The structure,tensile properties and water resistance of hydrolyzed feather keratin-based bioplastics☆

Feather,as a by-product of the poultry industry,has long been treated as a solid waste,which causes environmental and economic problems.In this work,the hydrolyzed feather keratin(HFK)was extracted from the chicken feather using a cost-effective method of alkali-extraction and acid-precipitation by applying urea and sodium sulfide.The aim was development and characterization of the eco-friendly films based on the HFK with variable glycerol contents by a thermoplastic process.The thermal analysis showed that high temperature and high pressure improved the compatibility between the glycerol and the HFK molecules.Also it was shown that the addition of water is necessary in the hot-pressing process of films.The FT-IR analysis indicated that the formation of the new hydrogen bonds between HFK and glycerol.By increasing the glycerol content,the film tensile strength(σ_b)decreases from 10.5 MPa to 5.7 MPa and the solubility increases from 15.3% to 20.9%,while the elongation at break(εb)achieves the maximum value of 63.8% for the film with 35% glycerol.The swelling was just below 16.9%at 25 °C for 24 h,suggesting a good stability of the films in water.The water vapor permeability(WVP)varied between 3.02 × 10~(-10)g · m~(-2)· s~(-1)· Pa~(-1)and 4.11 × 10~(-10)g · m~(-2)· s~(-1)· Pa~(-1)for the films with 20% and40% glycerol,respectively.The HFK film was uniform,translucent and tough,which could be used in packaging and agricultural field.     

Tailored Degradation and Dye Release from Poly(ester amides)

Poly(ester amides) based on L-valine and adipic acid with different aliphatic and aromatic diols were synthesized by interfacial polymerization. Four different diols such as ethylene glycol, 1,5-pentanediol, resorcinol, and catechol were used to systematically vary the chain lengths and position of the hydroxyl groups. The chemical structures, thermal properties, degradation, and dye release of these polymers were investigated. This study demonstrates that the release kinetics can be tailored through the control of the chain length of the diol and the position of the hydroxyl groups. These findings have important implications for designing biodegradable polymers for tailored release.     

Facile Formation of Medium-Chain-Length Poly-3-Hydroxyalkanoates (mcl-PHA)-Incorporated Nanoparticle Using Combination of Non-Ionic Surfactants

The assembly of nanoparticles incorporating bacterial medium-chain-length poly-3-hydroxyalkanoates (mcl-PHA) via phase inversion emulsification (PIE) was investigated. Sequential addition of water into an agitated mixture of carrier oil (jojoba oil), nonionic surfactants (Cremophor EL and Span 80) and melted mcl-PHA triggered phase inversion of water-in-oil (W/O) to oil-in-water (O/W) emulsion. The emulsion inversion point (EIP) at 30% w/w of water content was determined by abrupt changes in viscosity and conductivity of the suspension. Concurrently, infrared transmittance of the O–H group of water, the C–O–C group of surfactants and the C–H group of alkane chain were practically identical while Small Angle X-ray Scattering indicated the presence of a bi-continuous/lamellar structure. The morphology of the emulsion changed, with increasing water content, from W/O to bi-continuous/lamellar structure and finally to O/W. mcl-PHA appears to form a bridging polymeric network, covering the nanoparticle with a protective layer for enhanced protection of the encapsulated compound. A hypothetical mechanism for the mcl-PHA-based nanoparticle assembly is also proposed.     

Role of Urea on the Physico-Mechanical and Degradable Properties of Mercerized and Acid Hydrolyzed Coir (Cocos nucifera) Fibers Photocured with 1,6-Hexanediol Diacylate

Abstract

Coir fibers were modified with 1,6-hexanediol diacrylate (HDDA) by using ultraviolet (UV) radiation. Concentration of HDDA, soaking time, and radiation dose were optimized and found to be 30% HDDA in methanol along with photoinitiator Irgacure-500 (2%) and 120 min of soaking time the better performance registered as the optimum conditions, where polymer loading (PL) was 17% and tensile strength (TS) was 50%. Urea of different concentrations (0.5–2%) was incorporated with 30% HDDA to monitor its effect on the properties and 1% urea produced the enhanced PL (25%) and TS (82%). For the improvement of the properties, the fibers were subjected to surface treatment with alkali (5% potassium hydroxide) at various mercerizing times in hot and normal conditions. Among all the mercerized fibers, fibers treated with hot alkali for 6 h and cured under optimized condition demonstrated the maximum enhancement of PL (35.5%) and TS (130%). The fibers were also subjected to acid hydrolysis for different times with different acid (H₂SO₄) concentrations. Again the effect of urea (1%) on the properties of the pretreated fibers was scrutinized. Water uptake and degradable properties of the treated and virgin fibers were performed.     

Synthesis and Characterization of Maize Starch Acetates and its Biodegradable Film

Starch acetates (SA) were synthesized by maize starch reacting with acetic acid/acetic anhydride, using sulfuric acid as catalyst. The biodegradable films were produced by thermal gelatinization of starch suspensions blending raw starch or SA with different degree of esterification (DS) and polyvinyl alcohol (PVA). Fourier transform infrared spectrogram (FT-IR) data showed acetate was introduced into the molecule chain of starch. Different structure of aggregation supported between the modified starch and the raw starch was determined by the scanning electron microscopy (SEM). Differential scanning calorimetry indicated SA glass transition temperature reduced with increasing of its DS. X-ray diffraction pattern of SA revealed the crystallinity of chain starch was destroyed, forming many completely even amorphous areas. SEM studies showed that amorphous was raised with DS of starch acetates. The mechanical and hydrophobic properties of the films were better than those of raw starch/PVA. In 50 days outdoor soil burial biodegradable experiment in summer, the weight loss of the films was almost 50%.     

Morphology,Thermal and Mechanical Properties of Biodegradable Poly(butylene succinate)/Poly(butylene adipate-co-terephthalate)/Clay Nanocomposites

Sodium montmorillonite (Na-MMT) was successfully modified by octadecylamine (ODA) through a cation exchange technique that showed by the increased of basal spacing of clay by XRD. The addition of the organoclay into the PBS/PBAT blends produced intercalated-type nanocomposites with improvements in tensile modulus and strength. The highest tensile strength of nanocomposite was observed at 1 wt% of organoclay incorporated. A TGA study showed that the thermal stability of the blend increased after the addition of the organoclay by 1 wt%. SEM micrographs of the fracture surfaces show that the morphology of the blend becomes smoother with presence of organoclay.     

Synthesis of biodegradable poly(trans-4-hydroxy-N-benzyloxycarbonyl-l-proline)-block-poly(ε-caprolactone) copolymers and micellar characterizations

A series of novel types of diblock poly(trans-4-hydroxy-N-benzyloxycarbonyl-l-proline)-block-poly(ε-caprolactone) (PHpr10-b-PCL) copolymers were synthesized by ring-opening polymerization from macroinitiator poly(trans-4-hydroxy-N-benzyloxycarbonyl-l-proline) (PHpr10) and ε-caprolactone (ε-CL) in the presence of organocatalyst dl-lactic acid (dl-LA). The M_n of the copolymers increased from 3370 to 19,040 g mol⁻¹ with the molar ratio (10-100) of ε-CL to PHpr10. These products were characterized by differential scanning calorimetry (DSC), ¹H NMR, and gel permeation chromatography. According to DSC, the glass-transition temperature (T_g) of the diblock copolymers depend on the molar ratio of monomer/initiator that were added. The hydrolytic degradation behavior of PHpr-b-PCLs was evaluated from weight-loss measurements and the change of M_n and M_w/M_n. With higher PCL contents resulted in a slower weight loss, while having a higher molecular weight loss percentage. Their micellar characteristics in an aqueous phase were investigated by fluorescence spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 1.33-4.22 mg L⁻¹. The micelles exhibited a spindly shape and showed a narrow monodisperse size distribution. The obtained micelles have a relatively high drug-loading of about 26% when the feed weight ratio of amitriptyline hydrochloride (AM) to polymer was 1/1. An increase of molecular weight and hydrophobic components in copolymers produced a higher CMC value and greater loading efficiencies were observed.     

The study of epoxidized rapeseed oil used as a potential biodegradable lubricant

The application of epoxidized rapeseed oil as a biodegradable lubricant is described. The epoxidation treatment has no adverse effect on the biodegradability of the base stock. Epoxidized rapeseed oil has superior oxidative stability compared to rapeseed oil based on the results of both oven tests and rotary oxygen bomb tests. Moreover, the oxidative stability can be dramatically promoted by the addition of a package of antioxidants. The epoxidized rapeseed oil has better friction-reducing and extreme pressure abilities according to tribological investigations. Formation of a tribopolymerization film is proposed as explanation of the tribological performance of epoxidized rapeseed oil.     

N-(2-Hydroxyethyl)formamide as a new plasticizer for thermoplastic starch

N-(2-Hydroxyethyl)formamide (HF) was synthesized efficiently and used as a new plasticizer for corn starch to prepare thermoplastic starch (TPS). The hydrogen bond interaction between HF and starch was proved by Fourier-transform infrared (FT-IR) spectroscopy. Scanning electron microscope (SEM) revealed that starch granules were completely disrupted and a continuous phase was obtained. The crystallinity of corn starch and HF-plasticized TPS (HTPS) were characterized by X-ray diffraction (XRD). The glass transitions of glycerol-plasticized TPS (GTPS) and HTPS were investigated by differential scanning calorimetry (DSC). The water resistance of GTPS was better than that of HTPS. In addition, the flexibility of HTPS was better than that of GTPS at low relative humidity.