π-Conjugated organic/polymer materials-based solar cells have attracted tremendous research interest in the fields of chemistry,physics,materials science,and energy science.To date,the best-performance polymer solar ...π-Conjugated organic/polymer materials-based solar cells have attracted tremendous research interest in the fields of chemistry,physics,materials science,and energy science.To date,the best-performance polymer solar cells(PSCs)have achieved power conversion efficiencies exceeding 18%,mostly driven by the molecular design and device structure optimization of the photovoltaic materials.This review article provides a comprehensive overview of the key advances and current status in aggregated structure research of PSCs.Here,we start by providing a brief tutorial on the aggregated structure of photovoltaic polymers.The characteristic parameters at different length scales and the associated characterization techniques are overviewed.Subsequently,a variety of effective strategies to control the aggregated structure of photovoltaic polymers are discussed for polymer:fullerene solar cells and polymer:nonfullerene small molecule solar cells.Particularly,the control strategies for achieving record efficiencies in each type of PSCs are highlighted.More importantly,the in-depth structure-performance relationships are demonstrated with selected examples.Finally,future challenges and research prospects on understanding and optimizing the aggregated structure of photovoltaic polymers and their blends are provided.展开更多
Biological soft tissues and hydrogels belong to the same category of soft and wet matter.Both of them are composed of polymer network and a certain amount of water,and permeable to small molecules.Biological tissues p...Biological soft tissues and hydrogels belong to the same category of soft and wet matter.Both of them are composed of polymer network and a certain amount of water,and permeable to small molecules.Biological tissues possess elaborated structures and exhibit outstanding functionalities.On the other hand,hydrogels are usually amorphous with poor functionality.In recent years,various hydrogels with robust functionalities have been developed by introducing aggregated structures into the gel networks,widely extend their applications in diverse fields,such as soft actuators,biological sensors,and structural biomaterials.Four strategies are usually used to fabricate aggregated structure into hydrogels,including molecular self-assembling,microphase separation,crystallization,and inorganic additives.Different aggregated structures entail the gel very different functionalities.A simple aggregated structure is able to bring multiple functionalities and a combination of mechanical performances of the hydrogels.In this review,we describe the strategies used to construct aggerated structure in hydrogels and discuss about the close relation between the aggregated structure and functionality.We also highlight the role of nonequilibrium aggregated structure in fabricating hydrogels with dynamic memorizing-forgetting behavior and point out the remaining challenges.展开更多
The structural parameters of the aggregated state of polyamide (PA)-1010 annealed at various temperatures were computed by means of the desmearing intensity from Smalt Angle X-ray Scattering (SAXS) measurements and by...The structural parameters of the aggregated state of polyamide (PA)-1010 annealed at various temperatures were computed by means of the desmearing intensity from Smalt Angle X-ray Scattering (SAXS) measurements and by using the concept of the distance distribution function. The results indicated that the structural parameters of the aggregated state were strongly dependent upon heat treatment conditions and the maximum values of the structural parameters were obtained for the samples annealed at T = 175 degrees C. The particle size Z annealed at different temperature was ranged between 8.1-12.8nm, and the values of the distance distribution function P-max(Z) were obtained when Z = 4.0-6.8 nm. Using one dimension electron density correlation function (1D EDCF) method long period (L) and thickness of the lamellar (d(0)) were estimated and were found to increase with the increase of the degree of crystallinity.展开更多
The aggregation behavior and structure of hydrophobically modified block copolymers of acrylamide and 2-phenoxylethylacrylate were investigated by viscometry, 1H NMR relaxation, 2D NOESY, fluorescence and dynamic ligh...The aggregation behavior and structure of hydrophobically modified block copolymers of acrylamide and 2-phenoxylethylacrylate were investigated by viscometry, 1H NMR relaxation, 2D NOESY, fluorescence and dynamic light scattering. It Was found that the aggregation behavior was strongly dependent on the concentration of polymer solution and the hydrophobe contents. With varying concentration from 2.0, 6.0, 8.0 to 12.0 g/L, there were different aggregate morphologies distributed in aqueous solutions, such as monopolymer chain, micelle-like aggregate, multi-micelle aggregate and cross-linked network. According to the model of aggregation, it can give a reasonable explanation on the large magnitude enhancement of viscosity with the increasing of polymer concentration. Additional data of 2D NOESY and fluorescence show that the copolymer with higher hydrophobe content(molar fraction≥ 1%) is likely to form intra-molecular association.展开更多
The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N'-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the ...The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N'-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the conformation simulations from AM1 semi-empirical quantum mechanics modeling. The results showed that in the solid film 1 molecules stacked with the perfluorinated phenyl groups straightly over or below the perylene cores of the adjacent 1 molecules.展开更多
Compacting process of fine powder is greatly affected by the aggregate structure of particles. According to the experiment in which several kinds of silicon nitrides in different partical shape and size were compacted...Compacting process of fine powder is greatly affected by the aggregate structure of particles. According to the experiment in which several kinds of silicon nitrides in different partical shape and size were compacted in uniaxialorientation, it is found that the volume compacting rate offorming body differs with the pressure. The aggregatestructure of each sample A, B or C was estimated by applying Cooper's equation to the analysis of the compacting process of each sample展开更多
The structure of aggregation state and isothermal crystallization behavior of Nylon-1010 have been studied by WAXD, DSE, Variance-Range Function and density measurement. The results show that crystallization of Nylon-...The structure of aggregation state and isothermal crystallization behavior of Nylon-1010 have been studied by WAXD, DSE, Variance-Range Function and density measurement. The results show that crystallization of Nylon-1010 has the most suitable annealing temperature, the crystals of the Nxlon-1010 are two-dimension heterogeneous nucleation. Both low treatment temperature and high crystallization te, temperature are disadvantageous for Nylon-1010 crystal growth.展开更多
A series of hydrophobically associating polyacrylamides modified by small amounts (〈 3 mol%) of a self- associative cationic monomer 4-(2-(acryloyloxy) ethoxy) benzyl tri-ethyl ammonium bromide (AEBA) as hydr...A series of hydrophobically associating polyacrylamides modified by small amounts (〈 3 mol%) of a self- associative cationic monomer 4-(2-(acryloyloxy) ethoxy) benzyl tri-ethyl ammonium bromide (AEBA) as hydrophobe were synthesized by radical copolymerization in aqueous solutions without external surfactants. The resulting eopolymers containing a multiblock structure exhibited a high tendency for hydrophobic association and a high thickening capacity. Solution properties and aggregation structures were investigated by viscometry and fluorescence technique. The high viscosity enhancement was found as the polymer concentration beyond a critical value c* and strongly depended on the copolymer microstructures. The number and length of hydrophobic microblocks within the copolymer backbones could be controlled by changing the AEBA concentration in copolymerization system. Addition of salt induced more hydrophobic association and viscosity enhancement. The synthesis method used was simple and environmentally friendly without any external surfactant contamination in comparison with the conventional micellar copolymerization.展开更多
A novel associating polymer P(AEBA) was synthesized by radical polymerization of the cationic amphiphilic monomer,4-(2-(acryloyloxy)ethoxy)benzyl tri-ethyl ammonium bromide(AEBA),in aqueous solutions.P(AEBA) displays ...A novel associating polymer P(AEBA) was synthesized by radical polymerization of the cationic amphiphilic monomer,4-(2-(acryloyloxy)ethoxy)benzyl tri-ethyl ammonium bromide(AEBA),in aqueous solutions.P(AEBA) displays a strong tendency for self-association in aqueous solutions and is sensitive to the external stimulation such as added salt.The associative properties and morphologies of P(AEBA) were studied by fluorescnece probe technique,viscometry and TEM.In dilute salt-free solutions P(AEBA) behaves as pol...展开更多
An ionic iridium(Ⅲ) complex[Ir(F2dpyb)(bzdpp)2Cl][OTf]with 1,3-difluoro-4,6-di(2-pyridinyl) benzene(F2dpybH) terdentate ligand and benzyldiphenylphosphine(bzdpp)ligand was synthesized and characterized.Th...An ionic iridium(Ⅲ) complex[Ir(F2dpyb)(bzdpp)2Cl][OTf]with 1,3-difluoro-4,6-di(2-pyridinyl) benzene(F2dpybH) terdentate ligand and benzyldiphenylphosphine(bzdpp)ligand was synthesized and characterized.The structure of iridium complex was verified by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/n with a =14.3654(7),b = 23.0026(10),c = 15.7964(7) A°,β = 97.6029(11),V= 5173.9(4) A°3,Z = 4,F(000) =2552,Dc = 1.645 Mg/m^3,Mr = 1281.49 and μ = 0.071 mm^-1.The UV-vis absorption and phosphorescence of the complex were discussed.The complex was 'aggregation induced emission(AIE)' active.It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation.The complex emitted a strong phosphorescence centered at493 nm when doped in PMMA.Its lifetime is 0.755 μs and quantum yield is approximately 0.134.展开更多
The influence of air-cooled blast furnace slag aggregates as replacement of natural aggregates on the water absorption of concrete and mortar was studied, and the mechanism was analyzed. The interface between aggregat...The influence of air-cooled blast furnace slag aggregates as replacement of natural aggregates on the water absorption of concrete and mortar was studied, and the mechanism was analyzed. The interface between aggregate and matrix in concrete was analyzed by using a micro-hardness tester, a laser confocal microscope and a scanning electron microscope with backscattered electron image mode. The pore structure of mortar matrixes under different curing conditions was investigated by mercury intrusion porosimetry. The results showed that when natural aggregates were replaced with air-cooled blast furnace slag aggregates in mortar or concrete, the content of the capillary pore in the mortar matrix was reduced and the interfacial structure between aggregate and matrix was improved, resulting in the lower water absorption of mortar or concrete. Compared to the concrete made with crushed limestone and natural river sand, the initial absorption coefficient, the secondary absorption coefficient and the water absorption capacity through the surface for 7 d of the concrete made from crushed air-cooled blast furnace slag and air-cooled blast furnace slag sand were reduced by 48.9%, 52.8%, and 46.5%, respectively.展开更多
The aging characteristics of the XLPE insulation of 110 kV power cables in the initial stage of operation are studied in this paper.The XLPE insulation from cables with different running time was tested by using elect...The aging characteristics of the XLPE insulation of 110 kV power cables in the initial stage of operation are studied in this paper.The XLPE insulation from cables with different running time was tested by using electrical and physicochemical methods,from which the degradation state of XLPE under multiple stresses during operation was derived.The broadband dielectric spectrum test taken from 10–1 to 10^(6) Hz showed that the dielectric constant and dielectric loss of the XLPE insulation first decrease and then increase with the increase of cable running time,which show obvious variation until 10 years of operation.The AC breakdown strengths of the XLPE insulation of operated cables with the service year no longer than 10 years were higher than that of new cables.The mechanical properties of the XLPE insulation showed no dependence with the cable running time.The crystallinity and perfection of the crystallization area were found to be enhanced during operation and the polar functional groups inside the XLPE insulation were found to be determined not only by the cross-linking by-products but also by the oxidation process during cable operation.The experimental results in this paper are important for improving the operation reliability and reducing the maintenance costs of the cables.展开更多
Polyimide films derived from representative PMDA/ODA were prepared with thickness ranging from 5 μm to 25 μm,and the effect of aggregation structure on thermal expansion behavior along different directions was studi...Polyimide films derived from representative PMDA/ODA were prepared with thickness ranging from 5 μm to 25 μm,and the effect of aggregation structure on thermal expansion behavior along different directions was studied.Both in-plane and out-of-plane linear thermal expansion(CTEand CTE) were respectively characterized by thermal mechanical analysis and FT-near-IR interference method.Volumetric and anisotropic behavior of thermal expan sion were also investigated.With increasing film thickness,CTEgradually increased from 32.2 ppm/℃ to46.1 ppm/℃ while CTEdecreased from 149.7 ppm/℃ to 128.2 ppm/℃.Volumetric thermal expansion of polyimide films was less sensitive to the va ried thickness,but anisotropy of thermal expansion was reduced.Polyimide film of 5 μm thickness showed large birefringence,indicating more considerable in-plane chain orientation anisotropy.Besides,molecular chains were more densely packed along in-plane direction when film thickness increased,while became loosely stacked in the out-of-plane direction.In contrast to the enhanced lateral chain packing for thicker film s,higher vertical chain packing order was found in thinner films.The variation of aggregation structure during thermal expansion procedure was analyzed by temperature-dependent WAXD.It is proved that thermal expansion behavior of thinner films could be largely attributed to molecular chain packing,whereas that may be influenced by many factors for thicker films in addition to the effect of chain packing.The results revealed that thermal expansion of films with thickness variation is closely related to molecular chain orientation and packing,which is associated with both chemistry and morphological structure of polyimide.展开更多
The traditional high-temperature preparation process of polyimide can cause many problems and limits the wider application in extreme conditions.An important challenge to be solved urgently is the reduction of imidiza...The traditional high-temperature preparation process of polyimide can cause many problems and limits the wider application in extreme conditions.An important challenge to be solved urgently is the reduction of imidization temperature.In this work,twelve kinds of polyimide films with different chain rigidity were prepared at low temperature of 200℃,in the absence or presence of imidazole used as the catalyst.The molecular rigidity and free volume were theoretically calculated,and relationship between structure and properties were systematically studied.The results show that imidization reaction under low temperatures is significantly affected by the rigidity of molecula r chains.The rigid structure of polyimide is not conducive to the low-temperature imidization,but this adverse effect can be eliminated by adding catalyst,resulting the notably increased imidization degree.The optical and thermal properties can be improved to a certain extent for the chemically catalyzed system,resulting in relatively higher heat resistance and thermal stability.While the mechanical performance could be determined by com plicating factors,greatly different from polyimide films prepa red by high temperature method.To investigate aggregation structures of film s,the effect of chain rigidity and catalyst on the stacking or orientation of molecular chains was further elaborated.This wo rk can contribute to the understanding of chemically catalyzed imidization that is rarely reported in the existing research,and will provide guidance for the low-temperature preparation of high-performance polyimides.展开更多
All-polymer solar cells(All-PSCs)have attracted tremendous research interest in the recent decade due to the great potentials in stretchable electronic applications in terms of long-term stability and mechanical stret...All-polymer solar cells(All-PSCs)have attracted tremendous research interest in the recent decade due to the great potentials in stretchable electronic applications in terms of long-term stability and mechanical stretchability.Driven by the molecular design of novel polymer acceptors and morphology optimization,the power conversion efficiency(PCE)of All-PSCs has developed rapidly and now exceeded 17%.This review outlines the promising strategies for high-performance All-PSCs from the aspect of morphology control with the motivation to rationally guide the optimization.In this review,we briefly discuss the thermodynamic mixing principles of all-polymer blends and the effects of the molecular structure of conjugated polymers on thin-film morphology in All-PSCs.The crucial role of molecular miscibility in influencing morphological features and performance metrics was highlighted.We also expound on the effective methods of controlling film morphology through properly tuning the aggregation behavior of polymers.In particular,insightful studies on the commonly used naphthalene diimide-based acceptor polymers and the newly emerging polymerized nonfullerene small molecule acceptors(ITIC-series,Y6-series,etc)are discussed in detail.Finally,we present an outlook on the major challenges and the new opportunities of All-PSCs for efficiency breakthroughs targeting 20%.展开更多
A series of novel poly(amide-imide)(PAl)films with different amide contents were prepared from pyromellitic dianhydride and four amide-containing diamines.These PAl films exhibited excellent mechanical and thermal pro...A series of novel poly(amide-imide)(PAl)films with different amide contents were prepared from pyromellitic dianhydride and four amide-containing diamines.These PAl films exhibited excellent mechanical and thermal properties with tensile strength of 203.7-297.4 MPa and Tg above 407℃.The rigid backbone structures combined with strong intermolecular interactions provided PAl films with ultralow in-plane CTE values from-4.17 ppm/℃to-0.39 ppm/℃in the temperature range of 30-300℃.The correlation between thermal expansion behavior and aggregation structures of PAl film was investigated.The results suggested that hydrogen bonding interactions could be maintained even at high temperature,thus resulting in good dimension reversibility of films in multiple heating-cooling cycles.It is demonstrated that dimensional stabilities of PAl films are determined by the rigidity,orientation,and packing of molecular chains.Heat-resistant PAl films with ultralow CTE can be developed as flexible substrates by regulating backbones and aggregation structures for optoelectronic application.展开更多
The kinetics of the hydrolysis of p-nitrophenyl esters of three types of single-chain carbo- xylic acids, namely, saturated, olefinic and acetylenic, was investigated in two aquiorgano binary sol- vent systems, DMSO-H...The kinetics of the hydrolysis of p-nitrophenyl esters of three types of single-chain carbo- xylic acids, namely, saturated, olefinic and acetylenic, was investigated in two aquiorgano binary sol- vent systems, DMSO-H_2O and dioxane (DX)-H_2O. The ester probes used are: octanoie (C8), do- decanoic (C12), stearic (C18), oleic (C18-ol), elaidic (C18-el) and stearolic (C18-st). The order of measured CAgC values is: C18-ol>C18-el>C18>C18-st, whereas the order of decreasing magnitude of the observed hydrolytic rate constants of the monomeric species (km) is: C18 >C18-el>C18-ol> C18-st. These rather unanticipated results are discussed.展开更多
Thienoacenes is one of most important groups of semiconducting materials due to the high stability and superior mobility.However,there are scarce studies on the emission properties of thienoacenes to date.Herein,we sy...Thienoacenes is one of most important groups of semiconducting materials due to the high stability and superior mobility.However,there are scarce studies on the emission properties of thienoacenes to date.Herein,we synthesized fluorinated and chlorinated dibenzo[d,d’]thieno[3,2-b;4,5-b’]dithiophenes(DBTDTs)derivatives F6-DBTDT and Cl6-DBTDT by sulfoxide cyclization,significantly lowering the energy levels relative to the parent compound DBTDT.According to single crystal structure analysis,F6-DBTDT molecules adopt one-dimensional slipped stacking with closeπ-πinteractions of 3.43Å(1Å=0.1 nm),which is different from the parent compound DBTDT with herringbone stacking motif.Interestingly,the halogenated DBTDT derivatives exhibit enhanced emission properties both in solution and in the solid state,opening up possiblities to improve photoluminescence of thienoacences by halogenation.展开更多
基金National Natural Science Foundation of China,Grant/Award Number:52073207National Key Research and Development Program of China,Grant/Award Number:2019YFA0705900MOST and the Basic and Applied Basic Research Major Program of Guangdong Province,Grant/Award Number:2019B030302007。
文摘π-Conjugated organic/polymer materials-based solar cells have attracted tremendous research interest in the fields of chemistry,physics,materials science,and energy science.To date,the best-performance polymer solar cells(PSCs)have achieved power conversion efficiencies exceeding 18%,mostly driven by the molecular design and device structure optimization of the photovoltaic materials.This review article provides a comprehensive overview of the key advances and current status in aggregated structure research of PSCs.Here,we start by providing a brief tutorial on the aggregated structure of photovoltaic polymers.The characteristic parameters at different length scales and the associated characterization techniques are overviewed.Subsequently,a variety of effective strategies to control the aggregated structure of photovoltaic polymers are discussed for polymer:fullerene solar cells and polymer:nonfullerene small molecule solar cells.Particularly,the control strategies for achieving record efficiencies in each type of PSCs are highlighted.More importantly,the in-depth structure-performance relationships are demonstrated with selected examples.Finally,future challenges and research prospects on understanding and optimizing the aggregated structure of photovoltaic polymers and their blends are provided.
基金supported by the Japan Society for the Promotion of Science(JSPS)KAKENHI(Grant Nos.JP17H06144 and JP19K23617)the Institute for Chemical Reaction Design and Discovery(ICReDD)established by World Premier International Research Initiative(WPI),MEXT,Japan.
文摘Biological soft tissues and hydrogels belong to the same category of soft and wet matter.Both of them are composed of polymer network and a certain amount of water,and permeable to small molecules.Biological tissues possess elaborated structures and exhibit outstanding functionalities.On the other hand,hydrogels are usually amorphous with poor functionality.In recent years,various hydrogels with robust functionalities have been developed by introducing aggregated structures into the gel networks,widely extend their applications in diverse fields,such as soft actuators,biological sensors,and structural biomaterials.Four strategies are usually used to fabricate aggregated structure into hydrogels,including molecular self-assembling,microphase separation,crystallization,and inorganic additives.Different aggregated structures entail the gel very different functionalities.A simple aggregated structure is able to bring multiple functionalities and a combination of mechanical performances of the hydrogels.In this review,we describe the strategies used to construct aggerated structure in hydrogels and discuss about the close relation between the aggregated structure and functionality.We also highlight the role of nonequilibrium aggregated structure in fabricating hydrogels with dynamic memorizing-forgetting behavior and point out the remaining challenges.
基金The Project was supported by the National Key Projects for Fundamental Research"Macromolecular Condensed State",The State Science and Technology Commission of China
文摘The structural parameters of the aggregated state of polyamide (PA)-1010 annealed at various temperatures were computed by means of the desmearing intensity from Smalt Angle X-ray Scattering (SAXS) measurements and by using the concept of the distance distribution function. The results indicated that the structural parameters of the aggregated state were strongly dependent upon heat treatment conditions and the maximum values of the structural parameters were obtained for the samples annealed at T = 175 degrees C. The particle size Z annealed at different temperature was ranged between 8.1-12.8nm, and the values of the distance distribution function P-max(Z) were obtained when Z = 4.0-6.8 nm. Using one dimension electron density correlation function (1D EDCF) method long period (L) and thickness of the lamellar (d(0)) were estimated and were found to increase with the increase of the degree of crystallinity.
基金Supported by the Youth Research Fund of Beijing Institute of Petrochemical Technology(No.N07-04)
文摘The aggregation behavior and structure of hydrophobically modified block copolymers of acrylamide and 2-phenoxylethylacrylate were investigated by viscometry, 1H NMR relaxation, 2D NOESY, fluorescence and dynamic light scattering. It Was found that the aggregation behavior was strongly dependent on the concentration of polymer solution and the hydrophobe contents. With varying concentration from 2.0, 6.0, 8.0 to 12.0 g/L, there were different aggregate morphologies distributed in aqueous solutions, such as monopolymer chain, micelle-like aggregate, multi-micelle aggregate and cross-linked network. According to the model of aggregation, it can give a reasonable explanation on the large magnitude enhancement of viscosity with the increasing of polymer concentration. Additional data of 2D NOESY and fluorescence show that the copolymer with higher hydrophobe content(molar fraction≥ 1%) is likely to form intra-molecular association.
文摘The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N'-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the conformation simulations from AM1 semi-empirical quantum mechanics modeling. The results showed that in the solid film 1 molecules stacked with the perfluorinated phenyl groups straightly over or below the perylene cores of the adjacent 1 molecules.
文摘Compacting process of fine powder is greatly affected by the aggregate structure of particles. According to the experiment in which several kinds of silicon nitrides in different partical shape and size were compacted in uniaxialorientation, it is found that the volume compacting rate offorming body differs with the pressure. The aggregatestructure of each sample A, B or C was estimated by applying Cooper's equation to the analysis of the compacting process of each sample
文摘The structure of aggregation state and isothermal crystallization behavior of Nylon-1010 have been studied by WAXD, DSE, Variance-Range Function and density measurement. The results show that crystallization of Nylon-1010 has the most suitable annealing temperature, the crystals of the Nxlon-1010 are two-dimension heterogeneous nucleation. Both low treatment temperature and high crystallization te, temperature are disadvantageous for Nylon-1010 crystal growth.
文摘A series of hydrophobically associating polyacrylamides modified by small amounts (〈 3 mol%) of a self- associative cationic monomer 4-(2-(acryloyloxy) ethoxy) benzyl tri-ethyl ammonium bromide (AEBA) as hydrophobe were synthesized by radical copolymerization in aqueous solutions without external surfactants. The resulting eopolymers containing a multiblock structure exhibited a high tendency for hydrophobic association and a high thickening capacity. Solution properties and aggregation structures were investigated by viscometry and fluorescence technique. The high viscosity enhancement was found as the polymer concentration beyond a critical value c* and strongly depended on the copolymer microstructures. The number and length of hydrophobic microblocks within the copolymer backbones could be controlled by changing the AEBA concentration in copolymerization system. Addition of salt induced more hydrophobic association and viscosity enhancement. The synthesis method used was simple and environmentally friendly without any external surfactant contamination in comparison with the conventional micellar copolymerization.
文摘A novel associating polymer P(AEBA) was synthesized by radical polymerization of the cationic amphiphilic monomer,4-(2-(acryloyloxy)ethoxy)benzyl tri-ethyl ammonium bromide(AEBA),in aqueous solutions.P(AEBA) displays a strong tendency for self-association in aqueous solutions and is sensitive to the external stimulation such as added salt.The associative properties and morphologies of P(AEBA) were studied by fluorescnece probe technique,viscometry and TEM.In dilute salt-free solutions P(AEBA) behaves as pol...
基金Supported by the National Natural Science Foundation of China(21572001)the Natural Science Foundation from Bureau of Education of Anhui Province(KJ2013A063)the Anhui Province Undergraduate Innovation and Entrepreneurship Training Program(201510360119)
文摘An ionic iridium(Ⅲ) complex[Ir(F2dpyb)(bzdpp)2Cl][OTf]with 1,3-difluoro-4,6-di(2-pyridinyl) benzene(F2dpybH) terdentate ligand and benzyldiphenylphosphine(bzdpp)ligand was synthesized and characterized.The structure of iridium complex was verified by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/n with a =14.3654(7),b = 23.0026(10),c = 15.7964(7) A°,β = 97.6029(11),V= 5173.9(4) A°3,Z = 4,F(000) =2552,Dc = 1.645 Mg/m^3,Mr = 1281.49 and μ = 0.071 mm^-1.The UV-vis absorption and phosphorescence of the complex were discussed.The complex was 'aggregation induced emission(AIE)' active.It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation.The complex emitted a strong phosphorescence centered at493 nm when doped in PMMA.Its lifetime is 0.755 μs and quantum yield is approximately 0.134.
基金Funded by the National Natural Science Foundation of China(Nos.51778003 and 51308004)the Project of Anhui Provincial Education Department for Sending Visiting Scholars to Research Abroad(No.gxfx ZD2016134)+1 种基金the Anhui Province Higher Education Revitalization Program Talent Project([2014]No.11)the National Key Research and Development Plan(No.2017YFB0310001)
文摘The influence of air-cooled blast furnace slag aggregates as replacement of natural aggregates on the water absorption of concrete and mortar was studied, and the mechanism was analyzed. The interface between aggregate and matrix in concrete was analyzed by using a micro-hardness tester, a laser confocal microscope and a scanning electron microscope with backscattered electron image mode. The pore structure of mortar matrixes under different curing conditions was investigated by mercury intrusion porosimetry. The results showed that when natural aggregates were replaced with air-cooled blast furnace slag aggregates in mortar or concrete, the content of the capillary pore in the mortar matrix was reduced and the interfacial structure between aggregate and matrix was improved, resulting in the lower water absorption of mortar or concrete. Compared to the concrete made with crushed limestone and natural river sand, the initial absorption coefficient, the secondary absorption coefficient and the water absorption capacity through the surface for 7 d of the concrete made from crushed air-cooled blast furnace slag and air-cooled blast furnace slag sand were reduced by 48.9%, 52.8%, and 46.5%, respectively.
文摘The aging characteristics of the XLPE insulation of 110 kV power cables in the initial stage of operation are studied in this paper.The XLPE insulation from cables with different running time was tested by using electrical and physicochemical methods,from which the degradation state of XLPE under multiple stresses during operation was derived.The broadband dielectric spectrum test taken from 10–1 to 10^(6) Hz showed that the dielectric constant and dielectric loss of the XLPE insulation first decrease and then increase with the increase of cable running time,which show obvious variation until 10 years of operation.The AC breakdown strengths of the XLPE insulation of operated cables with the service year no longer than 10 years were higher than that of new cables.The mechanical properties of the XLPE insulation showed no dependence with the cable running time.The crystallinity and perfection of the crystallization area were found to be enhanced during operation and the polar functional groups inside the XLPE insulation were found to be determined not only by the cross-linking by-products but also by the oxidation process during cable operation.The experimental results in this paper are important for improving the operation reliability and reducing the maintenance costs of the cables.
基金financially supported by the National Natural Science Foundation of China (No.51803221)。
文摘Polyimide films derived from representative PMDA/ODA were prepared with thickness ranging from 5 μm to 25 μm,and the effect of aggregation structure on thermal expansion behavior along different directions was studied.Both in-plane and out-of-plane linear thermal expansion(CTEand CTE) were respectively characterized by thermal mechanical analysis and FT-near-IR interference method.Volumetric and anisotropic behavior of thermal expan sion were also investigated.With increasing film thickness,CTEgradually increased from 32.2 ppm/℃ to46.1 ppm/℃ while CTEdecreased from 149.7 ppm/℃ to 128.2 ppm/℃.Volumetric thermal expansion of polyimide films was less sensitive to the va ried thickness,but anisotropy of thermal expansion was reduced.Polyimide film of 5 μm thickness showed large birefringence,indicating more considerable in-plane chain orientation anisotropy.Besides,molecular chains were more densely packed along in-plane direction when film thickness increased,while became loosely stacked in the out-of-plane direction.In contrast to the enhanced lateral chain packing for thicker film s,higher vertical chain packing order was found in thinner films.The variation of aggregation structure during thermal expansion procedure was analyzed by temperature-dependent WAXD.It is proved that thermal expansion behavior of thinner films could be largely attributed to molecular chain packing,whereas that may be influenced by many factors for thicker films in addition to the effect of chain packing.The results revealed that thermal expansion of films with thickness variation is closely related to molecular chain orientation and packing,which is associated with both chemistry and morphological structure of polyimide.
基金financially supported by the National Key Research and Development Program of China(No.2022YFB3603105)Key Programs of the Chinese Academy of Sciences(No.ZDRW-CN-2023-3-2)+1 种基金the National Natural Science Foundation of China(No.51803221)Natural Science Foundation of Beijing Municipality(No.2202068)。
文摘The traditional high-temperature preparation process of polyimide can cause many problems and limits the wider application in extreme conditions.An important challenge to be solved urgently is the reduction of imidization temperature.In this work,twelve kinds of polyimide films with different chain rigidity were prepared at low temperature of 200℃,in the absence or presence of imidazole used as the catalyst.The molecular rigidity and free volume were theoretically calculated,and relationship between structure and properties were systematically studied.The results show that imidization reaction under low temperatures is significantly affected by the rigidity of molecula r chains.The rigid structure of polyimide is not conducive to the low-temperature imidization,but this adverse effect can be eliminated by adding catalyst,resulting the notably increased imidization degree.The optical and thermal properties can be improved to a certain extent for the chemically catalyzed system,resulting in relatively higher heat resistance and thermal stability.While the mechanical performance could be determined by com plicating factors,greatly different from polyimide films prepa red by high temperature method.To investigate aggregation structures of film s,the effect of chain rigidity and catalyst on the stacking or orientation of molecular chains was further elaborated.This wo rk can contribute to the understanding of chemically catalyzed imidization that is rarely reported in the existing research,and will provide guidance for the low-temperature preparation of high-performance polyimides.
基金National Natural Science Foundation of China,Grant/Award Number:52073207State Key Laboratory of Applied Optics,Grant/Award Number:SKLAO2021001A17Peiyang Scholar program from Tianjin University。
文摘All-polymer solar cells(All-PSCs)have attracted tremendous research interest in the recent decade due to the great potentials in stretchable electronic applications in terms of long-term stability and mechanical stretchability.Driven by the molecular design of novel polymer acceptors and morphology optimization,the power conversion efficiency(PCE)of All-PSCs has developed rapidly and now exceeded 17%.This review outlines the promising strategies for high-performance All-PSCs from the aspect of morphology control with the motivation to rationally guide the optimization.In this review,we briefly discuss the thermodynamic mixing principles of all-polymer blends and the effects of the molecular structure of conjugated polymers on thin-film morphology in All-PSCs.The crucial role of molecular miscibility in influencing morphological features and performance metrics was highlighted.We also expound on the effective methods of controlling film morphology through properly tuning the aggregation behavior of polymers.In particular,insightful studies on the commonly used naphthalene diimide-based acceptor polymers and the newly emerging polymerized nonfullerene small molecule acceptors(ITIC-series,Y6-series,etc)are discussed in detail.Finally,we present an outlook on the major challenges and the new opportunities of All-PSCs for efficiency breakthroughs targeting 20%.
基金This work was financially supported by the National Natural Science Foundation of China(No.51803221).
文摘A series of novel poly(amide-imide)(PAl)films with different amide contents were prepared from pyromellitic dianhydride and four amide-containing diamines.These PAl films exhibited excellent mechanical and thermal properties with tensile strength of 203.7-297.4 MPa and Tg above 407℃.The rigid backbone structures combined with strong intermolecular interactions provided PAl films with ultralow in-plane CTE values from-4.17 ppm/℃to-0.39 ppm/℃in the temperature range of 30-300℃.The correlation between thermal expansion behavior and aggregation structures of PAl film was investigated.The results suggested that hydrogen bonding interactions could be maintained even at high temperature,thus resulting in good dimension reversibility of films in multiple heating-cooling cycles.It is demonstrated that dimensional stabilities of PAl films are determined by the rigidity,orientation,and packing of molecular chains.Heat-resistant PAl films with ultralow CTE can be developed as flexible substrates by regulating backbones and aggregation structures for optoelectronic application.
基金Project supported by the National Natural Science Foundation of China.
文摘The kinetics of the hydrolysis of p-nitrophenyl esters of three types of single-chain carbo- xylic acids, namely, saturated, olefinic and acetylenic, was investigated in two aquiorgano binary sol- vent systems, DMSO-H_2O and dioxane (DX)-H_2O. The ester probes used are: octanoie (C8), do- decanoic (C12), stearic (C18), oleic (C18-ol), elaidic (C18-el) and stearolic (C18-st). The order of measured CAgC values is: C18-ol>C18-el>C18>C18-st, whereas the order of decreasing magnitude of the observed hydrolytic rate constants of the monomeric species (km) is: C18 >C18-el>C18-ol> C18-st. These rather unanticipated results are discussed.
基金supported by the Fundamental Research Funds for the Central Universities,China(No.buctrc202103)the National Natural Science Foundation of China(Nos.21975263,22171019,52373170)+2 种基金the Project of the China Petroleum and Chemical Corporation(No.222131)the Open Project Programs of Wuhan National Laboratory for Optoelectronics,China(No.2021WNLOKF005)the Project of the State Key Laboratory of Fine Chemicals(Dalian University of Technology),China(No.KF2201).
文摘Thienoacenes is one of most important groups of semiconducting materials due to the high stability and superior mobility.However,there are scarce studies on the emission properties of thienoacenes to date.Herein,we synthesized fluorinated and chlorinated dibenzo[d,d’]thieno[3,2-b;4,5-b’]dithiophenes(DBTDTs)derivatives F6-DBTDT and Cl6-DBTDT by sulfoxide cyclization,significantly lowering the energy levels relative to the parent compound DBTDT.According to single crystal structure analysis,F6-DBTDT molecules adopt one-dimensional slipped stacking with closeπ-πinteractions of 3.43Å(1Å=0.1 nm),which is different from the parent compound DBTDT with herringbone stacking motif.Interestingly,the halogenated DBTDT derivatives exhibit enhanced emission properties both in solution and in the solid state,opening up possiblities to improve photoluminescence of thienoacences by halogenation.