Study on the temperature-induced sol–gel transition of cellulose/silk fibroin blends in 1-butyl-3-methylimidazolium chloride via rheological behavior

Temperature-induced sol–gel transition of cellulose/silk fibroin/1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was studied from the viscosity and dynamic modulus of the mixtures. The shear thinning behavior of the mixture solution was very obvious with a decrease in temperature. The curves of storage modulus G′ and loss modulus G″ were parallel when the temperature was below 20 °C, indicating that a gel structure exists in the system. The sol–gel transition process was described according to Winter and Chambon’s theory. The gel structure of the mixture system was loosened with the increase of silk fibroin concentration.     

Silk fibroin solution properties related to assembly and structure

The impact of physiological factors on silk fibroin solution properties was studied. Specifically, the impact of fibroin concentration, protein purity, cation type and concentration, and pH on aqueous solution viscosity, shear behavior, and surface tension were assessed in the context of silk protein assembly. The results demonstrate that in vitro results could be correlated to in vivo processing events during silk spinning. Rheological properties with reference to the amphiphilic block structure of the protein are described, pH dependency of shear response was quantitatively correlated to the predicted pI values of the fibroin protein, and cooperativity among environmental factors such as pH and salts was identified. Stabilization of silk fibroin solution states by calcium was identified as a mode to control shear sensitivity of the fibroin solution. The cooperativities identified suggest tight control of fibroin aqueous solution rheological properties to gain a window of protection against premature crystallization of the fibroin during processing, assuring safe storage, transport, and finally successful fiber spinning.     

Melt rheology and morphology of thermoplastic elastomers from polyethylene/nitrile‐rubber blends: The effect of blend ratio,reactive compatibilization,and dynamic vulcanization

A study of the melt‐rheological behavior of thermoplastic elastomers from high‐density polyethylene and acrylonitrile butadiene rubber (NBR) blends was carried out in a capillary rheometer. The effect of the blend ratio and shear rate on the melt viscosity reveals that the viscosity decreases with the shear rate but increases with NBR content. Compatibilization by maleic anhydride modified polyethylene has no significant effect on the blend viscosity, but a finer dispersion of the rubber is obtained, as is evident from scanning electron micrographs. The melt‐elasticity parameters, such as the die swell, principal normal stress difference, recoverable shear strain, and elastic shear modulus of the blends, were also evaluated. The effect of annealing on the morphology of the extrudate reveals that annealing in the extruder barrel results in the coalescence of rubber particles in the case of the incompatible blends, whereas the tendency toward agglomeration is somewhat suppressed in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1104–1122, 2000     

Microrheological studies of regenerated silk fibroin solution by video microscopy

We have carried out studies on the rheological properties of regenerated silk fibroin (RSF) solution using video microscopy. The degummed silk from the Bombyx mori silkworm was used to prepare RSF solution by dissolving it in calcium nitrate tetrahydrate‐methanol solvent. Measurements were carried out by tracking the position of an embedded micron‐sized polystyrene bead within the RSF solution through video imaging. The time dependent mean squared displacement (MSD) of the bead in solution and hence the complex shear modulus of this solution was calculated from the bead's position information. We present here the results of rheological measurements of the silk polymer network in solution over a frequency range, whose upper limit is the frame capture rate of our camera at full resolution. By examining the distribution of MSD of beads at different locations within the sample volume, we demonstrate that this probe technique enables us to detect local inhomogeneities at nanometre length scales, not detectable either by a rheometer or from diffusing wave spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2555–2562, 2007     

Poly(ether ether ketone)/poly(aryl ether sulfone) blends: Melt rheological behavior

Dynamic rheological measurements were carried out on blends of poly(ether ether ketone) (PEEK)/poly(aryl ether sulfone) (PES) in the melt state in the oscillatory shear mode. The data were analyzed for the fundamental rheological behavior to yield insight into the microstructure of PEEK/PES blends. A variation of complex viscosity with composition exhibited positive–negative deviations from the log‐additivity rule and was typical for a continuous‐discrete type of morphology with weak interaction among droplets. The point of transition showed that phase inversion takes place at composition with a 0.6 weight fraction of PEEK, which agreed with the actual morphology of these blends observed by scanning electron microscopy. Activation energy for flow, for blend compositions followed additive behavior, which indicated that PEEK/PES blends may have had some compatibility in the melt. Variation of the elastic modulus (G′) with composition showed a trend similar to that observed for complex viscosity. A three‐zone model used for understanding the dynamic moduli behavior of polymers demonstrated that PEEK follows plateau‐zone behavior, whereas PES exhibits only terminal‐zone behavior in the frequency range studied. The blends of these two polymers showed an intermediate behavior, and the crossover frequency shifted to the low‐frequency region as the PEEK content in PES increased. This revealed the shift of terminal‐zone behavior to low frequency with an increased PEEK percentage in the blend. Variation of relaxation time with composition suggested that slow relaxation of PEEK retards the relaxation process of PES as the PEEK concentration in the blend is increased because of the partial miscibility of the blend, which affects the constraint release process of pure components in the blend. A temperature‐independent correlation observed in the log–log plots of G′ versus loss modulus (G″) for different blend systems fulfilled the necessary condition for their rheological simplicity. Further, the composition‐dependent correlations of PEEK/PES blends observed in a log–log plot of G′ versus G″ showed that the blends are either partially miscible or immiscible and form a discrete‐continuous phase morphology. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1548–1563, 2004     

Structure and microporous formation of cellulose/silk fibroin blend membranes: Part II. Effect of post-treatment by alkali

Blend membranes (RCF1) were prepared from mixture solution of cellulose and silk fibroin (SF) in cuoxam by coagulating with acetone–acetic acid (4:1 by volume). The blend membranes were subjected to post-treatment with 10% NaOH aqueous solution, and their structure and properties were characterized by FT-IR, X-ray diffraction, DSC, SEM and DMTA. In previous work, cellulose/SF blend membranes (RCF2) prepared by coagulating with 10% NaOH aqueous solution formed a microporous structure, in which the SF as a pore former was almost completely removed from the membrane. However, when the blend membranes RCF1 were immersed in 10% NaOH aqueous solution for post-treatment, a strong hydrogen bonding between cellulose and SF inhibited the removal of SF. Although alkali is a good solvent for SF, the blend membranes RCF1 such obtained from cellulose and SF were alkali resistant. The crystallinity and the mean pore size of the blend membranes slightly decreased with increasing post-treatment time. This work provided a cellulose/silk blend membrane, which can be used under alkaline medium.     

Physical properties and phase separation structure of Antheraea pernyi/Bombyx mori silk fibroin blend films

The physical structure and compatibility of solution-cast Antheraea pernyi/Bombyx mori silk fibroin blend films were stuided by differential scanning calorimetry (DSC), thermomechanical (TMA) and thermogravimetric (TGA) analysis, dynamic viscoelastic measurement, infrared spectroscopy, and x-ray diffractometry. The DSC curves of the blend films showed independent endotherms at 280 and 358°C, corresponding to the thermal decomposition of B. mori and A. pernyi silk fibroins with random coil conformation. The intensity was roughly proportionate to the amount of each component in the blend. The thermal behavior corresponding to the conformational transitions induced by heating on A. pernyi and B. mori silk fibroins overlapped in the temperature range 190–230°C. Thermal expansion and contraction properties, as well as weight retention behavior of the blend films were intermediate between the pure components, as shown by the TMA and TGA curves. The onset temperature of the storage modulus curve decreased markedly, approaching that of B. mori silk fibroin film when the amount of this component in the blend increased. The loss modulus curve of the blend films showed two peaks at ca. 190 and 210°C, the former corresponding to B. mori, and the latter to A. pernyi silk fibroin. Infrared spectra of the blends exhibited absorption bands characteristic of the pure components overlapping in the spectral region 2000–400 cm^?1. The x-ray diffraction peaks at 23 and 21.5°, attributed to the crystalline spacings of A. pernyi and B. mori fibroins, respectively, overlapped in the diffraction curves of the blends, while the peak at 11.4°, of A. pernyi, increased as the content of this fibroin in the blend increased. The degree of crystallinity, calculated from the x-ray diffraction curves, diminished as the amount of B. mori silk fibroin decreased. A low degree of compatibility exists between the two fibroins when they are cast from aqueous solution in the experimental conditions adopted in this work. © 1994 John Wiley & Sons, Inc.     

蚕体内不同丝腺部位丝蛋白溶液结构与性质的研究

采用偏光显微镜研究了蚕体内不同丝腺部位(包括前部、中部和后部)中丝蛋白溶液的性质变化,并采用了拉曼光谱和旋转流变仪对中部丝腺(包括前区、中区及后区)的丝蛋白分子结构和流变性能进行了分析。结果发现:蚕体内只有前部丝腺及中部丝腺前区的丝蛋白溶液具有偏光现象;丝蛋白溶液在由中部丝腺后区向前区流动的过程中,粘度及弹性均逐渐变小,其构象则由无规卷曲逐渐向α-螺旋转变,并进一步形成β-折叠构象。由此表明,在蚕体内中部丝腺前区的丝蛋白溶液很可能已经形成了液晶态结构。     

Preparation and Characterization of Natural Silk Fibroin Hydrogel for Protein Drug Delivery

In recent years, hydrogels have been widely used as drug carriers, especially in the area of protein delivery. The natural silk fibroin produced from cocoons of the Bombyx mori silkworm possesses excellent biocompatibility, significant bioactivity, and biodegradability. Therefore, silk fibroin-based hydrogels are arousing widespread interest in biomedical research. In this study, a process for extracting natural silk fibroin from raw silk textile yarns was established, and three aqueous solutions of silk fibroin with different molecular weight distributions were successfully prepared by controlling the degumming time. Silk fibroin was dispersed in the aqueous solution as “spherical” aggregate particles, and the smaller particles continuously accumulated into large particles. Finally, a silk fibroin hydrogel network was formed. A rheological analysis showed that as the concentration of the silk fibroin hydrogel increased its storage modulus increased significantly. The degradation behavior of silk fibroin hydrogel in different media verified its excellent stability, and the prepared silk fibroin hydrogel had good biocompatibility and an excellent drug-loading capacity. After the protein model drug BSA was loaded, the cumulative drug release within 12 h reached 80%. We hope that these investigations will promote the potential utilities of silk fibroin hydrogels in clinical medicine.     

Phase behavior and its viscoelastic response of polylactide/poly(ε-caprolactone) blend

Polylactide (PLA)/polycaprolactone (PCL) blends with various blend ratios were prepared via melt mixing. The morphology, linear and non-linear viscoelastic properties of the blend were studied using scanning electron microscope (SEM) and cone-plate rheometer. Three typical immiscible morphologies, i.e., spherical droplet, fibrous and co-continuous structure can be observed at various compositions. The elasticity ratio was proposed to play an important role together with the viscosity on the phase inversion because PLA/PCL blend presents a high viscosity ratio between two components. Two emulsion models were used to predict the linear viscoelastic properties of the blend with various morphologies. The Palierne model gives better fit compared with the G–M model, but both fail to predict the viscoelastic properties of the co-continuous blend. The viscoelastic behavior of those blends shows different temperature dependence due to their different morphologies. The principle of time–temperature superposition (TTS) is only valid for the co-continuous blend while fails with the rheological data of those blends with discrete spherical and fibrous domain structure. Moreover, although the discrete phase is difficult to be broken up due to the high viscosity ratio of the systems, the change of viscoelastic responses of those blends before and after preshear shows large difference, indicating that different morphologies have different sensitivity to the steady shear flow.     

Miscibility and biodegradability of silk fibroin/carboxymethyl chitin blend films

Blend films of silk fibroin and carboxymethyl chitin were prepared by solution casting using water as a cosolvent. The blend films were subjected to post-treatment with an aqueous methanol solution to induce beta-sheet formation of silk fibroin. The miscibility of the blend films both before and after methanol treatments was investigated in terms of chemical interactions, morphologies, thermal properties, and crystal structures by using FTIR spectroscopy, SEM, DSC, and XRD. The results indicate that the blend between silk fibroin and CM-chitin was semi-miscible because only the amorphous parts of the polymers were compatible with each other. The enzymatic degradation showed that the incorporation of CM-chitin enhanced biodegradability and swelling ability of silk fibroin.     

Rheology and morphology of linear polyurethane and poly(methyl methacrylate) blends formed in situ

The rheological properties and morphology of flow during the in situ formation of linear polyurethane and poly(methyl methacrylate) blends of various compositions are studied. At a certain conversion of the components, the initial homogeneous blend undergoes phase separation, as evidenced by the nonadditive dependence of the logarithm of viscosity on blend composition. For individual components, the gel points correspond to appreciably different conversions. For components in blends of various compositions, this difference is less pronounced and associated with the kinetic conditions of blend formation. The morphology of flow of the reaction blend over the time (or conversion) between the onset of phase separation and gelation during flow with a high shear rate is determined by the blend composition and the ratio between the viscosity of the dispersion phase and the matrix.     

Rheology of a mixture of liquid-crystal polymers in solution

The rheological behavior of a mixture of two liquid-crystal polymers, hydroxypropyl cellulose and ethyl cellulose, in acetone solution is studied. The total polymer concentration in the solvent is held constant (40%) as the ratio of the two polymers is varied. The mixtures are anisotropic, isotropic, or biphasic (isotropic/anisotropic), depending on the concentration. Curves of viscosity vs shear rate for all the mixtures studied show three regions of viscosity, as described by Onogi and Asada for liquid-crystal polymers. The viscosity as a function of the weight ratio of the two polymers at constant shear rate exhibits deviations from additivity of viscosities of the two components at all concentrations. In mixtures of two polymers in the melt, deviations are also observed; the negative ones are attributed to phase separation and the positive ones to homogenous mixing (comparison with the phase diagram). All the mixtures studied (anisotropic, isotropic, or biphasic), show ranges of shear rates where the first normal-stress difference is negative, as is generally observed for anisotropic liquid-crystal polymers. It is concluded that the isotropic solutions become anisotropic under shear, as they are not far from the critical concentration. © 1994 John Wiley & Sons, Inc.     

茂金属聚乙烯和低密度聚乙烯共混物的流变行为

研究了茂金属催化乙烯丁烯1共聚物mPE和LDPE共混物的流变行为.测定了一系列共混物的稳态剪切粘度和动态粘弹性,用改进Cross模型拟合实验数据.mPE的零切粘度η₀较小,从牛顿型转变为非牛顿型所需的剪切速率较大,转变应力较高,在挤出加工剪切速率范围内熔体粘度高,对剪切敏感性差,这是由于它有较低的重均分子量、窄的分子量分布(M_w/M_n=21)所致.对于对数加和规律,共混物η₀在mPE/LDPE为50/50和25/75时有强烈的正偏差,这是由于共混物自由体积减小所致.共混物的转变应力τ^*和非牛顿指数n随LDPE加入量增大而降低,表明共混物对剪切的敏感性提高,加工性得到改善.G'和G”的一致性说明mPE和LDPE共混是相容的.     

Rheology and microstructures formation of immiscible model polymer blends under steady state and transient flows

Viscoelastic properties of model immiscible blend were studied here under steady state condition at different initial conditions and transient flow conditions. The flow‐induced microstructure has been studied on these model blends. For this system, the elastic properties of the blend are mainly governed by the interface. Measurement of the dynamic modulus and of the first normal stress difference, both reflecting this enhanced elasticity, have been used to prove the blend morphology. The dynamic moduli after cessation of shear flow, the mean diameter of the disperse phase as generated by the shear flow, have been calculated using the model of Palierne. A procedure based on a direct fitting of the dynamic moduli with the model is compared with the one that uses a weight relaxation spectrum. On the other hand, the steady state normal stress data have been related to the morphology of the blend by means of Doi and Ohta model. The specific interfacial area is found to be inversely proportional to the ratio of interfacial tension over shear stress for the blend. The flow behavior during transient shear flow was also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3519–3533, 2005     

Rheokinetics of the gelling process of water-soluble STMP-modified carboxymethyl hydroxyethyl cellulose

To improve the viscosity of carboxymethyl hydroxyethyl cellulose (CMHEC) solution and broaden its application, sodium trimetaphosphate (STMP) was used to modify CMHEC to obtain water-soluble STMP-CMHEC for the first time. The STMP-CMHEC solution shows better viscous performance than CMHEC solution. For the concentration of 0.5% (wt%), the viscosity of STMP-CMHEC solution is 2.6 times higher than that of CMHEC solution. To be applied in fracturing fluids, STMP-CMHEC solution was further cross-linked with organic zirconium. The changes of viscosity and viscoelasticity modulus with time in the cross-linking process were studied. The effects of shear rate and temperature on the gelling process were investigated. The four-parameter cross-linking rheokinetics equation could describe the viscosity–time curves under different shear rates.     

Influence of cellulose nanofibers on the rheological behavior of silica-based shear-thickening fluid

In this work, the influence of cellulose nanofibers (CNFs) on the rheological behavior of silica-based shear-thickening fluid (STF) is investigated. CNFs of 150–200 nm in diameter were extracted from cotton fibers using a supermasscolloider. CNF-reinforced STF of different concentrations (0.1–0.3 wt.%) was prepared via an ultrasonication technique. The presence of CNFs and their interaction with the silica nanoparticles in the STF were analyzed using SEM and FTIR. The addition of a minute quantity of CNF to the STF (0.3% CNF-reinforced STF) caused a marked increase in the peak viscosity, from 36.8 (unmodified STF) to 139.0 Pa s (0.2% CNF-reinforced STF), and a concomitant decrease in the critical shear rate from 33.45 to 14.8 s^?1 . The presence of a large number of hydroxyl groups on the CNFs enhanced their interaction with the nanoparticles via hydrogen bonding, which induced shear thickening. The mechanism of the interaction between silica nanoparticles and CNF was also demonstrated. Oscillatory dynamic rheological analysis showed that the addition of even a small amount of CNF led to higher elastic behavior in the system at lower shear rates. In contrast, a more viscous nature was demonstrated at higher angular frequencies. As the concentration of  nanofibers in the STFs increased, the crossover point between storage and loss modulus shifted to higher angular frequencies, implying stronger interaction between the constituents of the STF. The dynamic viscosity profile of all samples also exhibited shear-thickening behavior.     

蚕丝蛋白与硅溶胶复合材料的研究

采用动态力学测试手段(DMA)并结合扫描电镜和拉曼光谱等方法,考察了用桑蚕丝蛋白与二氧化硅水分散体系(硅溶胶)制备的复合材料的结构与性质.结果表明,在此共混体系中,直径约为100 nm的二氧化硅聚集体与丝蛋白连续相的界面相容性良好.动态力学测试发现,复合材料的动态力学性能在15℃到55℃范围相对于纯丝蛋白材料得到了改善,二氧化硅组分的加入对丝蛋白分子链段的运动性有所阻碍,从而导致了40℃模量损耗的消失.     

醋酸淀粉/聚乳酸的制备及性能的影响研究

采用自设计的双螺杆结构挤出制备聚乳酸(PLA)/醋酸淀粉(AS)的全生物降解材料,考察材料的AS的含量和取代度对复合材料动态流变性能、机械性能的影响。研究结果表明,AS含量明显影响复合材料的力学性能、复合黏度和储能模量:当AS含量从45%增加到70%,材料的拉伸强度下降,复数黏度和储能模量则提高。随着AS取代度由1.0上升为3.0,复合材料的复数黏度和储能模量下降,拉伸强度由12.0MPa上升为15.5MPa。对复合材料进行电镜扫描分析发现,AS以海岛结构形式分散在PLA的连续相中,取代度2.0的AS与PLA相容性最好,当其质量含量达到70%,材料的拉伸强度仍然不低于10.0MPa,具有较好的机械强度。     

Regenerated protein fibers. II. Viscoelastic behavior of silk fibroin solutions

The dynamic viscoelastic behavior of a concentrated solution of silk fibroin dissolved in the “MU” solvent is measured. The dynamic viscosity η′ and dynamic elasticity G′ increase with increasing concentration of silk fibroin at constant frequency; however, the increasing frequency decreases η′ and G′ at a constant concentration of silk fibroin. When the mixing ratio of C₂H₅OH/H₂O in the “MU” solvent is increased at a constant concentration of LiBr·H₂O, η′ and G′ sharply increase at constant frequency. If the LiBr·H₂O concentration is varied in the “MU” solvents whose ratio of C₂H₅OH/H₂O is kept constant at 100 : 0, both η′ and G′ are greater for LiBr·H₂O concentrations of 50% by weight compared to concentrations of 40% by weight. The dependence of η′ on the temperature of the solution can be predicted by Andrade's viscosity equation. Spinnability improves when the SF concentration is increased. © John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1955–1959, 1997