Thermal,swelling and stability kinetics of chitosan based semi-interpenetrating network hydrogels

The present study is focused on studying the swelling kinetics, thermal and aqueous stabilities, and determination of various forms of water in the chitosan (CS) and polyacrylonitrile (PAN) blend and semi-interpenetrating polymer network (sIPN). CS/PAN blend hydrogel films were prepared by solution casting technique. The blend film with optimum swelling properties was selected for the synthesis of sIPN. CS in the blend was crosslinked with the vapors of Glutaraldehyde (GTA) to prepare sIPN. The fabricated CS/PAN blend and sIPN hydrogels films were characterized with Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA) and field emission scanning electron microscope (FESEM). The kinetics of swelling, bound and unbound waters and aqueous stability were determined experimentally. FESEM showed good miscibility between CS and PAN, FTIR showed no chemical interaction between CS and PAN; however, it did show a doublet for the sIPN, TGA showed improved thermal stability and swelling kinetic followed second order kinetics. The degree of swelling of the sIPN hydrogels samples at room temperature varied from ~2200 % (with a fair degree of stability (~30 %)) to ~1000 % (with high degree of aqueous stability (43 %)) with increase in the crosslinking time. The calculated unbound water (W_UB) max., for the blend was 52.3 % whereas for the bound (W_B) the max., was 41.9 %. However, for sIPN hydrogel films, the W_UB water decreased (max. 21.0 %) where as the W_B increased (max. 52.0 %). The decrease in W_UB and increase in the W_B is attributed to the formation of a compact structure and increase in the contact area between the water and polymers in sIPN hydrogels due to the induction of new water contacting point in these hydrogel films, respectively.     

Preparation of PHEMA/nHAP nanocomposites via <Emphasis Type="Italic">in situ</Emphasis> polymerization in supercritical carbon dioxide for biomedical applications

Poly(2-hydroxyethylmethacrylate) (PHEMA)/hydroxyapatite (HAP) nanocomposites were synthesized through a new route involving nano-sized HAP (nHAP) particles or modified nHAP mixed with monomer 2-hydroxyethylmethacrylate via in situ polymerization in supercritical carbon dioxide (scCO₂). Fourier-transform infrared spectroscopy showed phosphate peak increased with nHAP content in composite. X-ray diffraction patterns of PHEMA/nHAP revealed the presence of crystallized nHAP. Thermogravimetric analysis showed that the ultimate nHAP content in PHEMA/nHAP composites is consistent with its initial amount. Scanning electron microscopy revealed that nanocomposite particles are much smaller than PHEMA particles. PHEMA/nHAP composites with average diameter of approximately 600 nm were obtained in scCO₂ with 94 % yield. Mechanical properties of PHEMA/nHAP nanocomposites were better than those of PHEMA, and compressive modulus and strength of composites with 30 wt.% nHAP were 193 and 29 MPa, respectively. Nanocomposite adsorption toward bovine serum albumin was evaluated, and results indicated that analyte adsorption amount can reach up to 282 mg/g.     

The grafting of recycled polyol from waste polyurethane foam onto new polyurethane and its impact on shape recovery and water vapor permeation

Recycled polyols from waste polyurethane (PU) foams were grafted onto PU to improve the properties such as tensile strength, shape recovery, low-temperature flexibility, and water compatibility. The recycled polyol was either purified by column chromatography before grafting or was used directly for grafting. The soft segment melting temperature of PU did not notably increase with the addition of polyol, whereas the glass transition temperature increased with increased polyol content. The tensile strength sharply increased at low polyol content and decreased at high polyol content, while the strain at break did not significantly change with an increase in polyol content. The shape recovery at 10 oC notably improved compared with unmodified PU and remained high after four cyclic tests. Polyol-grafted PU demonstrated better lowtemperature flexibility and reduced the water vapor permeability of PU membranes. Overall, grafting recycled polyol onto PU significantly improved the tensile stress, shape recovery, and low-temperature flexibility of PU.     

Synthesis and characterization of a novel charring agent and its application in intumescent flame retardant polyethylene system

A novel charring agent poly(pentaerythritol spirocyclic phosphorusoxy spirocyclic diethanolamine borate) (PPSPSDB) was synthesized successfully with diethanolamine borate (DEAB) and spirocyclic pentaerythritol bisphosphorate disphosphoryl chloride (SPDPC), which was combined with ammonium polyphosphate (APP) to endow linear low-density polyethylene (LLDPE) with flame retardance. The structure of PPSPSDB was characterized by FTIR and 1H-NMR. The study of thermal stability of various LLDPE composites showed that PPSPSDB/APP system could effectively improve the thermal degradation and thermal-oxidative stability of the char residues, and PE3 containing 30 wt% APP/ PPSPSDB with a 2 weight ratio left the highest amount of char residue at 800 oC. The results of flammability revealed that PE3 had the best combination property; the limited oxygen index value was 29.6, and vertical burning reached UL-94 V-0 rating, and the tensile strength and notched impact strength were 11.853 MPa and 28.8 kJ/m2 respectively. The investigation of structure and morphology of char residue indicated that the compact foaming char layer, as a good barrier against the transmission of heat and volatiles, was formed for PE3 during combustion.     

An investigation on the comparison of wet spinning and electrospinning: Experimentation and simulation

Polysulfonamide (PSA) has been widely used in many fields because of its excellent thermodynamic properties. In this study, PSA fibers were prepared separately via two different spinning ways, including conventional wet spinning and electrospinning. Fluid motion of wet spinning and electrostatic field of electrospinning were modeled using finite element analysis to investigate the spinning process. The properties of fabricated PSA fibers were characterized systematically by scanning electron microscope (SEM), fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), thermal gravity analysis (TGA) and electronic strength tester. Based on the simulation and theoretical analysis of spinning process, it was found that the extruding force of the wet spinning is larger than that of the electrospinning. The larger extruding force makes the alignment of macromolecules inside fiber relatively uniform, and a higher proportion of crystallization happens. Accordingly, the mechanical properties and thermal stability of PSA fibers could be improved due to a higher proportion of crystallization. The experimental results of mechanical strength and TG test are coincided with the simulation results. PSA fiber prepared by wet spinning has better thermal stability and mechanical properties than that fabricated by electrospinning.     

Electrical properties of graphene/waterborne polyurethane composite films

Graphene is classified as a carbon-based material. Structurally, graphene is made up of carbon-based two-dimensional atomic crystals and a one atom thick planar sheet of sp²-bonded carbon atoms. This sort of arrangement in graphene makes it a unique material with exceptional mechanical, physicochemical, thermal, electrical, optical, and biomedical properties. Methods for graphene-based fabric production mainly use graphene-based materials such as graphene (G), graphene oxide (GO), and reduced graphene oxide (rGO) coated on fabric or yarn. Waterborne polyurethane (WPU) is one of the most rapidly developing and active branches of polyurethane chemistry. More and more attention is being paid to graphene-coated fabrics owing to their low temperature flexibility, the presence of zero or very few VOCs (volatile organic compounds), water resistance, pH stability, superior solvent resistance, excellent weathering resistance, and desirable chemical and mechanical properties. It is used as a coating agent or adhesive for fibers, textiles, and leather. Also, graphene-containing materials have been used to enhance the properties of WPU. In this study, graphene/WPU composite solution and film was prepared to conduct basic research for developing electrical heating textiles which is not harmful to the human body, flexible and excellent in electrical properties. Graphene/WPU composite solutions were prepared with a graphene content of 0, 2, 4, 8, and 16 wt%, and graphene/WPU film was prepared with solution casting method. The graphene contents were analyzed for their surface morphology, electrical properties, and electrical heating properties.     

LED-UV grafting of vinylsulfone dyes onto photo-oxidized wool fabrics

Photografting coloration of wool was carried out under UV-LED irradiation at room temperature using aqueous vinylsulfone dye solution containing vinylsulfonic acid as a comonomer. UV-LED irradiation of the 395 nm emission is more energy efficient, less damaging to the dyes, and much safer to human eyes compared with polychromatic mercury UV lamps. However, in case of the UV-LED lamps, the wool needs to be photo-oxidized either by UV/ozone or polychromatic UV irradiation before the dye photografting. The surface treatments increased the sulfur and oxygen contents in the modified wool surfaces. While the optimally photografted wool fabrics under the UV-LED lamp yielded a K/S value of 9.9, the K/S of the grafted wool increased to 25.2 and 13.6 after the UV/Ozone or polychromatic UV preoxidation at UV energies of 10.6 J/cm² and 25 J/cm² respectively. The color fastness properties of the photografted fabrics were far better than with those of the conventionally reactive-dyed fabrics, implying that the high-molecular-weight photografted dyes seemed to be more durable than the low-molecular dyes.     

Properties of polymers as a nanoscale material for fibers in leather

Hyperbranched polymers, an innovative class of nano-polymers, could enhance the properties of fibers owning to their unique structures. In this study, the ester compound (HPAE) of 3-(bis(2-hydroxyethyl)amino)propionic acid and pentaerythritol was treated with undecylenic acid to obtain novel hyperbranched multiterminal alkenyl polymers (HPAE-UAs). The sizes of the HPAE-UAs could be controlled conveniently from 400 to 1300 nm by adjusting the capped fraction of the hydroxyl groups with undecylenic acids. The molecular structures of HPAE-UAs were characterized by means of FT-IR and ¹H-NMR. Then, the effect of the HPAE-UAs on the structures, thermal, and mechanical properties of the wet blue leather were investigated. TEM and SEM demonstrated that the spacing between fibers was enlarged. The thermogravimetric analysis showed that the residual volume of leather could reach up to 30.3 % at about 500 °C. Furthermore, the shrinkage temperature increased to 89.4 °C. It was found that the HPAE-UAs used in leather could improve the thermal performance, physical and mechanical properties. All of these results indicate that HPAE-UAs can be used as a fatliquor with retanning in leather process.     

Synthesis,characterization and ultrafiltration of reactive dyes. Application by exhaustion and/or ink-jet printing. IV.

Three new bis azo reactive dyes of different metallic salts (Na, K, Li) were synthesized. The synthesis was obtained by diazotization of 4-amino-2:5 di methoxy phenylene-beta hydroxyl ethyl sulphone sulphate ester and coupling with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid) (moles ratio 2:1). The dyes were purified-concentrated by ultrafiltration technology, characterized and applied on cotton, wool and nylon 6,6 fabric by exhaustion (dyeing) and by ink-jet printing. Fastness properties of the dyeings were measured. Wash fastness was investigated according to international standard methods and was found to be very good to excellent in all cases, while light fastness values were medium to low. Ink-jet ink formulations were prepared using the ultra filtrated reactive blue dyes UF RB(a-c) and their properties pH, conductivity, surface tension and viscosity were monitored over a period of 90 days. The inks were used to print digitally cotton and nylon 6,6 samples and wash- and light fastness properties of the prints were measured. Wash fastness properties were excellent while light fastness values are low Colour measurements of the dyeings and prints were conducted.     

Mechanical behavior of nylon 66 tyre cord under monotonic and cyclic extension: Experiments and constitutive modeling

Many industrial products are made of cord-rubber composite materials. Their mechanical behavior not only depends on rubber but also depends on cord. Nylon 66 cord is one of the most important reinforcement in these products. This paper research the mechanical behavior of nylon 66 cord under various load cases. A series of experiments were carried out to obtaining stress-strain curves under different load cases. Complex changes of the modulus and Mullins effect can be found in monotonic and cyclic tension, respectively. Mechanism of these behaviors has been analyzed considering both the twisted structure and material. A phenomenological constitutive model, accounting for different loading conditions, has been firstly proposed base on strain energy density function and damage mechanics method. The proposed model has been verified by comparing the predicted results with experimental data. It has been found that the proposed model predicted the stress-strain curves that were consistent with the experimental data. The proposed model can be implemented in finite element software for engineering design and application.