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Abstract The neural crest hypothesis posits that selection for tameness resulted in mild alterations to neural crest cells during embryonic development, which directly or indirectly caused the appearance of traits associated with the “domestication syndrome” (DS). Although representing an appealing unitary explanation for the generation of domestic phenotypes, support for this hypothesis from morphological data and for the validity of the DS remains a topic of debate. This study used the frameworks of morphological integration and modularity to assess patterns that concern the embryonic origin of the skull and issues around the neural crest hypothesis. Geometric morphometric landmarks were used to quantify cranial trait interactions between six pairs of wild and domestic mammals, comprising representatives that express between five and 17 of the traits included in the DS, and examples from each of the pathways by which animals entered into relationships with humans. We predicted the presence of neural crest vs mesoderm modular structure to the cranium, and that elements in the neural crest module would show lower magnitudes of integration and higher disparity in domestic forms compared to wild forms. Our findings support modular structuring based on tissue origin (neural crest, mesoderm) modules, along with low module integration magnitudes for neural crest cell derived cranial elements, suggesting differential capacity for evolutionary response among those elements. Covariation between the neural crest and mesoderm modules accounted for major components of shape variation for most domestic/wild pairs. Contra to our predictions, however, we find domesticates share similar integration magnitudes to their wild progenitors, indicating that higher disparity in domesticates is not associated with magnitude changes to integration among either neural crest or mesoderm derived elements. Differences in integration magnitude among neural crest and mesoderm elements across species suggest that developmental evolution preserves a framework that promotes flexibility under the selection regimes of domestication.

Abstract Background In horses, the morphological changes induced by the process of domestication are reportedly less pronounced than in other species, such as dogs or pigs – although the horses’ disparity has rarely been empirically tested. We investigated shape differences and modularity of domesticated horses, Przewalski’s horses, donkeys and zebras. Mandibular and tooth shape have been shown to be valuable features for differentiating wild and domesticated forms in some mammals. Results Both mandible and teeth, show a pattern of shape space occupation analogous to that of the cranium, with domesticated horses occupying a similar extension in shape space to that of wild equids. Only cranial shape data exhibit a tendency to separate domesticated horses and Przewalski’s horses from donkeys and zebras. Maximum likelihood model-based tests confirm the horse cranium is composed of six developmental modules, as reported for placental mammals in general. The magnitude of integration in domesticated horse skull was lower than in wild equids across all six cranial modules, and lower values of integration were associated with higher disparity values across all modules. Conclusion This is the first study that combines different skeletal features for the description and comparison of shape changes in all living equid groups using geometric morphometrics. We support Darwin’s hypothesis that the shape variation in the skull of domesticated horses is similar to the shape variation of all wild equid species existing today. Lower magnitudes of module integration are recovered in domesticated horses compared to their wild relatives.

Background Much of the shape variation found in animals is based on allometry and heterochrony. Horses represent an excellent model to investigate patterns of size-shape variation among breeds that were intentionally bred for extreme small and large sizes. Methods We tested whether ponies (wither height < 148 cm) have a diverging size-shape relationship in skull shape as compared to regular-sized horse breeds (wither height > 148 cm, here-after called horses) during ontogenetic growth. We used a dataset of 194 specimens from 25 horse and 13 pony breeds, two of which are miniature breeds (wither height < 96.5 cm)—Falabella, Shetland. We applied three-dimensional geometric morphometrics, linear measurements, and multivariate analyses (Procrustes ANOVAs) to quantitatively examine and compare the ontogenetic trajectories between pony and horse breeds with an emphasis on the miniature breeds as an extreme case of artificial selection on size. Additionally, we tested for juvenile characteristics in adult horse and miniature breeds that could resemble “paedomorphosis”—retention of juvenile characteristics in adult stage; e.g. large eyes, large braincase-to-face-relationship, and large head-to-body relationship. Results Allometric regression of size on shape revealed that 42% of shape variation could be explained by variation in size in all breeds. The ontogenetic trajectories of ponies and horses vary in slope and therefore in rate of change per unit size, and length. The differences in trajectory lengths and slopes result in ponies having a similar skull shape in an older age stage than horses of the same size in a younger age stage. This pattern could cause the generally perceived “paedomorphic” appearance of ponies. Miniature breeds have larger heads in relation to wither height compared to horses, a non-paedomorphic feature in horses specifically. Also, rostra (faces) are longer in adult individuals than in juveniles across all kinds of breeds. This pattern can be explained by the long-face hypothesis for grazing ungulates and could possibly be caused by the mismatch of selection by humans for shorter rostra and the dentition of ruminants. Conclusions Miniature breed specimens do not exhibit any of the classical mammalian “paedomorphic” features (large orbits, large heads), except for the adult Falabella that has enlarged orbits, possibly because they are herbivorous ungulates that are affected by functional and metabolic constraints related to low nutrient-food consumption. Instead ponies, including miniature breeds, have faster and shorter ontogenetic growth compared to horses, resulting in adult pony skulls looking in part like juvenile horse skulls.

As shown in a taxonomically broad study, domestication modifies postnatal growth. Skull shape across 1128 individuals was characterized by 14 linear measurements, comparing 13 pairs of wild versus domesticated forms. Among wild forms, the boar, the rabbit and the wolf have the highest proportion of allometric growth, explaining in part the great morphological diversity of the domesticated forms of these species. Wild forms exhibit more isometric growth than their domesticated counterparts. Multivariate comparisons show that dogs and llamas exhibit the greatest amount of differences in trajectories with their wild counterparts. The least amount is recorded in the pig–boar, and camel and horse pairs. Bivariate analyses reveal that most domesticated forms have growth trajectories different from their respective wild counterparts with regard to the slopes. In pigs and camels slopes are shared and intercepts are different. There is a trajectory extension in most domesticated herbivores and the contrary pattern in carnivorous forms. However, there is no single, universal and global pattern of paedomorphosis or any other kind of heterochrony behind the morphological diversification that accompanies domestication.

The present work investigates the aquatic biodegradation of poly(3-hydroxybutyrate) (PHB)/nanoclay bionanocomposites containing PP-g-MA as compatibilizing agent. Both pristine and organically modified (Cloisite20A®) montmorillonite clay were used as fillers in different content (1 and 3 wt%). The bionanocomposites were prepared by melt intercalation in a single screw extruder. There after films (50x50x0.5mm) were prepared by compression and assessed by X-ray diffraction. Aquatic biodegradation of the films was appraised by visual inspection, optical microscopy, counting and identification of bacteria. Results proposed that the water of the Parnaíba River in the city of Teresina (Piauí, Brazil) has microorganisms (Pseudomonas putida and Pseudomonas aeruginosa) capable of degrading these bionanocomposite films, particularly the films with 3 wt% organoclay. Our data indicated the bacteria Pseudomonas aeruginosa degraded dexterously all the films. This work collaborates with the preservation of the environment and expands the use of bionanocomposites in expendable items with the development of films with properties favorable to biodegradation in aquatic environments. It is believed that PHB/clay/PP-g-MA films emerge as a promising alternative for the packaging industry.

The development of polymeric biocomposites containing natural fibers has grown over the years due to the properties achieved and its eco-friendly nature. Thus, biocomposites involving a polymer from a renewable source (Biopolyethylene (BioPE)) and babassu fibers (BFs), compatibilized with polyethylene grafted with maleic anhydride (MA) and acrylic acid (AA) (PE-g-MA and PE-g-AA, respectively) were obtained using melt mixing and injection molded into tensile, impact, and HDT specimens. Babassu fiber was characterized with Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TGA), and scanning electron microscopy (SEM). The biocomposites were characterized using torque rheometry, TGA, tensile strength, impact strength, thermomechanical properties, Shore D hardness, and SEM. The data indicate that the torque during the processing of compatibilized biocomposites was higher than that of BioPE/BF biocomposites, which was taken as an indication of a possible reaction between the functional groups. Compatibilization led to a substantial improvement in the elastic modulus, tensile strength, HDT, and VST and a decrease in Shore D hardness. These results were justified with SEM micrographs, which showed babassu fibers better adhered to the surface of the biopolyethylene matrix, as well as an encapsulation of these fibers. The system investigated is environmentally sustainable, and the results are promising for the technology of polymeric composites.

Abstract In this study, green high-density polyethylene (GHDPE) composites with 5, 10 and 15% natural powdered cork (CP) with and without 5% maleic anhydride (PE-g-MA) were developed in order to evaluate the potential of these materials for civil construction applications. The composites were produced in a co-rotating twin-screw extruder and injection molded. An impedance tube was used to determine the acoustic behavior of the composites, which were then used as ceiling tiles in prototypes of provisional constructions in order to study ascertain their performance with respect to thermal comfort in the City of Teresina, PI - Brazil. Our data indicates that composites sound absorption coefficient values are good between 500 and 1200 Hz, especially for those with a higher percentage of cork, with the lowest absorption rate observed for composites containing PE-g-MA. The composites used in the prototypes provided a decrease in the internal temperature of the built structure.

This work developed ternary films based on Poly(Lactic Acid) (PLA), Cloisite 30B (C30B) and Oregano Essential Oil (OEO) as proposal to be applied in food packaging. The films thus manufactured were unscathed, with reduced surface defects. Their thickness and moisture content varied according to the composition and content of each component in the formulation. Optical micrographs indicated a homogeneous morphology, with good distribution of clay in the matrix. FTIR data confirms the incorporation of OEO into the films. TGA analysis indicated that the thermal stability of the films was not significantly affected by the incorporation of C30B and OEO. OEO incorporation did not promote an efficient antimicrobial action which is probably due to its retention by the clay. Further studies are needed to confirm this hypothesis. The combination between C30B and OEO in the PLA polymeric matrix is a promising proposal.

Growing demands for the use of biodegradable polymer films in food packaging have led to studies on several sources of non-conventional starches. Corn starch (CS), is the most investigated starch source for food packaging due to its abundance and stability under processing and manufacturing conditions. Other sources of starch such as rice, potatoes and cassava have also been investigated and, more recently, babassu mesocarp starch (BMS), native to Northeastern Brazil, has been explored for its innovative potential in the manufacture of biodegradable films. In this work is we have extracted and characterized the starch contained in babassu mesocarp and to compared its morphology, structure, thermal stability and viability for polymer film manufacturing with that of commercial corn starch. Our data showed babassu mesocarp native starch granules to have an oval shape and to display flaking and fractured surfaces while corn starch granules exhibited polygonal shapes with smooth surfaces and without aggregates. XRD analysis revealed two different types of crystalline forms for both starches. Although babassu starch is less thermally stable than commercial corn starch, both starches have similar characteristics and it is believed that babassu mesocarp starch can be used as new renewable and biodegradable resource for food packaging applications.

It is well known that the inadequate disposal of polymeric materials causes significant environmental problems. Recycling and the use of biodegradable polymers are among the methods used to minimize these problems. However, the low mechanical performance of the majority of biodegradable polymers hinders the direct substitution of synthetic polymers, such as polyethylene (PE), polypropylene (PP) and polystyrene (PS), by biodegradable ones. Blending synthetic and biodegradable polymers is a way to develop recyclable biodegradable products with a good set of mechanical properties. Therefore, in this work we investigate the influence of extrusion cycles on the degradation of a polypropylene/poly (butylene adipate-co-terephthalate)/thermoplastic starch blend before and after inoculation with Aspergillus sp. and Penicillium sp. fungi degradaded for 30 days. The samples were exposed to the fungi and their mass loss, chemical structure, hydrophilicity, and morphology were observed as a function of inoculation time and processing cycles. Our results indicate that thermo-mechanical degradation favors the deposition of fungi in the samples and enables changes in film morphology and hydrophilicity. Keywords: Fungi degradation, Mechanical recycling, Hydrophilicity

The aim of this work was to produce filaments of PLA/PBAT and NPK fertilizer adsorbed on organophilized bentonite intended for application in the prototyping of biodegradable agricultural artifacts in 3D printing, using the Fused Deposition Modeling (FDM) technique. This is the first time that we have reported this composite for a 3D printing approach. Systems containing PLA/PBAT, organobentonite and NPK were initially processed in an internal mixer and later extruded as filaments in a single-screw extruder. The prototypes were printed by FDM. Structural, morphological and thermal properties, as well as NPK releasing, were investigated. The results suggest that exfoliated and/or intercalated nanocomposites were obtained by the organoclay addition to the PLA/PBAT blend. The morphological analysis revealed a good surface quality of the impressions. Systems containing organobentonite released approximately 22% less fertilizer in 24 h compared to the systems without organobentonite. This difference is due to the higher concentration of nanoparticles that generate more barriers to the diffusion of NPK. The release data for these systems had a better fit to the kinetic model of Korsmeyer-Peppas. Thus, studied filaments have the potential to retard the release of fertilizer and are suitable for further development of structures for agricultural applications by FDM.

The aim of this study was to manufacture and characterize bionanocomposites based on a poly(hydroxybutyrate)/polyethylene glycol blend (PHB/PEG) filled with an organobentonite (CLT1 and CLT3) or an organovermiculite (VMT1 and VMT3) in concentrations of 1 and 3 wt%. The systems were prepared by solution intercalation and further characterized by X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. The use of these bionanocomposites aimed at improving the processing and compatibility of this blend in search of new properties and possible applications of these films in food disposable packaging. The thermal stability of the system varied according to the type of clay and, consequently, the chemical structure of the quaternary ammonium salt used. The VMT1, VMT3 and CLT3 systems showed increased degrees of crystallinity compared to neat PHB. Differences in bionanocomposites structure can be related to the type of clay used as two types of PHB/PEG blend. Keywords: PHB, Blends, Bionanocomposites, Clays, Thermal behavior

In this work, of poly(hydroxybutyrate) (PHB) and glass microspheres (HGM) in different compositions with polypropylene-grafted-maleic anhydride (PP-g-MA) composites were developed by melt intercalation, and then, films from the composites and the polymer matrix were obtained. Subsequently, the morphological, thermal, and mechanical properties were evaluated. A good distribution and intermediate dispersion of the filler throughout the matrix with the formation of some agglomerates was observed, while adhesion between the components was not achieved. The HGM did not affect significantly the thermal properties of the systems; there were discrete variations in the initial degradation temperature (Tonset), peak temperature (Tp), and melting temperature (Tm). However, the degree of crystallinity decreased with the addition of the HGM, and the film with 3% HGM had a variation above 11%. Additionally, it was noticed that the composites (regardless of the presence of PP-g-MA) presented small values of elongation and ultimate stress compared with those of pure PHB. Keywords: Polymer composite, PHB, Thin films, Mechanical properties, Thermal properties, Hollow glass microspheres

Abstract The use of polymer blends and composites based on fossil-based and bio-based polymers has become an important environmentally protective alternative for common use and disposable plastics applications such as packaging, bottles and trays. The disposal of these more degradable products, however, may also harm the environment and, therefore, recycling these systems becomes relevant. Recycling involves reprocessing which can significantly change the morphology and properties of polymeric products. Therefore, this study deals with the effects of reprocessing cycles on the properties and morphology of blends and nanocomposites based on fossil and bio-based polymers. The systems investigated were: a) neat polypropylene (PP), b) a polypropylene/poly(3-hydroxybutyrate) (PP/PHB) blend and c) PP/PHB/organoclay nanocomposite compatibilized with polypropylene-g-maleic anhydride (PP-g-MA) and erucamide. These materials were submitted to up to seven extrusion cycles in a single screw extruder operating at 60 rpm. Samples were taken after the first, third, fifth and seventh extrusion cycles and their tensile properties and morphology were determined. Scanning electron microscopy indicated that two phases were observed in the blend which showed spherical PHB domains. The addition of clay, PP-g-MA and erucamide improved the adhesion between the nanocomposites components. X-ray diffraction analysis showed that crystallinity tended to increase with the number of reprocessing cycles for all systems investigated up to the fifth cycle and then tended to decrease. A 10% crystallinity increase was observed for neat PP in the fifth cycle. In general, the tensile properties of all systems decreased with reprocessing and the highest losses were observed for the PP/PHB blend after seven processing cycles with 50% and 37% decreases in stress at break and elastic modulus, respectively. Impact strength of the PP matrix and of the PP/PHB blend tended to decrease with reprocessing, except for the nanocomposite which showed a slight increase especially after the seventh processing cycle in which an 18% increase in impact strength was observed.

Abstract This study aims to evaluate the effects of natural weathering in the city of Teresina, State of Piauí, Brazil, on the morphology and mechanical properties of eco-composites based on high-density green polyethylene, powdered cork and compatibilizer processed in a twin-screw extruder and injection molded. The analyses revealed that although weathering induced surface bleaching of eco-composites and cracking, these effects were not intense in the compatibilized samples. The tensile properties of the investigated materials were affected by abiotic degradation, which led to a reduction of the tensile strength and elastic deformation of the eco-composites, however, the incorporation of PEgMA was fundamental for the maintenance of mechanical performance after natural aging. In general, the results obtained were satisfactory for external applications of the compatibilized eco-composite with 15% cork in the proposed weathering range, which indicates its possible use in temporary constructions.

Polymeric syntactic foams are composites made from the mixture of Hollow Glass Microspheres (HGM) and polymer matrices. One of their main characteristics is their low density and the production of these composites using a matrix derived from renewable sources potentiates their development without neglecting sustainability. In this paper , the properties of High Density Polyethylene (HDPE)/HGM syntactic foams containing 1% and 5% w/w HGM and 5% w/w of a compatibilizer are assessed. The composites were prepared by two processing routes: single screw extruder and twin screw extruder. The morphology and mechanical properties (tensile and impact) of the syntactic foams thus manufactured were ascertained. Morphological analysis indicated that matrix/filler adhesion was poor for all samples and that the best HGM dispersions were obtained in twin screw extruded samples. Mechanical properties were affected by the processing route adopted and by the content of hollow glass microspheres added. Elastic modulus, tensile strength and strain were reduced by 20, 10 and 23%, respectively, in systems processed in a twin screw extruder. Impact strength was the exception, with an increase of more than 300%. Higher contents of hollow glass microspheres led to reductions in mechanical strength of the syntactic foams, varying from 5% for the elastic modulus to 50% for strain.

Abstract Nonisothermal crystallization and melting of the biodegradable thermoplastics poly(3-hydroxybutyrate) (PHB), poly(butylene adipate-co-terephthalate) (PBAT), and a 1:1 PHB/PBAT blend were investigated by differential scanning calorimetry (DSC) over an extensive range of heating/cooling rates (2 to 64°C/min). The different phase transition behavior of the neat components was reflected in the mixture and suggest an immiscible blend. Pseudo-Avrami, Ozawa and Mo classical macrokinetic models were used to describe the evolution of the melt crystallization process. Results suggest that none of these models could be used to predict the experimental results of crystallization kinetics of the blend with sufficient precision for polymer processing applications. However, some methods may be of used for the neat resins over restricted ranges of cooling rate, temperature or conversion (e.g., Ozawa for PHB at low cooling rate, Mo for PBAT).

Compression molded biodegradable films based on poly(butylene succinate) (PBS) and poly(butylene adipate-co-terephthalate) (PBAT) at varying weights were prepared, and their relevant properties for packaging applications are here reported. The melt rheology of the blends was first studied, and the binary PBS/PBAT blends exhibited marked shear thinning and complex thermoreological behavior, due to the formation of a co-continuous morphology in the 50 wt% blend. The films were characterized by infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), mechanical tensile tests, scanning electron microscopy (SEM), and oxygen and water vapor permeability. PBS crystallization was inhibited in the blends with higher contents of PBAT, and FTIR and SEM analysis suggested that limited interactions occur between the two polymer phases. The films showed increasing stiffness as the PBS percentage increased; further, a sharp decrease in elongation at break was noticed for the films containing percentages of PBS greater than 25 wt%. Gas permeability decreased with increasing PBS content, indicating that the barrier properties of PBS can be tuned by blending with PBAT. The results obtained point out that the blend containing 25 wt% PBS is a good compromise between elastic modulus (135 MPa) and deformation at break (390%) values. Overall, PBS/PBAT blends represent an alternative for packaging films, as they combine biodegradability, good barrier properties and reasonable mechanical behavior.

Resumo Este trabalho teve como objetivo preparar e avaliar filmes PHB/vermiculita natural e modificada nas quantidades em peso de 1%, 3% e 6% através dos métodos intercalação por fusão e intercalação por solução. Os bionanocompósitos obtidos pelo método intercalação por fusão foram preparados em uma extrusora monorosca e posteriormente os filmes foram moldados via compressão. Na preparação dos filmes por solução, os sistemas foram submetidos à agitação e aquecimento a 80 °C. Os sistemas foram avaliados por difração de raios-X e o comportamento de biodegradação foi avaliado de acordo com a norma ASTM G 160-03. O acompanhamento da biodegradação foi realizado por meio de inspeção visual e perda de massa. Observou-se que o percentual de argila e o método de obtenção dos filmes influenciaram na estrutura formada e na biodegradação dos sistemas.

A inflamabilidade de nanocompósitos com três tipos de polipropileno (homo e copolímeros) contendo 5% de argila montmorilonita organofílica (Cloisite 20A), 5 e 15% de polipropileno enxertado com anidrido maleico como agente compatibilizante e 0, 0,5 e 1% de cis-13-docosenamida (Erucamida) como agente co-intercalante foi estudada através do teste de queima horizontal UL94HB. Concentrados foram preparados em misturador interno e diluídos com a matriz de polipropileno em extrusora de dupla rosca corrotacional com diferentes configurações de rosca e velocidades rotação de 240 e 480 rpm. Os resultados indicaram aumento da velocidade de queima dos compósitos quando comparados às das matrizes e que a velocidade de queima não foi afetada pelas condições de processamento. Em todos os casos, foi observado durante o ensaio uma redução da emissão de fumaça, ausência de gotejamento de material e a formação de uma camada carbonácea, levando à preservação da estrutura interna da amostra.

Compósitos de PP/argila/PP-g-MA/erucamida contendo 5% (em peso) de argila montmorilonita organofílica (Cloisite 20A), 5 e 15% de PP-g-MA como agente compatibilizante e 0, 0,5% e 1% de cis-13-docosenamida (erucamida) como agente co-intercalante, foram preparados por intercalação no estado fundido. Concentrados de argila e compatibilizantes foram processados em misturador interno e em seguida diluídos com a matriz de polipropileno em extrusora de dupla rosca corrotacional. Os compósitos foram caracterizados através das propriedades mecânicas, difração de raios X e microscopia óptica. Os resultados indicaram o efeito reforçante da argila organofilizada. A presença de co-intercalante aumentou significativamente a distância interlamelar da argila em todos os compósitos, em geral, não afetando notavelmente o comportamento mecânico dos compósitos. Por microscopia óptica foi possível observar o efeito dispersivo do perfil de rosca utilizado, que promoveu a quebra dos aglomerados de argila.