Polylactic acid (PLA) and montmorillonite (CB) as filler were studied as coatings for cellulose based packages. Amorphous (AM) and semi crystalline (SC) PLA were used at different concentrations according to a 2 × 6 × 3 full factorial experimental design. CB loading was three concentrations and coating was performed by casting. Contact angle (CA), water vapor (WVP) and grease permeabilities were measured for each resultant package and were compared to commercial materials (Glassine Paper, Grease Proof Papers 1 and 2 produced commercially). Significant differences were found and the main factors were the type and concentration of PLA. The best values were: for grease penetration, +1800 s; WVP from 161.36 to 237.8 g·µm·kPa−1·m−2·d−1 and CA from 69° to 73° for PLA–AM 0.5% and CB variable. These parameters are comparable to commercial packages used in the food industry. DSC revealed three different thermal events for PLA–SC and just Tg for PLA–AM. Crystallinity was also verified, obtaining a ΔHcrys of 3.7 J·g−1 for PLA–SC and 14 J·g−1 for PLA–SC–BC, evidencing clay interaction as a crystal nucleating agent. Differences found were explained on terms of the properties measured, where structural and chemical arrays of the coatings play a fundamental role for the barrier properties.
The reduction of polylactide acid (PLA) molecular weight for amorphous and semicrystalline grade nanocomposites with 5 wt% load of organomodified montmorillonite Cloisite30B (C30B) was investigated in periods of up to 360 h under artificial weathering. A correlation between artificial and natural weathering was established. The nanocomposites were prepared by mixing the C30B in PLA matrix using two stages of extrusion followed by injection molding. In addition, we also studied materials without C30B in PLA matrix prepared by a single stage of injection, as well as with two stages of extrusion followed by injection, in order to assess thermal effects. XRD (X-ray diffraction) and TEM (Transmission electron microscope) were used to determine the layer dispersion of the C30B within the PLA. An increase in the interlayer spacing of a sandwich structure corresponding to a partial exfoliation of the C30B was found, leading to the creation of small particles at nanoscale of one (1.29 nm) to eight (11.76 nm) platelets. Also, GPC (Gel permeation chromatography) was used to evaluate the molecular weight decay of neat PLA and its nanocomposites due to thermal processing and subsequent artificial weathering exposure. From thermal processing, a more significant decrease of polydispersity in amorphous PLA than in semicrystalline PLA counterparts could be observed. First order fitting of molecular weight decay of samples versus time of exposure under artificial weathering was found for all materials tested. It was observed that the addition of clay favored PLA degradation in amorphous PLA, in comparison with semicrystalline PLA in both thermal processing and artificial weathering. Moreover, a possible effect of C30B interactions with PLA chains under artificial weathering could be postulated.
Paper recycling has increased in recent years. A principal consequence of this process is the problem of addressing some polymeric components known as stickies. A deep characterization of stickies sampled over one year in a recycled paper industry in México was performed. Based on their chemical structure, an enzymatic assay was performed using lipases. Compounds found in stickies by Fourier-transform infrared spectrometry were poly (butyl-acrylate), dioctyl phthalate, poly (vinyl-acetate), and poly (vinyl-acrylate). Pulp with 4% (w/w) consistency and pH = 6.2 was sampled directly from the mill once macrostickies were removed. Stickies were quantified by counting the tacky macrostructures in the liquid fraction of the pulp using a Neubauer chamber before the paper was made, and they were analyzed with rhodamine dye and a UV lamp. Of the two commercial enzymes evaluated, the best treatment condition used Lipase 30 G (Specialty Enzymes & Biotechnologies Co®, Chino, CA, USA) at a concentration of 0.44 g/L, which decreased 35.59% of stickies. SebOil DG (Specialty Enzymes & Biotechnologies®) showed a stickies reduction of 21.5% when used at a concentration of 0.33 g/L. Stickies in kraft paper processes were actively controlled by the action of lipases, and future research should focus on how this enzyme recognizes its substrate and should apply synthetic biology to improve lipase specificity.
Renewable polymers possess the potential to replace monomers from petrochemical sources. The design and development of polymeric materials from sustainable materials are a technological challenge. The main objectives of this study were to study the microstructure of copolymers based on itaconic acid (IA), di-n-butyl itaconate (DBI), and lauryl methacrylate (LMA); and to explore and to evaluate these copolymers as pressure-sensitive adhesives (PSA). The copolymer synthesis was carried out through batch emulsion radical polymerization, an environmentally friendly process. IA was used in a small fixed amount as a functional comonomer, and LMA was selected due to low glass transition temperature (Tg). The structure of synthesized copolymers was studied by FTIR, 1H-NMR, Soxhlet extraction, and molecular weight analyses by GPC. Furthermore, the viscoelastic and thermal properties of copolymer films were characterized by DMA, DSC, and TGA. The single Tg displayed by the poly(DBI-LMA-IA) terpolymers indicates that statistical random composition copolymers were obtained. Moreover, FTIR and NMR spectra confirm the chemical structure and composition. It was found that a cross-linked microstructure and higher molecular weight are observed with an increase of LMA in the feed led. The Tg and modulus (G′) of the copolymers film can be tuned with the ratio of DBI:LMA providing a platform for a wide range of applications as a biobased alternative to produce waterborne PSA.
Herein, a methodology is employed based on the Flory–Rehner equation for estimating the Flory–Huggins interaction parameter (χ12*) of crosslinked elastomer blends. For this purpose, binary elastomer blends containing polybutadiene rubber (BR), styrene–butadiene rubber (SBR) and nitrile–butadiene rubber (NBR), were prepared in a mixing chamber at a temperature below the activation of the crosslinking agent. Swelling tests with benzene were employed to determine the crosslinked fraction, finding that after 20 min of thermal annealing, the BR and NBR were almost completely crosslinked, while the SBR only reached 60%. Additionally, the BR-SBR blend increased by 2–3 times its volume than its pure components; this could be explained based on the crosslink density. From the mechanical tests, a negative deviation from the rule of mixtures was observed, which suggested that the crosslinking was preferably carried out in the phases and not at the interface. Furthermore, tensile tests and swelling fraction (ϕsw) results were employed to determine the average molecular weight between two crosslinking points (Mc), and subsequently χ12*. Calculated χ12* values were slightly higher than those reported in the literature. The calculated thermodynamic parameters for the blends showed positive ΔGmix values and endothermic behavior, suggesting their immiscible nature.
Thermal stability as well as enhanced mechanical properties of poly-lactide (PLA) can increase PLA applications for short-use products. The conjunction of adequate molecular weight (MW) as well as satisfactory thermo-mechanical properties, together, can lead to the achievement of suitable properties. However, PLA is susceptible to thermal degradation and thus an undesired decay of MW and a decrease of its mechanical properties during processing. To avoid this PLA degradation, nanofiller is incorporated as reinforcement to increase its thermo-mechanical properties. There are many papers focusing on filler effects on the thermal stability and mechanical properties of PLA/nanocomposites; however, these investigations lack an explanation of polymer/filler interactions. We propose interactions between PLA and Cloisite30B (C30B) as nanofiller. We also study the effects on the thermal and mechanical properties due to molecular weight decay after exposure to artificial weathering. PLA blank and nanocomposites were subjected to three time treatments (0, 176, and 360 h) of exposure to artificial weathering in order to achieve comparable materials with different MW. MW was acquired by means of Gel Permeation Chromatography (GPC). Thermo-mechanical properties were investigated through Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-ray Diffraction (XRD), Dynamic Mechanical Thermal Analysis (DMTA) and Fourier Transform Infrared Spectroscopy (FTIR).