Use of Biochar as Filler for Biocomposite Blown Films: Structure-Processing-Properties Relationships

In this work, biocomposite blown films based on poly(butylene adipate-co-terephthalate) (PBAT) as biopolymeric matrix and biochar (BC) as filler were successfully fabricated. The materials were subjected to a film-blowing process after being compounded in a twin-screw extruder. The preliminary investigations conducted on melt-mixed PBAT/BC composites allowed PBAT/BC 5% and PBAT/BC 10% to be identified as the most appropriate formulations to be processed via film blowing. The blown films exhibited mechanical performances adequate for possible application as film for packaging, agricultural, and compost bags. The addition of BC led to an improvement of the elastic modulus, still maintaining high values of deformation. Water contact angle measurements revealed an increase in the hydrophobic behavior of the biocomposite films compared to PBAT. Additionally, accelerated degradative tests monitored by tensile tests and spectroscopic analysis revealed that the filler induced a photo-oxidative resistance on PBAT by delaying the degradation phenomena.

The Effects of Chain-Extending Cross-Linkers on the Mechanical and Thermal Properties of Poly(butylene adipate terephthalate)/Poly(lactic acid) Blown Films

This study investigates the effects of four multifunctional chain-extending cross-linkers (CECL) on the processability, mechanical performance, and structure of polybutylene adipate terephthalate (PBAT) and polylactic acid (PLA) blends produced using film blowing technology. The newly developed reference compound (M·VERA® B5029) and the CECL modified blends are characterized with respect to the initial properties and the corresponding properties after aging at 50 °C for 1 and 2 months. The tensile strength, seal strength, and melt volume rate (MVR) are markedly changed after thermal aging, whereas the storage modulus, elongation at the break, and tear resistance remain constant. The degradation of the polymer chains and crosslinking with increased and decreased MVR, respectively, is examined thoroughly with differential scanning calorimetry (DSC), with the results indicating that the CECL-modified blends do not generally endure thermo-oxidation over time. Further, DSC measurements of 25 µm and 100 µm films reveal that film blowing pronouncedly changes the structures of the compounds. These findings are also confirmed by dynamic mechanical analysis, with the conclusion that tris(2,4-di-tert-butylphenyl)phosphite barely affects the glass transition temperature, while with the other changes in CECL are seen. Cross-linking is found for aromatic polycarbodiimide and poly(4,4-dicyclohexylmethanecarbodiimide) CECL after melting of granules and films, although overall the most synergetic effect of the CECL is shown by 1,3-phenylenebisoxazoline.

Physical Properties, Spectroscopic, Microscopic, X-ray, and Chemometric Analysis of Starch Films Enriched with Selected Functional Additives

Biodegradable materials are used in the manufacture of packaging and compostable films and various types of medical products. They have demonstrated a large number of potential practical applications in medicine and particularly in the treatment of various cardiac, vascular, and orthopedic conditions in adults as well in children. In our research, the extrusion-cooking technique was applied to prepare thermoplastic starch (TPS), which was then utilized to obtain environmentally friendly starch-based films. Potato starch was the basic raw material exploited. Polyvinyl alcohol and keratin were used as functional additives in amounts from 0.5 to 3%, while 20% of glycerol was harnessed as a plasticizer. The processing of the thermoplastic starch employed a single screw extruder-cooker with an L/D ratio of 16. The film blowing process was carried out using a film-blowing laboratory line with L/D = 36. FTIR Spectroscopy was applied for the assignment of the prominent functional groups. The results showed that the processing efficiency of thermoplastic starch with functional additives varied depending on the level of polyvinyl alcohol and keratin addition. Moreover, the FTIR data correlated with the changes in the physical properties of the tested films. The analysis of FTIR spectra revealed several changes in the intensity of bands originating from stretching vibrations characteristic of the –OH substituent. The changes observed depended on the presence/lack of the hydrogen bonding occurring upon interactions between the starch molecules and the various additives used. In addition, notable changes were observed in bands assigned to glycoside bonds in the starch.

The preparation of modified polyamide clay nanocomposite/recycled maleic anhydride polyamide 6 and blending with low density polyethylene for film blowing application

Generally, polyamide cannot be used as film blowing material because of its unsuitable properties. In this study, polyamide 6 clay nanocomposite (cPA) and styrene maleic anhydride copolymer (SMA) were mixed in various ratios for the preparation of modified polyamide 6 clay nanocomposite SxcPAy resins by reactive extrusion. The S1cPA14 resin was blended with recycled maleic anhydride polyamide (rPA) to form the (S1cPA14)x rPAy resins. Finally, they were mixed with LDPE in 1:9 ratio to afford (SxcPAy)1LDPE9 and ((S1cPA14)x rPAy)1LDPE9 resins, respectively, followed by film blowing and the analyses of the physicochemical properties of resins. The FTIR spectrum illustrated that the C=O symmetric and asymmetric absorption fingerprint peaks in the anhydride (-OC-O-CO-) group of SMA disappeared and the new characteristic absorption peak of-CO-N-CO- of imides was observed. The anhydride functional group of SMA underwent reactive extrusion with the terminal amino group of cPA to generate the imides structure. The thermal properties showed that the glass transition temperature and crystallinity of SxcPAy and (S1cPA14)x rPAy resins increased with increasing SMA and S1cPA14 contents. The Tg (85.4.0°C) of (S1cPA14)12 rPA1 resin were enhanced significantly, with 30°C higher than cPA. In terms of tensile mechanical properties, S1cPA14 test pieces demonstrated the highest Young’s modulus and tensile strength. After mixing with LDPE, the tensile mechanical properties of (SxcPAy)1LDPE9 and ((S1cPA14)x rPAy)1LDPE9 resins and films were both higher than that of LDPE. ((S1cPA14)12 rPA1)1LDPE9 film shown the best tensile properties and barrier performance compared with other films due to the optimal rPA content could assisted SMA as a better compatibilizer to improve the dispersion and compatibility of cPA in HDPE. It was worth noting that (SxcPAy)1LDPE9 and ((S1cPA14)x rPAy)1LDPE9 resins were formed by film blowing at the processing temperature of 140°C followed by successful preparation of the film.

Modern Biodegradable Plastics—Processing and Properties Part II

Four different plastics were tested: potato starch based plastic (TPS-P)–BIOPLAST GF 106/02; corn starch based plastic (TPS-C)–BioComp BF 01HP; polylactic acid (polylactide) plastic (PLA)—BioComp BF 7210 and low density polyethylene, trade name Malen E FABS 23-D022; as a petrochemical reference sample. Using the blown film extrusion method and various screw rotational speeds, films were obtained and tested, as a result of which the following were determined: breaking stress, strain at break, static and dynamic friction coefficient of film in longitudinal and transverse direction, puncture resistance and strain at break, color, brightness and gloss of film, surface roughness, barrier properties and microstructure. The biodegradable plastics tested are characterized by comparable or even better mechanical strength than petrochemical polyethylene for the range of film blowing processing parameters used here. The effect of the screw rotational speed on the mechanical characteristics of the films obtained was also demonstrated. With the increase in the screw rotational speed, the decrease of barrier properties was also observed. No correlation between roughness and permeability of gases and water vapor was shown. It was indicated that biodegradable plastics might be competitive for conventional petrochemical materials used in film blowing niche applications where cost, recyclability, optical and water vapor barrier properties are not critical.

Bionanocomposite Blown Films: Insights on the Rheological and Mechanical Behavior

In this work, bionanocomposites based on two different types of biopolymers belonging to the MaterBi® family and containing two kinds of modified nanoclays were compounded in a twin-screw extruder and then subjected to a film blowing process, aiming at obtaining sustainable films potentially suitable for packaging applications. The preliminary characterization of the extruded bionanocomposites allowed establishing some correlations between the obtained morphology and the material rheological and mechanical behavior. More specifically, the morphological analysis showed that, regardless of the type of biopolymeric matrix, a homogeneous nanofiller dispersion was achieved; furthermore, the established biopolymer/nanofiller interactions caused a restrain of the dynamics of the biopolymer chains, thus inducing a significant modification of the material rheological response, which involves the appearance of an apparent yield stress and the amplification of the elastic feature of the viscoelastic behavior. Besides, the rheological characterization under non-isothermal elongational flow revealed a marginal effect of the embedded nanofillers on the biopolymers behavior, thus indicating their suitability for film blowing processing. Additionally, the processing behavior of the bionanocomposites was evaluated and compared to that of similar systems based on a low-density polyethylene matrix: this way, it was possible to identify the most suitable materials for film blowing operations. Finally, the assessment of the mechanical properties of the produced blown films documented the potential exploitation of the selected materials for packaging applications, also at an industrial level.