Assembling of a few particles into a cluster commonly occurs in many systems.However,it is still challenging to precisely control particle assembling,due to the various amorphous structures induced by thermal fluctuat...Assembling of a few particles into a cluster commonly occurs in many systems.However,it is still challenging to precisely control particle assembling,due to the various amorphous structures induced by thermal fluctuations during cluster formation.Although these structures may have very different degrees of aggregation,a quantitative method is lacking to describe them,and how these structures evolve remains unclear.Therefore a significant step towards precise control of particle self-assembly is to describe and analyze various aggregation structures during cluster formation quantitatively.In this work,we are motivated to propose a method to directly count and quantitatively compare different aggregated structures.We also present several case studies to evaluate how the aggregated structures during cluster formation are affected by external controlling factors,e.g.,different interaction ranges,interaction strengths,or anisotropy of attraction.展开更多
Donor–acceptor(D-A)conjugated polymers have demonstrated great potential in organicfield-effect transistors application,and their aggregated structure is a crucial factor for high charge mobility.However,the aggregat...Donor–acceptor(D-A)conjugated polymers have demonstrated great potential in organicfield-effect transistors application,and their aggregated structure is a crucial factor for high charge mobility.However,the aggregated structure of D-A conjugated polymerfilms is complex and the structure–property relationship is difficult to understand.This review provides an overview of recent progress in controlling the aggregated structure of D-A conjugated polymerfilms for higher mobility,including the mechanisms,methods,and properties.Wefirst discuss the multilevel microstructures of D-A conjugated polymerfilms,and then summarize the current understanding of the relationship betweenfilm microstructures and charge transport properties.Subsequently,we review the theory of D-A conjugated polymer crystallization.After that,we summarize the common methods to control the aggregated structure of semi-crystalline and near-amorphous D-A conjugated polymerfilms,such as crystallites and aggregates,tie chains,film alignment,and attempt to understand them from the basic theory of polymer crystallization.Finally,we provide the current challenges in controlling the aggregated structure of D-A conjugated polymerfilms and in understanding the structure–property relationship.展开更多
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 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
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
Vitrimers have emerged as a prominent research area in the field of polymer materials.Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures,while the impact of chemic...Vitrimers have emerged as a prominent research area in the field of polymer materials.Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures,while the impact of chemical structure on aggregate structure of vitrimers,particularly during polymer processing,remains insufficiently investigated.The present study employed commercial maleic anhydride-grafted-high density polyethylene(M-g-HDPE)as the matrix and hexanediol as the crosslinker to facilely obtain fiber-shaped HDPE vitrimers through a reaction extrusion and post-drawing process.Through chemical structure characterization,morphology observation,thermal and mechanical properties investigation,as well as aggregate structure analysis,this work revealed the influence of dynamic bonds on the formation of aggregate structures during fiber-shaped vitrimers processing.A small amount of dynamic bonds in HDPE restricts the motion of PE chain during melt-extruding and post-drawing,resulting in a lower orientation of the PE chains.However,lamellar growth and fibril formation during post-drawing at high temperature are enhanced to some extent due to the competition between dynamic bond and chain relaxation.The uneven morphology of fibershaped HDPE vitrimers can be attributed to the stronger elastic effect brought by dynamic bonding,which plays a more dominant role in determining the mechanical properties of fiber-shaped vitrimers compared to aggregate structure.Abstract Vitrimers have emerged as a prominent research area in the field of polymer materials.Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures,while the impact of chemical structure on aggregate structure of vitrimers,particularly during polymer processing,remains insufficiently investigated.The present study employed commercial maleic anhydride-grafted-high density polyethylene(M-g-HDPE)as the matrix and hexanediol as the crosslinker to facilely obtain fiber-shaped HDPE vitrimers through a reaction extrusion and post-drawing process.Through chemical structure characterization,morphology observation,thermal and mechanical properties investigation,as well as aggregate structure analysis,this work revealed the influence of dynamic bonds on the formation of aggregate structures during fiber-shaped vitrimers processing.A small amount of dynamic bonds in HDPE restricts the motion of PE chain during melt-extruding and post-drawing,resulting in a lower orientation of the PE chains.However,lamellar growth and fibril formation during post-drawing at high temperature are enhanced to some extent due to the competition between dynamic bond and chain relaxation.The uneven morphology of fibershaped HDPE vitrimers can be attributed to the stronger elastic effect brought by dynamic bonding,which plays a more dominant role in determining the mechanical properties of fiber-shaped vitrimers compared to aggregate structure.展开更多
The accumulation of soil organic carbon(SOC)and total nitrogen(TN)is easily accomplished by returning crop straw,which strongly affects the formation and pore structure of aggregates,especially in black soil.We return...The accumulation of soil organic carbon(SOC)and total nitrogen(TN)is easily accomplished by returning crop straw,which strongly affects the formation and pore structure of aggregates,especially in black soil.We returned maize straw at different rates(6,000,9,000,12,000 and 15,000 kg ha^(-1))for nine years to investigate its influence on the SOC and TN contents in the SOC fractions of aggregates by combining size and density fractionation.Their subsequent influences on pore morphology and size distribution characteristics were examined using X-ray microcomputed tomography scanning(μCT).The results showed that returning straw significantly increased the contents of C and N in the SOC fractions of aggregates,especially at the return rates of 12,000 and 15,000 kg ha^(-1),which in turn promoted aggregate formation and stability,and ultimately amended pore structure.The pore size>100μm,porosity(>2μm),and morphological characteristics(anisotropy,circularity,connectivity and fractal dimension)significantly increased,but the total number of pores significantly decreased(P<0.05).Our results indicated that the amendment of the pore morphology and size distribution of soil aggregates was primarily controlled by the higher contents of C and N in the density fractions of aggregates,rather than in the aggregate sizes.Furthermore,this pore network reconfiguration favored the storage of C and N simultaneously.The findings of this study offer valuable new insights into the relationships between C and N storage and the pore characteristics in soil aggregates under straw return.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 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
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 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
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 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
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
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
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
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
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 aggregation process plays a significant role in regulating the aggregate structures from molecules toward macroscopic photophysical properties.Pyrene(Py),as the simplest dimer candidate,serves as a suitable model ...The aggregation process plays a significant role in regulating the aggregate structures from molecules toward macroscopic photophysical properties.Pyrene(Py),as the simplest dimer candidate,serves as a suitable model for studying the aggregation.Herein,a series of Py-based aggregation-induced emission(AIE)materials have been investigated by clarifying the comprehensive roles of oxygen,substituents,molecular motion,and packing during aggregation,initially realizing the aim of controlling aggregate structures.With a largely planar and conjugated conformation,Py shows anomalous AIE characteristics due to the oxygen quenching at the molecular level but turn-on fluorescence in the aggregate state because of the oxygen isolation.Although introducing substituents induces molecular motion and similarly weakened luminescence in the molecular state,the impact of substituents on the aggregate-state photophysical properties enormously differs,exhibiting from weak blue,strong cyan,and strong green to weak yellow emissions,due to variable aggregate structures.Interestingly,the natural alicycle-substituted Py-dehydroabietylamine(Py-DAA)exhibits both mechanochromism and acidichromism,which can be synergistically applied in dynamic encryption-decryption.This work not only elucidates the unique AIE property of Py for the first time but also clarifies the bridging role of aggregation between single-molecular and aggregate states,achieving preliminary control over the aggregate structures.展开更多
文摘Assembling of a few particles into a cluster commonly occurs in many systems.However,it is still challenging to precisely control particle assembling,due to the various amorphous structures induced by thermal fluctuations during cluster formation.Although these structures may have very different degrees of aggregation,a quantitative method is lacking to describe them,and how these structures evolve remains unclear.Therefore a significant step towards precise control of particle self-assembly is to describe and analyze various aggregation structures during cluster formation quantitatively.In this work,we are motivated to propose a method to directly count and quantitatively compare different aggregated structures.We also present several case studies to evaluate how the aggregated structures during cluster formation are affected by external controlling factors,e.g.,different interaction ranges,interaction strengths,or anisotropy of attraction.
基金National Natural Science Foundation of China,Grant/Award Numbers:51933010,22203028。
文摘Donor–acceptor(D-A)conjugated polymers have demonstrated great potential in organicfield-effect transistors application,and their aggregated structure is a crucial factor for high charge mobility.However,the aggregated structure of D-A conjugated polymerfilms is complex and the structure–property relationship is difficult to understand.This review provides an overview of recent progress in controlling the aggregated structure of D-A conjugated polymerfilms for higher mobility,including the mechanisms,methods,and properties.Wefirst discuss the multilevel microstructures of D-A conjugated polymerfilms,and then summarize the current understanding of the relationship betweenfilm microstructures and charge transport properties.Subsequently,we review the theory of D-A conjugated polymer crystallization.After that,we summarize the common methods to control the aggregated structure of semi-crystalline and near-amorphous D-A conjugated polymerfilms,such as crystallites and aggregates,tie chains,film alignment,and attempt to understand them from the basic theory of polymer crystallization.Finally,we provide the current challenges in controlling the aggregated structure of D-A conjugated polymerfilms and in understanding the structure–property relationship.
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financially supported by the National Natural Science Foundation of China(Nos.22278065 and 22073015)。
文摘Vitrimers have emerged as a prominent research area in the field of polymer materials.Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures,while the impact of chemical structure on aggregate structure of vitrimers,particularly during polymer processing,remains insufficiently investigated.The present study employed commercial maleic anhydride-grafted-high density polyethylene(M-g-HDPE)as the matrix and hexanediol as the crosslinker to facilely obtain fiber-shaped HDPE vitrimers through a reaction extrusion and post-drawing process.Through chemical structure characterization,morphology observation,thermal and mechanical properties investigation,as well as aggregate structure analysis,this work revealed the influence of dynamic bonds on the formation of aggregate structures during fiber-shaped vitrimers processing.A small amount of dynamic bonds in HDPE restricts the motion of PE chain during melt-extruding and post-drawing,resulting in a lower orientation of the PE chains.However,lamellar growth and fibril formation during post-drawing at high temperature are enhanced to some extent due to the competition between dynamic bond and chain relaxation.The uneven morphology of fibershaped HDPE vitrimers can be attributed to the stronger elastic effect brought by dynamic bonding,which plays a more dominant role in determining the mechanical properties of fiber-shaped vitrimers compared to aggregate structure.Abstract Vitrimers have emerged as a prominent research area in the field of polymer materials.Most of the studies have focused on synthesizing polymers with versatile dynamic crosslinking structures,while the impact of chemical structure on aggregate structure of vitrimers,particularly during polymer processing,remains insufficiently investigated.The present study employed commercial maleic anhydride-grafted-high density polyethylene(M-g-HDPE)as the matrix and hexanediol as the crosslinker to facilely obtain fiber-shaped HDPE vitrimers through a reaction extrusion and post-drawing process.Through chemical structure characterization,morphology observation,thermal and mechanical properties investigation,as well as aggregate structure analysis,this work revealed the influence of dynamic bonds on the formation of aggregate structures during fiber-shaped vitrimers processing.A small amount of dynamic bonds in HDPE restricts the motion of PE chain during melt-extruding and post-drawing,resulting in a lower orientation of the PE chains.However,lamellar growth and fibril formation during post-drawing at high temperature are enhanced to some extent due to the competition between dynamic bond and chain relaxation.The uneven morphology of fibershaped HDPE vitrimers can be attributed to the stronger elastic effect brought by dynamic bonding,which plays a more dominant role in determining the mechanical properties of fiber-shaped vitrimers compared to aggregate structure.
基金the Chinese Academy of Sciences for their financial support and research facilitiesfunded by the National Key Research and Development Program of China(2022YFD1500100)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA28070100)the China Agriculture Research System of MOF and MARA(CARS04)。
文摘The accumulation of soil organic carbon(SOC)and total nitrogen(TN)is easily accomplished by returning crop straw,which strongly affects the formation and pore structure of aggregates,especially in black soil.We returned maize straw at different rates(6,000,9,000,12,000 and 15,000 kg ha^(-1))for nine years to investigate its influence on the SOC and TN contents in the SOC fractions of aggregates by combining size and density fractionation.Their subsequent influences on pore morphology and size distribution characteristics were examined using X-ray microcomputed tomography scanning(μCT).The results showed that returning straw significantly increased the contents of C and N in the SOC fractions of aggregates,especially at the return rates of 12,000 and 15,000 kg ha^(-1),which in turn promoted aggregate formation and stability,and ultimately amended pore structure.The pore size>100μm,porosity(>2μm),and morphological characteristics(anisotropy,circularity,connectivity and fractal dimension)significantly increased,but the total number of pores significantly decreased(P<0.05).Our results indicated that the amendment of the pore morphology and size distribution of soil aggregates was primarily controlled by the higher contents of C and N in the density fractions of aggregates,rather than in the aggregate sizes.Furthermore,this pore network reconfiguration favored the storage of C and N simultaneously.The findings of this study offer valuable new insights into the relationships between C and N storage and the pore characteristics in soil aggregates under straw return.
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 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.
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.
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.
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.
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supported by the National Natural Science Foundation of China(21601087)the Natural Science Foundation of Jiangsu Province(BK20231296)+3 种基金the Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Guangzhou 510640,China(South China University of Technology[2023B1212060003])the Shenzhen Key Laboratory of Functional Aggregate Materials(ZDSYS20211021111400001)the Science Technology Innovation Commission of Shenzhen Municipality(KQTD20210811090142053)the Key Research and Development Project of Yunnan Province(202303AC100010).
文摘The aggregation process plays a significant role in regulating the aggregate structures from molecules toward macroscopic photophysical properties.Pyrene(Py),as the simplest dimer candidate,serves as a suitable model for studying the aggregation.Herein,a series of Py-based aggregation-induced emission(AIE)materials have been investigated by clarifying the comprehensive roles of oxygen,substituents,molecular motion,and packing during aggregation,initially realizing the aim of controlling aggregate structures.With a largely planar and conjugated conformation,Py shows anomalous AIE characteristics due to the oxygen quenching at the molecular level but turn-on fluorescence in the aggregate state because of the oxygen isolation.Although introducing substituents induces molecular motion and similarly weakened luminescence in the molecular state,the impact of substituents on the aggregate-state photophysical properties enormously differs,exhibiting from weak blue,strong cyan,and strong green to weak yellow emissions,due to variable aggregate structures.Interestingly,the natural alicycle-substituted Py-dehydroabietylamine(Py-DAA)exhibits both mechanochromism and acidichromism,which can be synergistically applied in dynamic encryption-decryption.This work not only elucidates the unique AIE property of Py for the first time but also clarifies the bridging role of aggregation between single-molecular and aggregate states,achieving preliminary control over the aggregate structures.
