Steady shear and viscoelastic properties of a micro‐crosslinked acrylamide‐based terpolymer

A water‐soluble micro‐crosslinked associating polymer (PASA‐PL): poly (acrylamide/butyl styrene/sodium 2‐acrylamido‐2‐methylpropane sulphonate) (PASA)–phenolic aldehyde (PL) was prepared to reduce the critical associated concentration and enhance the thickening properties for the linear PASA polymer in aqueous and brine solutions. The consecutive steady shear and viscoelastic properties were investigated to explore the correlations between the rheologic performance and supramolecular structures for the PASA‐PL brine solutions. Upon consecutive steady shear, the intermolecular hydrophobic association is greatly reinforced because of the expansion of the coiled PASA‐PL chains at the suitable shear rate, and the brine solution exhibits obvious shear thickening behavior. The steady shear results show that the intermolecular hydrophobic association is reversible, and that the polymer chains do not degrade upon shearing. The PASA‐PL brine solutions with 50 g L⁻¹ NaCl have predominantly elastic character over the angular frequency range at the polymer concentration higher than 1.0 g L⁻¹, which is remarkably strengthened with a slight increase in polymer concentration. The PASA‐PL brine solutions display a salt‐thickening effect and predominantly exhibit elastic character over the angular frequency range at 10–50 g L⁻¹ NaCl. These results demonstrate that the viscoelastic behavior of the PASA‐PL solutions mainly depends on the formation of hydrophobically associated structures via the intermolecular association strengthened by the micro‐crosslink of PASA with PL. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improving dielectric properties of poly(vinylidene fluoride) composites: effects of surface functionalization of exfoliated graphene

To investigate the effects of surface functionalization of exfoliated graphene (EG) on the crystalline form of β-phase and dielectric properties of poly(vinylidene fluoride) (PVDF), we prepared PVDF-based composites reinforced by different functionalized EG. The X-ray photoelectron spectroscopy results indicated that a wide variety of chemical functional groups such as C–OH, C–O–C, C=O, COOH and C–F could be introduced on the surface of modified EG. As confirmed by results of Fourier transform infrared spectrum and X-ray diffraction, the β-phase PVDF can be produced in the composites with the incorporation of functionalized EG. In the frequency ranging from 10² to 10⁷ Hz, the dielectric permittivity of PVDF composites shows an obvious increase owing to a variation of the carbonyl group (C=O) content. Among all the composites, the EG grafted with polymethyl methacrylate/PVDF composite has the highest dielectric permittivity and dielectric loss.     

Morphology, polymorphism behavior and molecular orientation of electrospun poly(vinylidene fluoride) fibers

The morphology, polymorphism behavior and molecular orientation of electrospun poly(vinylidene fluoride) (PVDF) fibers have been investigated. We found that electrospinning of PVDF from its N,N-dimethylformamide/acetone solutions led to the formation of β-phase. In contrast, only α- and γ-phase was detected in the spin-coated samples from the same solutions. In the aligned electrospun PVDF fibers obtained using a rotating disk collector, the β-phase crystallites had a preferred orientation along the fiber axis. The degree of orientation did not, however, vary significantly with the speed of the rotation disk collector, and the β-phase was also not significantly enhanced with the increase in the rotation speed or the decrease in the size of spinnerets. These facts indicated that the orientation was likely to be caused by Columbic force rather than the mechanical and shear forces exerted by the rotating disk collector and spinnerets. The Columbic force may induce local conformational change to straighter TTTT conformation, and hence promote the β-phase. The addition of 3 wt.% of tetrabutylammonium chloride (TBAC) into the polymer solutions effectively improved the morphology of the electrospun fibers, and led to almost pure β-phase in the fibers. With spin coating, PVDF-TBAC did not, however, show any strong β-phase diffraction peak. The synergistic β-enhancement effect of TBAC and electrospinning is possibly due to the fact that while TBAC could induce more trans conformers, electrospinning promotes parallel packing, and hence inter-chain registration.     

高分子链结构对聚酰胺酰亚胺溶液流变行为的影响

以高分子主链分别含3个和10个亚甲基结构的脂肪族–芳香族聚酰胺酰亚胺(PAI)为模型聚合物,采用旋转流变仪研究了高分子链结构对PAI溶液流变行为的影响。研究结果表明,含10个亚甲基结构的PAI在较宽的剪切速率范围内表观黏度变化不大,但含3个亚甲基结构的PAI溶液在一定的剪切速率区间发生了剪切增稠现象,并且随着温度的升高,剪切增稠现象逐渐减弱,同时剪切增稠所对应的剪切速率向高剪切速率方向移动。     

Pyroelectric performances of 1-3 ferroelectric composites based on barium titanate nanowires/polyvinylidene fluoride

Pyroelectric properties of 1–3 ceramic/polyvinylidene fluoride (PVDF) composites by using barium titanate nanowires (BTnws) and dopamine modified BTnws (DM-BTnws) as inclusions were firstly reported. 0–3 composites based on dopamine modified BT nanoparticles (DM-BTnps)/PVDF were also prepared for comparison. It was found that low contents of DM-BTnws in PVDF are beneficial for achieving high fraction of β-phase content based on the analysis results of X-ray diffraction (XRD), Fourier transform infrared (FTIR) and electric displacement-electric field (D-E) measurements. The enhancement of β-phase content in the DM-BTnws/composited film was believed to originate from strong hydrogen bonds interactions between poly-dopamine and PVDF molecules, which induced phase transition in PVDF from α-phase into β-phase. However, although DM-BTnws improved β-phase content and, accordingly, pyroelectric coefficient of the composites, they deteriorated dielectric performances of PVDF, reducing pyroelectric performances of the composites in terms of voltage and detectivity figures of merit.     

Impact of vanadium-, sulfur-, and dysprosium-doped zinc oxide nanoparticles on various properties of PVDF/functionalized-PMMA blend nanocomposites: Structural,optical, and morphological studies

The polymeric blend was fabricated with crystalline poly(vinylidene fluoride) (PVDF)/amorphous functionalized-poly(methyl methacrylate) (PMMA) in 70/30 w/w ratio by chemical mixing method. Functionalization of PMMA was achieved with 2-amino-5-nitrobenzoic acid. The prepared polymer blend was used as a matrix to synthesize nanocomposites with undoped/doped zinc oxide (ZnO) nanoparticles. Doping in ZnO was achieved with vanadium, sulfur, and dysprosium elements as a dopant. The structural, optical, electronic, and morphological properties of undoped/doped nanosized ZnO and blended nanocomposites were accessed through sophisticated analytical techniques, that is, Fourier transform infrared (FTIR), ultraviolet–visible (UV–vis), UV–vis–diffuse reflectance spectra, nuclear magnetic resonance, fluorescence spectroscopy, X-ray diffraction (XRD), transmission electron microscopy, and scanning electron microscopy. The FTIR band at 1165–1176 cm⁻¹ in functionalized-PMMA indicate the formation of aliphatic C-N bond along with aromatic ¹H chemical shift (δ) at 7.134, 7.829 and 8.210 ppm confirm the successfully functionalization of PMMA. The prominent XRD peak at 2θ = 20.8° in nanocomposites shown improvement in β-phase of PVDF. The results show that Dy doped ZnO nanoparticles create remarkable effect on various properties of nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47116.     

不同体系剪切增稠液体的流变行为研究

剪切增稠液体是指其表观粘度随剪切速率增加而变大的一类流体。工业生产中,剪切增稠的出现会阻碍输送管道,破坏生产设备。针对这种情况,人们对如何降低流体粘度造成的不利影响进行了大量研究。另一方面,剪切增稠液体是“液体防弹材料”的关键组成部分,并且在减震、控制方面也具有可观的应用潜力。该文采用原生粒径为50 nm 的SiO2和80～100 nm 的 CaCO3分别作为分散相,聚乙二醇（PEG）200为分散介质,采用超声分散法制备得到不同固含量的剪切增稠液。并通过纳米粒度仪和扫描电镜对分散相粒子团聚情况进行分析;通过应力控制流变仪分别对 SiO2/PEG200和 CaCO3/PEG200悬浮分散体系的稳态流变性能进行分析。结果表明,两种体系试样在测试中均出现剪切增稠现象,并且分散相质量分数越高,剪切增稠效果越明显;而高质量分数的 SiO2/PEG200体系的粘度变化范围更大,增稠现象更为明显。     

Rheological behavior in the molten state and solution of hyperbranched polyester of fourth and fifth generation

The rheological behavior in the molten state and solution of hyperbranched polyol polyesters (HBPs) obtained by one step (HBP4, HBP5), step by step (HBP4P, HBP5P), and combination of both (HBP1‐4, HBP1‐5) was studied. Under conditions of dynamic oscillatory shear, all HBPs presented a shear‐thinning behavior and under steady shear they showed a Newtonian behavior. Also, the steady shear viscosities decreased with increasing temperature. The behavior of HBPs was mainly viscous, except for the HBP4P that showed higher storage modulus and reduction of complex viscosity when increasing the angular frequency. The HBPs presented higher complex viscosity than steady shear and they did not follow the Cox‐Merz rule. The HBPs in solution presented a plateau region at shear rate lower than 40 s⁻¹ but a shear‐thickening behavior at shear rate higher than 40 s⁻¹. The viscosities of HBPs in solution (in the plateau region) and molten state increase in the following order: HBP5P > HBP1‐5 > HBP4P > HBP1‐4 > HBP4 > HBP5. These results are not in agreement with the values of the number average molar mass obtained by vapor pressure osmometry due to different interaction between HBPs molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

An examination of the shear‐thickening behavior of high molecular weight polymers dissolved in low‐viscosity Newtonian solvents

The anomaly of shear thickening at high shear rates can be observed under certain conditions for high molecular weight polymers dissolved in low‐viscosity Newtonian solvents despite the fact that shear‐thinning behavior is considered the norm for these fluids. The nature of the shear‐thickening region of the flow curve is examined herein through the application of a recent rheological model that has the capability of quantifying not only the rheological properties of the material, but its internal microstructural state as well. The results of this examination provide a self‐consistent explanation of the full flow characterization of this anomalous behavior, including both rheological and optical experimental measurements. The results presented herein suggest that the shear‐thickening behavior is actually caused by the destruction of structures formed during shear at lower shear rates, not by their formation, as previously assumed. The linear birefringence and linear dichroism observed experimentally in correlation with the shear‐thickening behavior are well described by the rheological model and give predictions in line with experimental measurements. Furthermore, quantitative predictions are made for rheological characteristic functions, such as the first and second normal‐stress coefficients, for which experimental measurements for these solutions have not yet been made. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1714–1735, 2002     

Crystallization behavior of nano-composite based on poly(vinylidene fluoride) and organically modified layered titanate

To understand the effect of the nano-filler particles on the crystallization kinetics and crystalline structure of poly(vinylidene fluoride) (PVDF) upon nano-composite formation, we have prepared PVDF/organically modified layered titanate nano-composite via melt intercalation technique. The layer titanate (HTO) is a new nano-filler having highly surface charge density compared with conventional layered silicates. The detailed crystallization behavior and its kinetics including the conformational changes of the PVDF chain segment during crystallization of neat PVDF and HTO-based nano-composite (PVDF/HTO) have been investigated by using differential scanning calorimetric, wide-angle X-ray diffraction, light scattering, and infrared spectroscopic analyses. The neat PVDF predominantly formed α-phase in the crystallization temperature range of 110-150 °C. On the other hand, PVDF/HTO exhibited mainly α-phase crystal coexisting with γ- and β-phases at low T_c range (110-135 °C). A major γ-phase crystal coexists with β- and α-phases appeared at high T_c (=140-150 °C), owing to the dispersed layer titanate particles as a nucleating agent. The overall crystallization rate and crystalline structure of pure PVDF were strongly influenced in the presence of layered titanate particles.     

剪切增稠液体的性能及其在柔性防刺材料中的应用

介绍了剪切增稠液体的特点、增稠机制及其流变性能的主要影响因素。在此基础上,又从机织物、针织物、非织造布角度列举并介绍了剪切增稠液体在柔性防刺材料中的研究现状,并对其在柔性防刺材料中的研究以及未来的发展做出了展望。     

Achieving β-phase poly(vinylidene fluoride) from melt cooling: Effect of surface functionalized carbon nanotubes

Poly(vinylidene fluoride) (PVDF) based nanocomposites with different surface-functionalized multi-walled carbon nanotubes (MWCNTs) were prepared by melt mixing in a small scale compounder. With the incorporation of commercial functionalized MWCNTs, the β-phase in PVDF can be directly achieved from melt cooling, as verified by results of Fourier transform infrared spectrum and X-ray diffraction. Interestingly, nanocomposites with amino group functionalized MWCNTs showed the highest percentage of β-phase (17.4%) formation in PVDF, followed by those with hydroxyl groups (11.6%) and unmodified MWCNTs (9.4%). However, the nanocomposites containing MWCNTs with carboxyl groups which were thought to be able to well interact with the dipoles on PVDF chains have the lowest amount of β-phase, i.e. 4.7%. The analysis on the mechanism of the influence of surface functionalization of MWCNTs on the formation of β-phase in PVDF shows that the combined effects of the dispersion of MWCNTs and the nanotube–polymer interactions account for the formation of the β-phase in PVDF.     

Introducing reactive groups into polymer chains by radiation induced grafting technique

Abstract

An oil soluble monomer, glycidyl methacrylate, which contains an epoxy group, was grafted onto poly(vinylidene fluoride) (PVDF) powder via pre-irradiation induced graft polymerisation in water under shear dispersion without additives. The existence of graft chains was proven by Fourier transform infrared spectroscopy, and the epoxy groups in graft chains are ready for further chemical modification. Graft polymerisation kinetic was studied, and the results showed high monomer conversion, which exceeded 70%. Microfiltration membranes were cast from grafted PVDF powder via phase inversion method, and the morphology of those microfiltration membranes was investigated by scanning electron microscopy. The images of the membrane cast from grafted powder revealed similar asymmetric morphology to the membrane cast from pristine PVDF powder.     

Simultaneously improving thermal conductivity and dielectric properties of poly(vinylidene fluoride)/expanded graphite via melt blending with polyamide 6

Poly(vinylidene fluoride)/polyamide 6/expanded graphite (PVDF/PA6/EG) composite is prepared via one-step melt extrusion. The EG is well dispersed with the addition of PA6 and mainly distributed in the PA6 phase due to the stronger affinity between them. As a result, the PVDF/PA6/EG sample presents higher dielectric permittivity than the PVDF/EG sample and maintain a low dielectric loss due to its sea-island phase structure, which impedes the formation of conductive path in the composite. The mean interlayer spacing of the EG in the polymer matrix decreases obviously due to its improved dispersion state, which is in favor of the phonon transportation in the composite. As a result, the PVDF/PA6/EG sample exhibits a significantly improved thermal conductivity of about 0.48 W m⁻¹ K⁻¹, which is 140% higher than that of the PVDF sample and 37% higher than that of the PVDF/EG sample. Moreover, the PVDF/PA6/EG sample presents higher Young's modulus and tensile strength than the PVDF/EG sample. While the elongation at break of the PVDF/PA6/EG sample is only a little lower than that of the PVDF/EG sample. This means that the tensile properties of the composite are not destroyed obviously by melt blending with the immiscible PA6.     

Shear-induced gelation of associative polyelectrolytes

Copolymer of N,N-dimethylacrylamide (DMA) and acrylic acid (AA) was functionalized with pendant alkyl groups. Their dynamic mechanical properties in aqueous solution were investigated using continuous shear and oscillatory shear. Shear flow showed an abrupt divergence of the viscosity at a critical shear stress (σ_c). Oscillatory shear showed, with increasing applied stress, slight shear thinning followed by strong shear thickening above σ_c. The effect of the polymer concentration and the oscillation frequency (ω) was investigated. The behaviour at all concentrations and frequencies was fully determined by the product of the oscillation frequency and the terminal relaxation time (τ) of the systems at rest. Master curves of the data determined at different concentrations and frequencies were obtained if the reduced shear modulus was plotted versus the reduced applied stress at constant ω.τ. The effect of shear increased with decreasing value of ω.τ. At low frequencies the storage shear modulus crossed the loss modulus with increasing shear. A model is proposed for this phenomenon of shear-induced gelation.     

Towards β-phase formation probability in spin coated PVDF thin films

This work aimed towards the study on variations in the percentage of β-phase in Poly vinylidene fluoride (PVDF) thin films deposited by spin coating technique. PVDF is a semi-crystalline polymer which exhibits α, β, γ and δ polymorphs. Among these polymorphs, generally it crystallizes in a non-polar α-phase, which is of little importance as far as its applications are concerned. However, the β-phase, which exhibits spontaneous polarity created tremendous interest and showed a path towards the devices based on its pyro- and piezoelectric properties. Fourier Transform Infrared (FTIR) spectroscopy and XRD techniques were used to study the percentage of formation of β-phase in spin coated PVDF thin films at different processing conditions viz. spin rotation speed (rpm), solution concentration and annealing temperature. We identified the β-phase percentage in PVDF thin films, which are (i) Deposited with different rotation speeds ranging from 1000 to 9000 rpm, (ii) Annealed at different temperatures viz.; room temperature to 100C, and (iii) Deposited at various solution concentrations. It is identified that percentage of formation of β-phase is high in the films deposited with 15(w/v)% solution concentration which is annealed at 100C. The films deposited at higher rpm is showing low enhancement in the β-phase with annealing temperature.     

Comparative studies of rheological properties of polyacrylamide and partially hydrolyzed polyacrylamide solutions

The present work is concerned with experimental results of rheological characteristics of polyacrylamide (PAM) and of partially hydrolyzed polyacrylamide (HPAM) (degree of hydrolysis up to 80%) in aqueous and aqueous/sodium chloride solutions with changing experimental conditions such as polymer concentration, temperature, solvent quality, and shear rate applied. It has been observed that the all‐aqueous and aqueous/NaCl solution of PAM and of HPAM exhibited the non‐Newtonian behavior with shear‐thinning and shear‐thickening areas. The onset of shear‐thickening at depends mainly on the degree of HPAM hydrolysis, as well as on solution concentration, temperature, solvent quality, and polymer molecular weight. Rheological parameters from power law (Ostwald de Waele model) and activation energy of viscous flow (E_a) are determined and discussed. The changes in apparent shear viscosity during aging of solutions of PAM and HPAM are also described. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2235–2241, 2007     

The rheological properties of shear thickening fluid reinforced with ZnO of different friction characteristics

The viscosity of shear thickening fluid (STF) changes significantly with low concentrations of additives. However, existing research has suggested that there has not been any consistent enhancement mechanism of additives. The possible reason for this research gap is that existing research has focused on the effect of the shape and content of additives on shear thickening (ST) performance, whereas the friction characteristics of additives on ST performance have not been considered. Accordingly, nanoparticle-enhanced STF with various friction characteristics of ZnO was synthesized in this study to investigate the enhancement mechanism of additives. The aspect ratio of ZnO with different shapes was obtained through SEM analysis. The friction characteristics of ZnO were examined. Lastly, the rheological behavior of reinforced STFs was evaluated. The results indicated that ST performance was enhanced compared with that of neat STF, which was significantly dependent on the friction characteristics of ZnO.     

Poly(vinylidene fluoride)/thermoplastic polyurethane flexible and 3D printable conductive composites

This work focus on the development of polymeric blends to produce multifunctional materials for 3D printing with enhanced electrical and mechanical properties. In this context, flexible and highly conductive materials comprising poly(vinylidene fluoride)/thermoplastic polyurethane (PVDF/TPU) filled with carbon black-polypyrrole (CB-PPy) were prepared by compression molding, filament extrusion and fused filament fabrication. In order to achieve an optimal compromise between electrical conductivity, mechanical properties and printability, blends composition was optimized and different CB-PPy content were added. Overall, the electrical conductivities of PVDF/TPU 50/50 vol% co-continuous blend were higher than those found for PVDF/TPU 50/50 wt% (i.e., 38/62 vol%) composites at same filler content. PVDF/TPU/CB-PPy 3D printed samples with 6.77 vol% filler fraction presented electrical conductivity of 4.14 S m⁻¹ and elastic modulus, elongation at break and maximum tensile stress of 0.43 GPa, 10.3% and 10.0 MPa, respectively. These results highlight that PVDF/TPU/CB-PPy composites are promising materials for technological applications.     

Suppression of AC conductivity by crystalline transformation in poly(vinylidene fluoride)/carbon nanofiber composites

Poly(vinylidene fluoride) (PVDF) is an important ferroelectric semi-crystalline polymer with multiple-phase behavior. In this study, remarkable effects of the various crystalline structures of PVDF nanocomposites on alternating current (AC) conductivity were discovered using carbon nanofibers (CNF). It was found that the transformation from α-phase to β-phase in PVDF, induced by the addition of CNFs, had a surprisingly suppressive effect on the AC conductivity of the nanocomposites. These unexpected results indicate that the decline in conductivity occurs after re-crystallization treatment (annealing) of the nanocomposites, and the reduction levels increase with increasing amounts of CNFs. Interestingly, the AC conductivity of annealed 5 wt% CNF/PVDF composites becomes even lower than that of re-crystallized nanocomposites with 3 wt% CNFs. These findings are believed to be very significant for fabrication and long-term service of PVDF composites in industry, which often involves exposure to repeated thermal cycling.