Liangbin Li

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Name: 李良彬; Li, LiangBin
Organization: University of Science and Technology of China , China
Department: National Synchrotron Radiation Lab and College of Nuclear Science and Technology
Title: Professor(PhD)

TOPICS

Co-reporter:Lixian Song, Zhen Wang, Xiaoliang Tang, Liang Chen, Pinzhang Chen, Qingxi Yuan, and Liangbin Li
Macromolecules September 26, 2017 Volume 50(Issue 18) pp:7249-7249
Publication Date(Web):September 8, 2017
DOI:10.1021/acs.macromol.7b00539
Adding silica nanofiller in silicone rubber can toughen the matrix 3 orders in terms of fracture energy, which is far larger than most other nanofiller–rubber systems. To unveil the astonishing toughening mechanism, we employ in situ synchrotron radiation X-ray nanocomputed tomography (Nano-CT) technique with high spatial resolution (64 nm) to study the structural evolution of silica nanofiller in silicone rubber matrix at different strains. The imaging results show that silica nanofiller forms three-dimensional connected network, which couples with silicone chain network to construct a double-network structure. Stress-induced phase separation between silica nanofiller and silicone polymer chain networks is observed during tensile deformation. Unexpectedly, though the spatial position and morphology of nanofiller network changes greatly at large strains, the connectivity of nanofiller network shows negligible reduction. This indicates that nanofiller network undergoes destruction and reconstruction simultaneously, during which silica nanofiller serves as reversible high functionality cross-linker. The reversible bonding between silica nanofiller and silicone rubber or between nanofiller particles can dissipate mechanical energy effectively, which may account for the 3 orders enhancement of toughness.
Co-reporter:Fei Lv, Xiaowei Chen, Caixia Wan, Fengmei Su, Youxin Ji, Yuanfei Lin, Xueyu Li, and Liangbin Li
Macromolecules September 12, 2017 Volume 50(Issue 17) pp:6385-6385
Publication Date(Web):August 29, 2017
DOI:10.1021/acs.macromol.7b01153
Temperature effects on deformation behaviors of extracted ultrahigh molecular weight polyethylene (UHMWPE) precursor fibers are studied with the in situ synchrotron radiation wide-angle X-ray scattering technique (WAXS) during tensile deformation at temperatures from 25 to 130 °C. The structural and mechanical evolution behaviors during tensile deformation can be divided into four temperature regions with boundaries located at temperatures of αI and αII relaxations and the onset of melting, respectively, which reveal that the deformation behaviors of polymer crystals are determined by the interplay between intrinsic structural dynamic or chains mobility and external stress field. Irrespective of temperature, yield and strain-softening proceed via partial melting while crystal slip via cutting crystal planes occurs in the strain-hardening zone. Finally we construct morphological diagrams containing crystallinity, crystal size, and orientation in temperature–strain space, which may serve as a roadmap for UHMWPE fibers processing.
Co-reporter:Ling-pu Meng;Xiao-wei Chen;Yuan-fei Lin
Chinese Journal of Polymer Science 2017 Volume 35( Issue 9) pp:1122-1131
Publication Date(Web):05 July 2017
DOI:10.1007/s10118-017-1965-y
Young’s modulus of biaxially oriented polypropylene (BOPP) films prepared with homemade film stretcher was investigated, which can be used to indicate the softness of films. It was found that the modulus of films was decreased by about 69% as the content of polyethylene (PE) added into polypropylene (PP) reached 30%. Also, increasing draw temperature can induce lower stress level during stretching, which may lead to the formation of crystals with low orientation level and thus decreased modulus of films. Based on laboratory study, BOPP films produced on commercial line were studied by differential scanning calorimetry (DSC), wide and small-angle X-ray scattering (WAXS, SAXS) with varying contents of PE. SAXS results show that the crystals are oriented in both machine direction (MD) and transverse direction (TD), and the crystals are more oriented in TD than MD according to the WAXS results for all films. Also, the orientation parameter of crystal along TD increases from 0.68 to 0.83 as the contents of PE increase from 0% to 25%. Meanwhile, the modulus of films in MD declines with increase of PE contents generally, improving the film softness. Orientation of crystals is thus an effective structure parameter to adjust the film softness. The relationship of processing-structure-property is also established.
Co-reporter:Liang Chen, Weiming Zhou, Fengmei Su, Wenhua Zhang, Pinzhang Chen, Youxin Ji, Liangbin Li
Polymer 2017 Volume 115(Volume 115) pp:
Publication Date(Web):21 April 2017
DOI:10.1016/j.polymer.2017.03.043
•The oscillatory distribution of crystallinity around glass bead is obtained by micro-focused scanning X-ray diffraction.•The distribution of crystallinity tends to form soft-hard double network with multi-scale hierarchical structures.•The double network increases fracture energy to three orders of magnitude as compared to the homogeneous distribution.Crystallinity distribution of natural rubber around filled micrometer-size glass beads under different strains are studied with in-situ micro-focused scanning X-ray diffraction (μ-SXRD), where the glass beads are taken to serve as a model of filler. The experimental results suggest, due to the gradient stress field around the glass bead, the oscillatory distribution of crystallinities around the glass bead tends to form soft-hard double network with multi-scale hierarchical structures and spontaneously responds to external strains. The double network spreads stress in larger region and avoids stress concentration, in which the hard domains with high crystallinities effectively sustain the external stress while the soft domains with low crystallinity store elastic energy. According to the equal strain and equal stress conditions, the quantitative calculation on enhancement factor indicates that the soft-hard double network structure can increase the fracture energy to about three orders of magnitude as comparing to that of structure with homogeneous distribution of crystallinity.Due to the gradient stress field around the glass bead, the oscillatory distribution of crystallinities around the glass bead tends to form soft-hard double network with multi-scale hierarchical structures for toughness increase, which spontaneously responds to external strains. The mesh sizes along the long axis of the network structure along its long axis decrease slightly, suggesting denser network structures forming as strains increasing from 4.0 to 5.0. According to the equal strain condition, the quantitative calculation on fracture energy enhancement factors (RE) are from 607 to 1444 times magnitude as comparing to that of structure with homogeneous distribution of crystallinity.Download high-res image (162KB)Download full-size image
Co-reporter:Jing Li, Youxin Ji, Jiarui Chang, Nan Tian, Lixian Song, Liang Chen, Liangbin Li
Polymer 2017 Volume 119(Volume 119) pp:
Publication Date(Web):16 June 2017
DOI:10.1016/j.polymer.2017.05.013
•Mechanical response of fluoroelastomer F2314 shows fast transition from yielding to strain hardening.•Unusual yielding results from destruction of CTFE-domains.•Fast strain hardening is related to formation of fibril crystal.•Destruction of CTFE-domains and formation of fibril crystal is origin of mechanical response.The mechanical response of fluoroelastomer F2314 under uniaxial extension and its relation with strain-induced structural change are investigated by mechanical analysis, in-situ small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS). Yielding of samples followed by strain hardening is found without necking. Meanwhile, the strain range of strain softening is short, which is 0.77 at 25 °C and 0.3 at 60 °C. Microscopically, solution-cast F2314 shows microphase separation and low crystallinity. Results of WAXS and SAXS indicate strain-induced formation of fibrillar crystal during strain hardening. Based on these findings, it is supposed that the fast relay between destruction of microphase separated domains and formation of fibrillar crystal is the origin of the unique mechanical response.Download high-res image (212KB)Download full-size image
Co-reporter:Jianzhu Ju, Fengmei Su, Zhen Wang, Haoran Yang, Xiaoliang Tang, Xiaowei Chen, Yankun Lv, Jie Lu, Nan Tian, Liangbin Li
Polymer 2017 Volume 131(Volume 131) pp:
Publication Date(Web):22 November 2017
DOI:10.1016/j.polymer.2017.09.059
•γ-irradiated isotactic polypropylene is prepared to study flow induced crystallization in dynamically asymmetric system.•Asymmetric relaxation of cross-linked and branching/dangling chains results in the decrease of crystallization kinetic.•Network-like parent-daughter crystals with large dimension can be induced in the dynamically asymmetric system.Extension induced crystallization of γ-irradiated isotactic polypropylene (γ-iPP) was studied with the combination of extensional rheology and in-situ wide-angle X-ray scattering (WAXS). The high gel content and markedly frequency-dependent storage modulus of γ-iPP indicates the occurrence of slight crosslinking accompanied by formation of free branching/dangling chains during irradiation. With WAXS, it is found that an abnormal slowing down of crystallization occurs when engineering stress passes its maximum. Lamellar network built of parent and daughter crystal also appears in this region, where daughter crystallization is commonly frustrated under such strong flow. Further increasing strain, crystallization is accelerated gradually and the acceleration becomes more significant after occurrence of strain-hardening. Interestingly, the orientation of crystal increases monotonically during this process. It is supposed that the difference in relaxation rate of cross-linked network and free branching/dangling chains is the origin of the abnormal deceleration and unique structure morphology.Download high-res image (317KB)Download full-size image
Co-reporter:Zhen Wang;Jianzhu Ju;Lingpu Meng;Nan Tian;Jiarui Chang;Haoran Yang;Youxin Ji;Fengmei Su
Soft Matter (2005-Present) 2017 vol. 13(Issue 19) pp:3639-3648
Publication Date(Web):2017/05/17
DOI:10.1039/C7SM00107J
Structural and morphological transitions of flow-induced crystallization (FIC) in poly(1-butene) (PB-1) melt have been studied by combining extensional rheology and in situ synchrotron radiation ultrafast wide- and small-angle X-ray scattering (WAXD/SAXS) measurements. Unexpectedly, metastable Form III is crystallized directly from the PB-1 melt by high-speed extension, which has a short lifetime of several tens of milliseconds and manifests the thermodynamic and kinetic competition among Form III, Form II and melt under flow. Relative crystallinity evolution of Form II after extension reveals a crystal melting dominated process within the observation time of 120 s even under high supercooling. This is opposite to the common case of FIC but supports the idea that flow alters the obtained crystal size and its thermodynamic stability. Additionally, a morphological transition from a flow-induced network to shish is observed by SAXS with increasing extension temperature from below to above the melting point of Form II. With above observations, we construct nonequilibrium structural and morphological diagrams of FIC in strain rate-temperature space, which may guide the industrial processing of the PB-1 material.
Co-reporter:Zhen Wang;Jianzhu Ju;Lingpu Meng;Nan Tian;Jiarui Chang;Haoran Yang;Youxin Ji;Fengmei Su
Soft Matter (2005-Present) 2017 vol. 13(Issue 19) pp:3639-3648
Publication Date(Web):2017/05/17
DOI:10.1039/C7SM00107J
Structural and morphological transitions of flow-induced crystallization (FIC) in poly(1-butene) (PB-1) melt have been studied by combining extensional rheology and in situ synchrotron radiation ultrafast wide- and small-angle X-ray scattering (WAXD/SAXS) measurements. Unexpectedly, metastable Form III is crystallized directly from the PB-1 melt by high-speed extension, which has a short lifetime of several tens of milliseconds and manifests the thermodynamic and kinetic competition among Form III, Form II and melt under flow. Relative crystallinity evolution of Form II after extension reveals a crystal melting dominated process within the observation time of 120 s even under high supercooling. This is opposite to the common case of FIC but supports the idea that flow alters the obtained crystal size and its thermodynamic stability. Additionally, a morphological transition from a flow-induced network to shish is observed by SAXS with increasing extension temperature from below to above the melting point of Form II. With above observations, we construct nonequilibrium structural and morphological diagrams of FIC in strain rate-temperature space, which may guide the industrial processing of the PB-1 material.
Co-reporter:Rui Zhang;You-xin Ji 纪又新;Qian-lei Zhang
Chinese Journal of Polymer Science 2017 Volume 35( Issue 12) pp:1508-1516
Publication Date(Web):05 September 2017
DOI:10.1007/s10118-017-2000-z
A setup of blown film machine combined with in situ synchrotron radiation X-ray diffraction measurements and infrared temperature testing is reported to study the structure evolution of polymers during film blowing. Two homemade auto-lifters are constructed and placed under the blown machine at each end of the beamline platform which move up and down with a speed of 0.05 mm/s bearing the 200 kg weight machine. Therefore, structure development and temperature changes as a function of position on the film bubble can be obtained. The blown film machine is customized to be conveniently installed with precise servo motors and can adjust the processing parameters in a wide range. Meanwhile, the air ring has been redesigned in order to track the structure information of the film bubble immediately after the melt being extruded out from the die exit. Polyethylene (PE) is selected as a model system to verify the feasibility of the apparatus and the in situ experimental techniques. Combining structure information provided by the WAXD and SAXS and the actual temperature obtained from the infrared probe, a full roadmap of structure development during film blowing is constructed and it is helpful to explore the molecular mechanism of structure evolution behind the film blowing processing, which is expected to lead to a better understanding of the physics in polymer processing.
Co-reporter:Wei Chen;Lihui Wu;Liang Chen;Zeming Qi
Journal of Applied Polymer Science 2016 Volume 133( Issue 15) pp:
Publication Date(Web):
DOI:10.1002/app.43282

ABSTRACT

The miscibility behaviors in blends of isotactic polypropylene (iPP) and polybutene-1 (PB) have been studied using in-situ FTIR imaging. The heterogeneous melt of 3/7 iPP/PB blends were formed at 250, 220, and 180°C and then quenched to the same crystallization temperature of iPP at 125°C, respectively. Evolution processes of composition distribution during crystallization were monitored according to their characteristic peaks, and the results suggest a trend from local concentration to uniform dispersion of PB fraction. Further studies of the PB fraction as the distance from the growth front of iPP spherulite indicate an irreversible phase behavior with the progress of thermal history. The cyclic melting and crystallization favor the mixing of iPP/PB blend. Meanwhile, the nonlinear growth rate of iPP spherulite is mainly responsible for compatible promotion of iPP/PB blend, which hinders the transportation of iPP chains to its growth front. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43282.

Co-reporter:Xueyu Li;Lingpu Meng;Yuanfei Lin;Xiaowei Chen;Qianlei Zhang;Rui Zhang;Lihui Wu;Wenhua Zhang
Macromolecular Chemistry and Physics 2016 Volume 217( Issue 8) pp:974-986
Publication Date(Web):
DOI:10.1002/macp.201500471
Co-reporter:Xueyu Li, Yuanfei Lin, Youxin Ji, Lingpu Meng, Qianlei Zhang, Rui Zhang, Wenhua Zhang, Liangbin Li
Polymer 2016 Volume 105() pp:264-275
Publication Date(Web):22 November 2016
DOI:10.1016/j.polymer.2016.10.043
•Combining reciprocal and real space, micropore formation mechanism of HDPE membrane is unveiled.•Deformation of oriented HDPE lamellar stacks is studied via SAXS and WAXS.•Cold stretching-morphology-performance of membrane relationship is established.•An optimal cold stretching window for HDPE microporous membrane is found.Aiming to unveil the effect of cold stretching conditions including strain and temperature on the morphology and performance of membrane product, high density polyethylene (HDPE) microporous membranes were prepared by uniaxial stretching. The evolutions of lamellar stacks and micropore formation were tracked by combining in-situ and ex-situ X-ray scattering and scanning electron microscopy methods. It was found that cold stretching strain mainly affected separation degree of lamellar stacks under strain lower than 60%, while slip of crystal at higher strain. As for cold stretching temperature, stretching below 60 °C can promote separation of lamellar stacks, while stretching over 80 °C is beneficial to pull out molecular chains from lamellae, resulting in fibrils. A linear relation between separation degree of lamellar stack and air permeability of final membrane was established, which can provide guidance for producing HDPE microporous membranes with high performance.The evolution of lamellar stacks and micropore formation mechanism were tracked by combining in-situ and ex-situ X-ray scattering and scanning electron microscopy, which provide guidance for microporous membrane preparation.
Co-reporter:Qianlei Zhang, Rui Zhang, Lingpu Meng, Yuanfei Lin, Xiaowei Chen, Xueyu Li, Wenhua Zhang, Liangbin Li
Polymer 2016 Volume 101() pp:15-23
Publication Date(Web):28 September 2016
DOI:10.1016/j.polymer.2016.08.054
•A sequential biaxial stretching mode is adopted to investigate SIC of PET above Tg.•A molecular model is proposed to interpret structure changes during SIC of PET.•Improving chain mobility is necessary before SIC occurs slightly above Tg.•The enhanced chain mobility by stretching has no directionality.•The external work is the mainly driven force in SIC of PET slightly above Tg.Strain-induced crystallization (SIC) of poly(ethylene terephthalate) (PET) slightly above glass transition temperature (Tg) is investigated by adopting a sequential biaxial stretching mode in this work. Small angle X-ray scattering (SAXS) and wide angle X-ray diffraction (WAXD) are employed to study variation of orientation parameter and crystallinity of stretch films in machine and transverse draw ratio space. Our results reveal that improving chain mobility by stretching is necessary before crystallization occurs slightly above Tg, during which the total external work of sequential biaxial stretching is not dissipated but “stored” in polymer chains with high mobility. The total crystallinity is precisely correlated with the total external work, which does not relate to stretch direction and demonstrate that enhanced chain mobility have no directionality. Considering the structures that restrict the polymer chains in the initial sample, a molecular model is proposed to interpret the structure changes during SIC of PET above Tg.
Co-reporter:Haoran Yang, Dong Liu, Jianzhu Ju, Jing Li, Zhen Wang, Guanyun Yan, Youxin Ji, Wenhua Zhang, Guangai Sun, and Liangbin Li
Macromolecules 2016 Volume 49(Issue 23) pp:9080-9088
Publication Date(Web):November 23, 2016
DOI:10.1021/acs.macromol.6b01945
By combining extensional rheological and in situ small-angle neutron and synchrotron X-ray scattering (SANS, SR-SAXS) techniques, the correlation between chain deformation and morphology of nucleus in a lightly cross-linked deuterated PE (D-PE)/hydrogenated PE (H-PE) blend has been studied at different draw ratios. The deformation of molecular chain obtained by SANS shows that shish forms at a rather small chain deformation of about 1.3, which does not support either coil–stretch transition or the simple stretch network model. Combining these data with the SAXS results, we speculate that the conformation ordering couples with density, instead of single chain conformation, is the key factor for shish formation. Meanwhile, due to the different alignment of the center of mass of the stretched network in samples with different draw ratios, a periodic concentration modulation of D-PE appears after crystallization of the samples stretched to the hardening zone, which, however, does not occur under the small draw ratio.
Co-reporter:Youxin Ji, Fengmei Su, Kunpeng Cui, Ningdong Huang, Zeming Qi, and Liangbin Li
Macromolecules 2016 Volume 49(Issue 5) pp:1761-1769
Publication Date(Web):February 19, 2016
DOI:10.1021/acs.macromol.5b02161
The influence of mixing of iPB-1/iPP blend on the polymorphism of iPB-1 under processing-relevant conditions is studied with emphasis on the competition between the thermodynamically stable form I′ crystal and the kinetically favored form II. In situ optical microscopy measurements reveal that the upper critical solution temperature (UCST) of iPB-1/iPP blend locates in the range of 180–200 °C. Unexpectedly, by quenching mixed iPB-1/iPP melt down to temperatures below UCST and melting point, form I/I′ can be produced directly which is further identified as form I′ by temperature-dependent WAXS and DSC. The formation of form I′ is promoted by increasing the annealing time above UCST, while is suppresses by raising the quenching temperature. In addition, the crystallization of iPP also displays a similar trend as iPB-1 does. The correlated crystallization of each constituent with dependence on the initial mixing degree suggests that the crystallization behavior of the binary blends is determined by the interplay between simultaneous processes concomitant with the liquid–solid transition. The experimental results reveal the possibility to modify the crystallization pathway of iPB-1 in iPB-1/iPP blend through the mixing degree which is initially controlled by annealing but is subject to evolve during the subsequent thermal treatment. Possible mechanisms are discussed including the roles of phase separation and concentration fluctuation in crystallization.
Co-reporter:Zhen Wang, Zhe Ma, and Liangbin Li
Macromolecules 2016 Volume 49(Issue 5) pp:1505-1517
Publication Date(Web):February 18, 2016
DOI:10.1021/acs.macromol.5b02688
Flow-induced crystallization (FIC) of polymers is a long-standing, industrial relevant, nonequilibrium thermodynamic challenge. Thanks to the development of in situ time and spatial resolved techniques like rheology and synchrotron radiation X-ray scattering, substantial progress on the understanding of FIC has been achieved in past 20 years. In this Perspective, we first discuss some recent modifications and improvements on early coarse-grained approaches like the coil–stretch transition model for shish formation and the entropic reduction model for the enhancement of nucleation rate. Then breaking out the two-phase model of classical nucleation theory, flow-induced coil–helix transition, density fluctuation or phase separation, and isotropic–nematic transition are considered as intermediate orders in FIC. Establishing flow morphology and phase diagrams is essential for revealing the nonequilibrium nature of FIC, which will serve as structural roadmap for the processing of high performance polymer products.
Co-reporter:Chengsha Wei, Mingming Chen, Dong Liu, Weiming Zhou, Majid Khan, Xibo Wu, Ningdong Huang and Liangbin Li  
Polymer Chemistry 2015 vol. 6(Issue 22) pp:4067-4070
Publication Date(Web):16 Apr 2015
DOI:10.1039/C5PY00366K
In this communication, we report the recyclability of a disulfide bond cross-linking ion gel with high toughness and ionic conductivity based on re-shaping and restructuring under heat and pressure in the gel state. The restructuring was realized by disulfide metathesis catalyzed by both an ionic liquid (IL) and the residual copper salt from the click reaction. The ion gels could undergo the breaking–restructuring cycles at least six times with little performance loss (less than 10%), exhibiting good recyclability.
Co-reporter:Weiming Zhou, Lingpu Meng, Jie Lu, Zhen Wang, Wenhua Zhang, Ningdong Huang, Liang Chen and Liangbin Li  
Soft Matter 2015 vol. 11(Issue 25) pp:5044-5052
Publication Date(Web):13 May 2015
DOI:10.1039/C5SM00738K
The effect of flow on crystallization is commonly attributed to entropic reduction, which is caused by stretch and orientation of polymer chains but overlooks the role of flow on final-state free energy. With the aid of in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) and a homemade constrained uniaxial tensile testing machine, polycrystals possessing single-crystal-like orientation rather than uniaxial orientation are found during the constrained stretch of natural rubber, whereas the c-axis and a-axis align in the stretch direction (SD) and constrained direction (CD), respectively. Molecular dynamics simulation shows that aligning the a-axis of crystal nuclei in CD leads to the lowest free energy increase and favors crystal nucleation. This indicates that the nomenclature of strain-induced crystallization may not fully account for the nature of flow-induced crystallization (FIC) as strain mainly emphasizes the entropic reduction of initial melt, whereas stress rather than strain plays the dominant role in crystal deformation. The current work not only contributes to a comprehensive understanding of the mechanism of flow-induced crystallization but also demonstrates the potential application of constrained uniaxial tensile stretch for the creation of functional materials containing polycrystals that possess single-crystal-like orientation.
Co-reporter:Chengsha Wei, Mingming Chen, Dong Liu, Weiming Zhou, Majid Khan, Xibo Wu, Ningdong Huang and Liangbin Li  
RSC Advances 2015 vol. 5(Issue 29) pp:22638-22646
Publication Date(Web):06 Feb 2015
DOI:10.1039/C4RA15095C
In this article, we report the synthesis of a disulfide bonded reversibly chemically cross-linked ion gel with high toughness and conductivity by sequential triblock copolymer self-assembly and the subsequent oxidation of thiol groups. Through reversible thiol-disulfide exchange, the ion gels had both high toughness of chemicals and recyclability of physical cross-linked ion gels. The triblock copolymer (SOS-SH) was prepared as follows: first, the RAFT copolymerization of styrene and 4-vinylbenzyl chloride (VBC) using CTA–PEO–CTA as a bi-functional macroRAFT agent was performed to obtain a triblock copolymer (SOS-Cl); then, the chloride group of SOS-Cl was replaced by an azido group to obtain SOS-N3; and finally, the click reaction of SOS-N3 with O-ethyl-S-prop-2-ynyl carbonodithioate and subsequent aminolysis were conducted to obtain SOS-SH. The disulfide bonded reversibly chemically cross-linked ion gel could be re-dissolved when mixed with a little amount of mild reducing agent (e.g., DTT) in CH2Cl2 with vigorous stirring, which reformed again after the removal of solvent and oxidation of thiol groups. The ion gels could undergo the reduction–oxidation cycle at least twice with a little loss of ionic conductivity and toughness (less than 25%), exhibiting good recyclability. Raman measurements were performed to confirm the existence and the key role of disulfide bond on the recyclability.
Co-reporter:Kunpeng Cui, Zhe Ma, Zhen Wang, Youxin Ji, Dong Liu, Ningdong Huang, Liang Chen, Wenhua Zhang, and Liangbin Li
Macromolecules 2015 Volume 48(Issue 15) pp:5276-5285
Publication Date(Web):July 31, 2015
DOI:10.1021/acs.macromol.5b00819
On the basis of the duality of the shish-kebab superstructure, coil–stretch transition (CST) is well recognized as the molecular mechanism for shish-kebab formation in polymer melts, which, however, is challenged by recent results in flow-induced crystallization (FIC). In this work, we perform a real time investigation on FIC of polyethylene bimodal blends by combing a unique homemade extensional rheometer and synchrotron radiation small-angle X-ray scattering. The results show that the critical strain for shish formation decreases with increasing long chain concentration, which contradicts the role of CST but agrees well with stretched network model (SNM). Quantitative analyses indicate that the formation of shish is determined by the degree of network deformation rather than solely by strain or long chain concentration at a specific temperature. In addition, three types of shish with different stability are observed sequentially by increasing strain. On the basis of our results, strong support is given to the idea that shish formation is a kinetic process. When stretched to a critical deformation degree, the aligned segments couple with each other to form fibrillar-like type I shish, which further transform into type II shish embedded with sporadic lamellae and type III shish embedded with well-defined periodic lamellae sequentially by increasing flow intensity. Our results and the resulting conceptual model not only demonstrates that shish formation is derived from SNM but unveils its kinetic process from initial chain configuration to final stable nuclei.
Co-reporter:Liang Chen, Weiming Zhou, Jie Lu, Jing Li, Wenhua Zhang, Ningdong Huang, Lihui Wu, and Liangbin Li
Macromolecules 2015 Volume 48(Issue 21) pp:7923-7928
Publication Date(Web):October 20, 2015
DOI:10.1021/acs.macromol.5b01301
Double network structure constructed with filler network of carbon black and molecular network of natural rubber possesses excellent toughness and strength. However, due to lack of proper in situ imaging techniques to detect the structural evolutions under loading, the reinforcement mechanism of filler network is still under debate. Here in situ synchrotron radiation X-ray nano-computed tomography with high spatial resolution (100 nm) is employed to study structural evolution of carbon black in a large volume of natural rubber matrix. For the first time, strain-induced deformation, destruction, and reconstruction of filler network are directly observed under cyclic loading. Combining mechanical test, the reinforcing and toughening effect of filler network is quantitatively assigned to three mechanisms, namely elastic deformation, destruction, and friction of filler network. Elastic deformation mainly occurs at low strain for energy storage, while network destruction plays the dominant role at larger strain to dissipate strain energy. Additionally, friction is another energy dissipation mainly at low strain.
Co-reporter:Mingming Chen;Chengsha Wei;Xibo Wu;Majid Khan;Dr. Ningdong Huang;Dr. Guobin Zhang;Dr. Liangbin Li
Chemistry - A European Journal 2015 Volume 21( Issue 11) pp:4213-4217
Publication Date(Web):
DOI:10.1002/chem.201406296

Abstract

Two linear rod-like platinum complexes, which only differed in the linkage, were prepared. They both self-assemble into metallogels in nonpolar solvents; however, a very big contrast was observed. Unexpectedly, a much weaker gel was acquired upon replacing the ester linkage by an amide group. The intermolecular hydrogen bonding offered by the amide motif leads to a different stacking fashion and mechanism. The results demonstrated herein contribute to the rational design of metallogels as well as other functional supramolecular materials.

Co-reporter:Ling-pu Meng;Yuan-fei Lin;Jia-li Xu;Xiao-wei Chen
Chinese Journal of Polymer Science 2015 Volume 33( Issue 5) pp:754-762
Publication Date(Web):2015 May
DOI:10.1007/s10118-015-1623-1
A biaxial stretching equipment was designed and constructed to enable fundamental studies of the relationship between film processing conditions and structures of oriented film products. With programmable drive motors and scissor-like mechanism, all stretching modes, including uniaxial stretching with constant and free width, simultaneous and sequential biaxial stretching, can be applied to a square-shaped sheet. Parameters related to film stretching manufacturing, such as temperature, draw ratio and stretching speed can be set independently to meet the requirement of different polymers. The force information during stretching is recorded by two miniature tension sensors in two directions independently, which can monitor the mechanical stimulus and stress response. Using this equipment, experiments are conducted to investigate the influence of stretching parameters on the structure of polypropylene films, which provides an effective method to tailor the processing conditions to obtain the films with desired properties.
Co-reporter:Kunpeng Cui, Dong Liu, Youxin Ji, Ningdong Huang, Zhe Ma, Zhen Wang, Fei Lv, Haoran Yang, and Liangbin Li
Macromolecules 2015 Volume 48(Issue 3) pp:694-699
Publication Date(Web):January 28, 2015
DOI:10.1021/ma502412y
Based on classical nucleation theory, the current entropic reduction model (ERM) of flow-induced crystallization (FIC) treats external work as perturbation on the framework of equilibrium thermodynamics, which, however, obscures the nonequilibrium nature of FIC. In this work, in situ investigation on FIC under strong flow by combining a unique homemade extensional rheometer and ultrafast X-ray scattering reveals a constant critical strain or time for nucleation in isotactic polypropylene melt in a wide temperature range from 130 to 170 °C. Our discovery contradicts the strain–temperature equivalence predicted by ERM but unveils the nonequilibrium nature of FIC. To account for the temperature independence of flow-induced nucleation, a tentative kinetic pathway of nucleation describing stretch-induced hierarchical structural transitions is proposed through which the capability of flow as driving force is justified.
Co-reporter:Dong Liu;Kunpeng Cui;Ningdong Huang;Zhen Wang
Science China Chemistry 2015 Volume 58( Issue 10) pp:1570-1578
Publication Date(Web):2015/10/01
DOI:10.1007/s11426-015-5361-6
Flow-induced preordering or precursor (FIP) has been studied in a series of lightly cross-linked high-density polyethylene with a combination of extensional rheology and in situ synchrotron radiation small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) measurements. Based on the incipient strains of SAXS and WAXD signals during extension in a large temperature range, strain-temperature diagrams for flow-induced preordering and nucleation were constructed and revealed that flow-induced crystallization (FIC) undergoes two stages: melt-precursor transition (MPT) and precursor-nuclei transition (PNT). At different temperatures, FIP with different inner structures and morphologies can be induced by strain; these embryos have shape and structure that are related to those of the corresponding critical nuclei. With the strain-temperature diagrams, the thermodynamic properties of FIP are deduced, which shows that compared with the relative nuclei the FIP always has a lower bulk free energy (ΔH) and a much lower surface free energy (σe). In extreme cases (high temperature), the σe of FIP can be negligible. The quantitative estimation of the thermodynamic parameters suggests the existence of variant FIPs, which plays a vital role for the subsequent progress of PNT and the whole process of FIC.
Co-reporter:Wei Chen;Xiang-yang Li;Yan-ping Liu;Jing Li
Chinese Journal of Polymer Science 2015 Volume 33( Issue 4) pp:613-620
Publication Date(Web):2015 April
DOI:10.1007/s10118-015-1613-3
On the basis of research method in FTIR imaging, we made a heterogeneous thin film of isotactic polypropylene (iPP) that contains a few large spherulites (∼150 μm) which are surrounded by small spherulites (∼15 μm) for tensile testing. The evolution processes of crystalline and amorphous orientations of iPP are monitored with its characteristic peaks at 998 and 973 cm−1, respectively. By introducing the correlation images, the analysis demonstrates the relationships between the orientation evolutions of crystalline and amorphous phases in a space of 250 μm × 250 μm detecting area. During the plastic deformation, crystalline orientation is higher than amorphous orientation outside the large spherulite, while that is opposite inside the region. In addition, the evolutions of crystalline and amorphous orientations almost keep a positive correlation.
Co-reporter:Chengsha Wei, Mingming Chen, Jiaojiao Tao, Xibo Wu, Majid Khan, Dong Liu, Ningdong Huang and Liangbin Li  
Polymer Chemistry 2014 vol. 5(Issue 24) pp:7034-7041
Publication Date(Web):26 Aug 2014
DOI:10.1039/C4PY00946K
In this paper, we described a new and simple method to produce degradable core cross-linking (CCL) micellar clusters that utilized CdS nanorods to assist thermal oxidation of the polythiol segment of a diblock copolymer, polystyrene-b-polythiol (PS-b-polythiol), at high concentration (2.3 wt%) in a common organic solvent (toluene). The CdS nanorods acted not only as catalysts, but also as templates. The diblock copolymer, PS-b-polythiol, was obtained by aminolysis of polystyrene-b-poly(2-(ethyl-xanthate)ethylmethacrylate) (PS-b-P1), a block copolymer synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization using a macroRAFT transfer agent, PS-CTA, and a methacrylate monomer that possessed a protected thiol group, in the presence of n-butylamine and tributyl phosphine. The CdS nanorods were synthesized conveniently by thermolysis of an alkyl xanthate, Cd-HDX. The TEM image clearly showed the formation of micellar clusters and the oxidation procedure was investigated by 1H-NMR and XPS. The formation of core cross-linking (CCL) micelles was confirmed to be reversible by reduction utilizing DTT as the reducing agent.
Co-reporter:Ningdong Huang, Jiaojiao Tao, Jun Liu, Shenghui Wei, Liangbin Li and Ziyu Wu  
Soft Matter 2014 vol. 10(Issue 24) pp:4236-4240
Publication Date(Web):14 Mar 2014
DOI:10.1039/C3SM52925H
While salt mediated association between similarly charged poly-electrolytes occurs in a broad range of biological and colloidal systems, the effects of mono-valent salts remains little known experimentally. In this communication we systematically study influences of assorted mono-valent salts on structures of and interactions in two dimensional ordered bundles of charged fibrils assembled in water using Small Angle X-ray Scattering (SAXS). By quantitatively analyzing the scattering peak features, we discern two competing effects with opposite influences due to partitioning of salts in the aqueous complex. While electrostatic effects from salts residing between the fibrils suppress attraction between fibrils and expand the bundles, it is compensated by external osmotic pressure from peripheral salts in the aqueous media. The balance between the two effects varies for different salts and gives rise to ion-specific equilibrium behavior as well as structure of ordered bundles in salty water. The specific ions effects in like charged aggregates can be attributed to preferential distribution of ions inside or outside the bundles, correlated to the ranking of ions in Hofmeister series for macromolecules. Unlike conventional studies on Hofmeister effects by thermodynamic measurements relying on modeling for data interpretation, our study is based directly on structural analysis and is model-insensitive.
Co-reporter:Weiming Zhou, Liang Chen, Jie Lu, Zeming Qi, Ningdong Huang, Liangbin Li and Wanxia Huang  
RSC Advances 2014 vol. 4(Issue 97) pp:54500-54505
Publication Date(Web):17 Oct 2014
DOI:10.1039/C4RA09095K
Aiming to study the mechanical enhancement by the filler network in a rubber composite, three-dimensional images are acquired with in situ full field transmission X-ray microscopy (TXM), and the network structure of carbon black (CB) aggregates in a rubber matrix are studied with and without strain. Statistical analysis shows that the frequency of similar-sized aggregates decreases with the increase of aggregate size as well as the inter-aggregate distance monotonically without strain. An oscillation of the frequency-size plot is induced by strain on top of the damping trend, which is interpreted as stretch-induced breakage and re-aggregation of CB aggregates. Calculations adopting a soft-hard network model, predict a reduction of the contribution of the CB network to the mechanical property of the rubber composite by about 60%, caused by the breakage and re-aggregation of CB aggregates compared to those without strain. The experimental results directly prove the structural origin of the Payne effect and also show that TXM is a valuable tool to study the mechanical enhancement mechanism of filled rubber composites.
Co-reporter:Nan Tian, Dong Liu, Lingpu Meng, Weiqing Zhou, Tingting Hu, Xiangyang Li and Liangbin Li  
RSC Advances 2014 vol. 4(Issue 19) pp:9632-9638
Publication Date(Web):10 Dec 2013
DOI:10.1039/C3RA46504G
Extension-induced crystallization in a heterogeneous polyethylene oxide (PEO) melt is investigated by small angle X-ray scattering (SAXS) and extensional rheology. The crystalline complex of PEO and sodium bromide is the heterogeneous component, which simulates the roles of crystal or strongly interacted additives during flow. It is aimed to demonstrate how the altered chain relaxation by the heterogeneous particle affects the crystallization. The main findings are listed as follows: (i) strain hardening occurs in heterogeneous melts but not in pure PEO. This indicates that the crystalline complex strengthens the entanglement network of free chains, leading to slower chain relaxation. (ii) In morphology, the orientation of lamellae becomes easier with the existence of the crystalline complex. A jump in the long period is also observed with large strain, accompanied by changes in the evolutional trend at the early stage. (iii) The crystallization kinetics converge with increasing strain; even the stress response significantly differs in different samples. Based on these findings, a quasi-network consisting of the crystalline complex and the entangled free chain is anticipated. Nucleation induced by the stretch of the quasi-network is supposed to lead to the change in crystallization observed.
Co-reporter:Lingpu Meng, Jiali Xu, Xiaowei Chen, Nan Tian, Yuanfei Lin, Kunpeng Cui, Jing Li, Liangbin Li
Polymer Testing 2014 Volume 36() pp:110-118
Publication Date(Web):June 2014
DOI:10.1016/j.polymertesting.2014.04.002
Constrained and free uniaxial stretching induced crystallization of high density polyethylene (HDPE) film were studied with in situ synchrotron radiation small and wide-angle X-ray scattering (SR-SAXS, SR-WAXS). According to the initial structure after stretching, as well as the structural evolution, three characteristic regions can be defined in strain space for both stretching modes, while the strain boundaries between different regions are different for the two stretching modes. Region I is located at low strain levels where completely twisted lamellae are induced. Region II is in an intermediate strain level, which induces the formation of partially twisted lamellae with relatively large lateral size (defined as quasi-micro-fibrils). Region III with large strain produces flat lamellae with small lateral dimensions (micro-fibrils). During the crystallization process, a new type of lamellar stack with smaller long period forms in regions II and III while no new types of lamellae appear in region I for both stretching modes. Along the strain space, the scenario of constrained stretching delays the transition from region I to region II, as well from region II to region III. Also, the draw ratio windows of region I and region II are enlarged by constrained stretching, which is more favorable for film processing.
Co-reporter:Kunpeng Cui, Yanping Liu, Lingpu Meng, Xiangyang Li, Zhen Wang, Xiaowei Chen, Liangbin Li
Polymer Testing 2014 Volume 33() pp:40-47
Publication Date(Web):February 2014
DOI:10.1016/j.polymertesting.2013.11.004
A novel apparatus was designed and constructed combining polymer extrusion processing and x-ray scattering. It allows direct, real time monitoring of structure and temperature development in polymer material during extrusion. The apparatus involves a vertical industrial extruder equipped with a four-roll stretching device to mimic the processing environments of uni-axially oriented films or sheets, a simultaneous small and wide angle x-ray scattering system and an infrared thermometer as detection unit. The charging barrel of the extruder and the stretching device can be moved upward and downward precisely. By moving the sample along the center line, structure and temperature development as a function of position can be obtained. The performance of the apparatus was verified by a test experiment, which allows us to establish the relationship between processing parameters and evolution of structure with different length scales, and may lead to a better understanding of the physics in polymer processing.
Co-reporter:Jiaojiao Tao, Ningdong Huang, Junjun Li, Mingming Chen, Chengsha Wei, Liangbin Li, and Ziyu Wu
The Journal of Physical Chemistry Letters 2014 Volume 5(Issue 7) pp:1187-1191
Publication Date(Web):March 18, 2014
DOI:10.1021/jz5003132
Despite the important role and potential application of charged cylindrical polyelectrolytes, biomacromolecules, and self-assembles, salt-modulated organization of those 1D charged nanostructures remains a topic relatively unexplored with an obscure underlying mechanism. In this Letter, the aggregation of oriented nanotubes self-assembled by ionic aromatic oligoamide in aqueous solution of NaCl over a wide concentration range is probed via small-angle X-ray scattering and a transmission electron microscope. The arrangement of nanotubes undergoes order–disorder transition sequences from an ordered rectangular phase to hexagonal packing and then to a lamellar gel. The observed transitions are understood by ionic effects on the electrostatic interaction between charged nanotubes and osmotic pressure due to ion partitioning. Above the physiological condition, electrostatic interactions are largely screened by the salts, while osmotic effects start to regulate the aggregation behavior and concomitantly deform the nanotubes. The study demonstrates rich phase behaviors of ordered, charged 1D nanostructures by tuning the ionic strength and underlying key physical principles.Keywords: electrostatic interaction; ionic screening; organized 1D nanostructure; osmotic pressure; self-assembly; small-angle X-ray scattering; structural transition;
Co-reporter:Jing Li, Hailong Li, Lingpu Meng, Xiangyang Li, Liang Chen, Wei Chen, Weiming Zhou, Zeming Qi, Liangbin Li
Polymer 2014 Volume 55(Issue 5) pp:1103-1107
Publication Date(Web):10 March 2014
DOI:10.1016/j.polymer.2014.01.033
The plastic deformation behavior of isotactic polypropylene (iPP) film is studied with in-situ Fourier transformation infrared microspectroscopic imaging (FTIRI). During uniaxial tensile test, spatial distributions of crystallinity and orientations are obtained in necking region (NR), transition front (TF) and non-necking region (NNR). A low valley of crystallinity exists at TF, while both NNR and NR have crystallinities at a high plateau. This provides a direct evidence of deformation-induced melting–recrystallization mechanism of plastic deformation. The non-monotonic evolution of amorphous orientation from NR, TF to NNR further supports the occurrence of deformation-induced melting–recrystallization. The decrease of amorphous orientation behind TF is attributed to recrystallization.
Co-reporter:Xiang-yang Li;Zhe Ma;Feng-mei Su;Nan Tian
Chinese Journal of Polymer Science 2014 Volume 32( Issue 9) pp:1224-1233
Publication Date(Web):2014 September
DOI:10.1007/s10118-014-1502-1
In this study, recovery processes of isotactic polypropylene (iPP) melted spherulites at 135 °C after melting at higher temperatures (170 °C–176 °C) were investigated with polarized optical microscopy and Fourier transform infrared spectroscopy. The recovery temperature was fixed to exclude the interference from heterogeneous nuclei. After melting at temperatures between 170 °C and 174 °C, the melted spherulite could recover back to the origin spherulite at low temperatures. Interestingly, a distinct infrared spectrum from iPP melt and crystal was observed in the early stage of recovery process after melting at low temperatures, where only IR bands resulting from short helices with 12 monomers or less can be seen, which indicates that the presence of crystal residues is not the necessary condition for the polymer memory effect. Avrami analysis further indicated that crystallization mainly took place in melted lamellae. After melting at higher temperatures, melted spherulite cannot recover. Based on above findings, it is proposed that the memory effect can be mainly ascribed to melted lamellae, during which crystalline order is lost but conformational order still exists. These conformational ordered segments formed aggregates, which can play as nucleation precursors at low temperatures.
Co-reporter:Yanping Liu;Zhihua Hong;Liangui Bai;Nan Tian;Zhe Ma
Journal of Materials Science 2014 Volume 49( Issue 8) pp:3016-3024
Publication Date(Web):2014 April
DOI:10.1007/s10853-013-7998-x
The cross-hatched structural evolution of isotactic polypropylene (iPP) during uniaxial tensile deformation was investigated with in situ synchrotron radiation wide angle X-ray scattering. An effective way was developed to study parent and daughter lamellae separately with in situ environment. iPP sample was preoriented to generate a bimodal orientation of lamellae for distinguishing the parent and daughter lamellae, which will orient in orthogonal directions under flow-induced crystallization. The dumbbell samples were prepared along different angles with respect to preorientation direction to achieve multisided stretching. The structural evolution of parent and daughter lamellae was followed by recording the scattering from (110) crystallographic plane. It was observed that the parent lamellae were destroyed earlier than daughter ones, no matter which the tensile direction was. Mesophase was observed at very small strain of 0.3, immediately after the damage of cross-hatched structure, which may be attributed to the destruction of parent lamellae. Deformation induced mesophase was proved to be the small crystal cluster which was transformed from parent and daughter lamellae.
Co-reporter:Mingming Chen;Chengsha Wei;Jiaojiao Tao;Xibo Wu;Dr. Ningdong Huang;Dr. Guobin Zhang;Dr. Liangbin Li
Chemistry - A European Journal 2014 Volume 20( Issue 10) pp:2812-2818
Publication Date(Web):
DOI:10.1002/chem.201304315

Abstract

Two structurally similar trans-bis(pyridine) dichloropalladium(II)- and platinum(II)-type complexes were synthesized and characterized. They both self-assemble in n-hexane to form viscous fluids at lower concentrations, but form metallogels at sufficient concentrations. The viscous solutions were studied by capillary viscosity measurements and UV/Vis absorption spectra monitored during the disassembly process indicated that a metallophilic interaction was involved in the supramolecular polymerization process. For the two supramolecular assemblies, uncommon continuous porous networks were observed by using SEM and TEM revealed that they were built from nanofibers that fused and crosslinked with the increase of concentration. The xerogels of the palladium and platinum complexes were carefully studied by using synchrotron radiation WAXD and EXAFS. The WAXD data show close stacking distances driven by π–π and metal–metal interactions and an evident dimer structure for the platinum complex was found. The coordination bond lengths were extracted from fitting of the EXAFS data. Moreover, close PtII–PtII (PdII–PdII) and PtCl (PdCl) interactions proposed from DFT calculations in the reported oligo(phenylene ethynylene) (OPE)-based palladium(II) pyridyl supramolecular polymers were also confirmed by using EXAFS. The PtII–PtII interaction is more feasible for supramolecular interaction than the PdII–PdII interaction in our simple case.

Co-reporter:Kunpeng Cui, Lingpu Meng, Youxin Ji, Jing Li, Shanshan Zhu, Xiangyang Li, Nan Tian, Dong Liu, and Liangbin Li
Macromolecules 2014 Volume 47(Issue 2) pp:677-686
Publication Date(Web):January 15, 2014
DOI:10.1021/ma402031m
The role of long chains in extension flow-induced crystallization was studied with a combination of extension rheological and in situ small-angle X-ray scattering (SAXS) measurements at 52 °C. To elucidate the effects of long chains, bidisperse blends of poly(ethylene oxide) (PEO) with the long-chain concentration above the overlap concentration were prepared, constructing long-chain entanglement network in short-chain matrix. Rheological data of step extension on PEO melt are divided into two regions with fracture strain of pure short-chain sample as a boundary. Distinctly different features of crystallization kinetics and crystal morphologies are observed in these two regions, exactly corresponding to rheological behavior. A new mechanism based on entanglement network perspective is proposed, in which the second entanglement network constructed by long chains has three effects: (i) helping flow to change the free energy of polymer melt more effectively; (ii) ensuring the specific work can impose on the system; (iii) favoring the formation of precursors. This mechanism captures both rheological observation and crystallization behavior successfully and offers a new viewpoint for FIC study.
Co-reporter:Fengmei Su, Weiming Zhou, Xiangyang Li, Youxin Ji, Kunpeng Cui, Zeming Qi, and Liangbin Li
Macromolecules 2014 Volume 47(Issue 13) pp:4408-4416
Publication Date(Web):June 23, 2014
DOI:10.1021/ma5005293
Shear-induced precursors obtained by fiber pulling with high shear rate in undercooled melts of isotactic polypropylene (iPP) at a wide temperature range were investigated by highly time and space resolved synchrotron radiation scanning X-ray microdiffraction (SR-μSXRD). X-ray diffraction patterns in spot area of 4.9 × 5.3 μm2 were obtained by scanning proximities around the fiber with step size of 7 μm immediately after shear and during the sequent crystallization process. The crystallinity derived from SR-μSXRD indicates that the structure of precursors was determined by shear temperature, providing a high shear rate was imposed. At shear temperatures around or below the melting temperature, the presence of crystal diffraction immediately after shear indicates the formation of crystalline precursors with reduced density by increasing shear temperature. At shear temperatures in between melting and equilibrium melting temperature, the formation of noncrystalline precursors is supported by three evidence: (i) formation of shear-induced ordered structure indicated by preference of crystallization on fiber surface; (ii) absence of crystal signal immediately after shear; (iii) induction time necessary for transforming noncrystalline precursor into crystal. The experimental results suggest that the structure of noncrystalline precursors probably is aggregates of partially ordered chain segments which orient along the shear direction.
Co-reporter:Dong Liu, Nan Tian, Ningdong Huang, Kunpeng Cui, Zhen Wang, Tingting Hu, Haoran Yang, Xiangyang Li, and Liangbin Li
Macromolecules 2014 Volume 47(Issue 19) pp:6813-6823
Publication Date(Web):September 24, 2014
DOI:10.1021/ma501482w
Extension-induced crystallization under near-equilibrium condition has been studied in a series of lightly cross-linked high density polyethylene (XL-HDPE) with a combination of extensional rheology and in situ synchrotron radiation small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) measurements. According to crystal morphology and structure, four regions were defined in strain-temperature space, namely “orthorhombic lamellar crystal” (OLC), “orthorhombic shish crystal” (OSC), “hexagonal shish crystal” (HSC) and “oriented shish precursor” (OSP), respectively. This indicates that flow not only induces entropic reduction of initial melt, but also modifies the free energies of the final states, which is overlooked in the classical stretched network model (SNM) for flow induced crystallization (FIC). Incorporating the free energies of various final states, a modified SNM is developed and employed to analyze strain-temperature equivalence on nucleation in FIC, which reveals that the critical nucleus thickness l* at different regions leads to a natural transition from lamellar to shish nuclei. The results suggest that classical nucleation theory is still valid for FIC under near-equilibrium condition provided that the free energy changes of initial melt and final states induced by flow are taken into account.
Co-reporter:Chaosheng Yuan;Lei Su;Kun Yang;Zijiong Li
Journal of Sol-Gel Science and Technology 2014 Volume 72( Issue 2) pp:344-350
Publication Date(Web):2014 November
DOI:10.1007/s10971-014-3437-y
Sol–gel transition behavior of ionic liquid gel based on poly (ethylene glycol) (PEG) and ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate [EMIM][EtSO4] has been investigated under the pressure up to 250 MPa. The Temperature versus Pressure phase diagram of PEG/[EMIM][EtSO4] gel is constructed, and it indicates that the melting point is an increasing function of pressure. Based on the phase diagram, the PEG/[EMIM][EtSO4] gels are prepared by cooling under the pressure of 300 MPa and atmospheric pressure, respectively. From the differential scanning calorimetry result of the recovered samples, it is found that PEG/[EMIM][EtSO4] gel prepared under high pressure has a higher crystallinity and smaller crystal size polymer network, comparing with under atmospheric pressure. The cyclic voltammograms and impedance spectra tests indicate that the PEG/[EMIM][EtSO4] gel prepared under high pressure exhibit higher ionic conductivity comparing with atmospheric pressure. It could be speculated these excellent properties might be attributed to the loose gel structure and high ionic density induced by high pressure.
Co-reporter:Nan Tian, Dong Liu, Xiangyang Li, Zhen Wang, Shanshan Zhu, Kunpeng Cui, Weiqing Zhou and Liangbin Li  
Soft Matter 2013 vol. 9(Issue 45) pp:10759-10767
Publication Date(Web):09 Oct 2013
DOI:10.1039/C3SM52152D
The time evolution of the long period in the extension-induced crystallization of polyethylene oxide (PEO) is investigated with a combination of rheological measurement and in situ small angle X-ray scattering (SAXS), aiming to show the dynamic change in the spatial arrangement of nuclei in terms of both the chain stretching and orientation. The main findings are summarized as follows. (i) Strain hardening is observed when the strain is larger than 3.0, indicating a transition from chain orientation to chain stretching. (ii) The time evolution of the long period differs before and after strain hardening, reflecting changes in the evolution of nuclei arrangement. The full strain range is thus divided into two regions, namely the large strain region and the small strain region. In the large strain region the long period exhibits a two-step monotonic decrease. For the small strain region, an increase-plateau-decrease behavior is observed. (iii) A large gap exists between the initial values of the long period in each of the two strain regions. (iv) The crystallization kinetics shows no secondary acceleration after strain hardening. Based on these results, a qualitative model emphasizing the chain relaxation propelled rearrangement of nuclei is proposed to explain the structural evolution.
Co-reporter:Xiangyang Li, Fengmei Su, Youxin Ji, Nan Tian, Jie Lu, Zhen Wang, Zeming Qi and Liangbin Li  
Soft Matter 2013 vol. 9(Issue 35) pp:8579-8588
Publication Date(Web):19 Jul 2013
DOI:10.1039/C3SM51799C
In this study, the memory effect of a polymer is investigated with a mesomorphic isotactic polypropylene (iPP) melt as the initial state. It is found that the nucleation density and crystallization rate at low temperatures are strongly dependent on the initial melting temperature and melting time, indicating a strong memory effect. High melting temperatures decrease the nucleation density, while a short melting time causes a faster crystallization rate than in the melt with its thermal history removed. At 180 °C, it takes about 1 hour for the crystallization rate to be restored to the normal value found in the melt with erasure of its thermal history at 220 °C. Further experiments indicate that the increase in spherulite growth rate is mainly responsible for acceleration of the overall crystallization kinetics. Through comparison between meso crystallization and self-seeding crystallization, it is suggested that some ordered structures with higher thermal stability exist in the mesomorphic iPP melt. The high thermal stability of the ordered structure may be due to the random arrangement of helices of different tacticity. We propose that the ordered structure accelerates spherulite growth, however, long melting times at 180 °C can break down the ordered structure, leading to the formation of an ideal melt and restoration of the spherulite growth rate. This study indicates that a thermodynamically unstable ordered structure can survive in a supercooled melt for a long time and is involved in the crystallization process.
Co-reporter:Junjun Li, Ningdong Huang, Daoliang Wang, Lu Xu, Youju Huang, Mingming Chen, Jiaojiao Tao, Guoqiang Pan, Ziyu Wu and Liangbin Li  
Soft Matter 2013 vol. 9(Issue 18) pp:4642-4647
Publication Date(Web):22 Mar 2013
DOI:10.1039/C3SM50390A
Highly ordered templates are of great importance in fabricating well-arranged nanomaterials. Inspired by the hierarchical assembly of bio-macromolecules, we designed a water soluble three-arm ionic aromatic oligoamide which can spontaneously self-assemble into bundles of nanofibrils. Unlike conventional assemblies formed by synthetic oligoamides individually dispersed in solution, the nanofibrils in our present study tend to further arrange into orthorhombic arrays and form microfibers that can be up to millimeters in length. The surrounding ions play a key role in assembly behavior and possess a high metal-ion binding capacity, which provides a strategy for tuning ordered structures of functional materials and possibilities for understanding the assembly mechanism of biological counterparts.
Co-reporter:Youju Huang, Daoliang Wang, Lu Xu, Yuanhua Cong, Junjun Li, Liangbin Li
European Polymer Journal 2013 Volume 49(Issue 6) pp:1682-1687
Publication Date(Web):June 2013
DOI:10.1016/j.eurpolymj.2013.03.009
•We synthesized a fully rigid, water soluble discotic-shaped aromatic aramid molecule.•The designed molecules exhibit three states depending on the amount of water.•The designed molecules can spontaneously self-assemble into multiscale fibers.We synthesized a fully rigid, water soluble discotic-shaped aromatic aramid molecule, which can spontaneously self-assemble into multiscale fibers (from nano- to micro-scale in both length and diameter), depending on the molecular states (e.g., solution, liquid crystals and solid state). In diluted solution (below 0.086 g/mL), the discotic molecule tend to self-assemble into nanofibers. As the concentration increased (0.086–0.28 g/mL), it exhibits supramolecular liquid crystalline phase with microfiber texture. While, solid power under circumstance with 83% relative humidity favors the formation of rod-like shaped polymorphic crystals in macroscopic size. The unique ‘self-fiber-forming’ property of discotic molecules in different states makes them become an easy processing aramid fiber material, and also allow us to easily prepare microfilm with parallel-aligned nanofibers, which could be a promising candidate for ion conductivity material such as polymer proton exchange membrane (PEM) for fuel cell.Graphical abstract
Co-reporter:Dong Liu, Nan Tian, Kunpeng Cui, Weiqing Zhou, Xiangyang Li, and Liangbin Li
Macromolecules 2013 Volume 46(Issue 9) pp:3435-3443
Publication Date(Web):April 24, 2013
DOI:10.1021/ma400024m
Extension-induced crystallization of lightly cross-linked high density polyethylene (XL-HDPE) has been studied with a combination of extensional rheology and in situ synchrotron radiation small-angle X-ray scattering (SR-SAXS) measurements, where XL-HDPE is a dynamic asymmetric system containing both cross-linked network and free chains (23 wt % gel fraction). SR-SAXS results revealed that the nucleation morphologies can be divided into four regions in strain space, namely uncorrelated oriented point-nuclei, scaffold-network nuclei, microshish nuclei, and shish nuclei. The definition of these four regions coincides nicely with the transitions in stress–strain curves, which allows us to establish a correlation between extension-induced conformations of chains and morphologies of nuclei. Even orientation of cross-linked network and free chains leads to the formation of uncorrelated oriented point-nuclei in region I, while the emergence of dynamic asymmetric nature due to disentanglement of free chain results in scaffold-network nuclei in region II. Formation of microshish in region III requires not only orientation but also stretch of chain segments, and finally nearly full extension of chain segments corresponds to shish nuclei in region IV.
Co-reporter:Hailong Li, Weiming Zhou, Youxin Ji, Zhihua Hong, Bing Miao, Xiangyang Li, Jing Zhang, Zeming Qi, Xiao Wang, Liangbin Li, Zhong-Ming Li
Polymer 2013 Volume 54(Issue 2) pp:972-979
Publication Date(Web):24 January 2013
DOI:10.1016/j.polymer.2012.12.012
The deformation behaviors of three types of polyethylene (PE) with different molecular weights and short chain branch contents were studied by in-situ Fourier transformation infrared microspectroscopic imaging (FTIRI) with a Focal Plane Array (FPA) detector during uniaxial tensile test. The crystal orientation distributions within a 250 × 250 μm2 region during tensile test were obtained, especially in the front of necking profile. The results show that either increasing the molecular weight or adding the short chain branches could enhance the resistance of crystal to be orientated. With the aid of the Landau-de Gennes theory of nematic–isotropic transition, the spatial distribution of crystal orientation during the steady neck propagation is quantitatively analyzed, coupling with its corresponding mechanical behavior coherently. The theoretical analysis reveals that the constant Φ0Φ0 and the coefficient of the Gaussian term A in the Landau-de Gennes model are valid parameters to evaluate the mechanical property of PE materials, which may be generalized as a new method to quantify the mechanical property of semi-crystalline polymers.
Co-reporter:Nan Tian, Baijin Zhao, Xiangyang Li, Yanping Liu, Weiqing Zhou, Kunpeng Cui, Dong Liu, Liangbin Li
Polymer 2013 Volume 54(Issue 26) pp:7088-7093
Publication Date(Web):13 December 2013
DOI:10.1016/j.polymer.2013.10.055
In this work extension induced crystallization of end-linked polyethylene oxide (PEO) network was investigated with in-situ small angle X-ray scattering (SAXS) and rheological measurement. The coupling between crystallinity and stress of crosslinked network makes the morphology time dependent. With a large strain the structure evolution in the stretched network is found to follow a two-stage process: i) crystals with high numerical density and small dimension form first, which laterally correlate with adjacent ones; ii) continuous melting and fusing of adjacent crystal happen after the first nucleation stage, leading to increase of crystal dimension and stability. Decreasing strain a gradual transformation to normal lamellae formation is found. Strain tuned confinement and crystallization induced confinement release is supposed to induce the structural change.
Co-reporter:Fengmei Su, Xiangyang Li, Weiming Zhou, Wei Chen, Hailong Li, Yuanhua Cong, Zhihua Hong, Zeming Qi, Liangbin Li
Polymer 2013 Volume 54(Issue 13) pp:3408-3416
Publication Date(Web):7 June 2013
DOI:10.1016/j.polymer.2013.04.046
The crystal–crystal transition of isotactic polybutene-1 (iPB-1) from form II to I at room temperature is investigated with in-situ Fourier transform infrared spectroscopy (FTIR), Fourier transformation infrared microspectroscopic imaging (FTIRI) and synchrotron radiation scanning X-ray micro-diffraction (SR-μSXRD). The transition rate from form II to I shows a non-monotonic correlation with crystallization temperature on samples isothermally crystallized at different single temperatures. An abnormal spatial distribution of transition rate is observed in samples prepared with a two-step crystallization approach, in which samples crystallized at high temperature and then were quenched to low temperatures for further crystallization. A maximum transition rate occurs around the edge of large spherulites formed at high temperature, which cannot be interpreted by the effect of crystallization temperature alone. The accelerated transition rate in this region is attributed to internal stress, where an intermediate state, revealed with SR-μSXRD, may be the structural origin for the fast transition rate from form II to I.
Co-reporter:Weiqing Zhou, Kunpeng Cui, Nan Tian, Dong Liu, Yanping Liu, Lingpu Meng, Xiangyang Li, Jie He, Liangbin Li, Xiuhong Li, Feng Tian
Polymer 2013 Volume 54(Issue 2) pp:942-947
Publication Date(Web):24 January 2013
DOI:10.1016/j.polymer.2012.11.074
With three polymers (poly(1-butene), isotactic polypropylene and syndiotactic polypropylene) as model systems, the effect of extensional strain on the nucleation rate was studied using a home-made miniature extensional rheometer and in-situ X-ray scattering. A non-monotonic correlation between nucleation rate and strain is observed around rheological yield point. Increasing strain leads to an increase in nucleation rate as expected when strain is smaller than yield strain, however, it results in a decrease in nucleation rate when strain slightly exceeds yield. We proposed that disentanglement occurs at yield point and thus decelerates flow-induced nucleation. Disentanglement provides freedom for chains to retract and leads to a dissipation of the energy initially imposed by extensional flow, which consequently weakens the effect of flow field on the enhancement of nucleation.
Co-reporter:Wei Chen;Xiangyang Li;Hailong Li;Fengmei Su
Journal of Materials Science 2013 Volume 48( Issue 14) pp:4925-4933
Publication Date(Web):2013 July
DOI:10.1007/s10853-013-7273-1
Crystal–crystal transition of polybutene-1 from forms II to I inside and outside a large hedrite or spherulite during deformation is investigated with in situ Fourier transform infrared sepectroscopic imaging technique and miniature tensile tester. Three stages have been observed for both of samples. In the first stage (strain ε < 0.2), form I crystal formed slowly under the effect of deformation. When entering the second stage II (0.2 < ε < 1.2), the crystal–crystal transition was accelerated significantly. In the third stage, form II translates into form I almost completely. It was also found that the transition rate inside large hedrite and spherulite is slightly faster than the surrounding initially, especially for the hedrite. However, the difference inside and outside becomes negligible when ε > 0.8. We proposed that the difference in crystal–crystal transformation between spherulite and hedrite is attributed to the different alignment of lamellar stacks in two samples. The results demonstrate the effect of different morphologies on the crystal–crystal transition during deformation.
Co-reporter:Daoliang Wang ;Dr. Youju Huang ;Junjun Li;Lu Xu;Mingming Chen;Jiaojiao Tao ;Dr. Liangbin Li
Chemistry - A European Journal 2013 Volume 19( Issue 2) pp:685-690
Publication Date(Web):
DOI:10.1002/chem.201202944

Abstract

Unlike thermotropic liquid-crystalline C3-symmetric molecules with flexible chains, the herein-designed fully rigid three-armed molecules (C3-symmetric and unsymmetric) create a fancy architecture for the formation of lyotropic liquid crystals in water. First, hollow columns with triple-stranded helices, analogous to helical rosette nanotubes, are spontaneously constructed by self-organization of the rigid three-armed molecules. Then, the helical nanotubes arrange into hexagonal liquid-crystalline phases, which show macroscopic chirality as a result of supramolecular chiral symmetry breaking. Interestingly, the helical nanotubes constructed by the fully rigid molecules are robust and stable over a wide concentration range in water. They are hardly affected by ionic defects at the molecular periphery, that is, further decoration of functional groups on the molecular arms can presumably be realized without changing the helical conformation. In addition, the formed columnar phases can be aligned macroscopically by simple shear and show anisotropic ionic conductivity, which suggests promising applications for low-dimensional ion-conductive materials.

Co-reporter:Fengmei Su, Xiangyang Li, Weiming Zhou, Shanshan Zhu, Youxin Ji, Zhen Wang, Zeming Qi, and Liangbin Li
Macromolecules 2013 Volume 46(Issue 18) pp:7399-7405
Publication Date(Web):September 5, 2013
DOI:10.1021/ma400952r
Crystallization from memorized ordered melt (MOM) of isotactic polybutene-1 (iPB-1) is investigated with in situ Fourier transformation infrared microspectroscopic imaging and wide- and small-angle X-ray scattering. After being partially melted at high temperature, a small portion of form I crystal of iPB-1 recovers back when the temperature is lowered. This is different from a disordered melt, which crystallizes into form II directly. The recovery of form I crystal is attributed to the presence of MOM, which may keep the conformation order of form I crystal. Experimental evidence show that MOM possesses three characteristics, namely: (i) associating with the preserved form I; (ii) occupying only a small portion of the melt in the partially melted sample; (iii) being stable at high temperature. All this experimental evidence suggests that MOM locates at the boundary of crystal and melt. This is in line with the physical picture of nonclassical nucleation and growth theory or the multistage approach, where a partially ordered melt layer locates at the boundary of crystal and melt.
Co-reporter:Lu Xu, Youju Huang, Junjun Li, Daoliang Wang, Mingming Chen, Jiaojiao Tao, Kunpeng Cui, Guoqiang Pan, Ningdong Huang, and Liangbin Li
Langmuir 2013 Volume 29(Issue 11) pp:3813-3820
Publication Date(Web):February 22, 2013
DOI:10.1021/la400206s
A novel fully rigid, rod-shaped oligo(p-benzamide) (OPBA-6) molecule was designed and synthesized, which can be recrystallized into a three-dimensional (3D) multilayer material via an antiparallel molecular packing model. Intermolecular hydrogen bonding and π–π interaction are brought to ensure a strong intralayer interaction, while decoration of layer surface with sulfonic groups promotes water to enter interlayer space and facilitates the swelling and exfoliation of sample. With a simple dispersion in water, the obtained multilayer material can be easily swollen by water without destruction of in-plane morphology and subsequently delaminated into 2D nanosheets with thickness of about 5.38 nm. This achievement may be the first attempt to exfoliate layered organic materials and thus provide a new strategy to prepare 2D organic nanosheets without using any substrates or templates as required by conventional and widely used self-assembly routes. Based on exfoliated nanosheets, poly(vinyl alcohol) nanocomposites were prepared using a simple water solution processing method. A 64% increase in tensile stress and a 63% improvement in Young’s modulus were achieved by addition of 7 wt % OPBA-6 loading.
Co-reporter:Yanping Liu, Kunpeng Cui, Nan Tian, Weiqing Zhou, Lingpu Meng, Liangbin Li, Zhe Ma, and Xiaolin Wang
Macromolecules 2012 Volume 45(Issue 6) pp:2764-2772
Publication Date(Web):March 15, 2012
DOI:10.1021/ma2026513
Deformation induced crystal–crystal transition of polybutene-1 (PB-1) from forms II to I at different temperatures is studied with in situ synchrotron radiation wide-angle X-ray scattering (WAXS). Analyses on the evolution of crystallinity and orientations of forms II and I during tensile deformation show that stretch accelerates the transformation from forms II to I, which is interpreted based on either a direct crystal–crystal transition or an indirect approach via an intermediate state of melt, namely a melting recrystallization process. A three-stage mechanical deformation including linear deformation, stress plateau, and strain hardening is observed in the engineering stress–strain curves, which corresponds to a process of incubation, nucleation, and gelation of form I crystals. It establishes a nice correlation between phase transition and mechanical behavior in this study.
Co-reporter:Yuanhua Cong, Zhihua Hong, Weiming Zhou, Wei Chen, Fengmei Su, Hailong, Li, Xiangyang Li, Ke Yang, Xiaohan Yu, Zeming Qi, and Liangbin Li
Macromolecules 2012 Volume 45(Issue 21) pp:8674-8680
Publication Date(Web):2017-2-22
DOI:10.1021/ma301595k
The growth front of isotactic polypropylene (iPP) spherulites is studied with series of in-situ microanalyzing techniques: conventional source infrared microspectroscopic (CS-μIR), polarized infrared microspectroscopic imaging (SR-μPIR), and scanning X-ray microdiffraction (SR-μSXRD). By SR-μSXRD, the actual growth front boundary of spherulite was clearly defined, which is the boundary observed with an optical microscope. Measurements of CS-μIR and SR-μPIR on growing spherulites reveal that a growth front layer (GFL) with high content of conformational ordered long helices exists outside the growth front of spheurlite, which has a thickness up to 30 μm above 142 °C. These long helices preferentially orient perpendicular to the radial direction of spherulite, whose growth fashion seems correlating with the growth of spherulite.
Co-reporter:Baijin Zhao;Nan Tian;Yanpin Liu;Tingzi Yan;Weiqing Zhou;Yingui Zhou;Gengsheng Weng;Guangsu Huang
Journal of Polymer Science Part B: Polymer Physics 2012 Volume 50( Issue 23) pp:1630-1637
Publication Date(Web):
DOI:10.1002/polb.23172

Abstract

Strain-induced crystallization (SIC) of natural rubber (NR) samples with different strain rates at a fixed strain was investigated by synchrotron radiation X-ray diffraction measurements, which provided the evolution trends of crystal sizes and crystallinity during the SIC process. It was found that the Avrami index was about 1 during the crystallization of NR after the cessation of stretch, which demonstrated that sporadic nucleation occurred during SIC process. The increase of the crystallinity was attributed to the increase of the number of new crystallites rather than the growth of the crystal size. An unexpected relationship between the final crystallinity and the strain rates was observed. The increase of physical crosslink points originated from either entanglement or crystallite was considered as the reason that leads to the nonmonotonic variation of the final crystallinity with strain rates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

Co-reporter:Zhihua Hong, Yuanhua Cong, Zeming Qi, Hailong Li, Weiming Zhou, Wei Chen, Xiao Wang, Yingui Zhou, Liangbin Li
Polymer 2012 Volume 53(Issue 2) pp:640-647
Publication Date(Web):24 January 2012
DOI:10.1016/j.polymer.2011.12.009
The deformation behavior of a single spherulite embedded in quenched isotactic polypropylene (iPP) film is studied with in-situ infrared microspectroscopic imaging (FTIRI) with Focal Plane Array (FPA) detector during uniaxial tensile test. Imaging an area of 250 × 250 μm2 with 4096 Fourier transform infrared (FTIR) spectra, the absorption distributions of crystalline (998 cm−1 band) and amorphous (1153 cm−1 band) phases with radiation polarized parallel and perpendicular to tensile direction are obtained, which are employed to construct the orientation distribution images at different strains. The daughter lamellae in equatorial region are slightly rotated first toward tensile direction, which may postpone the sliding deformation of parent lamellae. The orientation evolution of crystal during tensile deformation suggests that a single spherulite can be divided into three different mechanical zones, corresponding with the crystallinity distribution at different regions of spherulite as estimated through the ratio of 998 cm−1 to the summation of 998 cm−1 and 1153 cm−1. The results may provide a more realistically mechanical model for computer simulation and demonstrate the advantages of FTIRI on the study of structure-property of polymers.
Co-reporter:Kunpeng Cui, Lingpu Meng, Nan Tian, Weiqing Zhou, Yanping Liu, Zhen Wang, Jie He, and Liangbin Li
Macromolecules 2012 Volume 45(Issue 13) pp:5477-5486
Publication Date(Web):June 19, 2012
DOI:10.1021/ma300338c
Extension flow induced crystallization of isotatic polypropylene (iPP) has been studied with a combination of extension rheological and in situ small-angle X-ray scattering (SAXS) measurements at 140 °C. Rheological data of step extension on iPP melt are divided into before and beyond fracture strain zones in strain–strain rate space, where intermediate strains between them lead to fracture of samples. Coincidently, weak and strong accelerations of nucleation are observed in the before and beyond fracture strain zones respectively, where distinctly different features of crystallization kinetics and nucleation form occur in these two zones. The microrheological model explains the acceleration of nucleation in the “before fracture strain zone” well, while a “ghost nucleation” mechanism is proposed to interpret the strong acceleration of nucleation in the “beyond fracture strain zone”. The “ghost nucleation” is due to the displacement of initial parent point nuclei, where daughter nuclei are induced along the trails. This new mechanism explains well the acceleration of nucleation in orders of magnitude and the formation of shish in iPP melt.
Co-reporter:Lu Xu, Junjun Li, Daoliang Wang, Youju Huang, Mingming Chen, Liangbin Li, Guoqiang Pan
Polymer 2011 Volume 52(Issue 4) pp:1197-1205
Publication Date(Web):17 February 2011
DOI:10.1016/j.polymer.2010.12.058
A series of rod-coil-rod triblock copolymers containing polycaprolactam (PA6) as the coil block and poly (p-benzamide) (PBA) as the rod block were synthesized by a two-step polycondensation reaction. Proton nuclear magnetic resonance (1H NMR), UV–vis spectrophotometry (UVS) and differential scanning calorimetry (DSC) were performed to determine the fundamental molecular structure and thermal property of copolymers. UV–vis spectrophotometry results revealed that the content of PBA homopolymer increased with the block length (number of monomer) of PBA and reached a plateau value ranging from 22 to 40 monomers of PBA. The wide angle X-ray diffraction (WAXD) measurements indicated that the crystallization of PA6 blocks was strongly suppressed due to the stretching from rods after annealed at temperature above the melting point of PA6. Only a few imperfect crystals of PA6 existed in the samples with low volume fraction of PBA. Moreover, the variation of PA6 block length hardly affected the crystallinity of PBA, which was dominantly controlled by the block length of PBA as diffusion was the control step for PBA crystallization at the annealing temperature.
Co-reporter:Nan Tian, Weiqing Zhou, Kunpeng Cui, Yanping Liu, Yuye Fang, Xiao Wang, Liangbao Liu, and Liangbin Li
Macromolecules 2011 Volume 44(Issue 19) pp:7704-7712
Publication Date(Web):September 13, 2011
DOI:10.1021/ma201263z
Crystallization of poly(ethylene oxide) (PEO) induced by extensional flow has been studied by in-situ small-angle X-ray scattering (SAXS). A constant Hencky strain was applied to the melt with strain rates varying in 3 orders of magnitude. The evolution of the long period with crystallization time is qualitatively different for high and low strain rates. In the region of high strain rates the long period first increases, reaches a plateau, and decreases in the later stage of crystallization. In contrast, for low strain rates only a monotonic decrease is observed. Given the high orientation in the high strain rate region, we propose a localized nucleation mechanism (like row-nuclei). The initial increase of the long period for high strain rates indicates a decrease of nucleation density, which is the inverse of the long period. On the basis of the microrheological model proposed by Coppola et al., in which the flow induced free energy change under steady state flow is calculated with the Doi–Edwards model, we develop a framework describing the nucleation after a step strain with high strain rates. By introducing the memory function, the dynamic process of relaxation is taken into account, leading to a continuous decrease of the nucleation density. Numerical fitting the model to the experimental data gives a good agreement with the terminal relaxation time τd, the volume filling rate B, and a constant C3 determined by surface free energy of the nuclei as fitting parameters. The results confirm the localized nucleation mechanism in highly oriented melt. Furthermore, the fitted value of C3 indicates a drop in surface free energy of nuclei under strong flow.
Co-reporter:Yuanhua Cong, Hao Liu, Daoliang Wang, Baijin Zhao, Tingzi Yan, and Liangbin Li, Wei Chen and Zhiyuan Zhong , Ming-Champ Lin, Hsin-Lung Chen , Chuanlu Yang
Macromolecules 2011 Volume 44(Issue 15) pp:5878-5882
Publication Date(Web):July 14, 2011
DOI:10.1021/ma201249y
Co-reporter:Yuanhua Cong, Zhihua Hong, Zeming Qi, Weiming Zhou, Hailong Li, Hao Liu, Wei Chen, Xiao Wang, and Liangbin Li
Macromolecules 2010 Volume 43(Issue 23) pp:9859-9864
Publication Date(Web):November 12, 2010
DOI:10.1021/ma1019686
The conformational ordering in spherulites of isotactic polypropylene during growing process is studied with in situ infrared microspectroscopic imaging. A comparison between the intensity distribution of bands representing crystal and conformational ordering indicates that large concentration of conformational ordered segments exist in the growth boundary region of spherulites, which suggests that conformational ordering takes place before packing into crystal lattice in the growth boundary layer. The width of the growth boundary layer is sensitive to temperature but keeps relative constant during isothermal crystallization process. Though the interchain organization of the conformational ordered segments is not clear yet, conformational ordering in the growth boundary layer is assigned to be a preordering step of crystallization.
Co-reporter:Yong Geng;Guanglin Wang;Yuanhua Cong;Liangui Bai;Chuanlu Yang
Journal of Polymer Science Part B: Polymer Physics 2010 Volume 48( Issue 2) pp:106-112
Publication Date(Web):
DOI:10.1002/polb.21849

Abstract

The conformational ordering and crystallization of polyethylene oxide (PEO) in the presence of KBr surface were studied with in situ Fourier transform infrared spectroscopy (FTIR). KBr was chosen because of its low absorption on IR, which allows adding large amounts KBr into PEO matrix without sacrificing IR signal significantly. The presence of KBr enhances conformational order well above the melting temperature of PEO, which can further accelerate or decelerate the crystallization process. Low concentrations of KBr powder in the PEO melt promotes crystallization process, whereas high concentration of KBr restricts large portion of PEO chains on KBr surfaces, which hinder the diffusion and rearrangement of conformation and consequently slow down the crystallization process. Acceleration of crystallization requires a synergetic effect between the adsorbed chains with ordered conformation and the free chains with a fast diffusion rate, where the former and the later are responsible to lower the nuclei barrier and to maintain the low activation energy of diffusion, respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 106–112, 2010

Co-reporter:Tingzi Yan, Baijin Zhao, Yuanhua Cong, Yuye Fang, Shiwang Cheng, Liangbin Li, Guoqiang Pan, Zijian Wang, Xiuhong Li and Fenggang Bian
Macromolecules 2010 Volume 43(Issue 2) pp:602-605
Publication Date(Web):December 31, 2009
DOI:10.1021/ma9020642
A combination of extensional rheological and in situ synchrotron radiation small-angle X-ray scattering (SR-SAXS) measurements was introduced to investigate critical strain ε* for shish formation and validate whether coil−stretch transition or stretched-network is responsible for shish-kebab formation in high density polyethylene melt. With strain rates ε̇ larger than a specific value, the critical strain ε* required to induce shish formation turns out to be a constant of about 1.57, which ensure full extension of chain segments with critical entanglement molecular weight locked between two adjacent entanglement points. The results clearly demonstrate that the formation of shish-kebab in polymer melt stems from stretched network instead of coil−stretch transition.
Co-reporter:Liangui Bai, Zhihua Hong, Daoliang Wang, Junjun Li, Xiao Wang, Guoqiang Pan, Liangbin Li, Xiuhong Li
Polymer 2010 Volume 51(Issue 23) pp:5604-5611
Publication Date(Web):29 October 2010
DOI:10.1016/j.polymer.2010.09.038
Deformation-induced phase transition behavior of polyamide 12 (PA12) in its segmented copolymers with polytetrahydrofuran (PTHF) was studied with in-situ wide angle X-ray scattering (WAXS) at different temperatures. In these segmented copolymers, which contain a high content of PTHF, a transformation from the stable γ phase to a metastable α″ phase is observed during tensile deformation at room temperature, which shows a similar diffraction behavior to that of the α phase but without an obvious melting point. The deformation-induced α″ phase is not a thermodynamic stable phase but arises from kinetic origins, which is in line with the condition for its formation. After the release of tensile force following deformation, the metastable α″ phase can partially transform back to the initial γ phase. The reversible phase nature may contribute somewhat to the elasticity of PTHF–PA12 systems as a result of this enthalpic contribution. Upon increasing the content of PTHF in the copolymer, the critical stress required to induce the new α″ phase increases. Upon increasing strain, the α″ phase will disappear in the samples that possess a particularly high content of PA12. Higher temperatures also prevent the γ phase from transforming to the α″ phase.
Co-reporter:Daoliang Wang, Chunguang Shao, Baijin Zhao, Liangui Bai, Xiao Wang, Tingzi Yan, Junjun Li, Guoqiang Pan and Liangbin Li
Macromolecules 2010 Volume 43(Issue 5) pp:2406-2412
Publication Date(Web):February 12, 2010
DOI:10.1021/ma1000282
Deformation-induced phase transition of polyamide 12 (PA 12) was studied with in situ wide-angle X-ray scattering (WAXS) at temperatures below and above glass transition temperature. Irrespective to the testing temperature, a transient α′′ phase occurred in the early plastic deformation stage, whose lifetime is decreasing with the increase of temperature. At temperature below glass transition temperature, the transient α′′ phase further transforms into a mesomorphic state with increasing the strain, while high temperature promotes the transient α′′ phase transforming into γ′ phase. The different final states at temperatures below and above glass transition temperature is due to the competition and coupling between external work and thermal activation. External work from tensile deformation is responsible for the appearance of the transient α′′ phase and the final mesomorphic state at temperature below glass transition temperature, while thermal activation drives the transition from the transient α′′ phase to γ′ phase. All these phase transitions occur in the plastic deformation region, which shows a close correlation between the mechanical response and the structural evolution during tensile deformation.
Co-reporter:Junjun Li, Youju Huang, Yuanhua Cong, Lu Xu, Daoliang Wang, Zhenfei Hong, Liangbin Li, Guoqiang Pan
Polymer 2010 Volume 51(Issue 1) pp:232-239
Publication Date(Web):6 January 2010
DOI:10.1016/j.polymer.2009.11.035
A series of rod–coil–rod triblock copolymers were synthesized by two-step polycondensation with polycaprolactam (PA6) as the flexible block and poly(p-benzamide) (PBA) as the rod. Proton nuclear magnetic resonance (1H NMR), UV–vis spectrophotometry and differential scanning calorimetric (DSC) were first performed to determine the fundamental molecular structure and thermal property of each polymer. Through wide angle X-ray scattering (WAXS), and Fourier transformation infrared spectroscopy (FT-IR) measurements, frustrated structures of both components were studied. For PA6, a quasi-γ mesomorphic order was found in the transition-region nearby the PBA domain which is more favored with the increase of the PBA content owing to stretching from the PBA rod block and different cross-section areas of the rod and coil chains. On the other hand, the mesomorphic order of PA6 segments imposes stretching and constraint on the PBA blocks, which leads to a reduction of order of PBA block when the volume fraction of rod reaches approximately 45%. α crystals of PA6 can form only in the triblock copolymer with low volume fraction of PBA, which exhibit the Brill transition feature during the heating process though this transition ends prematurely as the melting of crystals.
Co-reporter:Youju Huang, Yuanhua Cong, Junjun Li, Daoliang Wang, Jingtuo Zhang, Lu Xu, Weili Li, Liangbin Li, Guoqiang Pan and Chuanlu Yang  
Chemical Communications 2009 (Issue 48) pp:7560-7562
Publication Date(Web):10 Nov 2009
DOI:10.1039/B912472A
The designed aromatic amide discotic molecule with sulfonic acid groups at its periphery exhibits a hexagonal supramolecular columnar liquid crystalline phase, which leads to the achievement of anisotropic ionic conductivity through macroscopically aligning the ionic channels.
Co-reporter:Xiangyang Li, Zhenfei Hong, Jie Sun, Yong Geng, Youju Huang, Haining An, Zhe Ma, Baijin Zhao, Chunguang Shao, Yapeng Fang, Chuanlu Yang and Liangbin Li
The Journal of Physical Chemistry B 2009 Volume 113(Issue 9) pp:2695-2704
Publication Date(Web):February 11, 2009
DOI:10.1021/jp8061866
Whether a phase separation or a cocrystallization occurs in poly(hexamethylene succinate-co-hexamethylene adipate) (P(HS-co-HA)) copolymers was studied with a combination of wide-angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR) spectroscopy. With HA as the majority, the presence of HS comonomers leads to weakening and broadening of (10l) peaks in the X-ray fiber diffraction patterns, while a crystal structure similar to PHS is formed in the copolymer with HS as the majority. The X-ray diffraction patterns imply possible cocrystallization between HS and HA comonomers, but cannot lead to an unambiguous conclusion, which was clarified with the compensative tool of FTIR. Following the characteristic absorption bands of crystals, cocrystallization of HS and HA comonomers was observed in copolymers with HA comonomer as the majority during which HA initiated the nucleation at high temperatures. With HA as minority, cocrystallization of HS and HA can still be achieved with a fast quenching to below 0 °C, while a phase separation occurs and only HS comonomer crystallizes at high temperatures. This demonstrates that P(HS-co-HA) has an asymmetric phase diagram. Because of the sensitivity to local conformations, FTIR spectroscopic method is demonstrated to be a powerful tool on study phase behaviors of polymers with similar crystal structure.
Co-reporter:Yong Geng, Guanglin Wang, Yuanhua Cong, Liangui Bai, Liangbin Li and Chuanlu Yang
Macromolecules 2009 Volume 42(Issue 13) pp:4751-4757
Publication Date(Web):May 21, 2009
DOI:10.1021/ma9004567
Flow-induced conformational ordering in the supercooled isotactic polypropylene (iPP) is studied with in situ Fourier transform infrared spectroscopy (FTIR) coupled to an extrusion slit die. At temperature around the normal melting point of iPP, helices with monomer numbers up to 12 and 14 can be induced by shear. A window of shear strength exists to induce helices with different lengths, which increases with temperature. After the cessation of shear, the intensity of the 841 cm−1 band in FTIR spectra, corresponding to helices with 12 monomers, increases sharply in the first stage, which is followed by a slow growth process, whereas a reduction of shorter helices is observed after the cessation of shear. The different trends of intensity evolutions of the long and short helical bands suggest that a coupling between coil−helix transition and intermolecular ordering occurs with helices with a length of 12 monomers, which eventually leads to an isotropic−liquid-crystal transition. Therefore, the flow-induced precursor may be a liquid crystal phase, which will transform into crystal and initiate crystal growth later.
Co-reporter:Zhe Ma, Chunguang Shao, Xiao Wang, Baijin Zhao, Xiangyang Li, Haining An, Tingzi Yan, Zhongming Li, Liangbin Li
Polymer 2009 50(12) pp: 2706-2715
Publication Date(Web):
DOI:10.1016/j.polymer.2009.04.010
Co-reporter:Baijin Zhao, Xiangyang Li, Youju Huang, Yuanhua Cong, Zhe Ma, Chunguang Shao, Haining An, Tinzi Yan and Liangbin Li
Macromolecules 2009 Volume 42(Issue 5) pp:1428-1432
Publication Date(Web):February 17, 2009
DOI:10.1021/ma802679h
Co-reporter:Yuanhua Cong, Guanglin Wang, Menghua Xiong, Youju Huang, Zhenfei Hong, Daoliang Wang, Junjun Li and Liangbin Li
Langmuir 2008 Volume 24(Issue 13) pp:6624-6629
Publication Date(Web):June 4, 2008
DOI:10.1021/la801124z
Magnetic Fe3O4 hollow spheres were successfully synthesized with a water in oil in water (W/O/W) emulsion. During the facile procedure, no high pressure, high temperature, or other complex reaction conditions were required. Transmission electric microscope (TEM) images showed that all the hollow structural products have a good spherical morphology with an average diameter of 160 nm. The average size and the size distribution were further determined with dynamic light scattering (DLS), which reveals that the hollow nanospheres have a narrow size distribution. The average size from DLS was about 180 nm, which approximated that from TEM data. X-ray diffraction (XRD) demonstrates that the products were all Fe3O4 phase without any impurity. By increasing or decreasing the dosage of precipitate and precipitant sources, we controlled the shell thickness successfully in the tens of nanometers range. The formation mechanism of those hollow magnetic nanospheres was discussed by using the “reverse micelle transport” mechanism.
Co-reporter:Xiangyang Li, Jie Sun, Youju Huang, Yong Geng, Xiao Wang, Zhe Ma, Chunguang Shao, Xiao Zhang, Chuanlu Yang and Liangbin Li
Macromolecules 2008 Volume 41(Issue 9) pp:3162-3168
Publication Date(Web):April 2, 2008
DOI:10.1021/ma702888d
The crystal structures of poly(hexamethylene sebacate-co-hexamethylene adipate), P(HSe-co-HA), copolymers have been studied with Fourier transformation infrared spectroscopy (FTIR) and X-ray fiber diffraction. All characteristic FTIR absorption bands of the crystals of HSe and HA comonomers are present in all copolymers, and each copolymer has only one melt temperature, which supports that P(HSe-co-HA) copolymers cocrystallize in a whole range of comonomer compositions. In addition to peak shift, some new diffraction peaks were observed in X-ray fiber diffraction patterns of the copolymers, which correspond to new crystals with different unit cells from those of the homopolymers. The crystal structures of the copolymers were analyzed, which varied with the composition of HA and HSe comonomers. Interestingly, the lattice constants c of P(HSe-co-20 mol % HA) and P(HSe-co-35 mol % HA) crystals are even larger than those of either homopolymers, which implies a new length scale may be induced in the random copolymers. This supports the formation of new crystals instead of normal lattice distortion.
Co-reporter:Haining An, Xiangyang Li, Yong Geng, Yunlong Wang, Xiao Wang, Liangbin Li, Zhongming Li and Chuanlu Yang
The Journal of Physical Chemistry B 2008 Volume 112(Issue 39) pp:12256-12262
Publication Date(Web):September 6, 2008
DOI:10.1021/jp802511b
The shear-induced coil−helix transition of isotactic polypropylene (iPP) has been studied with time-resolved Fourier transform infrared spectroscopy at various temperatures. The effects of temperature, shear rate, and strain on the coil−helix transition were studied systematically. The induced conformational order increases with the shear rate and strain. A threshold of shear strain is required to induce conformational ordering. High temperature reduces the effect of shear on the conformational order, though a simple correlation was not found. Following the shear-induced conformational ordering, relaxation of helices occurs, which follows the first-order exponential decay at temperatures well above the normal melting point of iPP. The relaxation time versus temperature is fitted with an Arrhenius law, which generates an activation energy of 135 kJ/mol for the helix−coil transition of iPP. At temperatures around the normal melting point, two exponential decays are needed to fit well on the relaxation kinetic of helices. This suggests that two different states of helices are induced by shear: (i) isolated single helices far away from each other without interactions, which have a fast relaxation kinetic; (ii) aggregations of helices or helical bundles with strong interactions among each other, which have a much slower relaxation process. The helical bundles are assumed to be the precursors of nuclei for crystallization. The different helix concentrations and distributions are the origin of the three different processes of crystallization after shear. The correlation between the shear-induced conformational order and crystallization is discussed.
Co-reporter:Jun Lu;Rui Huang;Yong Chen
Journal of Polymer Science Part B: Polymer Physics 2006 Volume 44(Issue 21) pp:3148-3156
Publication Date(Web):27 SEP 2006
DOI:10.1002/polb.20953

Morphologies of extended-chain crystals with different characteristics were observed with scanning electron microscopy (SEM) in the high-pressure crystallized polyethylene terephthalate/polycarbonate (PET/PC) blends. The crystals memorize their nucleation and growth process, which reveal an involvement of different mechanisms simultaneously. The presence of sliding diffusion during crystal thickening is indicated by a wedge shape of some crystals, while bent crystals suggest the occurrence of transesterification in the formation of the large extended-chain crystals. The observation of two morphological features on one group of crystals shows that two mechanisms may work simultaneously. The connection between folded-chain and extended-chain crystals is demonstrated by the S-shaped extended-chain crystals as well as their direct morphological connection observed with SEM. Though transesterification plays the essential role in the formation of the large crystals, which acts in different aspects during the process, the thermodynamic driving force is the enthalpy gain associated with large crystals. This is a high-pressure self-assembly with a coupling between crystallization and transesterification, which may be instructive to grow such large crystals in similar polymer systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3148–3156, 2006

Co-reporter:Youju Huang;Yuanhua Cong;Junjun Li;Daoliang Wang;Jingtuo Zhang;Lu Xu;Weili Li;Guoqiang Pan;Chuanlu Yang
Chemical Communications 2009(Issue 48) pp:
Publication Date(Web):2009/11/30
DOI:10.1039/B912472A
The designed aromatic amide discotic molecule with sulfonic acid groups at its periphery exhibits a hexagonal supramolecular columnar liquid crystalline phase, which leads to the achievement of anisotropic ionic conductivity through macroscopically aligning the ionic channels.
Benzenemethanol, 3,4,5-tris(dodecyloxy)-
Potassium ion (1+)
.ALPHA.-EICOSENE
Formamide, N,N-dimethyl-
N,N,N-trimethylmethanaminium
O-ethyl S-prop-2-yn-1-yl carbonodithioate