Tailoring poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) microstructure and physicochemical properties by exploring its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) (PVDF‐CTFE) membranes were prepared by solvent casting from dimethylformamide (DMF). The preparation conditions involved a systematic variation of polymer/solvent ratio and solvent evaporation temperature. The microstructural variations of the PVDF‐CTFE membranes depend on the different regions of the PVDF‐CTFE/DMF phase diagram, explained by the Flory‐Huggins theory. The effect of the polymer/solvent ratio and solvent evaporation temperature on the morphology, degree of porosity, β phase content, degree of crystallinity, mechanical, dielectric, and piezoelectric properties of the PVDF‐CTFE polymer were evaluated. In this binary system, the porous microstructure is attributed to a spinodal decomposition of the liquid‐liquid phase separation. For a given polymer/solvent ratio, 20 wt % , and higher evaporation solvent temperature, the β phase content is around 82% and the piezoelectric coefficient, d₃₃, is ? 4 pC/N © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 761–773     

Influence of Mixed Common Solvent on the Co-assembled Morphology of PS-b-PEO and CdS Quantum Dots

The hybrid structures of polystyrene-b-poly(ethylene oxide)(PS-b-PEO) block copolymer and inorganic nanoparticles with good stability and biocompatibility have potential applications in drug delivery and bioimaging. Spherical co-assemblies of PS120-b-PEO318 and oleylamine-capped Cd S quantum dots(QDs) are produced successfully in this work by adding water to a mixed common solvent, such as N,N-dimethylmethanamide(DMF)/chloroform, DMF/tetrahydrofuran(THF), or DMF/toluene. The energy dispersive X-ray(EDX) spectrum indicates that QDs are located at the interface between the core and shell of the spherical co-assemblies. The co-assembly process during water addition is traced by transmission electron microscopy(TEM) and turbidity measurement. Spherical co-assemblies are formed through budding from bilayers of the block copolymer and QDs. The morphology of the co-assemblies is related to the miscibility of the QD-dispersing solvents with water and the morphology changes from a spherical to a vesicle-like structure with DMF/toluene. Increasing THF content in the mixed solvent causes morphological transitions from spherical co-assemblies to multi-branched cylinders and micelles where QDs are located in the central core. Increasing chloroform content yields vesicle-like structures with protruding rods on the surface. The mechanism of the morphological transitions is also discussed in detail.     

Electrospinning of poly(vinylidene fluoride)/dimethylformamide solutions with carbon nanotubes

For conductive carbon nanotube (CN)/polymer composite fibers to be obtained, CNs were incorporated into poly(vinylidene fluoride) (PVDF) in dimethylformamide (DMF) solutions and electrospun to form CN/PVDF fiber mats. The thinnest fiber was 70 nm thick. The percolation threshold for the insulator‐to‐conductor transition was 0.003 wt % CN for CN/PVDF/DMF solutions, 0.015 wt % CN for CN/PVDF spin‐coated films, and 0.04 wt % CN for CN/PVDF electrospun fiber mats. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1572–1577, 2003     

Influence of a mixing solvent with tetrahydrofuran and N,N‐dimethylformamide on electrospun poly(vinyl chloride) nonwoven mats

We evaluated the effects of the solvent composition with respect to the solution concentration, applied electric field, and tip‐to‐collector distance on the morphology of electrospun poly(vinyl chloride) (PVC) fibers. The solvent volume ratio was strongly correlated with the diameter of the electrospun fibers with respect to the other processing parameters. Electrospun PVC fibers dissolved in tetrahydrofuran (THF) had diameters ranging from 500 nm to 6 μm; those dissolved in N,N‐dimethylformamide (DMF) had an average diameter of 200 nm. The diameters of the electrospun fibers were obtained from narrow to broad distributions with the solvent composition. Also, the diameters of fibers electrospun from a mixed solvent of THF and DMF were less than 1 μm. The mechanical properties of electrospun PVC nonwoven mats depended on the fiber orientation and linear velocity of the drum surface. With increasing linear velocity of the drum surface, electrospun PVC fibers were arranged toward the machine direction, and the dimensions of the spiral path were shorter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2259–2268, 2002     

Aligned and molecularly oriented semihollow ultrafine polymer fiber yarns by a facile method

In this work, aligned and molecularly oriented bone‐like PLLA semihollow fiber yarns were manufactured continuously from an optimized homogeneous polymer‐solvent‐nonsolvent system [PLLA, CH₂Cl₂, and dimethyl formamide (DMF)] by a single capillary electrospinning via self‐bundling technique. Here, it should be emphasized that the self‐bundling electrospinning technique, a very facile electrospinning technique with a grounded needle (which is to induce the self‐bundling of polymer nanofibers at the beginning of electrospinning process), is used for the alignment and molecular orientation of the polymer fiber, and the take‐up speed of the rotating drum for the electrospun fiber yarn collection is very low (0.5 m/s). PLLA can be dissolved in DMF and CH₂Cl₂ mixed solvent with different ratios. By varying the ratios of mixed solvent system, PLLA electrospun semihollow fiber with the porous inner structure and compact shell wall could be formed, the thickness of the shell and the size of inner pores could be adjusted. The results of polarized FTIR and wide angle X‐ray diffraction investigations verified that as‐prepared PLLA semihollow fiber yarns were well‐aligned and molecularly oriented. Both the formation mechanism of semihollow fibers with core‐shell structure and the orientation mechanism of polymer chains within the polymer fibers were all discussed. The as‐prepared self‐bundling electrospun PLLA fiber yarns possessed enhanced mechanical performance compared with the corresponding conventional electrospun PLLA fibrous nonwoven membranes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1118–1125, 2010     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Controlling the surface structure,mechanical properties,crystallinity, and piezoelectric properties of electrospun PVDF nanofibers by maneuvering molecular weight

Polyvinylidene fluoride (PVDF) is a significant polymer in the formation of nanofiber webs via the electrospinning technique. In this paper, three PVDF-wrinkled fiber webs with different molecular weights (M_Ws) (180000, 275000, and 530000) were generated via the electrospinning method by using tetrahydrofuran/N,N-dimethylformamide at the solvent ratio of 1:1 as a mixed solvent. The formation mechanism of the wrinkled electrospun PVDF fibers is demonstrated. Furthermore, the relationships between the M_W and the surface structure, mechanical properties, crystalline phases, and piezoelectric properties of electrospun PVDF fibers are comprehensively investigated. The results reported that the surface structure, mechanical properties, crystalline phases, and piezoelectric properties of wrinkled electrospun PVDF fibers can be affected intensely by maneuvering the M_W. We believe this study can be served as a good reference for the effect of M_W on the morphology and properties of electrospun fibers.     

Electrospinning of ultrafine cellulose acetate fibers: Studies of a new solvent system and deacetylation of ultrafine cellulose acetate fibers

Electrospinning of cellulose acetate (CA) in a new solvent system and the deacetylation of the resulting ultrafine CA fibers were investigated. Ultrafine CA fibers (∼2.3 μm) were successfully prepared via electrospinning of CA in a mixed solvent of acetone/water at water contents of 10–15 wt %, and more ultrafine CA fibers (0.46 μm) were produced under basic pH conditions. Ultrafine cellulose fibers were regenerated from the homogeneous deacetylation of ultrafine CA fibers in KOH/ethanol. It was very rapid and completed within 20 min. The crystal structure, thermal properties, and morphology of ultrafine CA fibers were changed according to the degree of deacetylation, finally to those of pure cellulose, but the nonwoven fibrous mat structure was maintained. The activation energy for the deacetylation of ultrafine CA fibers was 10.3 kcal/mol. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 5–11, 2004     

Controlled crystallization of poly(vinylidene fluoride) chains from mixed solvents composed of its good solvent and nonsolvent

Poly(vinylidene fluoride) (PVDF) chains with the same expanded state were obtained by dissolving PVDF resin in good solvent. Then, the crystallization of PVDF chains from mixed solvents composed of its good solvent and nonsolvent was investigated. N,N‐dimethylformamide (DMF) and ethanol were used as good solvent and nonsolvent of PVDF, respectively. The crystalline phases of PVDF were characterized by Fourier transform infrared (FTIR) spectroscopy and wide angle X‐ray diffraction (WAXD). For the crystallization of PVDF chains from mixed solvents, low ethanol content favored the formation of β phase, while high ethanol content resulted predominantly in the α phase. Different crystallization morphology was observed from the scanning electron microscopy (SEM) images. The obvious spherulite morphology disappeared with the increase in ethanol content in mixed solvent. According to thermal analyses, the crystallized PVDF from mixed solvents with high ethanol content had lower onset melting temperatures than that from low ethanol content. Smaller lamellar thickness calculated from WAXD data reasoned the low onset melting temperatures. The above results indicated that the crystallization of PVDF chains from mixed solvent was a “controlled” process by ethanol content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 575–581, 2010     

Polyaniline/poly(methyl methacrylate) coaxial fibers: The fabrication and effects of the solution properties on the morphology of electrospun core fibers

Electrically conductive polyaniline (PANi)/poly(methyl methacrylate) (PMMA) coaxial fibers were prepared through the chemical deposition of PANi onto preformed PMMA fibers via in situ polymerization. PMMA fibers were prepared as core materials via electrospinning. Spectral studies and scanning electron microscopy observations indicated the formation of PANi/PMMA coaxial fibers with a diameter of approximately 290 nm and a PANi layer thickness of approximately 30 nm. The conductivity of the PANi/PMMA coaxial fibers was significantly higher than that of electrospun fibers of PANi/poly(ethylene oxide) blends and blend cast films of the same PANi composition. To reproducibly generate uniform‐core polymer fibers, the organic solution properties that affected the morphology and diameter of the electrospun fibers were investigated. The polymer molecular weight, solution concentration, solvent dielectric constant, and addition of soluble organic salts were strongly correlated to the morphology of the electrospun fiber mat. In particular, the dielectric constants of the solvents substantially influenced both the fiber diameter and bead formation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3934–3942, 2004     

静电纺制备纳米孔结构聚乳酸(PLLA)超细纤维

采用静电纺丝法制备了孔径为40～150 nm的PLLA纳米孔结构超细纤维,纳米孔不仅分布在纤维表面,而且存在于纤维内部.通过扫面电镜观察了纤维表面形貌.探讨了混合溶剂二氯甲烷/N,N-二甲基甲酰胺的比例、PLLA浓度、电场强度对PLLA纤维纳米孔大小、分布密度、深度的影响.结果表明通过调节PLLA溶液性质和纺丝参数,PLLA纤维的表面形貌可以在3种状态即光滑无孔、疏浅凹坑、密集深孔之间可控.二氯甲烷/N,N-二甲基甲酰胺比例为1∶4,PLLA浓度9%,电场强度1 kV/cm,环境温湿度分别为30℃和52%,静电纺丝所得PLLA超细纤维表面孔洞直径为150 nm,孔洞分布密集.纳米孔PLLA纤维形成的主要机理是由于静电纺丝过程中溶剂的快速挥发引起纤维表面温度急剧降低导致热致相分离而产生多孔结构.PLLA纤维膜的疏水性与纤维表面孔洞结构密切相关,纤维膜接触角最高可达146.6°.由于PLLA纤维的多孔结构,这种高疏水性的PLLA纤维膜能够快速、大量地吸油,90 s内吸收柴油达到90 g/g,25 min内可以达到145 g/g.     

核-壳结构壳聚糖/聚乙烯醇-聚碳酸亚丙酯超细纤维的制备

利用同轴电纺丝技术制备出具有核-壳结构的壳聚糖/聚乙烯醇-聚碳酸亚丙酯电纺丝纤维,考察了溶剂复配对成纤的影响,采用扫描电镜和透射电镜对纤维的形貌、结构、直径分布等进行了探索,并在优化的工艺条件下,将羟基磷灰石负载在内层结构中.研究表明,采用氯仿/N,N-二甲基甲酰胺(1/1)复配溶剂可有效避免聚合物溶液在喷丝口处的凝结现象.同单纺纤维相比,核壳结构的纤维直径分布较宽,纤维壳层和核层界限清晰;红外谱图分析证明羟基磷灰石可负载在纤维的核结构中.     

Influence of mixed common solvent on the co-assembled morphology of PS-<Emphasis Type="Italic">b</Emphasis>-PEO and CdS quantum dots

The hybrid structures of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymer and inorganic nanoparticles with good stability and biocompatibility have potential applications in drug delivery and bioimaging. Spherical co-assemblies of PS₁₂₀-b-PEO₃₁₈ and oleylamine-capped CdS quantum dots (QDs) are produced successfully in this work by adding water to a mixed common solvent, such as N,N-dimethylmethanamide (DMF)/chloroform, DMF/tetrahydrofuran (THF), or DMF/toluene. The energy dispersive X-ray (EDX) spectrum indicates that QDs are located at the interface between the core and shell of the spherical co-assemblies. The co-assembly process during water addition is traced by transmission electron microscopy (TEM) and turbidity measurement. Spherical co-assemblies are formed through budding from bilayers of the block copolymer and QDs. The morphology of the co-assemblies is related to the miscibility of the QD-dispersing solvents with water and the morphology changes from a spherical to a vesicle-like structure with DMF/toluene. Increasing THF content in the mixed solvent causes morphological transitions from spherical co-assemblies to multi-branched cylinders and micelles where QDs are located in the central core. Increasing chloroform content yields vesicle-like structures with protruding rods on the surface. The mechanism of the morphological transitions is also discussed in detail.     

Viscometric study of poly(vinyl chloride)/poly(vinyl acetate) blends in various solvents

The intermolecular interactions between poly(vinyl chloride) (PVC) and poly(vinyl acetate) (PVAc) in tetrahydrofuran (THF), methyl ethyl ketone (MEK) and N,N^′-dimethylformamide (DMF) were thoroughly investigated by the viscosity measurement. It has been found that the solvent selected has a great influence upon the polymer-polymer interactions in solution. If using PVAc and THF, or PVAc and DMF to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+THF) or (PVAc+DMF) is less than in corresponding pure solvent of THF or DMF. On the contrary, if using PVAc and MEK to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+MEK) is larger than in pure solvent of MEK. The influence of solvent upon the polymer-polymer interactions also comes from the interaction parameter term Δb, developed from modified Krigbaum and Wall theory. If PVC/PVAc blends with the weight ratio of 1/1 was dissolved in THF or DMF, Δb<0. On the contrary, if PVC/PVAc blends with the same weight ratio was dissolved in MEK, Δb>0. These experimental results show that the compatibility of PVC/PVAc blends is greatly associated with the solvent from which polymer mixtures were cast. The agreement of these results with differential scanning calorimetry measurements of PVC/PVAc blends casting from different solvents is good.     

Diameter control of electrospun chitosan‐collagen fibers

In this article, the effects of fundamental parameters including applied voltage, feed rate of solution, collecting distance of fibers, the ratio of chitosan to collagen in the fibers and polymer solution concentration on the diameter and morphology of electrospun collagen‐chitosan complex nanofibers were studied to produce ultrafine polymer fibers. Based on the systematic parametric study, it is possible to control the diameter and morphology of the electrospun polymer fibers. This will also be helpful for electrospinning of various polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1949–1955, 2009     

Li＋在PC＋DMF混合溶剂中优先溶剂化的13C NMR研究

利用¹³C NMR光谱技术研究了Li^＋在碳酸丙烯酯(PC)＋N,N-二甲基甲酰胺(DMF)混合溶剂中的优先溶剂化现象. 根据溶剂分子中碳原子的化学位移随锂盐浓度的变化关系, 确定了与Li^＋发生配位的原子. 碳原子的配位位移值随混合溶剂组成的变化关系表明, 在LiClO₄＋PC＋DMF混合物中, DMF分子对Li^＋的溶剂化作用较PC分子强. 定量计算得到, 在n(PC)∶n(DMF)＝1∶1(摩尔比)的混合溶剂中, PC与DMF分子数在Li^＋第一溶剂化层中的比率为0.12, 说明Li^＋优先被DMF分子溶剂化.     

Controlling the formation of long‐subchain hyperbranched polystyrene from seesaw‐type AB2 macromonomers: Solvent polarity and solubility

Through atom transfer radical polymerization of styrene with 1,3‐dibromomethyl‐5‐propargyloxy‐benzene as initiator followed by the conversion of bromine end‐groups into azide end‐groups, well‐defined seesaw‐type polystyrene (PSt) macromonomers with two molecular weights (M_n = 8.0 and 28.0 k) were obtained. Thus, a series of long‐subchain hyperbranched (lsc‐hp) PSt with high overall molar masses and regular subchain lengths were obtained via copper‐catalyzed azide–alkyne cycloaddition click chemistry performed in THF and DMF, respectively. The polycondensation of seesaw‐type macromonomers was monitored by gel permeation chromatography. Because DMF is the reaction medium with higher polarity, click reaction proceeds more easily in DMF. Therefore, the growth of lsc‐hp PSt in DMF has faster rate than that in THF for the shorter seesaw‐type macromonomer (Seesaw‐8k). However, THF is the solvent with better solubility to PSt and leads to looser conformation of PSt chains. Thus, for the longer seesaw macromonomer (Seesaw‐28k), lsc‐hp PSt in THF has higher overall molar mass. As well, the self‐cyclization of seesaw‐type macromonomers also depends on both solvent and molar mass of macromonomer. The self‐cyclization degrees of Seesaw‐8k in DMF and THF are almost the same while that of Seesaw‐28k macromonomer is obviously lower in THF. The experimental results suggest a physical consideration to control the growth of hyperbranched polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Confined crystallization of PVDF and a PVDF‐TFE copolymer in nanolayered films

Layer‐multiplying coextrusion was used in conjunction with isothermal recrystallization to study the confined crystallization of polyvinylidene fluoride (PVDF) and polyvinylidene fluoride‐tetrafluoroethylene (PVDF‐TFE) using polycarbonate (PC) and polysulfone (PSF) as confining materials. Three layered systems were produced (PC/PVDF, PSF/PVDF, and PC/PVDF‐TFE) with layer thicknesses ranging from 525 to 28 nm. The crystal morphology was affected by both layer thickness and recrystallization temperature. Specifically, increased recrystallization temperature and decreased layer thickness facilitated the formation of high aspect ratio in‐plane crystals in both PVDF based polymers. On the other side of the spectrum, thicker layers and lower recrystallization temperatures produced on‐edge PVDF crystals and isotropic PVDF‐TFE crystals. The morphology was correlated with oxygen permeability, which decreased by almost two orders of magnitude compared with the bulk. A variety of crystal structures were obtained and explained with nucleation and diffusion theory. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Controlling the self-assembly structure of magnetic nanoparticles and amphiphilic block-copolymers: from micelles to vesicles

We report how to control the self-assembly of magnetic nanoparticles and a prototypical amphiphilic block-copolymer composed of poly(acrylic acid) and polystyrene (PAA-b-PS). Three distinct structures were obtained by controlling the solvent-nanoparticle and polymer-nanoparticle interactions: (1) polymersomes densely packed with nanoparticles (magneto-polymersomes), (2) core-shell type polymer assemblies where nanoparticles are radially arranged at the interface between the polymer core and the shell (magneto-core shell), and (3) polymer micelles where nanoparticles are homogeneously incorporated (magneto-micelles). Importantly, we show that the incorporation of nanoparticles drastically affects the self-assembly structure of block-copolymers by modifying the relative volume ratio between the hydrophobic block and the hydrophilic block. As a consequence, the self-assembly of micelle-forming block-copolymers typically produces magneto-polymersomes instead of magneto-micelles. On the other hand, vesicle-forming polymers tend to form magneto-micelles due to the solubilization of nanoparticles in polymer assemblies. The nanoparticle-polymer interaction also controls the nanoparticle arrangement in the polymer matrix. In N,N-dimethylformamide (DMF) where PS is not well-solvated, nanoparticles segregate from PS and form unique radial assemblies. In tetrahydrofuran (THF), which is a good solvent for both nanoparticles and PS, nanoparticles are homogeneously distributed in the polymer matrix. Furthermore, we demonstrated that the morphology of nanoparticle-encapsulating polymer assemblies significantly affects their magnetic relaxation properties, emphasizing the importance of the self-assembly structure and nanoparticle arrangement as well as the size of the assemblies.     

Multicomponent latex IPN materials: 2. Damping and mechanical behavior

The integrals of the linear loss shear modulus vs. temperature (loss area, LA) and linear tan δ vs. temperature (tan δ area, TA) were characterized for various core/shell latex particles with synthetic rubber, poly(butadiene-stat-styrene) [P (Bd/S), 90/10], and interpenetrating polymer networks (IPN) as the cores. The IPN cores were composed of P(Bd/S) (T_g ≃ − 70°C) and an acrylate based copolymer (T_g around 10°C) for potential impact and damping improvement in thermoplastics. Poly(styrene-stat-acrylonitrile) (SAN, 72/28) was the shell polymer for all these polymers. Under the same loading, for both toughening and damping controls, among the IPN core/shell, blend of separate core/shell, and multilayered core/shell polymers, the IPN core/shell polymers were the best dampers. However, the other core/shell polymers also showed higher LA values than P(Bd/S)/SAN core/shell polymer. A comparison of LA values via a group contribution analysis method was made, the effect of particle morphology and phase continuity on damping being studied. Inverted core/shell latex particles (glassy polymer SAN was synthesized first) showed much higher LA and TA values than normal core/shell ones (rubbery polymer was synthesized first). Models for maximum LA and TA behavior are proposed. The damping property was essentially controlled by the phase miscibility and morphology of the core/shell latex particles. The LA values for each peak in these multiphase materials provided some indication of the several fractional phase volumes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1501–1514, 1997