of Nanoparticles in Polymer Melts by Mode-coupling Theory

Time-dependent diffusion coefficient and conventional diffusion constant are calculated and analyzed to study diffusion of nanoparticles in polymer melts. A generalized Langevin equa- tion is adopted to describe the diffusion dynamics. Mode-coupling theory is employed to calculate the memory kernel of friction. For simplicity, only microscopic terms arising from binary collision and coupling to the solvent density fluctuation are included in the formalism. The equilibrium structural information functions of the polymer nanocomposites required by mode-coupling theory are calculated on the basis of polymer reference interaction site model with Percus-Yevick closure. The effect of nanoparticle size and that of the polymer size are clarified explicitly. The structural functions, the friction kernel, as well as the diffusion coefficient show a rich variety with varying nanoparticle radius and polymer chain length. We find that for small nanoparticles or short chain polymers, the characteristic short time non-Markov diffusion dynamics becomes more prominent, and the diffusion coefficient takes longer time to approach asymptotically the conventional diffusion constant. This constant due to the microscopic contributions will decrease with the increase of nanoparticle size, while increase with polymer size. Furthermore, our result of diffusion constant from mode- coupling theory is compared with the value predicted from the Stokes-Einstein relation. It shows that the microscopic contributions to the diffusion constant are dominant for small nanoparticles or long chain polymers. Inversely, when nanonparticle is big, or polymer chain is short, the hydrodynamic contribution might play a significant role.

Deformation of Linked Polymer Coils

Linked polymer solution (LPS) is defined as the solution of linked polymer coils (LPCs) dispersed in water, composed of low concentration partially hydrolyzed polyacrylamide (HPAM) and aluminum citrate (crosslinker). In the work, the conformational changes of LPCs under different conditions were investigated by the methods of membrane filtering under low pressure, dynamic light scattering and core flooding experiments. The results showed that in some conditions the LPCs could be compressed mechanically to 1/158.5 of their original volume because of relatively lower HPAM cross-linking. The hydration property of LPCs was similar to that of normal polymer coils. The deformation of LPCs was more restricted than that of ordinary polymer coils under the flow shear stress or the shift of hydration equilibrium caused in the variation of the electrolyte concentration which is responsible for the effective plugging in the throats of porous media when LPCs are used for deep diverting.

Morphology and conductivity of in-situ PEO-LiClO_4-TiO_2 composite polymer electrolyte

PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.

Conductometric sensor based on oxytetracycline imprinted polymer membrane

A conductometric sensor sensitive to oxytetracycline hydrochloride （OTC.HCI） was developed on the basis of utilizing OTC.HCl imprinted polymer, synthesized under the optimized conditions by using non-covalent imprinted technology with OTC.HCl as a template, MAA as a functional monomer, and EGDMA as a cross-linker, which were the composition of the sensing membrane. The responses increased linearly with the increase of OTC.HCl concentration in the range of 0.99-12.0 μM. The response mechanism of the sensor was also discussed.

Water Permeability in Fly Ash-Based Geopolymer Concrete

This research investigated the water permeability coefficient of fly ash-based geopolymer concrete. The effect of sodium hydroxide （Na（OH）） concentrations and Si/AI ratios on water permeability and compressive strength of geopolymer concretes were studied. The geopolymer concrete were prepared from Mae Moh fly ash with sodium silicate （Na2SiO3） and sodium hydroxide （Na（OH）） solutions. In the first group, concentration of Na（OH） was varied at 8, 10, 12, and 14 molar and the Si/AI ratio was kept constant at 1.98. In the second group, a concentration of Na（OH） was kept constant at 14 molar and the Si/AI ratio was varied at 2.2, 2.4, 2.6, and 2.8. The hardened concretes were air-cured in laboratory. The compressive strength and water permeability were tested at the age of 28 and 60 days. The results showed that compressive strengths of geopolymer concrete significantly increased with the increase of a concentration of Na（OH） and Si/AI ratio. The water permeability coefficients increase with the decrease of compressive strength. In addition, the high reduction of water permeability coefficients with time was found in geopolymer concrete with lower Na（OH） concentration than that higher Na（OH） concentration.

Collapse of Four-Arm Stars Polyelectrolyte Brushes Under An Electric Field in the Presence of Trivalent Salt Coions

Langevin dynamics simulations were conducted to study the collapse of grafted partially charged 4-arm star chains onto the oppositely charged grafting electrode in the presence of trivalent salt coions.Simulation results reveal that the average charge fraction of the grafted star chains and the salt concentration play critical roles in the competitive adsorption of charged monomers and trivalent salt coions onto the oppositely charged electrode.For grafted star chains with relatively high charge fraction,charged monomers are the dominant species collapsing on the oppositely charged electrode with the emergence of charge reversal on the grafting electrode.At a low charge fraction such that the total amount of charges on a grafted star molecule is comparable to that of a trivalent salt coion,trivalent salt coions absorb more strongly onto the electrode than grafted stars even at very low salt concentration.It is found that at relatively low charge fraction of star chains,the addition of trivalent salt coions does not lead to charge overcompensation of the surface charges on the grafting electrode.The stretching of star brushes under an electric field in the presence of trivalent salt coions was also briefly investigated.

Which is More Efficient as Compatibilizer： Di-block or Multiblock Copolymer？

Monte Carlo simulations were used to investigate the compatibilizing behaviors of multi-block copolymers with different architectures in A/B/（block copolymer） ternary blends. The volume fraction of homopolymer A, employed as the dispersed phase, was 19%. The simulations illustrate how a di- or multi-block copolymer aggregates at the interfaces and influences the phase behaviour of such incompatible polymer blends. The di-block copolymer chains tend to ＂stand＂ on the interface whereas the multi-block chains lie on the interface. In comparison with the di-block copolymer, the block copolymers with 4, or 10 blocks can occupy more areas on the interface, and thus the multi-block copolymers have higher efficiency for the retardation of the phase separation.

Partial pore blockage and polymer chain rigidification phenomena in PEO/ZIF-8 mixed matrix membranes synthesized by in situ polymerization

Nanostructured zeolitic imidazolate frameworks(ZIF-8) was incorporated into the mixture of poly(ethylene glycol) methyl ether acrylate(PEGMEA) and pentaerythritol triacrylate(PETA) to synthesize mixed matrix membranes(MMMs) by in situ polymerization for CO_2/CH_4 separation. The solvent-free polymerization between PEGMEA and PETA was induced by UV light with 1-hydroxylcyclohexyl phenyl ketone as initiator. The chemical structural characterization was performed by Fourier transform infrared spectroscopy. The morphology was characterized by scanning electron microscope. The average chain-to-chain distance of the polymer chains in MMMs was investigated by X-ray diffraction. The thermal property was evaluated by differential scanning calorimetry. The CH_4 and CO_2 gas transport properties of MMMs are reported. The relationship between gas permeation–separation performances or physical properties and ZIF-8 loading is also discussed. However, the permeation–separation performance was not improved in Robeson upper bound plot compared with original polymer membrane as predicted. The significant partial pore blockage and polymer rigidification effect around the ZIFs confirmed by the increase in glass temperature and the decrease in the d-spacing, were mainly responsible for the failure in performance improvement, which offset the high diffusion induced by porous ZIF-8.

SYNTHESIS OF A COMB GRAFT COPOLYMER VIA RING OPENING METATHESIS POLYMERIZATION CATALYZED BY SUPPORTED RHUTHENIUM CARBENE COMPLEX

Chloromethyl-2-norbornene was synthesized via Diels-Alder reaction of cyclopentadiene and allyl chloride using a polymer supported boron trifluoride as the catalyst, and was then lithiated and used to initiate a living anionic polymerization of styrene to prepare a macromonome, 5-polystyryl-2-norbornene NBPS. Comb graft copolymer PNBgPS was synthesized via ring opening metathesis polymerization of the macromonomer under the catalysis of ruthenium carbene complex RuCl2(PPh3)2(=CCHtBu) and its polymer supported correspondent. Experimental results showed that the behavior of both the supported boron and supported ruthenium catalysts are superior to their unsupported counterparts. The possible promotion mechanism of the tailor-made supports is discussed.

Application of Geopolymer Cement for Groutless Decorative Building Materials

The present study describes the experiments on the application of geopolymer paste for groutless in situ casting or flooring. The paste was synthesized from fly ash and sodium silicate solution and cured at room temperature, 60 and 80℃ for 24 hours. To simulate flooring application, the geopolymer paste was casted on Portland cement cubes which have been fully hydrated for 28 days. Silica fume was added to reduce cracks but at the same time compressive strength decreased. Averaged compressive strength decreased from 53 MPa to 37 MPa for paste cured at 60℃. Curing at higher temperatures produced stronger geopolymer, with compressive strength of 12 MPa, 53 MPa and 67 MPa for geopolymer cured at room temperature, 60℃ and 80℃ respectively, however, higher curing temperature resulted in more cracking when the geopolymer paste was applied on the Portland cement substrate. Averaged hardness values were 65 and 43 Brinnel scale （BHN）, and wear rate, measured using Ogoshi machine, were 0.66 and 1.80 mm3/min for samples cured at 60 and 80℃ respectively. Unless surface hardening was applied, the material is not suitable for flooring but do so for decorative masonry.