Centrifugal spinning of viscoelastic nanofibres

The centrifugal spinning method is a recently invented technique to extrude polymer melts/solutions into ultra-fine nanofibres. Here, we present a superior integrated string-based mathematical model, to quantify the nanofibre fabrication performance in the centrifugal spinning process. Our model enables us to analyse the critical flow parameters covering an extensive range, by incorporating the angular momentum equations, the Giesekus viscoelastic constitutive model, the air-to-fibre drag effects and the energy equation into the string model equations. Using the model, we can analyse the dynamic behaviour of polymer melt/solution jets through the dimensionless flow parameters, namely, the Rossby ( $Rb$ ), Reynolds ( $Re$ ), Weissenberg ( $Wi$ ), Weber ( $We$ ), Froude ( $Fr$ ), air Péclet ( $Pe^*$ ) and air Reynolds ( $Re^*$ ) numbers as well as the viscosity ratio ( $\delta _s$ ), corresponding to rotational, inertial, viscous, viscoelastic, surface tension, gravitational, air thermal diffusivity, aerodynamic and viscosity ratio effects. We find that the nonlinear rheology remarkably affects the fibre trajectory, radius and normal stresses. Increasing $Wi$ leads to a thicker fibre, whereas increasing $\delta _s$ shows an opposite trend. In addition, by increasing $Wi$ , the fibre curvature is enhanced, causing the fibre to spiral closer to the rotation centre.

Polyply; a python suite for facilitating simulations of macromolecules and nanomaterials

Molecular dynamics simulations play an increasingly important role in the rational design of (nano)-materials and in the study of biomacromolecules. However, generating input files and realistic starting coordinates for these simulations is a major bottleneck, especially for high throughput protocols and for complex multi-component systems. To eliminate this bottleneck, we present the polyply software suite that provides 1) a multi-scale graph matching algorithm designed to generate parameters quickly and for arbitrarily complex polymeric topologies, and 2) a generic multi-scale random walk protocol capable of setting up complex systems efficiently and independent of the target force-field or model resolution. We benchmark quality and performance of the approach by creating realistic coordinates for polymer melt simulations, single-stranded as well as circular single-stranded DNA. We further demonstrate the power of our approach by setting up a microphase-separated block copolymer system, and by generating a liquid-liquid phase separated system inside a lipid vesicle.

Investigation of the Orientational Mechanical Properties of Biodegradable Extrusion Films Based on Polyolefins and Beet Pulp

The article discusses the possibility of obtaining biodegradable films based on polyolefins and beet pulp by the extrusion method. Biodegradable composites of two mixes with 15% and 25% beet pulp content have been obtained. Compounding was carried out on a twin-screw extruder, and then samples of biodegradable films were obtained by cast film extrusion. The influence of the vegetable filler particles’ orientation on the composites mechanical properties has been studied. It has been shown that composites mechanical properties significantly increase in the direction of polymer melt stretching.

Evolution of the Surface Structure and Functional Properties of the Electroconducting Polymer Coatings onto Porous Films

Composite systems containing electroconducting polymer coatings (polyaniline and polypyrrole) applied to porous films of semicrystalline polymers (polyethylene, polypropylene, and polyvinylidene fluoride) have been prepared. Porous supports were obtained in the process based on polymer melt extrusion with subsequent annealing, uniaxial extensions, and thermal stabilization. Conducting coatings were formed by the oxidative polymerization of the monomers directly onto the porous supports. The structure (overall porosity, permeability, pore sizes, factor of orientation) and morphology (specific surface and character of the film surface) of the supports were characterized by sorptometry, filtration porosimetry, atomic force microscopy (AFM), and X-ray scattering techniques. It was observed that the porous supports have a strongly developed relief surface which is formed in the pore formation process. It was proven by scanning electron microscopy (SEM) that the porous supports have an oriented structure, and the surface of the composites is defined by the morphology inherent in the conducting component. It was shown that these composites (porous support/conducting coating) demonstrate electric conductivity both along the surface and between surfaces. It was demonstrated that the deposition of conducting coatings leads to an increase in the water wettability of the composites compared with pronounced hydrophobic supports. The composites are characterized by good adhesion between components due to a relief film surface as well as high mechanical strength and elasticity provided by the oriented character of the supports.

Establishment of regularities of influence on the specific heat capacity and thermal diffusivity of polymer nanocomposites of a complex of defining parameters

This paper reports a series of experimental studies to establish regularities of the integrated effect exerted on the specific heat capacity of polymer nanocomposites by such factors as the temperature regime of their production, the value of the mass fraction of the filler, and the temperature of the composite material. The studies were conducted for nanocomposites based on polypropylene filled with carbon nanotubes. When obtaining composites, the method of mixing the components in the melt of the polymer was used. During the studies, the temperature of nanocomposites varied from 295 to 455 K, the mass fraction of the filler ‒ from 0.3 to 10 %. The basic parameter of the technological mode for obtaining composite materials, the value of overheating the polymer melt relative to its melting point, varied in the range of 10...75 K. It is shown that the temperature dependence of the specific heat capacity of the considered composites is sensitive to changes in the overheating of the polymer melt only in the region maximum values of the specific heat capacity. Concentration dependences of the specific heat capacity of the considered nanocomposites at different values of their temperature and the level of overheating of the polymer melt have been built. The studies have been carried out to identify the effects of the influence of the above parameters on the coefficient of thermal diffusivity of nanocomposites. It has been established, in particular, that an increase in the level of overheating the polymer could lead to a very significant increase in the coefficient of thermal diffusivity, which is all the more significant the higher the proportion of filler and the lower the temperature of the composite material. It is shown that the level of overheating the polymer melt relative to its melting point is a parameter that can be used as the basis for the creation of polymer composite materials with specified thermophysical properties.

New Considerations on the Determination of the Apparent Shear Viscosity of Polymer Melt with Micro Capillary Dies

Capillary rheometers have been widely used for the rheological measurement of polymer melts. However, when micro capillary dies are used, the results are usually neither accurate nor consistent, even under the same measurement conditions. In this work, theoretical modeling and experimental studies were conducted for a more profound understanding of the mechanism by which the initial and boundary conditions influence the inaccuracy in the apparent shear viscosity determination with micro capillary dies (diameters: 500 μm, 200 μm, 100 μm). The results indicate that the amount of polymer initially in the barrel, the pre-compaction pressure and the capillary die diameter have a significant influence on the development of the micro scale inlet pressure, which directly determines the accuracy of the measurement at low and medium shear rates. The varying melt compressibility was confirmed to be the main factor directly related to the inaccuracy in the micro scale apparent shear viscosity determination. It is suggested that measures such as reducing the amount of polymer initially in the barrel and increasing the pre-compaction pressure could be used to reduce the measurement inaccuracy.

Determination of the Degree of Crystallinity of Poly(2-methyl-2-oxazoline)

A new method for purification of 2-methyl-2-oxazoline using citric acid was developed and living cationic ring-opening polymerization of 2-methyl-2-oxazoline was carried out. Polymerization was conducted in acetonitrile using benzyl chloride—boron trifluoride etherate initiating system. According to DSC data, the temperature range of melting of the crystalline phase of the resulting polymer was 95–180 °C. According to small-angle X-ray scattering and wide-angle X-ray diffraction data, the degree of crystallinity of the polymer was 12%. Upon cooling of the polymer melt, the polymer became amorphous. Using thermogravimetric analysis, it was found that the thermal destruction of poly(2-methyl-2-oxazoline) started above 209 °C.

Melt electrospun fibrous architectures with target geometries

In the melt electrospinning technique, the polymer melt is stretched under high voltage and the cooled to form microfibers structures with a fibre diameter in the tens of micrometres range, although some studies have reported values ranging from hundreds of nanometres to hundreds of micrometres. In this respect, this technique has significance in the biomedical field, where tissue engineering scaffolds with bimodal (nano and micro) fibrous structures are preferred in regard to cell adhesion, spreading and infiltration to final tissue reconstruction. This paper gives a review of recently reported melt electrospinning devices, especially those based on the direct writing principle, and of their comparison with the new melt Spraybase electrospinning device. The Spraybase device provides high precision melt jet deposition into 2D and 3D programmed architectures, with versatile translation speeds of the collector plate in the X-Y and the melt head in the Z direction. The melt spun fibrous architectures are designed depending on the types of tissue cells used in scaffold development.